PROCESS FOR PRODUCING MESOPHASE OIL PICK BY HYDROGENATION OF HIGH-TEMPERATURE HULA TAR

专利摘要:
A process for producing mesophasic oil tar by high temperature coal tar hydrogenation is a process for producing mesophasic oil tar from high temperature coal tar comprising: salt removal and insoluble quinoline fraction from a high temperature coal tar to obtain a settling oil; using the settling oil as a hydrogenation feedstock, or pre-distilling the settling oil to obtain a residue with a boiling point greater than 230 ° C and formulating the residue into a hydrogenation feedstock; catalytically hydrolyze the hydrogenation feedstock to obtain a hydrofoil; distill the hydroforinated oil to obtain hydrogenated oil tar; and subjecting the hydrogenated oil tar to thermal polymerization to obtain the mesophasic oil tar. The process has features such as an easily controllable degree of hydrogenation, complete removal of impurities, good flowability of the raw material, not tending to form carbon deposition and coking during the process, and not tending to clog the reactor. The product has a high mesophasic oil tar content, a low softening point and a low impurity content.
公开号:BR112014017348B1
申请号:R112014017348-6
申请日:2012-04-06
公开日:2019-08-20
发明作者:Hongmei Zhao；Jieshan Qiu；Jincheng Xiao；Baoming Li；Junde Lv；Nan Xiao
申请人:Eco Environmental Energy Research Institute Limited；Dallian University Of Technology；
IPC主号:

专利说明:

PROCESS TO PRODUCE MESOPHASE PETROLEUM PICHE BY HYDROGENATION FROM HULK TAR AT HIGH TEMPERATURE
TECHNICAL FIELD [0001] The invention belongs to the new field of carbon material engineering and fuel chemistry, and refers specifically to a process suitable for preparing mesophasic petroleum tar from high-temperature coal tar on an industrial scale.
BASICS OF THE TECHNIQUE [0002] China is the world's largest producer of coke. Statistical information shows that China produced 388 million tons of coke in 2010, representing 60% of world production. Coal tar resources are abundant in China, where the production of recycled coal tar from coke oven gas reaches 18,000,000 tonnes.
[0003] In China, the technical way to process coal tar at high temperature is basically an approach to produce BTX fraction, carbolic oil, naphthalene oil, washing oil, anthracine oil and petroleum tar by distilling the tar, whose products have no variety. In recent years, since the project with a coal tar processing scale of 300,000 tonnes is implemented, the variety of the chemical refined from it is continuously increasing. However, due to the low yield of these products, it can converge only in the refining process of carbolic oil, naphthalene oil, washing oil and anthracine oil for current products. Meanwhile, the
2/79 main problem brought about by this processing route is serious environmental pollution. Since the resulting petroleum pitch can be further processed only to produce low added value products such as medium temperature petroleum pitch, petroleum pitch and modified petroleum pitch coke and so on, the oil pitch value does not it can be reflected, which means that the products in the project as a whole are of low added value, and of non-ideal benefits.
[0004] There is a growing and rapidly expanding global need for new materials, especially advanced carbon materials, with the progress of technology and the ever-increasing demands for environmental protection. All carbon fiber, carbon foam, C / C composite, tar-based mesocarbon microspheres and so on show an extremely wide application landscape. However, the scale of industrial production of new carbon materials, especially mesophasic petroleum tar, a precursor to advanced carbon materials, is stalling. Most of the technical solutions are still in the experimental stage, rarely to be adapted to the scale of industrial production. The existing technology for industrial production of mesophasic petroleum tar always faces problems with difficult technologies and high costs, which limits the application and promotion of new carbon materials.
[0005] The production of acicular coke and mesophasic petroleum tar from petroleum tar of
3/79 coal tar is always the focal point of research for Chinese engineers. After years of effort, positive progress has been made in the industrial production of ear coke. However, due to the limitations inherent to coal tar oil tar, although extensive research has been carried out, limited success has been achieved in the field of mesophasic oil tar due to either high costs or high industrialization difficulties.
[0006] The Chinese patent of No.CN8510744IA introduced a process to produce acicular super coke using coal tar or petroleum tar from insoluble quinine-free coal tar (IQ). However, the process has a low degree of catalytic hydrogenation, a difficult technology of direct hydrogenation of coal tar or coal tar oil tar, and a short catalyst life. This process does not make full use of hydrogenated solvent oil, a by-product, to optimize itself, which results in the loss of a large amount of valuable β resin, a low oil pitch yield and a low degree of hydrogenation of components. low boiling point.
[0007] Chinese patent No.CN87103787A introduced a process to produce mesophasic petroleum tar for high performance carbon fibers from coal tar or residual petroleum oil through heat treatment and solvent hydrogenation. The process requires a large amount of xylene, hydrogenated anthracine oil and washing oil solvent which cannot be self-produced by the process, resulting in a high production cost. As a technology for processing heat with pyrolysis and instant multistage vaporization is employed, it is very easy to cause coking and clogging in the system, resulting in difficulties in continuous large-scale production.
[0008] The Chinese patent of No.CN85105609A revealed a process for hydrogenating coal tar or coal tar oil tar, in which the catalyst metal has a low amount of charge and low activity, and was poor in removing heteroatom from oil pitch. The process employed a unique means of mild catalytic hydrogenation which could hardly change the molecular structure. In addition, coal tar or coal tar oil tar has a high colloid and asphaltene content, which causes easy carbon deposition and short catalyst life under fixed base catalytic conditions and a difficulty in hydrogenation, therefore, long-term hydrogenation can hardly be achieved.
[0009] Chinese patent No.ZL200610032060.7 introduced a process to produce fuel oil by hydrogenation of coal tar, which required converting all the high temperature coal tar distillation fractions into naphtha, gasoline and diesel, and had high requirements for catalyst activity and hydrogenation reaction conditions.
5/79 [0010] The Chinese patent of No.CN101074381A introduced a process to process and use coal tar, the target product of which is gasoline and diesel. It does not mention in its content the search for oil tar. The pre-processing of coal tar there needs to be optimized.
[0011] The invention aims to overcome the disadvantages in the prior art, raising a new approach to process and use coal tar at high temperature, and to provide a suitable process for industrialization application to produce mesophasic petroleum tar from the catalytic hydrogenation of high temperature coal tar with by-products such as carbolic oil, crude naphthalene, naphtha and gasoline and diesel blending components, to increase the value of coal tar processing products by a large margin.
SUMMARY OF THE INVENTION [0012] One aspect of the invention is to provide a process for producing mesophasic petroleum tar from high temperature coal tar, which comprises:
[0013] (1) removal of salts and insoluble fraction of quinoline from a coal tar at high temperature to obtain a settling oil;
[0014] (2) obtain a hydrogenation raw material from the settling oil using either of the following two approaches:
[0015] (2a) use the settling oil as the raw material for hydrogenation; or
6/79 [0016] (2b) pre-distill the settling oil to obtain a residue with a boiling point greater than 230 ^s C, and mix the residue with formulated oil to obtain the hydrogenation raw material, in which the formulated oil comprises one or more components selected from the group consisting of coal tar distillation fractions and the hydrogenated product of the coal tar distillation fractions;
[0017] hydrorrefining catalytically the hydrogenation raw material to obtain a hydrorrefined oil;
[0018] (3) distilling the hydrorefined oil to obtain hydrogenated petroleum pitch;
[0019] (4) subjecting the hydrogenated petroleum tar to thermal polymerization to obtain the mesophasic petroleum tar.
[0020] In some modalities, step (1) comprises:
[0021] (la) a salt removal step, which comprises mixing deionized water and an aromatic solvent with the coal tar at high temperature, and centrifuging them to remove wash water to obtain a desalted coal tar at high temperature with the aromatic solvent; wherein the aromatic solvent comprises one or more components selected from the group consisting of benzene, toluene, xylene, coal tar distillation fractions and hydrogenation product from coal tar distillation fractions.
[0022] In some modalities, in the step (la) of salt removal, the volume ratio of coal tar
Ί / Ί2 at high temperature for aromatic solvent is 1: 0.2 to 2, the volume ratio of deionized water to coal tar at high temperature is 0.5 to 3, and deionized water is used for wash coal tar at high temperature 1 to 3 times. Preferably, the volume ratio of coal tar at high temperature to the aromatic solvent is 1: 0.2 to 0.8.
[0023] In some modalities, step (1) comprises:
[0024] (lb) a step of removing the insoluble fraction of quinoline, which comprises adding an aliphatic solvent and optionally the aromatic solvent in the coal tar desalinated at high temperature with the aromatic solvent, and followed by centrifugation or sedimentation to remove the fraction quinoline insoluble; the aliphatic solvent comprises C ₄ -C ₆ aliphatic compounds; where the final volume ratio of coal tar at high temperature, aromatic solvent and aliphatic solvent is 1: 0.2 to 2: 0.2 to 1. Preferably, the final volume ratio of coal tar to high temperature
solvent aromatic and the aliphatic solvent is in 1: 0.3 to 0.8: 0.3 to 0.8. [0025] In some modalities, O solvent aliphatic it is n-octane or n-heptane. [0026] In some modalities,the pre- distillation in step (2b) comprises a step in recycle
aliphatic solvent.
8/79 [0027] In some embodiments, predestilation in step (2b) comprises a step of obtaining at least one of BTX fraction, carbolic oil and naphthalene oil.
[0028] In some embodiments, step (2) additionally comprises a filtering step to filter particles with a particle size greater than 10pm before the catalytic hydrorefining.
[0029] In some embodiments, in step (2), the catalytic hydrorefining is conducted under conditions of a total pressure of 12, OMPa at 20.0 MPa, an average reaction temperature of 320 ^Q C to 400 ^g C, space speed net hourly OjShr ' ¹ to 2.0 hr' ¹ , and a hydrogen-oil ratio of 600: 1 to 1500: 1. Preferably, the catalytic hydrorefining is carried out under conditions of a total pressure of 14, OMPa at 18.0 MPa, an average reaction temperature of 340 ^Q C at 390-C, net hourly space velocity from 0.8hr ¹ to 1.2 hr and a hydrogen-oil ratio of 800: 1 to 1200: 1.
[0030] In some embodiments, in step (2), the catalytic hydro-refining is conducted in the presence of the following catalyst:
[0031] hydro-refining catalyst A: employing alumina or silica-alumina as a carrier which has a specific surface area of 120 to 3 00m ² / g, a pore volume of 0.4 al, 4mL / g, a diameter pore size from 8 to 20nm, and an acidic surface content of 0.05 to 0.1mmol / g, and Mo or W from the VIB group of metals and Co or Ni from the VIII group of metals as active metal components, based on weight total of the hydrorefining catalyst A, the content of the VIB group of metals counted in oxide is 15 to 45¾ by weight,
9/79 and the content of group VIII of metals counted in oxide is 1.5 to 5% by weight.
[0032] In some embodiments, in step (2), the catalytic hydro-refining is conducted in the presence of the following two catalysts:
[0033] hydrorefining catalyst A: employing alumina or silicon-containing alumina as a carrier, which has a specific surface area of 120 to 300m ² / g, a pore volume of 0.4 to 4mL / g, a pore diameter of 8 to 20 nm, an acidic surface content of 0.05 to 0.1 mmol / g; and Mo or W of the VIB group of metals and Co or Ni of the group VIII of metals as active metal components, based on the total weight of the hydro-refining catalyst A, the content of the VIB group of metals counted in oxide is 15 to 45% by weight, and the content of group VIII of metals counted in oxide is 1.5 to 5% by weight;
[0034] hydrorefining catalyst B: employing alumina or alumina containing silicon as a carrier, which has a specific surface area of 120 to 300m ² / g, a pore volume of 0.4 al, 2mL / g, a diameter pore size from 7 to 15 nm; and Mo or W from the VIB group of metals and Co or Ni from the VIII group of metals as active metal components; based on the total weight of hydrorefine catalyst B, the content of the VIB group of metals counted in oxide is 10 to 22% by weight, and the content of group VIII of metals counted in oxide is 2 to 5% by weight.
[0035] In some modalities, in step (2), the hydrogenation raw material is catalytic hydro-refined
10/79 after passing through a protective catalyst and a demetallization catalyst, the demetallization catalyst employs alumina as a carrier which has a pore volume of 0.5 to 5mL / g, a specific surface area of 180 at 350m ² / g, a pore diameter of 10 to 50nm; based on the total weight of the demetallization catalyst, the demetallization catalyst contains 7 to 20% of the weight of molybdenum oxide and 2 to 5% of the weight of nickel oxide.
[0036] In some embodiments, in step (3), the distillation comprises a step of obtaining a hydrogenated solvent with a high boiling point with a dispersion of
boiling 300 at 360 ^Q C and a fraction distillation hydrogenated with a dispersion of boiling of 80 to 300 ^s C. [0037] In some modalities, the step (1)
comprises:
[0038] (la) a salt removal step, which comprises mixing deionized water and aromatic solvent with the coal tar at high temperature, and centrifuging them to remove the washing water, obtaining a coal tar desalinated at high temperature with the aromatic solvent, where the aromatic solvent is the hydrogenated solvent with a high boiling point.
[0039] In some modalities, step (1) comprises:
[0040] (lb) a step of removing insoluble fraction of quinoline, which comprises adding aliphatic solvent and optionally the aromatic solvent in the coal tar desalinated at high temperature with the solvent
ΊΊ / Ί9 aromatic, mix and centrifuge them or leave them for sedimentation to remove the insoluble fraction of quinoline, the aliphatic solvent comprises C ₄ -C ₁₆ aliphatic compounds, the aromatic solvent is the high boiling hydrogenated solvent, in that the final volume ratio of coal tar at high temperature, aromatic solvent and aliphatic solvent is 1: 0.3 to 0.8: 0.3 to 0.8. Preferably, the final volume ratio of coal tar at high temperature, hydrogenated solvent with high boiling point and aliphatic solvent is 1: 0.5 to 0.8: 0.5 to 0.8.
[0041] In some embodiments, in step (2b), the formulated oil comprises the hydrogenated solvent with a high boiling point and the hydrogenated distillation fractions.
[0042] In some embodiments, in step (2b), the formulated oil comprises the hydrogenated solvent with a high boiling point, BTX fraction, washing oil and the hydrogenated distillation fractions.
[0043] In some embodiments, the volume ratio of the BTX fraction or washing oil: of the hydrogenated solvent with a high boiling point: of the hydrogenated distillation fractions: of the residues is 0.2 to 1: 0 to 1: 0 to 1: 1. Preferably, the volume ratio of the BTX fraction or washing oil: of the hydrogenated solvent with a high boiling point: the hydrogenated distillation fractions: of the residues is 0.2 to 0.4: 0 to 0.5: 0 to 0 , 5: 1.
12/79 [0044] In some embodiments, the thermal polymerization in step (4) comprises a step of obtaining an oil of instant separation.
[0045] In some embodiments, the process of the invention additionally comprises:
[0046] (5) catalytically hydrocrack the hydrogenated solvent with a high boiling point and the oil of instant separation after mixing them to obtain a hydrocracking product.
[0047] In some embodiments, catalytic hydrocracking is conducted under conditions of a total pressure of 12.0MPa to 20.0 MPa, an average reaction temperature of 340-C to 420 ^Q C, a net hourly space velocity of 0, 5hr ¹ to 2.0hr ^-1 , and a hydrogen-oil ratio of 600: 1 to 1500: 1. Preferably, catalytic hydrocracking is conducted under conditions of a total pressure of 14, OMPa to 18.0MPa, an average reaction temperature of 350 ^B C to 390 ² C, a net hourly space velocity of O ^ hr ' ¹ al, 5hr ^_1 , and a hydrogen-oil ratio of 800: 1 to 1200: 1.
[0048] In some embodiments, catalytic hydrocracking is conducted in the presence of the following catalyst:
[0049] hydrocracking catalyst: employing alumina, amorphous silica-alumina and microporous and mesopore molecular sieve as a carrier, where, based on the total weight of the hydrocracking catalyst, the mesoporous molecular sieve is responsible for 10 to 15% of the weight, the microporous molecular sieve is responsible for 5
13/79 to 10% by weight, amorphous silica-alumina is responsible for 15 to 40% by weight, alumina is responsible for 35 to 70% by weight; the specific surface area is 150 to 350m ² / g, and the pore volume is 0.1 to 1.0mL / g; the charged catalyst contains 10 to 35% by weight of Mo0 ₃ and / or WO ₃ , and 2 to 5% by weight of Nio and / or CoO.
[0050] In some embodiments, catalytic hydrocracking is conducted in the presence of the following two catalysts:
[0051] hydrocracking catalyst: employing alumina, amorphous silica-alumina and mesoporous and microporous molecular sieve as a carrier; where, based on the total weight of the hydrocracking catalyst, the mesoporous molecular sieve is responsible for 10 to 15% of the weight, the microporous molecular sieve is responsible for 5 to 10% of the weight, the amorphous silica-alumina is responsible for 15 to 40% by weight, alumina is responsible for 35 to 70% by weight; the specific surface area is 150 to 350m ² / g, the pore volume is 0.1 to 1.0mL / g; the charged catalyst contains 10 to 35% by weight of Mo0 ₃ and / or W0 ₃ , and 2 to 5% by weight of NiO and / or CoO;
[0052] hydro-refining catalyst B: employing alumina or silicon-based alumina as a carrier, which has a specific surface area of 120 to 300m ² / g, a pore volume of 0.4 al, 2mL / g, a pore diameter from 7 to 15nm; and Mo or W from the VIB group of metals and Co or Ni from the VIII group of metals as active metal components; based on the total weight of the hydrorefining catalyst B, the content of the VIB group of metals
14/79 counted in oxide is 10 to 22% by weight, and the content of group VIII of metals counted in oxide is 2 to 5% by weight.
[0053] In some embodiments, the distillation is carried out after mixing the hydrorefined oil with the hydrocracking product in a volume ratio of 1: 0.2 to 0.5 in step {3).
[0054] In some embodiments, step (3) additionally comprises a filtering step to remove particles with a particle size greater than 10pm before distillation.
[0055] In some embodiments, step (3) comprises a step of obtaining naphtha, gasoline blending component and diesel blending component.
[0056] In some embodiments, thermal polymerization in step (4) is conducted for 180 to 1200 minutes under conditions of a pressure of 0.01 to 3.0MPa, a temperature of 380 to 460 ^and C, with a stirring rate of 10 to 60 rpm, and purge hydrogen, nitrogen or argon at the bottom and top of the reactor. Preferably, the thermal polymerization in step (4) is carried out for 180 to 600 minutes under pressure conditions of 0.01 al, 0MPa and a temperature of 400 to 440 ^Q C, with a stirring rate of 20 to 40 rpm, and purging nitrogen at the bottom and top of the reactor.
[0057] In some modalities, step (4) comprises viscosity analysis in real time.
[0058] In some embodiments, a step of extracting with a solvent is comprised between steps (3) and (4).
15/79 [0059] In some embodiments, the solvent is an aromatic solvent comprising benzene, toluene, pyridine, quinoline or tetrahydrofuran.
[0060] Through catalytic hydrogenation of coal tar in hydrogen and in the presence of hydrogenation solvent, the inventor of the application increases the H / C ratio of coal tar oil tar, adjusts the molecular structure of oil tar from coal tar, and removes atoms of S, N and O and metal impurities. The quality of mesophasic petroleum tar can be increased substantially by producing it from hydrogenated coal tar petroleum tar, which provides a feasible process path for industrial scale production of mesophasic oil tar. The resulting product has a high content of mesophasic petroleum tar, a low softening point and a low content of impurities.
DESCRIPTION OF THE FIGURES [0061] Figure 1 is a schematic diagram of the process of the invention for producing mesophasic petroleum tar from high-temperature coal tar;
[0062] Figure 2 is a flow chart of the detailed modalities of the invention;
[0063] Figures 3A and 3B show the IR spectrograms of the clean petroleum tar and hydrogenated petroleum tar obtained in Example 1, which indicate that after hydrogenation, the hydrogenated petroleum tar still maintains a greater aromaticity, and the structural units they also comprise a high level of alkyl side chains and cycloalkane structures which makes hydrogenated oil tar to tend to be more in the form of domain anisotropy;
[0064] Figure 4 shows the NMR H spectroscopy of the hydrogenated petroleum tar obtained in Example 1;
[0065] Figures 5A and 5B show the polarized optical micrographs of the mesophasic petroleum tar of the invention.
DETAILED MODALITIES [0066] The method of the invention will be described below in conjunction with the drawings.
[0067] As shown in Figure 1, the method of the invention for producing mesophasic petroleum tar from high-temperature coal tar comprises the following steps:
[0068] Step 100 is to remove salts and insoluble fraction of quinoline from coal tar at high temperature to produce a settling oil;
[0069] Specifically, step 100 comprises step 101 of removing salts and step 102 of removing insoluble fraction of quinoline. The salt removal step 101 comprises mixing deionized water and an aromatic solvent with the coal tar at high temperature, and centrifuging them to remove wash water to obtain coal tar desalted at high temperature with aromatic solvent; wherein, the aromatic solvent comprises one or more components selected from the following group consisting of benzene, toluene, xylene, coal tar distillation fraction and the product
17/79 hydrogenated fraction of coal tar distillation; step 102 of removing insoluble quinoline fraction comprises adding an aliphatic solvent and an optional aromatic solvent to the coal tar desalinated at high temperature with the aromatic solvent, mixing and centrifuging them or sedimenting them to remove the insoluble quinoline fraction; the aliphatic solvent comprises C4-C16 aliphatic compounds, and the aromatic solvent is the hydrogenated solvent with a high boiling point, where the final volume ratio of high temperature coal tar, aromatic solvent and aliphatic solvent is 1: 0.2 to 2: 0.2 to 1.
[0070] Step 200 is to produce a hydro-refined oil (step 210) by catalytic hydro-refining of a hydrogenation raw material prepared from the settling oil using either of the following two approaches. In one embodiment, the settling oil is taken as a raw material for hydrogenation; and in another embodiment, pre-distill the settling oil to obtain a residue that has a boiling point greater than 230 ° C (step 221), mix the residue with formulated oil (step 222) to obtain a raw material of hydrogenation (step 220), wherein the formulated oil comprises one or more components selected from the group consisting of the coal tar distillation fraction and the hydrogenated product of the coal tar distillation fraction;
[0071] Step 300 is to produce a hydrogenated petroleum tar by distilling the hydro-refined oil;
18/79 [0072] Step 400 is to produce a mesophasic petroleum tar by thermal polymerization of the hydrogenated petroleum tar.
[0073] Specifically, the invention relates to a process to produce mesophasic petroleum tar by thermal polymerization of hydrogenated petroleum tar which is prepared by catalytic hydrogenation in hydrogen in the presence of a hydrogenation solvent, with naphtha, gasoline and component by-products. mixture of diesel, carbolic oil and crude naphthalene. The four steps of the method will be described in detail below together with Figure 2, where the aromatic solvent is hydrogenated solvent with a high boiling point, and the aliphatic solvent is n-octane. Those skilled in the art may understand that in the event that the mesophasic petroleum tar is produced using other aromatic solvents such as aliphatic benzene, toluene and xylene, and other solvents such as n-heptane, as listed in this document, there may be a requirement to adjust the following technological processes accordingly.
When settling oil is taken as a raw material directly, the following technological processes must also have to be adjusted accordingly.
[0074]
In the desalination section (1), the coal tar at high temperature is mixed completely with the aromatic solvent (a hydrogenated solvent with a certain point followed by high boiling) and deionized water to be washed and centrifuged, to
19/79 remove most of the washing water in it; in the removal section the insoluble fraction of quinoline (IQ) (2), then the resulting high temperature coal tar is mixed with aliphatic solvent in a certain reason followed by
be centrifuged to remove the fraction insoluble in quinoline (IQ) to produce a mixture tar in purified coal and solvents, this ie, settling oil;[0075] 2) Heat the oil settling, and
pass the same over the evaporator (3) to separate water and BTX Fraction (<L20 ^and C), pass the separated water in a treatment system for waste regeneration (not shown), pass the BTX Fraction (<120-C) at BTX Fraction tank (<L20-C) (not shown), water-free settling oil is obtained at the bottom of the evaporator, and enters the distillation column (4) after being heated. The aliphatic solvent with low boiling point from the top of the distillation column is recycled, the BTX fraction (120-180 ^and C), the carbolic oil and the naphthalene oil from the middle of the distillation column are each passed through their tanks respectively (not shown), and the residues from the distillation column (4) are mixed with BTX Fractions from the BTX Fraction tanks (<120 ^Q C and 120 to 180-C), or hydrogenated distillation fraction, or hydrogenated solvent with high boiling point in a hydrogenation raw material mixer (5), and then enter the raw material hydrogenation tank (not shown) after being filtered through the filter group (6);
[0076] 3) Mix the hydrogenation raw material from the material hydrogenation tank
20/79 press with hydrogen, then heat it before passing it in a reactor conditioned with hydrogenation protection catalyst and demetallization catalyst to additionally remove impurities and metal ions. After that, pass it in a refinement reactor conditioned with hydrorefining catalyst A to be subjected to hydrorefining to obtain a refined oil. The above protection demetallized refining reaction can be carried out in an integrated protection demetallized refining reactor (7), or can be carried out step by step in the respective reactors. At the same time, a part of the hydrogenated solvent with a high boiling point from the vacuum distillation column (12) of the subsequent section and instant separation oil separated from the top of the synthetic reaction still (14) are passed in the reactor of cracking (8) packed with cracking catalyst to be subjected to hydrocracking reaction to obtain a cracking product. The ways of packaging the catalysts are as follows:
[0077] Refining reaction: the top of the reactor is conditioned with the refining catalyst A, while the bottom is conditioned with the refining catalyst B; or the reactor is packed with refining catalyst A, while the high temperature and high pressure separator is packed with refining catalyst B at the top, and hydrorefining catalyst A at the bottom.
[0078] Cracking reaction: the cracker is packaged with a cracking catalyst, at the same time
21/79 time that refining catalyst B is loaded at the bottom of the reactor; or the cracker is conditioned with cracking catalyst, while the high temperature and high pressure separator is conditioned with refining catalyst B.
[0079] 4) The liquid hydro-refined oil and the liquid cracking product are mixed followed by being passed through the metal filter (9) to be filtered, and then pass the filtered mixture through the distillation column (10) to separate the fraction of naphtha with a boiling point less than 120 ° C, water and acid gases before being passed through a common pressure distillation column (11). Fractions with a boiling point less than 180 ^to C distilled from the top of the common pressure distillation column (11) are passed into the gasoline mixing storage tank component (not shown), the fractions with boiling dispersion 180 to 300 ^and C distilled from the central part are passed into the diesel mixing storage tank component (not shown), and the residues are passed through the vacuum distillation column (12) after being heated. The hydrogenated solvent with a high boiling point and hydrogenated petroleum tar are separated from the vacuum distillation column (12), in which the hydrogenated solvent with a high boiling point is the component with a boiling dispersion of 300 to 360 ² C separated from a vacuum distillation column (12). A part of hydrogenated solvent with a high boiling point is used as a solvent for removing salt and IQ from coal tar and the component to formulate hydrogenation raw material, and the rest is used as the
22/79 raw material from the hydrocracking reactor (8). The hydrogenated petroleum tar is extracted with a solvent in the extraction column (13) to further remove impurities, or is passed through the synthetic reaction (14) without solvent extraction to be subjected to thermal polymerization to obtain mesophasic tar product. Petroleum. The oil gas from the top of the static reaction (14) is vented after cooling, separation and washing. The separated instant separation oil is used as a cracking raw material to be hydrocracked.
[0080] High quality mesophasic petroleum tar requires a pure organic raw material that has a low impurity content that should have no solid impurity, low metal element content, low content of oxygen-, sulfur- and nitrogen-containing heterocyclic compounds -, appropriate molecular weight and molecular structure.
1) Solid impurity [0081] The solid impurity in coal tar is mostly insoluble fraction of primary quinoline (IQ), such as carbon black (free carbon), coal powder, coke powder, rust, and so on. onwards. These primary IQ impurities are detrimental to the nucleation, growth and conversion of mesophase into a crude oil mesophasic tar structure. Although these primary IQ impurities can facilitate the appearance of the mesophase sphere, they block the growth and collection of the mesophase sphere during the period of mesophasic oil tar growth so that the mesophasic tar
23/79 oil that has good rheological properties cannot be obtained, because the primary IQ impurities are easy to be absorbed on the surface of the mesophase spheres that appear.
[0082] In the coking coal high temperature retorting path, the free carbon separates when the raw gas is under the high temperature of the coking chamber. The free carbon will then be dragged into the coal tar to form some micelles or colloids that have free carbon as a core coated with a high-boiling component on the outside in multilayers. According to the intermiscibility similarity theory, it is required that some heavy oil is added to the shell of these multilayer micelles resulting in the exposure of free carbon that is removed during pre-processing.
[0083] As coal tar is a very viscous liquid, the solid impurity contained in coal tar is easily obstructing the additional coal tar processing apparatus. Therefore, the coal tar purification treatment to remove primary IQ impurities and solid impurity contained therein is a key step.
[0084] Coal tar is heavy oil that has high density, high viscosity and complicated components. Processing conditions can be improved by adding some solvents to coal tar to reduce viscosity during pre
24/79 processing for pre-processing to run properly.
2) Metallic elements [0085] The metallic elements in the oil pitch, such as Na, K, Mg, Ca, Fe, Cu, Al, V, Ni and so on, congregate quickly resulting in a mosaic structure when the mesophase is forming. When producing a carbon material, impurities are generated from it, and the escape of part of the metal ions during the graphite carbonization results in the formation of defects. Therefore, the metallic elements have to be removed. The amount of impurities can be reduced to a size required by pre-processing washing and hydrogenation demetallization catalyst.
[0086] 3) Heterocyclic compounds containing oxygen, sulfur and nitrogen The atoms of O, S and N in the heterocyclic compounds containing oxygen, sulfur and nitrogen have a high electronegativity, they can readily induce polarization within a molecule, accelerate dehydrogenation polycondensation during formation of the mesophase, which is the sphere of mesophase. However, through the atoms of O, S and N the viscosity of the system increases which obstructs the mesophase spheres, reducing the molecules.
Meanwhile, a mosaic structure instead of a desired mesophase bonded structure will be formed by accumulating the compounds
25/79 heterocyclics containing oxygen, sulfur and nitrogen in the mesophase spheres that arose due to their high thermostability. The carbon product produced from mesophasic petroleum tar will swell during graphitization, resulting in microcracks in the product, affecting the quality of the product. These impurity atoms can be removed substantially through catalytic hydrogenation processing.
4) Molecular weight and molecular structure [0087] The atomic H / C ratio of the carbonaceous mesophase is 0.35 to 0.5, the volatile content is 15% to 20%, and the density is 1.4 at 1.6 / cm ³ . When compared to petroleum pitch raw material, the molecular weight of carbonaceous mesophase that averages approximately 2000 is 3 to 4 times greater, and the softening point is also increased by approximately 100 ° C. Naturally, these values change with the change of petroleum pitch raw materials and heat treatment conditions. It generally has a lower melting viscosity when above the softening point temperature, and can remain stable without decomposition for a longer time.
[0088] As a raw material to form the mesophasic petroleum tar, it is required that its molecule have an appropriate molecular weight, H / C ratio, a degree of aromaticity and appropriate cyclane structures, and short side chains. Only raw materials that have a molecular structure with the above characteristics are polymerized to form mesophasic oil tar under
26/79 specific conditions, the desired structure of mesophasic oil tar can be obtained. Generally, the characteristics of the hydrogenated petroleum tar molecules generated by hydrorefining are: comprise 5 to 10 aromatic rings, 1.5 substituting groups on average (mostly methyl), 1 to 5 cycloalkane structures, and a molecular weight of 250 to 400.
[0089] Therefore, the production of mesophasic oil tar based on coal is actually a process of purifying and formulating a tar tar oil from coal. In view of the inherent limitations of coal tar oil pitch, the method for producing a mesophasic oil tar started with coal tar through purification and formulation will become more feasible.
[0090]
In a process technology view, the process of the main process units, such as preprocessing, hydrorefining, the preparation of the mesophasic oil tar, and so on, which can be described as follows respectively:
Pre-processing of coal tar:
[0091]
The coal tar pre-processing unit helps the viscosity and density unit to formulate hydrogenation raw materials, adjust that of the hydrogenation raw materials, remove mechanical impurities, remove IQ from insoluble fractions of quinoline, water, salts, phenols in tar, naphthalene oil extract that has a
27/79 additional, obtain raw materials suitable for hydrorefining, and avoid corrosion and system blockage.
[0092] While removing the insoluble fraction of primary quinoline, the removal of β resin (that is, the fraction of insoluble toluene-quinoline-soluble (TI-QS)) and γ resin (that is, the fraction of heptane- insoluble-toluene-soluble (HI-TS)) is avoided as much as possible in order to increase the yield of the mesophasic oil tar and maintain the effective components. However, thermosensitive components must be removed to avoid carbon deposition on the catalyst base caused by them. The loss of β resin and γ resin can be reduced by removing IQ from coal tar instead of starting from coal tar oil tar.
[0093] There is an abundance of salts dissolved in the water contained in coal tar, when heated, the ammonium salts (predominantly NH ₄ C1) in it will produce highly corrosive free acids that will corrode pipes and equipment, and have negative effects on catalysts. Since the metal content of the oil pitch is required to be controlled, desalination cannot be conducted through an alkaline process. Ammonium salts and metal salts can be washed away. Meanwhile, the water in it is removed as much as possible to meet the standard of water-free raw material to reduce the contents of ammonium salts and metal salts in coal tar.
28/79 [0094] The oxy compound in coal tar is mostly concentrated in carbolic oil, therefore, removing carbolic oil from coal tar can reduce hydrogen consumption during hydrogenation, and avoid affecting system control pressure and catalysts brought by the combined water generated by the carbolic oil during hydrogenation.
[0095] The reason why washing oil with a high economic value is not extracted is that washing oil and its hydride are important solvents, can reduce the vaporization temperature during distillation, and avoid polymerization of the high molecular weight of the raw material before entering the hydrogenation reduction condition.
(1) Desalination of coal tar [0096] In addition to metal salts, there is an abundance of ammonium salts contained in coal tar. Volatile ammonium salts can be removed during the final dehydration process, while most ammonium salts are still in the dehydrated coal tar. Washing is an effective means of desalination, since the production of mesophasic petroleum tar requires strict control over the content of metal ions, and an alkaline process cannot be used here to neutralize ammonium salts. In addition, desalination by washing can also lighten the load on demetallization catalysts.
[0097] Ammonium salts and metallic salts are mostly hydrochlorides, sulfates, sulfites,
29/79 nitrates, thiocyanates, so most ammonium salts and metal salts can be washed away. However, coal tar is heavy oil that has high density and contains amounts of asphaltene colloid. A large amount of emulsified oil will be formed due to the poor intermiscibility of the two. Therefore, demulsification is necessary when coal tar is going to be dehydrated.
[0098] In practice, aromatic solvents, such as BTX fraction, hydrogenated BTX fraction, washing oil, hydrogenated washing oil, anthracine oil, hydrogenated anthracin oil and hydrogenated solvent with high boiling point, have a demulsification function due its ability to dissolve asphaltene colloid micelles. The results of the experiment indicate that the aromatic solvents above all have a good role in demulsification. After assisted centrifugal dehydration, the coal tar water content can be controlled to be less than 2%, and the salt content is also reduced substantially.
[0099] Hydrogenated solvent with a high boiling point is a fraction with a boiling dispersion of 300 to 360 ° C obtained by distilling the mixture of the hydro-refined oil and the cracking product. To allow the separation of the mixed oil and water and the recovery of the aliphatic solvents used to remove insoluble substances after washing, it is more reasonable to use the aromatic solvent with a high boiling point to remove the salts. Use washing oil, hydrogenated washing oil, anthracine oil,
30/79 hydrogenated anthracine oil and hydrogenated solvent with high boiling point has less impact on coal tar density. Formulating the density of the mixed oil to be 1.05 to 1.1 facilitates the separation of oil and water.
[00100] Since the corrosion of the equipment and the damage to the performance of the catalysts are mostly due to hydrochloric acid generated from the decomposition of ammonium chloride, the chloride ion content is taken as an index of washing control . After being washed, the coal tar will have a chloride ion content of less than 5ppm.
(2) The removal of insoluble fractions of quinoline (IQ) from coal tar [00101] Aliphatic solvents are required to be formulated in coal tar to remove insoluble fractions of quinoline. However, since formulating aliphatic solvents in coal tar can lead to a situation in which the density of the mixed oil can be less than 1, the removal of salts and the removal of insoluble fractions of quinoline cannot be carried out simultaneously, and the removal of insoluble fractions of quinoline likewise cannot be conducted prior to the removal of salts.
[00102] According to US Patent US4116815, when coal tar or coal tar oil tar is formulated with aromatic solvents and aliphatic solvents in different ratios, the oil region, the crystalline region, the tar region oil and mud area can be formed according to the different
31/79 solvent ratios, in which the IQ in the mud zone can be removed by free sedimentation.
[00103] The commonly used aromatic solvents introduced in the United States Patent mentioned above are benzene, toluene, xylene, creosote, washing oil, anthracine oil, and asphalt oil obtained by distillation of coal tar; and aliphatic solvents are n-hexane, petroleum naphtha, petroleum kerosene, gasoline and the like. When repeating the experiments listed in the US Patent above, the inventor of the present Application employed aliphatic solvents such as noctane, n-heptane, and the like, and aromatic solvents such as washing oil, anthracine oil, BTX fraction, hydrogenated BTX fractions, hydrogenated washing oil, hydrogenated anthracine oil, hydrogenated solvent with high boiling points and hydrogenated distillation fractions obtained from the coal tar distillation fractions. The results show that hydrogenated BTX fractions, hydrogenated washing oil and hydrogenated anthracin oil, due to their fat, can have a better IQ removal effect than BTX fractions,
wash and oil of anthracine. In particular, the solvent hydrogenated with Score high boiling it is a solvent most suitable aromatic to remove IQ by next reasons: [00104] a) a great effect of removal of IQ, the
which is mostly reflected in a lower percentage of aliphatic solvents, a higher percentage of coal tar, and low cost; Besides that,
32/79 [00105] b) a high degree of IQ curing, which leads to a lower IQ content in the settling oil after removing the IQ;
[00106] c) removal of most of the thermo-instable macromolecules together with removal of IQ; the coal tar yield is 85%; removing thermally unstable macromolecules leads to a drastic deceleration of the catalyst's carbon disposition during hydrogenation;
[00107] d) a wide extension of the crystalline region, which leads to a high efficiency of IQ removal aided by centrifugation;
[00108] e) removal of salts and IQ with hydrogenated solvent with high boiling point is useful for recycling aliphatic solvents; avoiding the formation of azeotropes caused by the low boiling fraction and by aliphatic solvents;
[00109] f) a good degree of hydrogenation of the petroleum tar caused by the presence of hydrogenated solvent with a high boiling point, which is useful for the smooth conduction of hydrogenation in a condition of soft operation.
(3) Hydrogenated solvent with high boiling point [00110] Hydrogenated solvent with high boiling point is one of the key points of the invention. The hydrogenated solvent with a high boiling point is the fraction with a boiling dispersion of 300 to 360 ° C from the mixture of the refined oil and the cracking product. The main molecular structure of it from the spectrometry of
The mass is 2 to 5 benzenes, in which 1 to 3 C ₄ -C ₆ cycloalkanes, 1 to 3 methyls and a few ethyls are comprised.
[00111] The following goals are achieved using hydrogenated solvent with high boiling point:
[00112] a) Easy to prevent the petroleum pitch micelles from becoming an independent asphaltene colloid during desalination to thereby produce the demulsification effect and separate IQ and thermo-instable macromolecules with the help of aliphatic solvents;
[00113] b) Facilitate the recycling of aliphatic solvents using hydrogenated solvent with high boiling point as the solvent for removing salts and IQ;
[00114] c) Facilitating the transfer of hydrogen to petroleum tar molecules as the hydrogenation of many cycloalkanes are reversible hydrogenation-dehydrogenation process, to conduct catalytic hydrogenation together with hydrogenation with the solvent, reducing the temperature of catalytic hydrogenation, reducing carbon deposition of the catalyst, and extending the life of the catalyst.
[00115] d) To disperse the petroleum tar molecules to avoid polymerization of the petroleum tar molecules during hydrogenation;
[00116] e} Facilitate the formation of petroleum pitch in the event that the high boiling fractions of the hydrogenated solvent with high boiling point join in the petroleum pitch, due to the naphthenic and methyl groups contained in the molecular structure of the solvent hydrogenated with high boiling point.
34/79 (4) Pre-distillation of settling oil [00117] A settling oil is a mixed oil obtained after the removal of salts and IQ from coal tar. The purpose of pre-distillation of decanting oil is to recover aliphatic solvents, extract naphthalene oil that has a high added value from tar, remove water from the mixed tar to meet the water-free tar standard, and recover carbolic oil.
[00118] The secondary distillation temperature of the settling oil should not be too high, the purpose of this is to avoid the formation of a new insoluble fraction of toluene (TI) and an insoluble secondary fraction of quinoline (IQ) caused by polymerization of the macromolecules due to their pyrolysis prior to hydrorefining, in addition to recovering aliphatic solvents and keeping carbolic oil and naphthalene oil.
(5) Formulation and filtration of the hydrogenation raw material [00119] The formulation of the hydrogenation raw material aims to slow down the carbon deposition of the catalyst during the hydrorefining to thus carry out the catalytic hydrogenation in hydrogen in the presence of hydrogenation solvents. The technology means adopted in the formulation of hydrogenation raw material are: 1) formulate the BTX fraction, hydrogenated distillation fractions and hydrogenated solvent with a high boiling point with pre-distilled high-boiling residue; and 2) protection filter.
35/79 [0012 0] Once the components of the BTX fraction, carbolic oil and naphthalene oil are removed in the pre-distillation unit and the resulting settling oil has increased density and viscosity, together with an increased likelihood of forming new TI and secondary IQ, it is required that a solvent formulation is conducted in the residues of the pre-distilled settling oil in order to meet the requirement for hydrogenation raw material. The formulated oil adopted in the above process comprises one or more of the components selected in the following group consisting of the coal tar distillation fractions, the hydrogenation product of the coal tar distillation fractions, and the mixed aliphatic solvent oil and distillation fractions of coal tar mentioned above or the hydrogenation product of the distillation fractions of coal tar. The coal tar distillation fractions include, but are not limited to, BTX fraction, washing oil, anthracine oil, and the coal tar distillation fractions mentioned in Coal Chemistry Product Technology (Xiao, Ruihua ate; Metallurgical Industry Press ; September 2008; version 2, pages 201 to 23 0). The hydrogenation product of the coal tar distillation fractions includes, but is not limited to, hydrogenated BTX fraction, hydrogenated washing oil, hydrogenated anthracin oil, hydrogenated solvent with a high boiling point, and the 80 to 300 ° fraction C of the hydrogenation product. Aliphatic solvent oils include cycloalkane and diesel solvents. The formulated oils also include benzene, toluene, and xylene.
36/79 [00121] The main functions of the formulation of the settling oil residue are of two types: one type is to reduce density and viscosity, to disperse asphaltene colloid, the solvents to be formulated for this type of function mostly comprise benzene solvents, the coal tar distillation fractions, the hydrogenation product of the coal tar distillation fractions and a small amount of aliphatic solvents; the other type is to formulate hydrogenation solvents during hydrogenation, so that coal tar is hydrogenated catalytically in the presence of hydrogenation solvents, and catalytic hydrogenation and hydrogenation with coal tar solvents are carried out simultaneously, the solvents for this type of Most functions comprise the hydrogenation product of the distillation fraction of coal tar and aliphatic solvents.
[00122] An asphaltene pellet must be formed at a lower temperature in the event that the hydrogenation raw material is formulated with a large amount of aliphatic solvents, as the settling oil residues contain large amounts of asphaltene and colloid components. Therefore, the formulation of aliphatic solvents must be premised on no petroleum tar sediment formed in the hydrogenation raw material, and the settling oil residues must not be formulated with the aliphatic solvents alone.
[00123] Add BTX fraction, washing oil and hydrogenated distillation fractions at their largest
37/79 part aims to reduce the viscosity and density of the hydrogenation raw material, reducing the concentration of colloidal asphaltene molecule and dispersing colloidal asphaltene. Disperse the colloidal asphaltene avoiding the deposition of micelles formed by the polymerization of colloidal asphaltene in the catalyst, so that the speed of absorption-desorbes the macromolecules in the catalyst. Meanwhile, dispersing colloidal asphaltene has a self-cleaning effect on the catalyst, thereby delaying the deposition of carbon in the catalyst and extending the service life of the catalyst.
[00124] Add hydrogenated solvent with high boiling point and formulate the hydrogenated fractions to transfer hydrogen from the hydrogenated solvent with high boiling point to asphaltene performed under catalytic. Meanwhile, the hydrogenated solvent with a high boiling point, which is a mixture of the polycyclic aromatic hydrocarbon containing 1 to C ₄ -C ₆ cycloalkane structures, with a molecular weight of
150 to 280, has the function of reducing the concentration of colloidal asphaltene to demand for carbon conditions in the catalyst.
most of it aims to ensure that impurities greater than 10pm in tar that are not removed by filter technology piping equipment are filtered to protect the catalysts.
(II) Hydro refining and cracking
38/79 [00126] Hydro refining raw materials are mixed with hydrogen at high pressure, the mixture is heated and fed into the hydrogenation protection demetallization reactor and refinement reactor to be catalytically hydrated, then the components of the liquid oil phase refined are mixed with the liquid phase components of the cracking product, and the mixture is fed into a fractionation system after being filtered.
[00127] Meanwhile, a part of the hydrogenated solvent with vacuum point of the fractionation system is used to remove salt and IQ from coal tar and formulate hydrogenation raw material, the rest is used as the catalytic hydrocracking raw material together with the instantaneous separation oil produced from the mesophasic petroleum tar thermal.
(1)
Hydro refining [00128]
a) IQ is additionally removed from coal tar.
of pre-processing, although a mass of IQ is removed, there are still some IQs that have a particle size of 0.5 to 2qm. When the pre-processed coal tar is just passed through the protective catalyst, in the channel on the surface of the protective catalyst at a high temperature. It is required that the IQ is removed in the initial refining stage, although the situation mentioned above is avoided by adding solvent in quantity.
39/79 [00129] b) Traces of metal components such as Na, K, Mg, Ca, Fe, Cu, Al, V, Ni and so on are removed, among which Na, Fe, V and Ni must receive particular attention, as most other metal components are removed during the pre-processing stage except
Na and Fe which will form metal complexes, and removing them requires demetallization catalyst
There is very little V and Ni contained in coal tar, so they have no obvious effect on the catalyst.
[00130] c) Atoms of impurities such as O, N and
S are removed from the macromolecule function groups.
[00131]
d) The reactivity of molecules can be reduced by hydrogenation saturations of the macromolecule side chain and the molecules that are easy to polymerize to form a methyl side chain; the aromatic ring of the polycyclic aromatic hydrocarbon part will be cycloalkylated, promoting the formation of cycloalkane structure; meanwhile, a hydrogen transfer will be carried out in the presence of the hydrogenation solvent to thereby promote the alteration of the molecular structure, to form a hydrogenated petroleum tar whose molecular structures and composition are consistent with the requirements for the preparation of mesophasic petroleum tar.
[00132] e) As long as the hydrogenation and dehydrogenation of the hydrogenation solvent are reversible, the hydro-refining in the presence of the
40/79 hydrogenation is favorable for increasing the hydrogen content in the oil tar molecule structure.
[00133] f) After the hydrogenation of the coal tar components free of IQ, due to their saturated molecular structure, the low boiling point components in petroleum tar are easier to be separated than to be polymerized when they are distilled, which leads to a narrower molecular weight distribution of hydrogenated petroleum tar for the preparation of mesophasic petroleum tar.
[00134] g) The cycloalkane and methyl side chain structures contained in the molecules are beneficial for the components of the hydrogenated petroleum tar group which become soluble together with a small change in molecular weight. Because the cycloalkane and methyl side chain structures contained in the petroleum tar molecules are beneficial to the congregation of mesophase spheres, the demand for molecular weight distribution of the hydrogenated petroleum tar is relaxed. Large molecules become soluble, and smaller molecules also take part in the reaction due to having cycloalkane and side chain structures to form much more catalytic condensation of polycyclic aromatic hydrocarbon. Meanwhile, the softening point of mesophasic petroleum tar is reduced and the formation of soluble petroleum mesophasic tar is facilitated.
(2) The main function of the hydrocrack section
41/79 [00135] a) Hydrocracking refined oil components from 300 to 360 ° C and instant separation oil produced by thermal polymerization of mesophasic petroleum tar to cause the high boiling fractions to have additional ring opening and breakage, to make the aromatic hydrocarbon structures of macromolecules to form more structures
of cycloalkane and structures side chain methyl, to increase the ratio H / C solvent oil, for to remove additionally S and Huh to product O solvent hydrogenated with point of high boiling meet the requirements.[00136] B) After hydrocracking, the biggest
part of the components (approximately 50% to 70%) is converted to gasoline and diesel blending components, and the rest of the cracking fractions with a boiling point greater than 300 ° C together with refined fractions of 300 to 360 " C are used as a hydrogenated solvent with a high boiling point.
(3) The index required by the hydrorefining [00137] a) Since the hydrorefined oil has complex components, the refining catalyst is required to have appropriate hydrogenation capacity. Excessive hydrogenation will destroy the molecular structure of the effective components leading to reduced production of mesophasic petroleum tar, and is very demanding on the catalyst leading to a high refining cost;
[00138] b) The rate of deoxofaction is approximately 70 to 90%, and the sulfur content in the
42/79 hydrogenated petroleum pitch should be less than 0.2%; the denitrification rate is approximately 50 to 90%, and the nitrogen content in the hydrogenated petroleum tar must be controlled to be less than 0.3%; the deoxygenation rate is approximately 50 to 90%, and the oxygen content in the hydrogenated petroleum tar must be controlled to be less than 0.3%;
[0013 9] c) The Na content is less than 10ppm; Fe content is less than 10%; the total content of metal ions is less than 50ppm;
[00140] d) The change in H / C ratio of hydrogenated petroleum tar is a major sign of the hydrogenation effect. When compared to clean oil pitch, a 20% increase in the H / C ratio can satisfy the preparation of mesophasic oil pitch. A higher H / C ratio of hydrogenated petroleum tar is beneficial for the preparation of mesophasic petroleum tar, lowering the softening point and increasing the content of soluble components. However, mesophasic petroleum tar which has an excessively high H / C ratio will produce bubbles when agitated, which results in fiber breakage.
(4) The hydrorefining conditions [00141] The hydrorefining reactor operational conditions are: the total pressure is 12.0MPa to 20.0MPa, the average reaction temperature is 320 ° C to 400 ^and C, the space speed net hourly is OjShr ' ¹ to 2.0hr' ¹ , and the appropriate hydrogen-oil volume ratio is 600: 1 to 1500: 1. The conditions are illustrated respectively as follows:
43/79
a) Temperature [00142] The requirement for effective hydrogenation of oil pitch is to heat the oil pitch to a temperature that is sufficient for the thermal decomposition of oil pitch. At this temperature, the petroleum tar molecules are cracked, in which some unstable molecules will be cracked into molecular fragments that have free radical properties. These active free radicals obtain hydrogen atom from hydrogen in the presence of catalyst or from hydrogenation solvents, so that free radicals are stabilized by being saturated to form hydrogenated petroleum tar which has an optimized molecular structure to achieve the objective to hydrogenate clean oil pitch effectively.
[00143] Petroleum tar molecules are more obviously cracked and obtain hydrogen atoms effectively at a temperature of 400 to 420 ^s C. However, the cracking effect will be bad at a temperature higher than the above temperature with a side effect that the active oil tar molecules are easy to polymerize to form a carbon deposition on the catalyst, affecting the activity of the catalyst. At this point, the side reaction becomes a main reaction instead of hydrogenation. Under catalytic conditions, the cracking temperature of petroleum tar molecules will be significantly reduced, so a desired temperature range must be controlled within 320 to 400 ^and C, so as to prevent the temperature
44/79 is greater than 4 00 ^and C, When the temperature is less than 390 ° C, the deposition of carbon in the catalyst will be delayed in order to protect the catalyst and extend its useful life. When the temperature is very low (<300 ^s C), organic sodium compounds are unable to be decomposed and removed effectively, and petroleum tar molecules cannot be activated to form free radicals.
b) The partial pressure of hydrogen [00144] The pressure in the refinement reactor must be controlled to be 12.0 to 20.0MPa. An appropriately increased partial pressure of hydrogen can increase the refining effect, decrease the coking speed in the catalyst, and extend the life of the catalyst.
c) Volumetric space velocity [00145] An excessively high volumetric space velocity leads to a poor hydrogenation effect, and requires a high catalyst activity, while an excessively low volumetric spatial velocity results in a long reaction time, a low charge, and an increased likelihood of carbon deposition on the catalyst. An adequate volumetric space velocity must be controlled within 0.5 to 2.Ohr ' ¹ .
d) Hydrogen-oil ratio [00146] Based on the chemical hydrogen consumption required by the refining reaction extension, 600 to 1500: 1 is preferred.
(5) Catalyst
45/79 [00147] The hydrogenation raw material is a pre-processed settling oil whose impurities such as insoluble fraction of quinoline and the like are removed, or formulated hydrogenation raw material from which carbolic oil and naphthalene oil are taken . Although most impurities have already been removed in the pre-processing stage, there is still a small amount of impurities including metal ions, insoluble fraction of quinoline and the like, which are able to deposit on the outer surface and pores within the catalyst during hydrogenation. In addition, unsaturated olefins and thermally unstable macromolecules contained in tar, especially heterocyclic compounds, are major substances of carbon deposition due to their high activity. They can easily convert to coke under heating and deposit on the catalyst surface resulting in obstruction of the catalyst channel and deactivation of the catalyst.
[00148] Metal ions such as organic iron, organic calcium and the like contained in coal tar affect catalysts for both hydrorefining and hydrocracking. Hydrogenation of organic iron from soluble oil is very fast. For the routine microporous catalyst, iron sulfide is mostly deposited on the catalyst particles or spreads on the surface of the catalyst circularly, and is unable to move. The increased amount of deposited iron appears only in the increased thickness of iron deposition on the catalyst surface, but the deposited iron will not permeate for
46/79 inside the catalyst. Therefore, it can be considered that the deposition of iron sulfide for the most part influences the surface of the catalyst, and has little effect on the pore volume of the catalyst. However, since the amount of iron deposit increases to a certain degree, the catalyst particles must be bonded, while a hard shell must be formed on the surface of the catalysts, which should result in an increased drop in pressure from the base and reduced use of the catalyst. Therefore, it is required that the demetallization catalyst design has macropores and high base porosity.
[00149] Similar to organic iron salts, organic calcium salts are easy to remove. In general, the components of catalyst hydrogenation activity are not required, and the reaction process is mostly thermal cracking. It is preferred that the removed calcium is deposited on the outer surface of the catalyst particles and forms larger grains. Therefore, the descaling reaction carried out by hydrogenation descaling protector should be mostly on the protective base with most of the calcium deposited in the pore channels of the demetallization catalyst to ensure that the pressure drop of the base will not increase or increase within a narrow range.
[00150] Organic sodium salts are present in the forms of sodium phenate and sodium naphthenate, and have a great influence on the deactivation of the catalyst, and also affect the quality of the mesophasic oil tar at the same time.
47/79 [00151] In order to ensure the long-term stable operation of the equipment, the protective catalyst and demetallization catalyst must be loaded before the primary catalyst to remove deposition and metal ions in the raw material, to thereby produce the purpose protection of the primary catalyst. Two reactors equipped with hydrogenation protector and demetallization catalyst can be connected in parallel, where the hydrogenation protection catalyst is loaded into the top reactor, while the demetallization catalyst is loaded into the bottom reactor, for convenient switching.
[00152] The carbon deposition in the primary catalyst is reduced by passing the raw material for hydrogenation through hydrogenation and demetallization protection catalysts, although hydrogen gas with a partial high pressure in the refining catalyst can partially inhibit the carbon deposition of the high components boiling point in coal tar. However, carbon deposition cannot yet be completely avoided in the long run. The reason is that coal tar contains a trace of olefins and an amount of colloid and asphaltene, and the pyrolysis of these substances is capable of generating active free radicals which condense easily to produce carbon deposition that deposits in the catalyst, blocking the base, causing increased pressure drop from the catalyst base. In this case, these active free radicals must be stabilized if there is a hydrogen atom or molecule, so that carbon deposition must be inhibited and alleviated. Increase the partial pressure of
46/79 hydrogen can significantly increase the concentration of active hydrogen atoms, but investment and operating costs will be increased significantly at the same time.
[00153] One of the effective means is to add solvent to disperse colloid and asphaltene, such as hydrogenated distillation fraction, hydrogenated solvent with high boiling point, BTX fraction and the like generated in the process of the present application. In addition to providing active hydrogen atoms, these liquid hydrogen donor solvents can promote the transition from hydrogen gas to the liquid phase, and accelerate the rate of hydrogenation. Meanwhile, the viscosity of the reaction mass is reduced, the colloidal asphaltene molecules are dispersed, the absorption and desorption rates are increased, and the carbon deposition is reduced, so that the hydrorefining reaction can be carried out smoothly. In addition, in the presence of hydrogen donor solvents, the requirements for refining reaction conditions can be reduced, and the degree of hydro refining reaction can be better controlled, preventing some of the macromolecules from being excessively cracked into small molecules resulting in reduced yield petroleum tar products. The formulation of components that have a low boiling point such as BTX fraction and the like for the most part reduces the viscosity and density of the hydrogenation raw material, and disperses colloidal asphaltene to make it difficult to polymerize to form micelles that deposit on the catalyst , so as to increase absorption rates and
49/79 desorption in the catalyst, which is favorable to the desorption of the macromolecules of the catalyst and has a self-cleaning effect for the catalyst. As previously described, the catalyst coking problem can be well inhibited by adding the BTX Fraction, washing oil, hydrogenated low boiling fraction and hydrogenated high boiling solvent generated in the process of the present application, so that life of the catalyst can be extended.
[00154] Compounds with heteroatoms such as S, N, O and the like contained in coal tar affect the nucleation, growth and conversion of the mesophase sphere, and impair the formation of fine fibrous or needle-like structures. For example, sulfur is a strong dehydrogenation agent that accelerates the dehydrogenated condensation of aromatic hydrocarbons, and is favorable to the appearance of a mesophase sphere; however, sulfur is also a cross-linking agent, which causes molecules to lose planarity and form a cross-linked structure, resulting in increased viscosity. This impairs the growth, collection of the mesophase sphere and that it is transformed to be an anisotropic structure, and instead, the mesophase sphere is transformed to be a mosaic structure.
[00155] It should be very advantageous for the formation of the mesophase that a certain amount of cycloalkane structures and short aliphatic side chains are contained in the coal tar oil tar molecules. This is due to the radical transfer of
50/79 hydrogen in cycloalkane happen during the pyrolysis process, whereby the reactivity of free radicals can be effectively stabilized, the fluidity and solubility of the mesophase product can be maintained to reach an optically extensive anisotropic texture.
[00156] The main functions of the hydro-refining catalyst here are: removing the heteroatoms such as S, N, O and the like contained in coal tar; to hydrogenate the unsaturated components and make them saturate to form polycyclic aromatic hydrocarbon with cycloalkane structure; to break the side chain of the active aromatic hydrocarbon with longer alkyl side chain in the raw material for more stable aromatic hydrocarbon with short side chain; and in the meantime supplying hydrogen to the hydrogen donor solvent in the presence of hydrogen to arrive in time to regenerate the hydrogen donor solvent, to promote the hydrogen gas to convert to liquid phase in time, and to accelerate the [00157]
Therefore, the refining catalyst is characterized by:
adequate pore volume and pore size, high tolerance to the appropriate.
Catalytic hydro-refining can also be activities in the presence of other refining strengths and weak catalysts with cracking appropriate pore volume and pore size.
[00158] According to the hydrogenation characteristic of coal tar, in order to ensure the stable hydrogenation operation, it cannot be placed
51/79 excessive emphasis on excessively high catalytic performance and excessively long catalyst life (this cannot be insisted on either). Naturally, the useful lives of various catalysts are different.
(III) Preparation of mesophasic petroleum tar
1) Preparation of hydrogenated petroleum tar [00159] After being filtered, a mixture of hydro-refined oil and cracking product is fed into the distillation column to separate low-boiling naphtha components, water and acid gas, and then the mixture it is fed into a common pressure distillation column. The gasoline mixing component distilled from the top of the common pressure distillation column is passed into a gasoline mixing storage tank component as a product, the diesel mixing component distilled from the central part is passed into a gasoline mixing storage tank component, and the high boiling bottom component is passed through a vacuum distillation column after being heated. The hydrogenated solvent with a high boiling point and hydrogenated petroleum pitch are separated from the vacuum distillation column, where a part of the hydrogenated solvent with a high boiling point is used as the solvent for removing salt and IQ from the tar. coal and a formulated component of hydrogenation raw material, and the rest is used as the raw material for the hydrogenation cracking reactor. The hydrogenated petroleum tar is extracted by solvents for an additional removal of impurities before being fed to a
52/79 static reaction to obtain a petroleum mesophasic tar product through thermal polymerization. The oil gas from the top of the static reaction is discharged after being cooled, separated and washed. The separated instant separation oil is passed into the cracking raw material tank as a hydrocracking raw material.
(1) Filtration [00160] Prepare a filter before the distillation column to filter refined oil and cracking product and remove particles of catalyst.
[00161] The analysis of IQ obtained from preprocessing coal tar by the laser particle analyzer shows that the IQ in coal tar is normally distributed within 0.3 to lpm. Through elementary analysis, these primary IQs with small particle size are mostly free carbon and another inorganic substance with particle size greater than 0.3 pm.
[00162] The refined oil is stopped for a long time to obtain deposit which is then filtered through a 500 mesh filter screen. There is very little residue on the filter screen, and the analysis results from the analysis of the element and the laser particle size analyzer indicates that the residues are mostly catalyst particles with a particle size greater than 30pm.
[00163] After being filtered through a 500 mesh filter screen, the filtered oil is subjected to suction filtration by 2 to 5pm, 5 to 10pm and 10 to 10
53/79
15pm respectively. All filtered oil passes through the buehners filter funnel at 10 to 15pm, while waste is left in the other two buehners filter funnels. Quinoline, toluene and n-heptane are used to dissolve the above residues respectively, where the residue is substantially insoluble in n-heptane, partially soluble in toluene, and is soluble in quinoline, which further indicates that the residues are fractions insoluble in toluene and quinoline soluble (TI-QS), and are macromolecular hydrocarbon polymers.
[00164] A filter with a hole diameter of 10 to 25 5pm is used to remove dust from the catalyst due to the high temperature of hydrorefining oil and cracking product and the low viscosity of the liquid phase. Two groups of the operation of filtering the components with sintering metal can be carried out in parallel, and the number of filter groups can be selected according to the flow. Oil from fraction 120 to 180 ^and C from the common pressure distillation column or BTX fraction and washing oil are used as the bath and backwash solvent.
(2) Distillation [00165] The distillation unit is established with the distillation column, common pressure distillation column and vacuum distillation column. The filtered hydrogenated oil mixture is fed to the distillation column first to separate naphtha (<L20 ^and C), water and acidic gas, and then it is fed to a common pressure distillation column. The gasoline mixing component (120 to
54/79
180 ^and C) fractionated from the top of the common pressure distillation column is passed into a gasoline mixing component storage tank as a product. The diesel mixing component (180 to 300-C) fractionated from the central part of the common pressure distillation column is passed into a diesel mixing component storage tank. The high-boiling components from the bottom are fed into the vacuum distillation column after being heated. The hydrogenated solvents with a high boiling point with a boiling dispersion of 300 to 366 ° C and hydrogenated petroleum pitch with a boiling point greater than ³⁷⁰ ° C are separated in the vacuum distillation column.
(3) Extraction of hydrogenated petroleum tar [00166] The hydrogenated petroleum tar is extracted at a temperature of 120 to 180-C, using toluene, quinoline, pyridine or tetrahydrofuran as a solvent with a hydrogenated petroleum tar ratio to the 1: 5 to 10 solvent oil. The extracted oil is filtered using a 5 to 10pm metal filter, and then the solvent and extraction and the extracted hydrogenated petroleum tar are distilled off.
2) Preparation of mesophasic petroleum tar [00167] Preparing mesophasic petroleum tar from hydrogenated petroleum tar is a controllable heat treatment process. The heat treatment processes in common use are heat treatment of bubbling inert gas, and heat treatment with compressed or decompressed heat. The principle of all the above processes is thermal processing of the petroleum tar from raw material in a polymerizer at a certain temperature and pressure for a certain time to conduct thermal polymerization to make the oil tar indices meet the desired quality requirements.
[00168] The main operational factors are: initial temperature, final temperature, temperature increase rate, constant temperature time, agitation rate, inert gas pressure, inert gas flow and the like. These factors need to be determined based on the characteristic of hydrogenated petroleum tar. The analysis for the effects on the process from the above factors is as follows.
(1) The temperature influence
[00169] THE temperature synthesis is inside in an interval of 380 at 460-C, and the temperature time constant is 180 at 1200min, preferably 400 The 440 ^and C, 180 to 600min A fee small increase in
Temperature is beneficial for the growth and congregation of the mesophase sphere to obtain mesophasic oil tar which has a great anisotropism and good rheology.
Methods of reacting at a high temperature for a short time and then at a low temperature for a long time and the like can also be used.
(2) Pressure influence [00170] Increasing the thermal processing pressure can inhibit the rapid escape of the fraction that has low molecular weight and increase the degree of carbonization. While
56/79 this, the fraction that has lower molecular weight coacervated in the liquid phase to improve viscosity and fluidity, to facilitate the assembly of the mesophase sphere and the rearrangement of crystals to increase the degree of anisotropism, but an excessively high pressure it is an impediment to the mesophase sphere congregation. The reduced pressure heat treatment can accelerate the synthetic reaction.
(3) The influence of the system's agitation situation [00171] Agitation during preparation can not only maintain the homogeneity of various components in the reaction system during mesophase formation, improve the intermiscibility of mesophasic petroleum tar and other liquid substance oil pitch, increase fluidity, and make the mesophase structure formed more uniform, but also inhibit premature congregation of the mesophase sphere at the beginning of mesophase formation, and promote mesophase formation in the system at the last stage of progress.
[00172] Since the mesophasic petroleum tar has a higher molecular weight, excessive agitation in the system causes an increased complexity of the internal structure of the petroleum tar which is bad for the formulation of domain anisotropy.
(4) Gas purge [00173] A flow of inert gas is used to purge the top and bottom of the calm reaction, and the light components are purged from the oil pitch. The interval
57/79 molecular weight of the resulting mesophasic petroleum tar is narrower, and aromatic hydrocarbon components that have appropriate molecular weight can be combined to form a mesophase that has a certain solubility and exhibits anisotropism. In addition, the agitation of the air flow can cause the flat aromatic hydrocarbon molecules to be arranged parallel to the direction of the air flow, which is beneficial for the congregation of mesophase spheres.
(5) Real time analysis of system viscosity [00174] During the preparation of mesophasic petroleum tar, in addition to factors such as temperature, pressure and so on, a method for measuring viscosity in real time is employed in the project , which can make a comparison of the actual temperature viscosity curve and the theoretical viscosity-temperature curve to verify the degree of preparation.
[00175] The advantages of the invention over the prior art are as follows:
[00176] The invention produces mesophasic petroleum tar from coal tar as a raw material and employs demetallization catalyst, hydro-refining catalyst and hydrocracking catalyst made by you suitable for the inherent characteristic of coal tar. The advantages are easy to control the degree of hydrogenation, complete removal of impurities, good fluidity of raw materials, not tending to create deposition of
58/79 carbon and coking during the technical process, and not tending to obstruct the reactor.
[00177] The main aromatic solvents used as the solvents to remove insoluble IQ and the high boiling hydrogenated solvent used as the hydrogenation solvent in hydrogenation in the invention are self-generated in the invention's manufacturing technique. Both of the above solvents have a good effect of removing impurities, a good ability to supply hydrogen and a low cost, and are easy to be produced continuously.
[00178] The main product of this technology is mesophasic petroleum tar, a good precursor of carbon material that has high added value. Meanwhile, the by-products are components of mixture gasoline and diesel, carbolic oil, crude naphthalene. The mesophasic petroleum tar has a low production cost, simple processing, a low level of requirement for the equipment, a process that is easily controllable parameters and a cost effective and reasonable process as a whole.
[00179] The invention will be further illustrated through the Examples below. It can be appreciated that the Examples below are optimizations of the invention, which are used only to illustrate the invention without limitation. Other combinations and various modifications can be made within the concept of the invention without departing from the intention or scope of the invention.
[00180] If not specified in the context of this document, all percentages are percentages by weight.
59/79 [00181] The reagents used in this document are chemically pure reagents purchased from the Damao chemical reagents factory in Tianjin, and the high temperature coal tar used in this document comes from the Anshan iron and steel group.
[00182] The following instruments are used to characterize the product in this document respectively:
infrared spectrometer (FT-IR 430, JASCO), NMR (AVANCE
II 400, Bruker in Switzerland), elemental analyzer (vario EL
ΙΠ,
Elementary company in Germany), GC-MS (HP
6890GC / 5973MSD,
Hewlett
Packard in the United States),
Instrument co. ,
LTD, Shanghai, China), ion chromatograph (ICS-90, Dionex, USC), vapor pressure osmometer (K
7000, Knauer GmbH, Germany), ICPAES (Optima 2000 DV, Perkin Elmer Company, United States), chemical adsorption apparatus (CHEMBET 3000, Account in the United States), automatic microporous physical adsorption analyzer and specific surface area (ASAP 2020. Micromeritics Instrument Corp), and X-ray Fluorescence (XRF1800, Shimadzu in Japan).
Example 1 [00183] Referring to Figure 2, the coal tar from the coal tar storage tank, deionized water and hydrogenated solvent with a high boiling point are fed into the desalination section (1), sufficiently mixed, and then centrifuged to remove waste water from washing, to obtain a desalinated coal tar which has a
60/79 Cl 'content of less than 5ppm. The wastewater is fed into a wastewater regeneration system. Desalinated coal tar is fed into the IQ removal section (2) after being mixed with aliphatic solvent (n-octane) and hydrogenated solvent with a high boiling point. After centrifugation and sedimentation to reduce the IQ concentration to 500ppm, a settling oil is obtained. IQ is fed into a served waste treatment system. After being heated, the settling oil is fed to a one stage evaporator (3) to remove water and BTX Fraction (<L20 ^and C). After being heated, the water-free settling oil is fed into the distillation column (4) to be pre-distilled to recover the aliphatic solvent, and to separate the BTX Fraction (120180 ^Q C), carbolic oil and naphthalene oil. The aliphatic solvent is returned to the IQ removal section (2) for use in recycling. The residues from the distillation column (4), BTX fraction (<L20 ^s C), BTX fraction (120 to 180 ^and C), hydrogenated solvent with high boiling point and other low boiling oils are mixed before being fed in the mixer (5) to formulate the viscosity and density of the mixed hydrogenation raw material. After being filtered through the filter (6), the formulated hydrogenation raw material is mixed with hydrogen and then fed into a demetallization and protection refinement reactor (7) conditioned with protection catalyst, demetallization catalyst, refining catalyst A and refining catalyst B to be hydro-refined catalytically. The refined liquid phase component and the liquid phase component from the cracking reactor (8) (the top of which is conditioned with cracking catalyst, and the bottom is conditioned with refining catalyst B) are mixed and passed through the filter ( 9). After being filtered, the mixture is passed through the distillation column (10) to separate naphtha, water and acid gases. The oil at the bottom of the distillation column is heated and passed through the common pressure distillation column (11) to separate gasoline and diesel mixture components. The oil from the bottom of the common pressure distillation column is reheated and passed through the vacuum distillation column (12) to separate hydrogenated solvent with a high boiling point and hydrogenated petroleum tar. The hydrogenated solvent with a high boiling point is used for the removal of salt from coal tar and the formulation of the raw material, and the rest together with the instant separation oil from the synthetic reaction are still mixed with hydrogen, and then fed in the cracking reactor (8). The hydrogenated petroleum tar is extracted through the extraction section (13) to obtain an extracted hydrogenated petroleum tar, which is further fed in the synthetic reaction (14) to be subjected to thermal polymerization to synthesize a mesophasic oil tar.
[00184] Coal tar at high temperature as shown in Table 1-1 is sufficiently mixed with hydrogenated solvent with a high boiling point with a boiling point greater than 3 00-C and deionized water in a volume ratio of 1 : 0,5: 0,5 and goes into a centrifuge after washing to remove most of the water from
62/79 wash in it, and the wash is repeated 3 times. The hydrogenated solvent with a high boiling point is obtained by hydro-refining the BTX Fraction and anthracine oil in a ratio of 0.4: 1 under the catalyst and the hydro-refining conditions of this example as shown in Table 1-2. The washed coal tar is passed into a tank to remove IQ, and n-octane is added to adjust the volume ratio to be: tar: hydrogenated solvent with high boiling point: n-octane = 1: 0.5 : 0.5. After stirring, the mixture is passed through a centrifuge to remove IQ to obtain purified settling oil. The conditions of the above operations are a temperature of 80 ^and C, an agitation rate of 120rpm, an agitation time of 5min, and a centrifugation rate of 4000rpm. Distill part of the settling oil to obtain clean oil pitch, and see Table 1-3 for the results of analysis of settling oil and clean oil pitch. 0 rest of decanting oil is processed by a distillation apparatus for separating water, BTX fraction of less than 120 ⁵ ° C, n-octane, BTX fraction from 120 to 180 C ^and, carbolic oil and naphthalene oil. The mixture of waste oil, BTX Fraction less than 120-C and BTX Fraction from 120 to 180 ^s C is mixed with an additional BTX Fraction in a ratio of 1: 0.4 to obtain a hydrogenation raw material.
[00185] The hydrorefining and cracking reactions are carried out in a set of continuous hydrogenation reaction devices with two reaction tubes. The two 20 ml reaction tubes that can be used in series or in parallel are placed in a fixed oven. Beyond
63/79 In addition, the two reaction tubes share a set of feeding system and refrigeration separation system, and are operated by a computer for automatic control and monitored control. The first reaction tube loaded with protection and demetallization catalysts and the second reaction tube loaded with refining catalyst A and refining catalyst B are used in series to carry out the hydrorefining reaction. When the hydrocracking reaction is required, the two tubes above are replaced by a 200mL reaction tube loaded with cracking catalyst and refining catalyst B, which is used alone in the reaction apparatus.
[00186] The hydrogenation raw material from a raw material hydrogenation tank is heated to 80 ^g C before being filtered through a metal filter. The heated and filtered hydrogenation raw material is mixed with hydrogen and passed in a reactor conditioned with hydrogenation protection catalyst and TJS1 demetallization catalyst shown in Table 1-4 for the additional removal of impurities and metal ions. Then the product from the above process is passed into a reactor which is loaded with JZ1 hydrofinishing catalyst shown in Table 1-4 at the top, and the JZ6 refining catalyst shown in Table 1-4 at its bottom to be subjected to hydrorefining. The operating conditions for the hydrorefining reaction are a total pressure of 16.0MPa, an average reaction temperature of 350 ² C, a net hourly space velocity of 1 ^ hr ' ¹ and a hydrogen-oil volume ratio of 1000: 1.
64/79 [00187] The fraction of 300 to 360 ^Q C obtained from the distillation of refined oil is used as a raw material that is fed into a hydrocracking reactor conditioned with cracking catalyst LH1 shown in Table 1-5 in its top and JZ6 refining catalyst at its bottom to perform a hydrocracking reaction to obtain a cracking product. The operating conditions are a total pressure of 16.0MPa, an average reaction temperature of 370 ^and C, a net hourly spatial speed of 1.0hr ^_1 , and a hydrogen: oil volume ratio of 1000: 1.
[00188] The hydro-refined oil is mixed with the cracking product in a ratio of 1: 0.35 before being filtered. The operating pressure of the filter is 0.2MPa, the temperature is 200 ^Q C, and the absolute filtering precision is 10pm. The filtered oil is processed by a common pressure distillation apparatus to separate water, naphtha components with a boiling point of less than 120 ^g C, a gasoline mixing component of 120 to 180 ^and C and a diesel mixing component of 180 to 3 00 ^s C, and then passed through a vacuum distillation apparatus. The fraction with a boiling dispersion of 300 to 360 ^s C is used as a hydrogenated solvent with a high boiling point and a raw material for hydrocracking, and the fraction with a boiling point greater than 360 ^and C is hydrogenated petroleum pitch. The analysis of distillation fractions is shown in Table 1-6, and the analysis of hydrogenated solvent with high boiling point is consistent with the analysis result shown in Table 1-2. The tar analysis of
65/79 hydrogenated petroleum is shown in Table 1-7, and the infrared spectroscopy and NMR analysis of the hydrogenated petroleum tar is shown in Figure 3B and Figure 4.
[00189] The hydrogenated petroleum tar shown in Table 1-7 is extracted in a soxhlet extractor using pyridine, and the extracted oil obtained is separated by a
evaporator rotating for get tar of oil hydrogenated extracted. The results of analysis are shown in Table 1-8. [00190] The tar in Petroleum hydrogenated
extracted is passed in a static reaction to obtain a petroleum mesophasic tar product through thermal polymerization. The oil gas from the top of the static reaction is vented, separated and washed after being cooled, and the separated instant separation oil is used as a cracking raw material component. The synthesis reaction conditions are still: common pressure, a temperature of 40 0 ^s C, a reaction time of 30 0min, an agitation rate of 30 rpm and with nitrogen purge at the bottom of the immobile reaction. The analysis of the separated instant separation oil is shown in Table 1-9, and the analysis of mesophasic petroleum tar is shown in Table 1-10.
Table 1-1: A fundamental analysis of coal tar
coal tar r — 1i — 1 1.14 27.7 8.09 3.12 O00O0Λ 5.25 66 Ό 0.51 2.45 r — 1 35.4 Oí — 1CN 6.5 0.6 0 Ί O > m Units % of weight thAND0Cn CP o Φ ao Όo ° % of weight % of weight % of weight % of weight % of weight % of weight And the And h h ppm ppm ppm Ê Λ h E lL h ANDO, ass HI CO / ttí | Analysis items Water Density at 20-C| Dynamic viscosity YOU IQ u πQC O Al Here Faith Cns (ONi Cl conventionalelementary metal <D ül rd rH '05Φ to H i — 1 '05β Φ Όtoç0 Ή Anions
67/79
Table 1-2 Analysis of hydrogenated solvent with high boiling point
Distillation interval Density at 20 ^s C Dynamic viscosity at 2 0 ^s C Ç H O N s g / cm ³ CP % ofWeight % ofWeight % ofWeight % ofWeight % of weight 300- 360 ^B C 0.99 55.7 89.17 9.5 0.51 0.70 0.12 Typical molecular structures are obtained from analyzes and GC-MS And fa
Table 1-3 Properties of settling oil and clean petroleum pitch
Conventional analysis Items fromanalyze Units Oilsettling Tar ofclean oil Water % of weight 1.8 - Density at 20-C g / cm ³ 1.09 1.27 Viscosity and dynamics at 20-C CP 25.1YOU % of weight 3.76 16.95 IQ % of weight 0.02 0.05 Concentration ofanions Cl ' ppm 2.49ions ofmetal Al ppm 8, 7 19.4 Here ppm 5.3 9.6 Faith ppm 10.4 20.8
68/79
Mg ppm 1.4 At ppm 0
Table 1-4 Properties of catalysts for demetallization and refining
Catalysts Demetallization Refining A Refining B TJS1 TJS2 JZ1 JZ3 JZ4 JZ6 JZ7 Pore volume cm ³ / g of 0.82 1.35 0.61 1.33 0.55 0.72 1.03 Specific surface area m ² / g in 187.8 321.3 253.5 175, 0 210.8 245.8 200.7 Diameter pore nm of 12.1 21.2 11, 0 18 8.9 7.8 10.3 ContentMmol / g acid - - 0.095 0.070 0.05 - - Mo0 ₃ % weight of 15.4 8.1 32, 9 26.3 39.0 15 21.4 NiO% by weight 2.3 3.14 2.52 2.7 4.13 2.1 2.64 P2O5%Weight of - - 2.4 1.7 2.9 1.5 1, 6
Table 1-5 Cracking catalyst properties
Catalystcracking LH1 LH2 LH3 Content% by weight of mesoporous molecular sieve 13.8 10.6 14.3 Content% by weight of the microporous molecular sieve 5.7 9.6 9.5 Content% by weight of amorphous silica-alumina 34, 5 26.7 33.3 Content% of macroporous pseudo-bohemian weight 46 53.1 42.9 Pore volume cm ³ / g 0.56 0.89 0.35 Specific surface area m ² / g 310.5 248.5 341.8
69/79
Mo0 ₃ % by weight 33.4 32.1 16 NiO% by weight 3.1 2.8 2.1
Table 1-6 Hydro-refined oil fraction analysis
Refined oil fraction <L20 ² C 120-180 ^and C 180-30 0 ^to C Refined oil fraction of <L20 ^and c 120 to 180 ^and C 180 to 300 C Composition (V%) 16.0 8.7 25.5 Boiling point starts 1 ( ^and C) 68 82 106 Density and at 20 ^s C 0.824 0.851 0.954 10% ( ^and C) 83 116 180 C /% ofWeight 88.93 89, 17 89.25 30% ( ^s C) 88 129 250 H /% by weight 10.35 10.02 9.58 50% ( ^Q C) 92 144 270 S /% ofWeight 0.11 0.03 0.03 70% ( ^s C) 100 168 289 N /% by weight 0.30 0.45 0.56 95% (- C) 117 175 298 0 /% ofWeight 0.31 0.33 0.58 Final boiling point ( ^e C) 121 182 305
Table 1-7 Analysis and comparison of hydrogenated petroleum tar and clean petroleum tar
Group composition analysis (weight%)HS HI-TS TI-PS PI-QS IQ Tar ofclean oil 27, 19 55.86 12.62 4.28 0.05 Tar ofPetroleum 71.55 27.40 0.74 0.20 0.11
70/79
hydrogenatedElementary analysis (weight%)Ç H 0 N s H / C Tar ofclean oil 92.09 4.74 1.51 1.14 0.52 0.62 Tar ofhydrogenated oil 92.48 6.60 0.20 0.34 0.38 0.86 ICP analysis (ppm)Al Faith Here Mg At tS- Tar ofclean oil 19.4 20.8 9.6 2.8 0 52.6 Tar ofhydrogenated oil 4.2 5.6 7.9 1.2 0 18.9
As listed above:
[00191] HS: fraction of soluble heptane;
[00192] HI-TS: fraction in heptane insoluble and soluble toluene; [00193] TI-PS: fraction in toluene insoluble and soluble pyridine; [00194] PI-QS: fraction in pyridine insoluble and
soluble quinoline;
[00195] IQ: fraction of insoluble quinoline
Table 1-8 The molecular weights of tar from hydrogenated oil and oil tar extracted and the composition analysis in group
Oil tarhydrogenated Oil tarhydrogenated extractedComposition /% of weight Molecular weight Composition /% of weight Molecular weight HS 71.55 267 71.62 268 HI-TS 27.40 332 27.56 345 TI-PS 0.74 587 0.82 565 PI-QS 0.20 - 0 - IQ 0.11 - 0 - Average value - 315 - 291
Ί3 / Ί9
Softening point ² C 83 83
Table 1-9 Analysis of instant separation oil from immobile synthesis
Distillation interval Density at 20 ^s C g / cm ³ Dynamic age viscos at 80 ^and C CP C% of weight H% by weight 0% ofWeight N% by weight S %of the weight 300 to 36 0 ^and C 1, 07 2.83 90.12 9.42 0.22 0.16 0.08 Typical molecular structures obtained by GC-MS analysis f: '·' ¹ AA-e- ¹ / r-rv ·
Table 1-10 Analysis of properties of mesophasic petroleum tar
Raw materials of mesophasic tarPetroleum Mesophase content (%) Point ofsoften ntoTO Ash content (ppm) IQ (%) Density of at 20 ^and C (g / cm ³ ) Tar ofhydrogen oil from 100 240 31 44.2 1.45 Tar ofhydrogen oil extracted 100 230 16 47.1 1.45
Ί2 / Ί3
Example 2 [00196] A settling oil is obtained by removing salts and IQ in the hydrogenated BTX fraction, hydrogenated washing oil and hydrogenated anthracin oil obtained from the high temperature coal tar shown in Table 1-1 with BTX fraction, oil wash and anthracine oil under the hydro-refining conditions of Example 1, shown in Table 2-1.
Table 2-1 Analysis of the settling oil obtained from the fraction of hydrogenated coal tar
Aromatic solvent BTX fractionhydrogenated Oilhydrogenated wash Oilhydrogenated anthracin Density at 20 ^s C (g / cm ³ ) 0.86 0.97 1.05 C% of weight 89.56 89.71 89.92 H% by weight 10.25 10.13 9.50 0% by weight 0.04 0.02 0.14 N% by weight 0.13 0.11 0.34 S% of weight 0.02 0.03 0.10 The coal tar to aromatic solvent ratio 1: 0.2 1: 0.5 1: 0.75 The coal tar to water ratio 1: 3 1: 3 1: 3 Quantity ofwash 1 1 1 Tar: aromatic solvent: n-octane 1: 0.5: 0.4 1: 0.5: 0.58 1: 0.75: 0.75 Cl 'content in settling oil (ppm) 4.8 3.7 5.1 IQ content in settling oil (ppm) 125 187 231 Total content of metal ions in the settling oil (ppm) 32.3 33.5 67.9
Ί3 / Ί9
Residues obtained from pre-distillation of settling oil
[00197] The separation fractions with a boiling point of less than 230 ^and C distilling the above settling oil to obtain residues (Γ), (f) and (f), which are formulated with BTX fraction, hydrogenated fraction with a boiling point less than 120 ^and C and hydrogenated solvent with a high boiling point respectively under the condition listed in Table 2-2, to obtain hydrogenation raw material @, (De®. Since the residue (3) obtained Since the distillation settling oil is rich in hydrogenated solvent with a high boiling point, the hydrogenation raw material may not need to be formulated with a hydrogenated solvent with a high boiling point.
Table 2-2 Formulation of hydrogenated coal tar fraction and settling oil residues
The settling oil residues BTX fraction: hydrogenated fraction <120 ^and C: hydrogenated solvent with high boiling point: distilled settling oil residues 0.2:0.4: 0:1 0.2:0.5:0.5: 1 0.4: 0: 0: 1 Raw material ofhydrogenation
[00198] The hydrogenation raw materials @ e are subjected to hydrorefining respectively according to the steps of Example 1 using protection catalyst and demetallization catalyst TJS2 and refining catalysts JZ3 and JZ7 shown in Table 1-4 under the following conditions of reaction: a pressure of 18MPa, a temperature
Ί ^ / Ί9 from 350 to 355 ^and C at the top of the reactor, a temperature from 340 to 345 ^and C at the bottom of the reactor, a space velocity of 0.8hr '* and a hydrogen-oil ratio of 800: 1, to obtain refined oils (T) and @.
[00199] The hydrogenation raw material @ is subjected to hydrorefining according to the steps of Example 1 using protection catalyst and demetallization catalyst TJS2 and refining catalysts JZ4 and JZ7 shown in Table 1-4 under the following reaction conditions: a pressure of 14MPa, a temperature of 385 to
390 ² C on top of reactor, a temperature in 375 a 380 ^to C in bottom of the reactor, an space speed of l ^ hr ' ¹ and a reason hydrogen- oil 1200: 1 to obtain the oil refined d). [00200] The refined oils ( D θ (1) are distillates for get the fractions of 300 The 360 ^and C which
are subjected to hydrocracking respectively according to the steps of Example 1 using the LH2 cracking catalyst shown in Table 1-5 under the following reaction conditions: a pressure of 18MPa, a temperature of 350 to 355 ^and C at the top of the reactor, a temperature of 340 to 345-C at the bottom of the reactor, a spatial speed of 0.8hr ^_1 and a hydrogen-oil ratio of 800: 1, to obtain the cracking products (T) and (2).
[00201] 0 oil refinedis < distilled for get a fraction in 300 at 360 ² C The what is subject The hydrocracking in according to phases Example 1
using the LH3 cracking catalyst shown in Table
1-5 under the following reaction conditions: a pressure of
75 / Ί9
14MPa, a temperature of 385 to 390 ^s C at the top of the reactor, a temperature of 3 70 to 3 7 5 ^and C at the bottom of the reactor, a spatial speed of 1.5hr ^_1 and a hydrogen-oil ratio of 1800: 1, to obtain the cracking product (5).
[00202] The water-refined oil (J) and the cracking product (Γ), the water-refined oil "and the cracking product", and the water-refined oil "and the cracking product (3) are respectively mixed, filtered and distilled from according to the steps of Example 1 to obtain the hydrogenated petroleum sticks (T), @ and (D shown in Table 2-3.
Table 2-3 the molecular weight of hydrogenated petroleum tar and the group composition analysis
Tar ofhydrogenated oil Q (DHS (% ofWeight) 66.71 65, 93 80.64 HI-TS (% of weight) 30.21 31, 90 18.12 TI-PS (% of weight) 1.81 1, 12 0.51 PI-QS (% of weight) 1.23 1.01 0.71 IQ (% ofWeight) 0.04 0.04 0.02 Average molecular weight 290 296 282 Softening point ^S C 82 84 80
[00203] Reacting non-extracted hydrogenated petroleum drums CD and @ directly to prepare the mesophasic petroleum drums (T) and @ under the following conditions:
a pressure of 0.01MPa (absolute pressure), a temperature
76/79 of 410 ^s C, a reaction time of 600 minutes, a stirring rate of 20 rpm, and nitrogen purging at the bottom of the reactor. The properties of the mesophasic oil leaks φ and (2) are shown in Table 2-4.
[00204] Reacting a non-extracted hydrogenated petroleum tar (3) directly to prepare the mesophasic petroleum tar (f) under the following conditions: a pressure of 1.0MPa, a temperature of 440 ^Q C, a reaction time of ISOmin , a stirring rate of 40rpm, and purging hydrogen at the bottom of the reactor. The properties of the mesophasic petroleum tar (3) are shown in Table 2-4.
Table 2-4 analysis of the properties of mesophasic oil tar
Mesophasic oil tar Mesophase content (AC%) Softening point (SP ^Q C) Ash content (ppm) IQ(Weight%) Density at 20 ² C (g / cm ³ )100 23 5 25 50.8 1.44 © 100 235 18 51.2 1.45 _ 100 228 53 43.3 1.44
Example 3 [00205] A settling oil is obtained under the conditions shown in Table 3-1 using the coal tar shown in Table 1-1 as a raw material and the hydrogenated distillation fraction shown in Table 1-6 as a solvent aromatic.
Table 3-1 Analysis of the settling oil produced from the hydrogenated distillation fraction of coal tar
Solvent The fraction of Component Component
77/79
aromatic naphtha mixinggasoline mixingdiesel The reason fortarcoal for aromatic solvent 1: 0.3 1: 0.5 1: 0.5 The coal tar to water ratio 1: 1.5 1: 1.5 1: 1.5 Wash times 2 2 2 Tar: aromatic solvent: noctane 1: 0.5: 0.30 1: 0.5: 0.37 1: 0.5: 0.5 The content of Cl 'in the settling oil (ppm) 4.0 4.2 3.5 The IQ content in the settling oil (ppm) 236 156 267 The total content of metal ions in the settling oil (ppm) 42.1 32.8 18.3 Oilsettling (D
[00206] The settling oil mentioned above is hydro-refined to obtain a hydro-refined oil using the catalyst of Example 1. The operating conditions of the hydro-refining reactor are a total pressure of 16, OMPa, an average reaction temperature of 380 ^and C, a net hourly space velocity of l.Ohr ' ¹ and a hydrogen: oil volume ratio of 1000: 1. The refined oil is subjected to suction filtration through 10pm buehner funnels, and then distilled to obtain the hydrogenated petroleum (T), © and @ pipes shown in Table 3-2.
78/79
Table 3-2 The molecular weight of hydrogenated petroleum tar and the group composition analysis
Tar ofhydrogenated oil(DHS (% ofWeight) 97.71 97.24 96.21 HI-TS (% ofWeight) 1, 05 1.56 2.30 TI-PS (% ofWeight) 0.81 0.84 0.94 PI-QS (% ofWeight) 0.41 0.35 0.51 IQ (% ofWeight) 0.02 0.01 0.04 Softening point ( ^to C) 78 75 81
[00207] The hydrogenated petroleum tar is fed in a static reaction to be subjected to thermal polymerization to obtain a mesophasic petroleum tar product. The oil gas from the top of the static reaction is cooled, separated and washed before being vented. The separated instant separation oil is used as a cracking raw material component. The synthesis conditions under which the mesophasic petroleum leaks (T), (D and (3) as shown in Table 3-3 are obtained using the static reaction are: a common pressure, a temperature of 4 3 0 ² C, a reaction time of 30 minutes, a stirring rate of 30 rpm, and purging nitrogen at the top of the static reaction.
Table 3-3 Analysis of the properties of mesophasic petroleum tar
Tar Content Point of Content IQ Density
79/79
mesophasic oil inmesophase(AC%) softening (SP ² C) ash (ppm) (Weight%) at 20-C (g / cm ³ )100 229 17 48.9 1.45100 228 15 49.3 1.44 _ 100 231 24 49.1 1.44
[00208] The resulting mesophasic petroleum tar is coated and fixed with an epoxy resin before being ground and polished, and then it is photographed by a polarizing microscope to obtain Figures 5A and 5B.

权利要求:
Claims (3)
[1]
(1) removal of salts and insoluble fraction of quinoline from a coal tar at high temperature to obtain a settling oil;
1. Process for producing mesophasic oil tar from coal tar at high temperature, characterized by the fact that it comprises:
[2]
2/10 mix deionized water and an aromatic solvent with the coal tar at high temperature, and centrifuge them to remove wash water to obtain a coal tar desalted at high temperature with the aromatic solvent; wherein the aromatic solvent comprises one or more components selected from the group consisting of benzene, toluene, xylene, coal tar distillation fractions and hydrogenation product from coal tar distillation fractions.
3. Process, according to claim 2, characterized by the fact that in the step (la) of salt removal, the volume ratio of coal tar at high temperature to the aromatic solvent is 1: 0.2 to 2 , the volume ratio of deionized water to coal tar at high temperature is 0.5 to 3, and deionized water is used to wash coal tar at high temperature 1 to 3 times.
4. Process according to claim 3, characterized by the fact that the volume ratio of coal tar at high temperature to the aromatic solvent is 1: 0.2 to 0.8.
5- Process, according to claim 2 or
3, characterized by the fact that step (1) comprises:
(1b) a step of removing the insoluble fraction of quinoline, which comprises adding an aliphatic solvent and optionally the aromatic solvent to the coal tar desalinated at high temperature with the aromatic solvent, and followed by centrifugation or sedimentation to remove the insoluble quinoline fraction ; the aliphatic solvent comprises C ₄ -C ₆ aliphatic compounds; where the reason for
3/10 final volume of coal tar at high temperature, aromatic solvent and aliphatic solvent is 1: 0.2 to 2: 0.2 to 1.
6- Process, according to claim 5, characterized by the fact that the final volume ratio of coal tar at high temperature, aromatic solvent and aliphatic solvent is 1: 0.3 to 0.8: 0, 3 to 0.8.
7. Process according to claim 5, characterized by the fact that the aliphatic solvent is noctane or n-heptane.
8. Process according to claim 1, characterized by the fact that the pre-distillation in step (2b) comprises a step of recycling the aliphatic solvent.
9. Process according to claim 1, characterized by the fact that pre-distillation in step (2b) comprises a step of obtaining at least one of BTX fraction, carbolic oil and naphthalene oil.
10. Process according to claim 1, characterized by the fact that step (2) additionally comprises a filtering step to filter the particles with a particle size greater than 10pm before the catalytic hydrorefining.
11- Process, according to claim 1, characterized by the fact that in step (2), the catalytic hydro-refining is conducted under conditions of a total pressure of 12.0 MPa to 20.0 MPa, an average reaction temperature of 320 ^Q C at 400 ⁹ C, net hourly space velocity from 0.5hr ' ¹ to 2.0 hr' ¹ , and a hydrogen-oil ratio of 600: 1 to 1500: 1.
12- Process, according to claim 11, characterized by the fact that in step (2), the hydro-refining
Catalytic 4/10 is conducted under conditions of a total pressure of 14.0MPa to 18.0 MPa, an average reaction temperature of 340 ^and C to 390 ^Q C, net hourly space speed of 0.8hr ' ¹ to 1.2 hr ' ¹ , and a hydrogen-oil ratio of 800: 1 to 1200: 1.
13. Process according to claim 11, characterized by the fact that in step (2), the catalytic hydro-refining is conducted in the presence of the following catalyst:
hydrorefine catalyst A: employing alumina or alumina containing silicon as a carrier which has a specific surface area of 120 to 300m ² / g, a pore volume of 0.4 al, 4mL / g, a pore diameter of 8 at 20nm, and a surface acid content of 0.05 to 0.1mmol / g, and Mo or W of the VIB group of metals and Co or Ni of the VIII group of metals as active metal components, based on the total weight of the catalyst hydrorefining A, the content of the VIB group of metals counted in oxide is 15 to 45% by weight, and the content of group VIII of metals counted in oxide is 1.5 to 5% by weight.
14- Process, according to claim 11, characterized by the fact that in step (2), the catalytic hydro-refining is conducted in the presence of the following two catalysts:
hydro-refining catalyst A: employing alumina or alumina containing silicon as a carrier, which has a specific surface area of 120 to 300m ² / g, a pore volume of 0.4 al, 4mL / g, a pore diameter of 8 to 20 nm, an acidic surface content of 0.05 to 0.1 mmol / g; and Mo or W of the VIB group of metals and Co or Ni of the VIII group of metals as active metallic components, based on the total weight of the hydrofin catalyst A, the content of the group
5/10
VIB of metals counted in oxide is 15 to 45% by weight, and the content of group VIII of metals counted in oxide is 1.5 to 5% by weight;
hydrorefine catalyst B: employing alumina or alumina containing silicon as a carrier, which has a specific surface area of 120 to 300m ² / g, a pore volume of 0.4 al, 2mL / g, a pore diameter of 7 to 15nm; and Mo or W from the VIB group of metals and Co or Ni from the VIII group of metals as active metal components; based on the total weight of hydrorefine catalyst B, the content of the VIB group of metals counted in oxide is 10 to 22% by weight, and the content of group VIII of metals counted in oxide is 2 to 5% by weight.
15. Process, according to claim 11, characterized by the fact that in step (2), the hydrogenation raw material is hydro-refined catalytic after passing through a protection catalyst and a demetallization catalyst, in which the demetallization catalyst employs alumina as a carrier which has a pore volume of 0.5 al, 5mL / g, a specific surface area of 180 to 350m ² / g, a pore diameter of 10 to 50nm; based on the total weight of the demetallization catalyst, the demetallization catalyst contains 7 to 20% of the weight of molybdenum oxide and 2 to 5% of the weight of nickel oxide.
16. Process according to claim 1, characterized in that in step (3), the distillation comprises a step of obtaining a hydrogenated solvent with a high boiling point with a boiling dispersion of 300 to 360 ^g C and a hydrogenated distillation fraction with a
6/10 boiling dispersion from 80 to 300 ^and C,
17. Process according to claim 16, characterized by the fact that step (1) comprises:
(la) a salt removal step, which comprises mixing deionized water and aromatic solvent with the coal tar at high temperature, and centrifuging them to remove the washing water, obtaining a coal tar desalinated at high temperature with the solvent aromatic, where the aromatic solvent is the hydrogenated solvent with high boiling point.
18. Process, according to claim 16, characterized by the fact that step (1) comprises:
(lb) a step of removing the insoluble fraction of quinoline, which comprises adding aliphatic solvent and optionally the aromatic solvent in the coal tar desalinated at high temperature with the aromatic solvent, mixing and centrifuging them or leaving them for sedimentation to remove the insoluble fraction of quinoline, the aliphatic solvent comprises C4-C16 aliphatic compounds, the aromatic solvent is the hydrogenated solvent with a high boiling point, in which the final volume ratio of high temperature coal tar, aromatic solvent and aliphatic solvent is 1: 0.3 to 0.8: 0.3 to 0.8.
19- Process, according to claim 18, characterized by the fact that the final volume ratio of the coal tar at high temperature, the hydrogenated solvent with a high boiling point and the aliphatic solvent is from 1: 0.5 to 0 , 8: 0.5 to 0.8.
20. Process according to claim 16,
7/10 characterized by the fact that in step (2b), the formulated oil comprises the hydrogenated solvent with high boiling point and the hydrogenated distillation fractions.
21. Process according to claim 16, characterized by the fact that in step (2b), the formulated oil comprises the hydrogenated solvent with high boiling point, BTX fraction, washing oil and the hydrogenated distillation fractions.
22. Process according to claim 21, characterized by the fact that the volume ratio of the BTX fraction or washing oil: of the hydrogenated solvent with a high boiling point: of the hydrogenated distillation fractions: of the residues is 0.2 to 1: 0 to 1: 0 to 1: 1.
23. Process according to claim 22, characterized by the fact that the volume ratio of the BTX fraction or washing oil: of the hydrogenated solvent with high boiling point: of the hydrogenated distillation fractions:
of waste is 0.2 to24. Process, 0.4: 0 to 0.5: 0 to 0.5: 1. in wake up with claim 16, characterized by the fact in that thermal polymerization at step (4) comprises an stage to get an oil in instant separation. 25. Process, in wake up with claim 24,
characterized by the fact that it additionally comprises:
(5) catalytic hydrocracking of the hydrogenated solvent with a high boiling point and the oil of instant separation after mixing them to obtain a hydrocracking product.
26- Process, according to claim 25, characterized by the fact that hydrocracking
Catalytic 8/10 is conducted under conditions of a total pressure of 12, OMPa at 2 0.0 MPa, an average reaction temperature of 340 ² C at 420 ^Q C, a net hourly space velocity of Ο, δϊιτ ' ¹ to 2 , 0 hr ¹ , and a hydrogen-oil ratio of 600: 1 to 1500: 1.
27- Process according to claim 26, characterized by the fact that the catalytic hydrocracking is carried out under conditions of a total pressure of 14, OMPa to 18.0 MPa, an average reaction temperature of 350 ^q C to 390 ^e C , a net hourly space velocity of Ο, δΗΓ ¹ al, 5hr ^_1 , and a hydrogen-oil ratio of 800: 1 to 1200: 1.
28. Process according to claim 25, characterized by the fact that catalytic hydrocracking is conducted in the presence of the following catalyst:
hydrocracking catalyst: employing alumina, amorphous silica-alumina and microporous and mesopore molecular sieve as a carrier, where, based on the total weight of the hydrocracking catalyst, the mesoporous molecular sieve is responsible for 10 to 15% of the weight, at molecular microporous sieve is responsible for 5 to 10% of the weight, amorphous silica-alumina is responsible for 15 to 40% of the weight, alumina is responsible for 35 to 70% of the weight; the specific surface area is 150 to 350m ² / g, and the pore volume is 0.1 to 1.0mL / g; the charged catalyst contains 10 to 35% by weight of MoO ₃ and / or WO ₃ , and 2 to 5% by weight of NiO and / or CoO.
29- Process, according to claim 25, characterized by the fact that the catalytic hydrocracking is conducted in the presence of the two catalysts at
9/10 follow:
hydrocracking catalyst: employing alumina, amorphous silica-alumina and molecular sieve of micropore and mesopore as a carrier; where, based on the total weight of the hydrocracking catalyst, the mesoporous molecular sieve is responsible for 10 to 15% of the weight, the microporous molecular sieve is responsible for 5 to 10% of the weight, the amorphous silica-alumina is responsible for 15 to 40% by weight, alumina is responsible for 35 to 70% by weight; the specific surface area is 150 to 350m ² / g, the pore volume is 0.1 to 1.0mL / g; the charged catalyst contains 10 to 35% by weight of MOO3 and / or WO ₃ , and 2 to 5% of the weight of NiO and / or CoO;
hydrorefine catalyst B: employing alumina or silicon-based alumina as a carrier, which has a specific surface area of 120 to 300m ² / g, a pore volume of 0.4 al, 2mL / g, a pore diameter from 7 to 15nm; and Mo or W from the VIB group of metals and Co or Ni from the VIII group of metals as active metal components; based on the total weight of the hydrorefine catalyst B, the content of the VIB group of metals counted in oxide is 10 to 22% by weight, and the content of group VIII of metals counted in oxide is 2 to 5% by weight.
30. Process according to claim 25, characterized by the fact that the distillation is carried out after mixing the hydro-refined oil with the hydrocracking product in a volume ratio of 1: 0.2 to 0.5 in step (3) .
31- Process, according to claim 25, characterized by the fact that step (3) comprises
10/10 additionally a filtration step to remove particles with a particle size greater than 10ym before distillation.
32. Process according to claim 1, characterized by the fact that step (3) comprises a step of obtaining naphtha, gasoline blending component and diesel blending component.
33. Process according to claim 1, characterized by the fact that the thermal polymerization in step (4) is conducted for 180 to 1200 minutes under conditions of a pressure of 0.01 to 3.0MPa, a temperature of 380 to 460 ^s C, with a stirring rate of 10 to 60 rpm, and purging hydrogen, nitrogen or argon at the bottom at the top of the reactor.
34. Process according to claim 33, characterized by the fact that thermal polymerization in step (4) is conducted for 180 to 600 minutes under pressure conditions of 0.01 to 1. OMPa and a temperature of 400 to 440 ^and C, with a stirring rate of 20 to 40 rpm, and purging nitrogen at the bottom and top of the reactor.
5- Process, according to claim 33, characterized by the fact that step (4) comprises viscosity analysis in real time.
36. Process according to claim 1, characterized by the fact that it comprises an extraction step with a solvent between steps (3) and (4).
(2) obtaining a hydrogenation raw material from the settling oil using either of the following two approaches:
(2a) use the settling oil as the raw material for hydrogenation; or (2b) pre-distill the settling oil to obtain a residue with a boiling point greater than 230 ^s C, and mix the residue with formulated oil to obtain the hydrogenation raw material, wherein the formulated oil comprises one or more more components selected from the group consisting of coal tar distillation fractions and the hydrogenated product of coal tar distillation fractions;
hydrorrefining catalytically the hydrogenation raw material to obtain a hydrorrefined oil;
(3) distilling the hydro-refined oil to obtain hydrogenated petroleum pitch;
(4) to submit the tar from hydrogenated oil The polymerization thermal to get the mesophasic tar in Petroleum. 2. Process, according with claim 1, featured by the fact that step (1) comprises:
(la) a salt removal step, comprising
[3]
Process according to claim 36, characterized in that the solvent is an aromatic solvent comprising benzene, toluene, pyridine, quinoline or tetrahydrofuran.

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同族专利:

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公开号 | 公开日

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RU2014132587A|2016-03-10|

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WO2013104092A1|2013-07-18|

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TW201329223A|2013-07-16|

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CN103205271A|2013-07-17|

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TWI555834B|2016-11-01|

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US20150076031A1|2015-03-19|

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EP2818535A4|2015-07-29|

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UA114102C2|2017-04-25|

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EP2818535A1|2014-12-31|

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EP2818535B1|2020-10-21|

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KR20140123530A|2014-10-22|

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JP5956610B2|2016-07-27|

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CN103205271B|2016-03-09|

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JP2015513320A|2015-05-07|

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WO2013104092A8|2014-08-07|

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BR112014017348B8|2019-09-10|

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RU2598452C2|2016-09-27|

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KR101766322B1|2017-08-08|

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US9994775B2|2018-06-12|

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法律状态:
2018-12-18| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-06-18| B09A| Decision: intention to grant|

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2019-08-20| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/04/2012, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/04/2012, OBSERVADAS AS CONDICOES LEGAIS |

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2019-09-10| B16C| Correction of notification of the grant|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/04/2012, OBSERVADAS AS CONDICOES LEGAIS. (CO) REFERENTE A RPI 2537 DE 20/08/2019, QUANTO AO ITEM (73) NOME DO TITULAR. |

优先权:

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申请号 | 申请日 | 专利标题

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CN201210009243.2|2012-01-12|

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CN201210009243.2A|CN103205271B|2012-01-12|2012-01-12|Hydrogenation of high temperature coal tar produces the method for mesophase pitch|

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PCT/CN2012/000451|WO2013104092A1|2012-01-12|2012-04-06|Process for producing mesophase pitch by hydrogenation of high-temperature coal tar|

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