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    公开号:BR112013016481B1
    申请号:R112013016481-6
    申请日:2011-06-24
    公开日:2018-07-03
    发明作者:Liu Zhongmin；Wei Yingxu；Qi Yue；Ye Mao；Li Mingzhi；Li Bing；Wang Xiangao；He Changging；Sun Xinde
    申请人:Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences；
    IPC主号:
    专利说明:

    (54) Title: PROCESS FOR THE CATALYTIC CRACKING REACTION OF METHANOL-CONNECTED NAFTA (51) Int.CI .: C07C 11/04; C07C 11/06; C07C 11/08; C07C 15/04; C07C 15/06; C07C 15/08; C07C 4/06;
    1/20 C07C; B01J 29/40; C10G 11/05 (30) Unionist Priority: 12/28/2010 CN 201010607910.8 (73) Holder (s): DALIAN INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES (72) Inventor (s): ZHONGMIN LIU; YINGXU WEI; YUE Ql; MAO YE; MINGZHI LI; BING LI; XIANGAO WANG; CHANGGING HE; XINDE SUN ‘PROCESS FOR THE CATALYTIC CRACKING REACTION OF METHANOL-CONNECTED NAFTA”
    FIELD OF THE INVENTION
    The invention relates to a process for the catalytic cracking reaction linked to naphtha methanol using a modified ZSM-5 molecular sieve catalyst.
    BACKGROUND OF THE INVENTION
    The olefin industry is an important basis for the development of the chemical industry. The production of low carbon olefins mainly uses the technical process of cracking naphtha with high temperature water vapor, in which the reaction needs to be conducted under the condition of 800 ° C or more, which is one of the processes that consumes relatively large energy in the chemical industry. Recently, the price of international crude oil continues to rise, the cost of raw materials for olefin increases enormously, and olefin corporations face a more severe situation. At the same time, the demand on the international market for propylene has a tendency to grow enormously, and the distribution of product from the cracking process with traditional water vapor that is dominated by ethylene would also not satisfy the growing need for propylene on the market. The above factors promote the development of new technology for olefin. The technology to produce ethylene and propylene by catalytic cracking at a relatively low temperature attracts wide attention. However, catalytic cracking can result in higher propylene yield, satisfying the growing need for propylene.
    Naphtha is a mixed C4-C12 hydrocarbon product, its composition is mainly saturated alkanes, which is responsible for 50 to 95% by weight of the total compositions. These light hydrocarbons have a low carbon number and a high degree of saturation. Currently, the commercial technology of producing low carbon olefins through the cracking reaction from these light hydrocarbons is only known as high temperature steam cracking. Large amounts of methanol and coke are produced in the reaction. In order to solve the defects of high energy consumption and low use of raw material, a series of catalytic cracking technologies are developed. Currently, catalytic cracking technologies for saturated hydrocarbons and naphtha dominated by saturated hydrocarbons are divided into two types of technologies, fixed bed and fluidized bed.
    In the process of fixed bed reaction, the former Soviet Union developed a Potassium-Vanadium Vniios process (USSR Pat 1298240.1987). This catalyst uses potassium vanadate as an active component, a-Al 2 O 3 as a carrier, and oxides such as B 2 O 3 and the like as an auxiliary. The semi-industrial and industrial naphtha cracking experiments were carried out at 800 ° C in the presence of steam. The yields of ethylene and propylene in this process are 38% and 14.5%, respectively, and the propylene / ethylene ratio is about 0.4. USP 3,767,567 uses A1 2 O 3 and an oxide of either CaO, SrO and BaO as a catalyst for the catalytic cracking of naphtha. The reaction temperature is relatively high. With the generation of ethylene and propylene, a relatively large amount of dry gases, CO and CO 2 are produced. USP 4,172,816 uses Ag-MOR / Al 2 O 3 as a catalyst, and conducts the reaction between 600 and 750 ° C. The yield of ethylene and propylene reaches 42%. USP 6.288.298 uses a SAPO-11 molecular silicon phosphorus sieve as a catalyst for cracking naphtha, cracking light naphtha components at 575 ° C, where conversion is
    39.2%, and the selectivity of propylene in converted products reaches 56%. Patent ZL 02152479.3 to the Dalian Institute of Chemical Physics, Chinese
    Academy of Sciences uses a modified molecular sieve as a catalyst, conducting the catalytic cracking of a naphtha raw material containing 60% by weight of an alkane chain and 30% by weight of a cyclic alkane which is reacted between 600 and 700 ° C , and the yield of ethylene and propylene reaches 45 to 50%.
    The process for producing olefins by the fluidized bed catalytic cracking disclosed in the patents mainly uses the high carbon atom number olefins as the cracking raw materials to drive the production of low carbon olefins, but the patent technologies using the saturated hydrocarbons as the main cracking raw material are very few. WO099 / 57085 and WOO1 / 64761 start from the olefin-rich raw material (20 to 70%), use a fluidized bed and a short residence time (1 to 10 s), and the raw material contacts the catalyst containing the molecular sieve to produce C2-C4 olefins under the condition of a catalyst to raw material ratio of 2 to
    10. EP 0109059 discloses a process for converting C4-C12 olefins to propylene. The catalyst used is the molecular sieve ZSM-5 or ZSM-11 with a silicon-aluminum ratio lower than 300, and the reaction is carried out at a spatial speed higher than 50 h ' 1 , and a reaction temperature from 400 to 600 ° C. The total yield of ethylene and propylene is 36 to 44%, where the yield of propylene is 30 to 40%. USP 4,830,728 introduces a fluidized catalytic cracking device used to maximize the olefin yield. This device has two elevators, in which the heavy crude diesel oil is converted into an elevator, while the lighter olefins or naphtha raw material is cracked in another elevator, and the adjustment of the condition for the crude diesel elevator can maximize the production of gasoline and olefins.
    The catalytic cracking described above has characteristics such that alkaline catalytic cracking in general needs to be obtained at a relatively high temperature. Although compared to thermal cracking, its reaction temperature is relatively low, it does not completely overcome the problem of high energy consumption and high methanol production. Using the acid molecular sieve catalyst, cracking of the hydrocarbons of the raw material can be obtained at a relatively low temperature, but there is still the problem of supplying heat to the system.
    The use of linking different reaction processes is an efficient procedure to reduce the thermal effect of the reaction. Nowak et al. adds C4 hydrocarbon during the methanol conversion process to conduct the heat bond (Appl. Cat. A 50 (1989) 149-155). At a reaction temperature of 600 to 700 ° C, when the ratio of the methanol to n-butane molecule is 3: 1, the reaction process in the HZSM-5 molecular sieve achieves thermal neutralization. The linked cracking of methanol and C6 hydrocarbons and naphtha also shows the promotion effect for the production of low carbon olefins. Patent ZL 02152480.7 of the Dalian Institute of Chemical Physics, Chinese Academy of Sciences suggests a linked technical routine of producing low carbon olefins using the catalytic cracking of compounds containing organic oxygen and petroleum hydrocarbons. By linking the reaction process having an exothermic effect, the appropriate exothermic reaction bonding of compounds containing organic oxygen causes the cracking of petroleum hydrocarbons to turn from a strong endothermic reaction process to a relatively strong or relatively weak endothermic reaction process , and can improve the yield of low carbon olefins such as ethylene, propylene, and so on.
    The methanol reaction and hydrocarbon cracking reaction mainly use different catalyst systems. The present invention applies a modified ZSM-5 catalyst for the bonded reaction of both, obtaining the cracking of hydrocarbons bound to methane. Compared with the cracked naphtha cracking reaction, the methanol-linked reaction catalyzed with modified ZSM-5 has a higher yield of low carbon olefins and co-producing aromatic hydrocarbons.
    SUMMARY OF THE INVENTION
    An objective of the present invention is to provide a process for the catalytic cracking reaction linked to naphtha methanol using a modified ZSM-5 molecular sieve catalyst, which comprises carrying out a methanol and naphtha coalimentation reaction on the ZSM- molecular sieve catalyst 5 modified to produce low carbon olefins and / or aromatic hydrocarbons. By using the methanol-cracked naphtha cracking reaction catalyzed by the modified ZSM-5 molecular sieve, it is able to improve the efficiency of the catalytic cracking of naphtha, and produce low-carbon olefins and high-yielding aromatic hydrocarbons.
    The catalyst provided in the present invention comprises a ZSM-5 molecular sieve, a binder and modifying elements. The molecular sieve ZSM-5 comprises from 25 to 80% by weight of the total weight of the catalyst, where the silicon-aluminum ratio is in the range of 12 to 100. The binder can be alumina, silicon oxide or the mixture of both, which comprises from 15 to 70% by weight of the total weight of the catalyst. Lanthanum or phosphorus are used as the modified elements for the catalyst, where lanthanum comprises from 2.2 to 6.0% by weight of the total weight of the catalyst, and P comprises from 1.0 to 2.8% by weight of the catalyst. total catalyst weight, the modifying process can be exchange or impregnation. The modified ZSM-5 molecular sieve catalyst can be used as a fluidized bed catalyst and a fixed bed catalyst. The modified ZSM-5 molecular sieve catalysts used for the fluidized bed catalyst and the fixed bed catalyst have different compositions. When the fluidized bed reactor is used, the modified ZSM-5 molecular sieve catalyst comprises, in terms of percentage by weight, from 25 to 38.6% by weight of the ZSM-5 molecular sieve, from 56 to 70% by weight of the binder, and the modifying elements, that is, from 2.2 to 3.4% by weight of lanthanum and from 2.0 to 2.8% by weight of phosphorus loaded in the ZSM-5 molecular sieve. When the fixed bed reactor is used, the modified ZSM-5 molecular sieve catalyst comprises, in terms of weight percentage, from 63 to 80% by weight of the ZSM-5 molecular sieve, from 15 to 30% by weight of the binder , and the modifying elements, that is, from 2.2 to 6.0% by weight of lanthanum and from 1.0 to 2.8% by weight of phosphorus loaded on the ZSM-5 molecular sieve.
    The production process for the modified ZSM-5 molecular sieve catalyst used for the fluidized bed is as follows.
    1) A ZSM-5 molecular sieve from which the standardizing agent has been removed is exchanged with a solution of ammonium nitrate at
    80 ° C three times. After the exchange, it was calcined at 550 ° C to obtain a H type ZSM-5 molecular sieve.
    2) The H type ZSM-5 molecular sieve is exchanged with a lanthanum nitrate solution at 50 ° C for 4 h, filtered, dried, and calcined at
    550 ° C in air for 6 h. The molecular sieve ZSM-5 modified by La is exchanged with a solution of phosphoric acid at 50 ° C for 4 h, filtered, dried, and then calcined at 550 ° C in air for 6 h.
    3) The modified ZSM-5 molecular sieve is mixed with clay, silicon sol, aluminum sol, and deionized water to form a slurry whose solid content is 20 to 50% by weight. The slurry is aged for 3 to 10 h, and then subjected to the formation of spray in order to obtain a microsphere catalyst from 20 to 100 pm.
    3) After the microsphere catalyst described above is calcined at 550 ° C in air for 4 to 10 h, it is treated in a steam atmosphere of 700 to 850 ° C for 3 to 15 h.
    The production process for the modified ZSM-5 molecular sieve catalyst used for a fixed bed catalyst is as follows.
    1) A ZSM-5 molecular sieve powder as synthesized containing a synthetic patterning agent is mixed with silicon sol and formed, dried, and then calcined at 550 ° C to remove the patterning agent, and ground into sieve particles molecular range from 20 to 40 meshes.
    2) The molecular sieve particles are exchanged with an ammonium nitrate solution at 80 ° C three times. After the exchange, the molecular sieve particles are calcined at 550 ° C in order to obtain ZSM-5 type H molecular sieve particles.
    3) The ZSM-5 type H molecular sieve particles are impregnated with the modifying components, that is, a solution of La (NC> 3) 3 and H3PO4, dried, calcined and then produced inside the modified ZSM-5 catalysts.
    Naphtha is a type of oil products during oil refining and processing. The naphtha feedstock used in the present invention comprises any of a full-range naphtha, a light naphtha, and a raffinate oil, or any mixture thereof, wherein the full-range naphtha feedstock has C4 chain alkanes -C12 and cyclic alkanes as the main components, light naphtha has C5-C7 chain alkanes as the main components, and the raffinate oil raw material has C4-C9 chain alkanes as the main components. Naphtha comprises from 63.8 to 89.5% by weight of chain alkanes, from 5.6 to 29.8% by weight of cyclic alkanes, from 0.6 to 4.5% by weight of aromatic hydrocarbons and 1.9 to 4.3% by weight of olefins. The chain alkanes comprise straight and branched alkanes.
    The specific compositions of various naphtha are shown in Tables 1 to 3.
    Table 1 Compositions of naphtha: full-range naphtha Carbon numbers Chain alkanes Cyclic alkanes Olefins Aromatic hydrocarbons
    c 4 1.4 - - - C 5 4.7 - - - Ce 9.1 6.7 - - c 7 8.0 6.1 1.6 - C 8 12.8 6.9 - 0.9 Cç 9.7 6.1 - 1.9 Cio 7.9 1.7 0.3 1.3 ç" 6.5 1.2 - 0.4 C] 2+ 3.7 1.1 - - Total 63.8 29.8 1.9 4.5
    Table 2 Compositions of naphtha: light naphtha
    Chain alkanes Cyclic alkanes Olefins Aromatic hydrocarbons C 4 1.5 - - c 5 50.8 7.4 - - C 6 31.0 2.8 - 0.4 c 7 3.4 3.4 - 0.5 C 8 - 0.1 - - Total 85.4 13.7 - 0.9 Table 3 Naphtha compositions: raffinate oil Chain alkanes Cyclic alkanes Olefins Aromatic hydrocarbons c 4 0.2 - - - c ; 17.4 3.5 0.8 - C 6 44.6 0.6 2.0 0.2 c 7 26.1 1.5 1.4 0.2 c s 1.2 - - 0.2 c 9 0.1 - - - Total 89.5 5.6 4.3 0.6
    In the present invention, the reaction raw material is converted to low carbon olefins and aromatic hydrocarbons through the catalytic cracking of naphtha catalyzed with ZSM-5 linked to modified methanol, in which the low carbon olefins comprise ethylene, propylene , and butylenes, and aromatic hydrocarbons comprise benzene, toluene, and xylenes.
    In the present invention, a fluidized bed reaction device and a fixed bed reaction device are used to conduct the catalytic cracking of a saturated hydrocarbon feedstock, wherein the fluidized bed comprises a fixed fluidized bed and a circulating fluidized bed.
    In a fluid bed reaction, the fluid bed reactor is charged with a fluid bed catalyst having a particle size in the range of 20 to 100 pm, and the catalyst is fluidized in the reactor. The raw materials of coalesced naphtha and methanol are added from the bottom of the reactor, while a dilution gas is introduced in order to reduce the partial pressure of the reaction materials and help in the catalyst fluidization. The dilution gas can be an inert gas or steam, more preferably steam. Naphtha, methanol, and dilution gas can be mixed with the catalyst and can fluidize the catalyst in the reactor, and be converted into products such as low carbon olefins, aromatic hydrocarbons, and the like under reaction conditions. . The reaction temperature ranges from 580 to 670 ° C, the reaction pressure is 0.1 to 0.3 MPa, and the spatial mass speed of naphtha and methanol is 0.3 to 5 h 1 .
    In a fixed bed reaction, naphtha and methanol are coalimented together with steam inside the reactor, and contacted with the fixed bed catalyst and reacted to produce low carbon olefins and aromatic hydrocarbons. The mass ratio between methanol and naphtha is 0.05 to 0.8, the ratio of steam to raw material (naphtha and methanol) is 0.1 to 0.5, the reaction temperature range is from 560 to 670 ° C, the spatial speed of mass of naphtha is 0.3 to 5 h ' 1 , the spatial speed of mass of methanol is from 0.01 to 4 h' 1 , and the spatial speed of total mass of naphtha and methanol is 1.0 to 5 h ' 1 .
    In the present invention, a modified ZSM-5 molecular sieve catalyst is applied to the catalytic cracking reaction of methane-bound naphtha. By the linked reaction of methanol and naphtha in the catalyst, the efficiency of the naphtha cracking reaction is improved, while the exothermic effect of methanol conversion can also provide heat for the strong endothermic cracking reaction, reducing the reaction temperature, and solving the defects in the present olefin technologies such as high reaction temperature, methanol yield and high coke, use of low raw material, and so on, thus obtaining the production of low carbon olefins under the condition of a temperature of relatively low reaction, reducing reaction energy consumption, improving the production efficiency of low carbon olefins, while being able to co-produce aromatic hydrocarbons.
    In the present invention, in the catalytic cracking reaction of methanol-linked naphtha catalyzed by the modified ZSM-5, the ethylene yield is 10 to 25% by weight, the propylene yield is 15 to 28% by weight, the yield of butylene is 5 to 15% by weight, the yield of BTX (benzene, toluene, and xylenes) is 4 to 20% by weight, where the production rate of ethylene and propylene in the product and the production rate of olefins with low carbon content (ethylene, propylene, and butylenes) and aromatic hydrocarbons can be adjusted by the active components of the modified catalyst and the operating conditions of the reaction (reaction temperature, spatial speed, and water / oil ratio, and so on) ).
    DETAILED DESCRIPTION OF THE INVENTION
    The present invention is described in detail in the Examples that follow.
    In the present invention, the unmodified ZSM-5 molecular sieve used is purchased from Nankai Catalyst Factory.
    In the present invention, the chemicals used are all commercially available products.
    Example 1
    This Example illustrates the preparation of a modified ZSM-5 fluidized bed catalyst.
    500 g of a ZSM-5 molecular sieve from which the standardizing agent was removed and exchanged with 2000 ml of an ammonium nitrate solution at a concentration of 1 N at 80 ° C three times. After the exchange, the ZSM-5 molecular sieve was calcined at 550 ° C to obtain a type H ZSM-5 molecular sieve.
    100 g of the ZSM-5 molecular sieve type H (Si / Al - 12.5) were exchanged with 200 ml of a La (NO 3 ) 3 solution with a concentration of 0.15 mol / L at 50 ° C for 4 hours, and the exchanged molecular sieve was filtered, dried, and then calcined at 550 ° C in air for 6 h. 100 g of La modified ZSM-5 molecular sieve was exchanged with 200 ml of an aqueous solution of H 3 PO 4 with a concentration of 0.25 mol / L at 50 ° C for 4 h, and the exchanged molecular sieve was filtered , dried, and calcined at 550 ° C in air for 6 h.
    g of the sample of ZSM-5 modified by La and P described above was mixed with 50 g of kaolin (containing 15% by weight of water), 8 g of silicon sol (the SiO 2 content was 25% by weight) , 138 g of aluminum sol (the alumina content was 22% by weight), and 128 g of deionized water to form a slurry, the solid content of the slurry was 25% by weight. 150 g of the slurry was aged at room temperature for 4 h and passed through a colloid mill, and then subjected to the formation of a spray in order to obtain a microsphere catalyst with a particle size of 20 to 100 pm, ie , the modified ZSM-5 fluidized bed A.
    500 g of a ZSM-5 molecular sieve from which the standardizing agent was removed were exchanged with 2000 ml of an ammonium nitrate solution at a concentration of 1 N at 80 ° C three times. After the exchange, the ZSM-5 molecular sieve was calcined at 550 ° C to obtain a type H ZSM-5 molecular sieve.
    100 g of the ZSM-5 type H molecular sieve (Si / Al = 12.5) were exchanged with 200 ml of a La (NO 3 ) 3 solution with a concentration of 0.27 mol / L at 50 ° C for 4 h, and the exchanged molecular sieve was filtered, dried, and then calcined at 550 ° C in air for 6 h. 100 g of the La modified ZSM-5 molecular sieve were exchanged with 200 ml of an aqueous solution of H 3 PO 4 with a concentration of 0.20 mol / L at 50 ° C for 4 h, and the exchanged molecular sieve was filtered , dried, and calcined at 550 ° C in air for 6 h.
    38.6 g of the sample of ZSM-5 modified by La and P described above were mixed with 50 g of kaolin (containing 15% by weight of water), 8 g of silicon sol (the content of SiO 2 was 25% by weight), 30.5 g of aluminum sol (the alumina content was 22% by weight), and 213 g of deionized water to form a slurry, the solid content of the slurry was 25% in weight. 200 g of the slurry were aged at room temperature for 4 hours and passed through a colloid mill twice, and then sprayed to form a microsphere catalyst with a particle size of 20 to 100 pm, that is, fluidized bed B of modified ZSM-5.
    After the microsphere catalysts described above were calcined at 550 ° C in air for 6 h, they were treated in the steam atmosphere at 800 ° C for 10 h.
    The compositions of the specific modified ZSM-5 microsphere catalysts are as shown in Table 4.
    Table 4 The compositions of the modified ZSM-5 fluidized bed catalysts
    Catalyst The Si / Al ratio of HZSM-5 Compositions (% by weight) ZSM-5 SY7-AI2O1 P Over there Modified ZSM-5 fluidized bed A 12 25.0 70.0 2.8 2.2 Modified ZSM-5 fluidized bed B 25 38.6 56.0 2.0 3.4
    Example 2:
    This Example illustrates the effect of the catalytic cracking reaction of linked naphtha with methanol catalyzed by the modified ZSM-5 in a fixed fluidized bed.
    The naphtha used in this Example comprised full range naphtha, light naphtha and raffinate oil, their specific compositions were shown in Table 5.
    The catalyst prepared in Example 1 was used as the reaction catalyst. 10 g of the catalyst was loaded into a fixed fluidized bed reactor, treated in an air atmosphere at 650 ° C for 1 h, and then purged with a nitrogen atmosphere for 0.5 h, and the reactor temperature was adjusted to a reaction temperature of 630 ° C. Naphtha, methanol, and water were introduced into a preheater via a feed pump. The raw materials were vaporized in the preheater at 300 ° C and then introduced into the fixed fluidized bed reactor in which methanol, naphtha and steam were contacted with the catalyst and the catalyst was fluidized, at which the total spatial velocity of the naphtha and methanol feed was 2 h '1; the mass ratio of water: (naphtha + methanol) was 0.15; the mass ratio of methanol: naphtha was 0.2; and the reaction pressure was 0.1 MPa. The reaction product was analyzed online using a Varian 3800 gas chromatograph (Varian) and Pona capillary chromatographic column (Varian). The results of the reaction were shown in Tables 6 and 7.
    Table 5 Naphtha compositions
    Naphtha Carbon number distribution Chain alkanes (%) Cyclic alkanes (%) Olefins(%) Aromatic hydrocarbons (%) Full range naphtha C 4 -C 12 63.8 29.8 1.9 4.5 Light naphtha C 4 -C 8 85.4 13.7 - 0.9 Oil Rafin C 4 -C 9 89.5 5.6 4.3 0.6
    Table 6 Reaction of cracking naphtha linked to methanol catalyzed by fluidized bed A of modified ZSM-5 in a fixed fluidized bed
    Feedstock Full range naphtha Light naphtha Raffinate oil Product Yield,% by weight Ethylene 18 20 20 Propylene 22 24 25 Butylenes 9 9 10 BTX 13 7 8
    Table 7 Cracking reaction of methanol-linked naphtha catalyzed by fluidized bed B of modified ZSM-5 in fixed fluidized bed
    Feedstock Full range naphtha Light naphtha Raffinate oil Product yields,% by weight Ethylene 19 21 20 Propylene 23 24 28 Butylenes 10 11 10 BTX 14 8 9
    Comparative Example 1
    This Comparative Example illustrates the effect of the catalytic cracking reaction only for naphtha catalyzed by the modified ZSM-5 in a fixed fluidized bed.
    A ZSM-5 fluidized bed catalyst A prepared in Example 1 was used as the reaction catalyst, and the reaction raw materials in Example 2 were changed from naphtha and methanol to naphtha so that the reaction raw material was only naphtha. without the addition of methanol, and the spatial speed for naphtha feeding was 2 h 1 , the mass ratio of water: naphtha was 0.15, and the other reaction conditions and analysis conditions were the same as those in Example 2. The reaction results are shown in Table 8.
    Table 8 Cracking reaction of naphtha only catalyzed by fluidized bed A of modified ZSM-5 in a fixed fluidized bed
    Raw material | Full range naphtha | Light naphtha | Raffinate oil
    Product yield,% by weight
    Ethylene 15 17 17 Propylene 20 20 21 Butylene 9 10 11 ΒΤΧ 11 5 6
    Example 3
    This Example illustrates the catalytic cracking reaction of full-range naphtha bound to methanol in a fixed fluidized bed under the condition of mass ratios other than methanol to naphtha.
    The fluidized bed A of catalyst ZSM-5 prepared in Example 1 was used as the reaction catalyst, full-range naphtha was used as naphtha, and the mass ratio of methanol to naphtha was adjusted to 0.05, 0, 4, and 0.8. Other reaction conditions and analysis conditions were the same as those in Example 2. The reaction results are as shown in Table 9.
    Table 9 The cracking reaction of naphtha linked to methanol in a fixed fluidized bed under the condition of mass ratios other than methanol to naphtha
    Methanol / naphtha (mass ratio) 0.05 0.4 0.8 Product Yields,% by weight Ethylene 15 22 23 Propylene 21 22 24 Butylenes 9 7 7 ΒΤΧ 12 15 17
    Example 4
    This Example illustrates the catalytic cracking reaction linked to full-range naphtha methanol catalyzed by the modified ZSM-5 molecular sieve in a fixed fluidized bed under the condition of different reaction temperatures.
    The fluidized bed A of catalyst ZSM-5 prepared in Example 1 was used as the reaction catalyst, the naphtha was full range naphtha, the reaction temperature was 550 ° C, 600 ° C, and 670 ° C, respectively, and other reaction conditions and analysis conditions were the same as those in Example 2. The reaction results are as shown in Table 10.
    Table 10 The cracking reaction of naphtha linked to methanol in a fixed fluidized bed under the condition of different reaction temperatures
    Reaction temperature (° C) 550 600 670 Product yields,% in Weight Ethylene 15 17 22 Propylene 21 23 25 Butylenes 13 10 7 BTX 8 11 16
    Example 5
    The present Example illustrates the catalytic cracking reaction of full-range naphtha bound to methanol catalyzed by the modified ZSM-5 molecular sieve in a circulating fluidized bed.
    Full-range naphtha was used as naphtha. Fluid bed A of catalyst ZSM-5 prepared in Example 1 is used as the reaction catalyst. 5 kg of the catalyst was loaded into a fluidized bed reaction system, and it was treated at 650 ° C in an air atmosphere for 1 h, and then purged with nitrogen gas for 0.5 h, and the reactor temperature was adjusted to a reaction temperature of 650 ° C, while the catalyst was adjusted to be a 1.0 kg inventory in the reactor. Naphtha, methanol, and water were introduced into a preheater via a feed pump. The raw materials were vaporized in the preheater at 300 ° C and then introduced into the fixed fluidized bed reactor for *
    contacted with the catalyst and the catalyst was fluidized. The spatial speed of the reaction was 1.0 h ' 1 , the mass ratio of water / naphtha was 0.2, the mass ratio of methanol / naphtha was 0.1 to 0.31, and the pressure of reaction was 0.1 MPa. The reaction product was analyzed online using a Varian3800 gas chromatograph (Varian) and Pona capillary chromatographic column (Varian). The reaction results are shown in Table 11.
    Table 11 The cracking reaction of methanol-linked naphtha under the condition of different methanol / naphtha mass ratios in a circulating fluidized bed
    Methanol / naphtha (mass ratio) 0.1 0.16 0.31 Product yields,% by weight Ethylene 18 19 20 Propylene 21 23 24 Butylenes 9 10 9 BIX 11 12 10
    Example 6
    This Example illustrates the preparation of the modified ZSM-5 fixed bed catalyst.
    A crude powder from the ZSM-5 molecular sieve containing a synthetic standardizing agent was mixed with silicon sol and aluminum sol, formed, dried, and then calcined at 550 ° C to remove the standardizing agent, and ground into particles of molecular sieve of 20 to 40 meshes. The molecular sieve particles were exchanged with an ammonium nitrate solution at 80 ° C three times. After the exchange, the molecular sieve particles were calcined at 550 ° C in order to obtain ZSM-5 molecular sieve particles of type H. The molecular sieve particles were impregnated with the modifying components, that is, a solution of La (NO 3 ) 3 and H 3 PO 4 , dried, calcined and then produced on the modified ZSM-5 catalysts. The compositions of the fixed bed catalysts obtained through different ways of preparation and modification were shown in Table 10.
    Table 10 The modified ZSM-5 fixed bed catalyst compositions
    Catalyst HZSM-5 Si / Al ratio Compositions (% by weight) HZSM-5 SiO 2 -Al 2 O 3 P Over there Modified ZSM-5 fixed bed A 23 80.0 15.0 2.8 2.2 Modified ZSM-5 fixed bed B 50 79.6 15.0 2.0 3.4 Modified ZSM-5 fixed bed C 100 63.0 30.0 1.0 6.0
    Example 7
    This Example illustrates the effect of the reaction of the modified ZSM-5 catalyst on the catalytic cracking of methanol-bound naphtha in a fixed bed.
    Full band naphtha and methanol were used as the raw material. The catalyst prepared in Example 6 was used as the reaction catalyst. 5 g of the catalyst was loaded into a fixed bed reactor, treated in an air atmosphere at 670 ° C for 1 h, and then purged in the nitrogen atmosphere for 0.5 h, and the reactor temperature was adjusted to a temperature reaction time of 630 ° C. Naphtha, methanol, and water were introduced into a preheater via a feed pump. The raw materials were vaporized in the preheater at 300 ° C and then introduced into the fixed fluidized bed reactor to be contacted with the catalyst. The spatial speed of total naphtha and methanol feeding was 5.0 h ' 1 , the mass ratio of water: (naphtha + methanol) was 0.5, the mass ratio of methanol: naphtha was 0.2 , and the reaction pressure was 0.1 MPa. The reaction product was analyzed online using a Varian3800 gas chromatograph (Varian) and Pona capillary chromatographic column (Varian). The reaction results are shown in Table 11.
    Table 11 The cracking reaction of methanol-linked naphtha catalyzed by modified fixed bed ZSM-5
    Catalyst Modified ZSM-5 fixed bed A Modified ZSM-5 fixed bed B Modified ZSM-5 fixed bed C Product yields,% by weight Ethylene 21 20 18 Propylene 26 27 28 Butylenes 9 8 10 ΒΤΧ 14 14 10
    Example 8
    This Example illustrates the effect of the catalyst reaction
    ZSM-5 modified in the catalytic cracking of naphtha linked to methanol mixed in a fixed bed.
    Naphtha was a mixture of two or three of a full-range naphtha, a light naphtha, and a raffinate oil. The ZSM-5 catalyst fluidized bed A prepared in Example 1 was used as the reaction catalyst, and other reaction conditions and analysis conditions were the same as those in Example 7. The reaction results were shown in Table 12.
    Table 12 The cracking reaction of mixed methanol-linked naphtha catalyzed by modified ZSM-5 in a fixed bed
    Feedstock Mixed raw material 1 (50% by weight of full range naphtha + 50% raffinate oil) Mixed raw material 2 (40% by weight of full range naphtha + 30% by weight of light naphtha 30% raffinate oil) Product yields,% by weight Ethylene 22 23 Propylene 27 26 Butylene 10 12 BTX 10 8
    权利要求:
    Claims (15)
    [1]
    1. Process for the catalytic cracking reaction of methanol-bound naphtha using a modified ZSM-5 molecular sieve catalyst, characterized by the fact that it comprises carrying out a methanol and naphtha coalimentation reaction on the modified ZSM-5 molecular sieve catalyst for produce low carbon olefins and / or aromatic hydrocarbons, in which the modified ZSM5 molecular sieve catalyst comprises, in terms of weight percentage, from 25 to 80% by weight of a ZSM-5 molecular sieve, from 15 to 70 % by weight of a binder, and from 2.2 to 6.0% by weight of lanthanum and from 1.0 to 2.8% by weight of phosphorus loaded on the ZSM-5 molecular sieve.
    [2]
    Process according to claim 1, characterized in saturated chain and from 5.6 to 29.8% by weight in that the naphtha comprises from 63.8 to 89.5% by weight of cyclic alkanes alkanes.
    [3]
    Process according to claim 1, characterized by the fact that naphtha and methanol are concurrently passed through a catalyst bed at a reaction temperature of 550 to 670 ° C.
    [4]
    4. Process according to claim 1, characterized by the fact that the mass ratio of methanol to naphtha is 0.05 to 0.8.
    [5]
    5. Process according to claim 1, characterized by the fact that naphtha and methanol are contacted and reacted under a reaction condition of a total mass space velocity of 1.0 to 5 h ' 1 .
    [6]
    6. Process according to claim 1, characterized by the fact that naphtha is any one of a full range naphtha, a light naphtha, and a raffinate oil, or any mixture thereof.
    [7]
    7. Process according to claim 1, characterized by the fact that the distribution range of the hydrocarbon carbon number in naphtha is C4-C12, and naphtha comprises from 63.8 to 89.5% by weight of alkanes of chain, from 5.6 to 29.8% by weight of cyclic alkanes, from 0.6 to 4.5% by weight of aromatic hydrocarbons and from 1.9 to 4.3% by weight of olefins.
    [8]
    8. Process according to claim 1, characterized by the fact that the reactor used for the methanol and naphtha coalimentation reaction is a fluidized bed reactor or a fixed bed reactor.
    [9]
    9. Process according to claim 8, characterized by the fact that when the fluidized bed reactor is used, the modified ZSM-5 molecular sieve catalyst comprises, in terms of percentage by weight, from 25 to 38.6% in weight of the ZSM-5 molecular sieve, from 56 to 70% by weight of the binder, and from 2.2 to 3.4% by weight of lanthanum and from 2.0 to 2.8% by weight of phosphorus loaded in the molecular sieve ZSM-5.
    [10]
    10. Process according to claim 8, characterized by the fact that when the fixed bed reactor is used, the modified ZSM-5 molecular sieve catalyst comprises, in terms of percentage by weight, from 63 to 80% by weight of the molecular sieve ZSM-5, from 15 to 30% by weight of the binder, and from 2.2 to 6.0% by weight of lanthanum and from 1.0 to 2.8% by weight of phosphorus loaded in the ZSM- 5.
    [11]
    Process according to claim 8, characterized in that the fluidized bed reactor includes a fixed fluidized bed and a circulating fluidized bed.
    [12]
    Process according to claim 1, characterized by the fact that low carbon olefins include ethylene, propylene, and butylene.
    [13]
    Process according to claim 1, characterized by the fact that aromatic hydrocarbons include benzene, toluene, and xylene.
    [14]
    Process according to any one of claims 1, 9 and 10, characterized in that the range of the silicon-aluminum ratio of the molecular sieve ZSM-5 is 12 to 100.
    4 ’
    [15]
    Process according to any one of claims 1, 9 and 10, characterized by the fact that the binder is silicon oxide, alumina, or a mixture thereof.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3767567A|1971-11-22|1973-10-23|Toyo Engineering Corp|Process for preparing olefins|
    RO64554A2|1976-12-07|1980-01-15|Institutul De Inginerie Tehnologica Si Proiectare Pentru Industria Chimica,Ro|CATALYTIC PROCESS FOR OBTAINING OLEFINS AND LOW DIOLEFINES THROUGH HYDROCARBON PIROLYSIS|
    EP0109059B1|1982-11-10|1987-07-15|MONTEDIPE S.p.A.|Process for converting olefins having 4 to 12 carbon atoms into propylene|
    SU1298240A1|1985-04-12|1987-03-23|Предприятие П/Я Р-6830|Method for producing unsaturated hydrocarbons|
    US4830728A|1986-09-03|1989-05-16|Mobil Oil Corporation|Upgrading naphtha in a multiple riser fluid catalytic cracking operation employing a catalyst mixture|
    EP0568913A3|1992-05-03|1995-03-22|Dalian Chemical Physics Inst|Process for the conversion of methanol to light olefins and catalyst used for such process.|
    CN1039392C|1992-09-22|1998-08-05|中国科学院大连化学物理研究所|Catalyst for converting methanol into light olefines and its reaction process|
    US6046372A|1996-10-02|2000-04-04|Mobil Oil Corporation|Process for producing light olefins|
    US6069287A|1998-05-05|2000-05-30|Exxon Research And Engineering Co.|Process for selectively producing light olefins in a fluid catalytic cracking process|
    EP1261649A2|2000-03-02|2002-12-04|ExxonMobil Chemical Patents Inc.|Process for producing polypropylene from c3 olefins selectively produced in a fluid catalytic cracking process from a naphtha/steam feed|
    US6118035A|1998-05-05|2000-09-12|Exxon Research And Engineering Co.|Process for selectively producing light olefins in a fluid catalytic cracking process from a naphtha/steam feed|
    US6455750B1|1998-05-05|2002-09-24|Exxonmobil Chemical Patents Inc.|Process for selectively producing light olefins|
    US6303534B1|1998-05-26|2001-10-16|Exxonmobil Chemical Patents Inc.|Silicoaluminophosphates having an AEL structure, and their preparation|
    US6835863B2|1999-07-12|2004-12-28|Exxonmobil Oil Corporation|Catalytic production of light olefins from naphtha feed|
    CN1206319C|2002-12-03|2005-06-15|中国科学院大连化学物理研究所|Method for preparing low carbon olefin by coupled catalytic cracking of petroleum hydrocarbon|
    CN1241684C|2002-12-03|2006-02-15|中国科学院大连化学物理研究所|Catalyst for preparing olefin with arene as side product by hydrocarbon catalytic cracking, preparing method and uses thereof|
    US20050227853A1|2004-04-02|2005-10-13|Ranjit Kumar|Catalyst compositions comprising metal phosphate bound zeolite and methods of using same to catalytically crack hydrocarbons|
    CN101157593B|2007-03-07|2010-09-22|中国科学院大连化学物理研究所|Method for producing light olefins by methanol or/and dimethyl ether|
    US7629498B2|2007-06-28|2009-12-08|Exxonmobil Chemical Patents, Inc.|Process of manufacturing para-xylene|
    JP2010042343A|2008-08-12|2010-02-25|National Institute Of Advanced Industrial & Technology|Catalyst for manufacturing lower olefin, method of manufacturing the same and method of manufacturing lower olefin using catalyst|CN102875304B|2011-07-12|2015-02-11|中国石油化工股份有限公司|Method for preparing low carbon olefins from methanol and naphtha|
    CN103007985B|2012-12-20|2014-09-24|清华大学|Catalyst for converting alcohols and ethers into aromatic hydrocarbons as well as preparation method and use method thereof|
    US20150099913A1|2013-10-04|2015-04-09|Exxonmobil Research And Engineering Company|Methanol conversion process|
    CN104557419A|2013-10-28|2015-04-29|中国石油化工股份有限公司|Method for preparing aromatic hydrocarbon from methanol or dimethyl ether|
    CN104557377B|2013-10-28|2018-07-13|中国石油化工股份有限公司|The method of oxygenatedchemicals and naphtha coupled reaction production ethylene and propylene|
    CN104174430B|2014-07-24|2016-02-24|清华大学|Alcohol ether is converted into paraxylene and C by one 2-C 3the Catalysts and its preparation method of alkene|
    WO2016018097A1|2014-08-01|2016-02-04|한국화학연구원|Naphtha and methanol mixed catalytic cracking reaction process|
    KR101803406B1|2014-08-01|2017-12-01|한국화학연구원|Process for catalytic cracking reaction of naphtha and methanol mixture|
    CN104151121B|2014-08-13|2016-01-20|中石化上海工程有限公司|The method that MTO technique is coupled with naphtha cracking predepropanization technique|
    CN106140266B|2015-03-27|2019-09-13|中国石油大学|A kind of metal-modified ZSM-5 molecular sieve catalyst and its preparation method and application|
    WO2016192041A1|2015-06-02|2016-12-08|中国科学院大连化学物理研究所|Process for converting naphtha|
    CN106431808B|2015-08-05|2019-10-11|中国石油天然气股份有限公司|A method of aromatic hydrocarbons is prepared using methanol and liquefied gas as raw material|
    EP3365313B1|2015-10-21|2020-04-29|Exelus Inc.|Process of making olefins or alkylate by reaction of methanol and/or dme or by reaction of methanol and/or dme and butane|
    CN105944749B|2016-05-05|2018-08-24|合肥神舟催化净化器股份有限公司|Use for diesel engine compound oxidizing catalyst based on modified molecular screen major catalyst|
    US10105689B2|2016-05-12|2018-10-23|Saudi Arabian Oil Company|Heat generating catalyst for hydrocarbons cracking|
    CN105838415B|2016-06-11|2017-08-01|东营市俊源石油技术开发有限公司|A kind of method that naphtha catalytic cracking produces alkane|
    EP3615208A1|2017-04-24|2020-03-04|Basf Se|A molding comprising a zeolitic material, phosphorous, one or more metals and a binder|
    CN108080022B|2017-12-14|2021-03-12|中石化炼化工程（集团）股份有限公司|Catalyst for preparing gasoline by naphtha coupled methanol and preparation method thereof|
    CN108191593A|2018-01-08|2018-06-22|中石化炼化工程（集团）股份有限公司|A kind of olefin preparation method and device|
    CN109046440A|2018-07-25|2018-12-21|江苏大学|A kind of preparation method and application of the composite modified multi-stage porous HZSM-5 molecular sieve catalyst of La-P|
    CN111099947A|2018-10-25|2020-05-05|中国石油化工股份有限公司|Method for preparing aromatic hydrocarbon by efficiently converting methanol|
    CN111233609A|2018-11-29|2020-06-05|中国科学院大连化学物理研究所|Raw material conversion device containing naphtha|
    CN111233608A|2018-11-29|2020-06-05|中国科学院大连化学物理研究所|Naphtha-containing raw material conversion method|
    CN112646598A|2019-10-10|2021-04-13|中国石油化工股份有限公司|Method for converting low-carbon alkane into aromatic hydrocarbon|
    CN110871107A|2019-11-06|2020-03-10|厦门大学|Catalyst for preparing low-carbon olefin by coupling catalytic cracking of low-carbon alcohol and naphtha as well as preparation method and application of catalyst|
    法律状态:
    2018-05-29| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2018-07-03| B16A| Patent or certificate of addition of invention granted|
    优先权:
    申请号 | 申请日 | 专利标题
    CN201010607910.8A|CN102531821B|2010-12-28|2010-12-28|Method for catalyzing catalytic cracking reaction of methanol coupled with naphtha using modified ZSM-5 molecular sieve based catalyst|
    CN201010607910.8|2010-12-28|
    PCT/CN2011/076298|WO2012088852A1|2010-12-28|2011-06-24|Process for catalytic cracking naphtha coupled with methanol using modified zsm-5 molecular sieve catalyst|
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