• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A dehydrocyclodimerization process for the production of C6-C8 aromatic hydrocarbons from C3 and C4 aliphatic hydrocarbons is characterized by the integrated product recovery steps employed to separate hydrogen and products from the reactor effluent. Following partial condensation of the reactor effluent stream, the resultant vapor is subjected to liquid absorption (scrubbing) followed by autorefrigeration to yield lighter gas streams. Liquids from the various steps are separated via fractionation.
    公开号:SU1523052A3
    申请号:SU853960443
    申请日:1985-10-09
    公开日:1989-11-15
    发明作者:Клейтон Стиси Пол
    申请人:Юоп Инк (Фирма)；
    IPC主号:
    专利说明:

    The product (aromatic С-С-hydrocarbons) from this colliuil was sent to the 2nd distillation column, in which the total overhead — benzene, was removed, and the bottom product (aromatic Cd-hydrocarbons and then
    luol}, a part of which is discharged as the target product, and the other part - for absorption as a depleted absorption liquid. These conditions provide a good process economy. 3 z.p, f-ly, J il.,. 3 tab.
    The invention relates to methods for separating the reaction products of the vapor-phase dehydrocyclo-dimerization of Ci-hydrocarbons in the presence of. gallium of a further catalyst based on a zeolite of the type ZSM-5 ..
    The vapor phase stream leaving the dehydrocyclodimerization zone contains unreacted Hydrocarbons, hydrogen, secondary, hydrocarbons, benzene, toluene, and Cg-aromatic hydrocarbons.
    The purpose of the invention is to develop a compact method for separating the products of the reaction of phasic dehydrocyclodimerization in the presence of a hydrogen-containing β-catalyst on the basis of a zeolite of type. ZSM-5,
    The method according to the invention can be carried out according to the technology, presented to the drawing
    The remaining liquid raw material stream, which is a mixture of hydrocarbons, rich in propane and containing some isobutane and normal butane, is divided into two parts, one of which is usually larger, using the following lines: 1 t.v. process of dehydrocycdimerization. , supplied via line 1, is mixed with the recycled product supplied by line 2, and via line 3 is introduced into the dehydrocyclization dichlorizer 4. The dehydrocyclodimerization reactor 4 is preferably a multi-stage flow reactor with: a moving catalyst bed having a diameter of 0.4-3; 175 mMo The catalyst contains from 0, ... O maslo galli, preferably 0 mas%, on a ZSM-5 zeolite
    The reaction zone of dehydrocyclodimerization preferably operates at temperatures in the range of 487-565 C and pressure up to 6895 kPaa.
    The newly regenerated catalyst in line 5 enters the top
    five
    0
    50
    0 Q
    five
    part of the reaction zone of the reactor 4 and passes downwards within the circular volume of the delay of the catalyst. The used catalyst is withdrawn from the bottom of the reaction zone through line 6 and transported to the appropriate catalyst regeneration device. The stream loaded into the reaction zone through line 3 preferably makes several turns through various sections catalytic during intermediate heating to supply heat for the endothermic dehydrocyclodimerization reaction. In the case of using a stream with a high content of olefins, the reaction is exothermic and intermediate refrigerators are required as a result. During the reaction, a vaporous stream is formed, which leaves the reaction zone through line 7 and contains aromatic hydrocarbons, byproducts and reaction products and hydrogen, in addition to unreacted propane and butane vapor from the reaction zone, the stream passing through line 7, partially condensed when passing through the device 8 indirect tag-exchange, a mixture of vapor and liquid passes into the first zone 9 of the vapor-liquid separation, where the separation takes place on the first vapor-phase flow, discharged along line 10, and the first liquid flow, single line
    Ii.
    The first vapor phase flow, discharged via line 10, contains hydrogen ,. and C-side products, propane, butane and benzene o This vapor stream is compressed in device 12 and fed to the bottom of the i3o absorption column. Preferably the pressure, the vapor stream is increased to 448-2068 kPa and higher. More preferably, the pressure of the vapor stream is increased to 2413 -5761 kPa, with particular preference being given
    pressure above 3103 kLa. The vapor under pressure is flowed countercurrently to the stream from the depleted absorption liquid introduced into the absorption column through a line of 14 °. Almost all the benzene contained in the introduced vapor phase flow is removed and becomes part of the liquid flow passing through absorber. As a result, a second vapor phase is formed. stream j containing hydrogen, C-C-hydrocarbons, source hydrocarbons and toluene, discharged through line 15, and a stream of enriched absorption liquid, discharged through line 16 o. The second vapor-phase stream through line 15 passes to drying zone 17
    In the drying zone, water is removed, which can cause freezing in low-temperature process equipment. The second vapor-phase flow, dried in this way, is fed through line 18 to indirect heat exchange device 19, which is used as a reboiler of a steam column .20. Additional cooling is provided by means of wearable device (not shown). The second vapor phase stream is cooled in this way and partially condensed to feed the second zone 21 vapor-liquid separation 3 The vaporous materials entering the separation zone 21 are separated and form the third vapor phase stream passing through line 22 and the second liquid stream. The vapor flow pressure is reduced in the power turbine 23, which generates useful mechanical energy for powering, for example, an electric generator. The stream coming out of the turbine at lower pressure and temperature passes through line 24 to the third vapor-liquid separator 25 where it is divided into the fourth vapor phase flow and the third liquid stream.
    The second liquid stream discharged from separation zone 21 enters through a line 26 into a stripping column 20. Similarly, the third liquid stream discharged from separator 25 through line 27 enters a stripping column. These liquid streams contain heavier hydrocarbons entering this self-cooling zone. Therefore, the second liquid stream contains toluene and initial propam
    S
    0
    0
    and. Vutans, Third Liquid Stream, Output Software, Line 27, contains the original propane. Both liquid streams also contain dissolved lighter hydrocarbons and hydrogen. These lighter compounds are removed from the LIQUID fluids in the stripping column 20 and a dry top steam flask is obtained through the line 28. This total steam flask contains hydrogen and hydrogen is mixed with the fourth vapor stream passing through line 29 and containing hydrogen, methane, as well as C hydrocarbons, and receive a stream of fuel gas withdrawn from the process via the line 30 "-Working of the stripping column; under such conditions that regulate the content of C" - hydrocarbons in the total bottom stream, since Some cases may be necessary & 1M re-circulate C-hydrocarbons in the reaction zone. Usually, C5-hydrocarbons are not formed from raw materials containing C-hydrocarbons - and therefore are present in the total bottom product in significant quantities only if S is contained
    in the original scan,
    t Preferably, the heating of the steam strippers is carried out with the help of heat, the image of the stripping:. due to the flow of the bottom liquid; through the indirect heat exchange passing through the line 31 and passing through the device 19;
    0 lines 32 in the form of a total bottom stream, containing feedstock hydrocarbons and toluene, which are heated in an indirect heat exchange device 33. Then this stream enters the fourth zone 34 of the parasite SNP-5D of bone separation, operating under conditions that contribute to the evaporation of a significant amount of propane and any of the hydrofluids in the case of their selection in the cubic product of the column 20 This is. the vaporizing 1-shs material as the fifth vapor stream is removed from separation zone 34 via line 35, compressed in unit 36, and then recycled to the reaction zone via line 2. The fourth liquid product, which is collected in the fourth separation, contains npeHi-ii -ffliecTBeHHO toluene It is derived by linking 37 o
    five
    five
    The stream of enriched absorption liquid containing benzene discharged from Pine 16 from the adsorption tank 13 is mixed with the first liquid stream passing along the line along the mixture of these two streams, flowing along line 38 along with the fourth liquid stream passing through line 37 , enters via line 39 in the first distillation column debutanizor tor 40 "
    In the first rectification column, via line 41, less residual hydrocarbons are supplied, as a part of hydrocarbons as irrigation with
    On line; 42, the total upper running tray containing similar hydrocarbons and practically comes out of the first rectification column; not containing Cg4rygJ1evodopodov. This noTok is mixed with a stream. Line 35 outlets from, fourth zone 34 semi-septal sepa: walkie-talkies5 and Line 2 as a recycle are mixed with the rest of the original Sd.
    SF hydrocarbons,
    the hydrocarbons that enter the cone, -40, are concentrated in the first total cubic footnote, which is fed along the lines 42 into the ... second classification column 43o
    Thus, C-hydrocarbons are recycled in the reaction zone and provide-. direct, production. From hydrocarbons: high degree of purity from hydrocarbons; 9 to be loaded into the second rectification column; separated by V; here, the second total upper deadline, derived from the .44 line, is preferably a stream of benzene of high purity, which also contains a relatively small amount of C, Hydrocarbons 5 form in the process of processing and entering into the ET of the column. S -yugly6 towns, which -. These lines pass through line 42, are converted into more than desired products. Toluene xylenes and heavier aromatic hydrocarbons from column 43 are removed as part of the second total bottom product through line 45. The second total bottom product is separated.
    On the flow of the target product, remove e-, Mogo on line 46 ,,. and a recycle stream, via line 14, entering the adsorption tower 13 as a stream Depleted absorption liquid
    0
    five
    0
    five
    D
    five
    0
    five
    Q
    five
    The scheme shown in the drawing, C of the protzen, since it does not show some heat exchangers, process control systems, pumps and systems for the selection of upper fractions of distillation columns and evaporators
    and t, by
    The simplicity of heat transfer, whose scheme is shown in the drawing, is minimized. The choice of heat exchange means used to achieve the necessary degree of heating and cooling at different points of the scheme depends on Toroj how they are used. For example, depending on the specific location and conditions of the process. it may be desirable to use heat exchange with steam, heated oil, or process streams from other process plants not shown in the drawing.
    PRI m and Re Theoretical operation of an industrial installation of degidrocyclo-dimerization, which uses a technological process, the scheme of which is shown in the drawing
    The calculated, example, results are sufficient for imaging. Real work: so. as actual flows almost do not differ from the calculated benefit p - deviations of the feed rate or various selectivities of the catalyst. and General. The flow rate of the feed stream to the process is 57253.3 kg / h. This stream contains 281.3 kg / h; levodorods, 151, 6 kg / h of C-unsaturated hydrocarbons, 21215 kg / h of levodorods, 5-80, 8 kg / h of iC -Henperedelnyh hydrocarbons, 14549.2 kg / h of 7 kg / h n SF-hydrocarbons and 256.7 kg / h i-Cj-hydrocarbon 85 wt% of this feed stream is introduced directly into the reaction zone. The second stream of similar composition, but containing only 15 wt.% Of the total feed, is sent to the upper part of the first distillation column debutanizer having 15 sieve plates. The main feed stream together with the recycle stream is passed through the reactor to produce leaking from the reactor. flow rate with a total flow rate on the order of 77818.2 kg / h, This stream contains 18204.4 kg / h of propane, 1175.6 kg / h of butane, 5606.1 kg / h of benzene, 12343.9
    91523052
    kg / h of toluene, 6381.3 kg / h of xylenes and significant amounts of hydrogen, methane and ethane. The effluent from the reactor also contains some quantities of ethylene, propylene, isobutylene, ethylbenzene and Ca1 - aromatic hydrocarbons. Resulting from
    : the reactor stream is cooled to a temperature of about 40 ° C and passed into
    a new vapor-liquid separation zone or a low pressure separator 9. This separator operates at a pressure of about 448 kPa excess. The effluent from the reactor enters the low pressure separator as a mixed phase stream, which is divided into the first liquid stream with a flow of about 25437.1 kg / h and the first vapor-phase flow, corresponding to consumption in the order of 52381.2 kg / h. Under these conditions, the first vapor stream contains more than 95% of hydrocarbons Cj and below, which enter the separation zone. The vapor stream contains heavier hydrocarbons, including about 1208 kg / h of C-e-hydrogen, 1484 kg / h benzene and about 968 kg / h of toluene.
    The first vapor phase stream leaving the low pressure separator is compressed in a two-stage compressor unit 12 equipped with a condenser and a condensate separation drum. As a result, a gas stream with a temperature of about 17 and pressure of about 3599 kPa is introduced into the lower part of the absorption column 13 (absorber) excess. This gas flow passes upwards through the absorber in countercurrent with respect to the flow of the desorbed absorbing liquid, which flows into the upper part of the absorber.
    Bera at a temperature of about 16 C at a flow rate of 2736.5 kg / h.
    As a result of this treatment of the gas stream, all benzene from the gas stream and some amount of propane are practically removed and toluene is released into the gas stream. The flow rate of the gas stream exiting the absorber is 44,528.8 kg / h. This gas stream is cooled from 17 ° C to a temperature of about by indirect heat exchange with a reboiler 19 of the stripping column 20. It is then cooled by indirect heat exchange to a temperature of -29 ° C.
    ten
    0
    0
    five

    0
    five
    0
    five
    0
    five
    and passed into the cold high pressure separator or into the second vapor-liquid separation zone 21 at a pressure in the order of 3344 kPa excess. The liquid collected by this cold high-pressure separator is removed at a flow rate of 18,243.8 kg / h. The three-phase vapor stream withdrawn from the high-pressure cold separator in the amount of 26,295 is fed into the expansion turbine, where its pressure drops to 414 kPa. Excessive flow temperature drops to -81 C. The effluent stream from the expander is passed through a vapor-liquid separator 25 and separated into a third liquid stream with a flow rate of about 4574.7 kg / h and a fourth vapor-phase stream, which is fed into the Fuel Gas System a This third liquid stream, together with the liquid stream withdrawn from the cold High Pressure Separator 21, is introduced into a stripper column 20, which has 15 perforated plates at different levels separated by at least two or more distillation plates. The net fuel gas flow rate is 30154.7 kg / h. Upper
    the vapor phase flow withdrawn from the stripping column of light fractions has a temperature of -38 ° C and a pressure of 414 kPa excess. The stripping column operates at a bottom liquid temperature of -17 ° C. The upper one-way flow of the stripping column contains about 1,664 kg / h of methane, 4448 kg / h of ethane and 1960 kg / h of propane. The total bottom stream of the stripping column also contains ztan, propylene, isobutane and normal butane and toluene together with small amounts of C aromatic hydrocarbons. The total bottoms stream is separated in the fourth zone 34 of vapor-liquid separation, operating at a temperature of about -16 ° C and excess pressure of 207 kPa. As a result of the separation, a vapor phase flow of 10,800.9 kg / h is obtained, which is returned to the reaction zone, and a liquid stream that is directed to the debutant in the amount of 3582.5 kg / h.
    The amount of the upper running debutanizer I flow is 18344.1 kg / h. This stream contains about 10878 kg / h of propane and 5137 kg / h of butane. It also contains a significant1 1523052
    High amounts of ethane and methane and large amounts of hydrogen from ethylene, propylene, isobutylene and benzene. The upper vapor-phase running flow of the dibutanizer has a temperature of about 36 ° C and a pressure of 862 kPa excess, the Debutanizer is operated at a bottom liquid temperature equal to about okolo. The flow rate of the total JQ of the debutanizer's bottom stream is: | L et 28927.5 kg / h. This stream contains about 5522 kg / h of benzene, 13908 kg / h of toluene and 2613 kg / h of aromatic hydrocarbons, while the rest of this stream is Cg-aromatic hydrocarbons
    This stream is separated in a second distillation column (benzene column) for high-purity benzene, 20 taken as a running stream in an amount of 5,582.1 kg / hr. The remaining hydrocarbons entering the benzene column are divided into a stream of depleted absorption liquid. and 25 total flow of C-aromatic hydrocarbons, the flow rate of which is 21,462.9 kg / h.
    The operating conditions for the main equipment in the above scheme and flows, indicated in the example, are listed in Table 1.
     at
    Table 2 presents the material balance of the process for raw materials and target products,
    The tabLOZ shows the costs of the main process flows according to the scheme in the draft.
    权利要求:
    Claims (1)
    [1]
    1. A method for separating the reaction products of the vapor-dehydrocyclo-dimerization of C-C-hydrocarbons in the presence of a 45 gallium-containing i catalyst based on a ZSM-5 type zeolite containing unreacted raw hydrocarbons, hydrogen, C-C side-carbon, benzene, toluene and Cg-aromatic hydrocarbons, that is, with the fact that the reaction product of vapor-phase dehydrocyclization is subjected to partial condensation with subsequent separation in the first vapor-liquid zone. separation to the first vapor phase stream containing hydrogen, C, –C hydrocarbons, initial hydrocarbons and benzene, and the first liquid
    55
    12
    Q
    0 5
    about
    five
    0
    50
    45
    55
    a stream containing initial hydrocarbons, benzene, toluene, and Cs-aromatic hydrocarbons, the first vapor stream is subjected to absorption by a depleted absorption liquid in conditions that ensure benzene uptake, to obtain a second vapor phase stream containing hydrogen, hydrocarbons, toluene, and a stream of enriched absorption liquid containing feedstock hydrocarbons, benzene and toluene, the second vapor-phase stream is partially condensed, followed by separation of the resulting two-phase In the second zone of vapor-liquid separation to the third vapor stream containing hydrogen, Cj-Cg hydrocarbons and feedstock hydrocarbons, and the second liquid stream containing feedstock hydrocarbons and toluene, the pressure of the third vapor stream is reduced in the energy generating device, under the conditions providing partial condensation of the third vapor stream, with its subsequent separation in the third zone of vapor-liquid separation into the fourth vapor phase stream containing iodine and methane, and the third liquid stream containing The second C and C hydrocarbons and feedstock hydrocarbons, the second and third liquid streams, are fed from a steam column, in which, under conditions that provide for the separation of hydrocarbons, a total upper running stream containing C – C carbon and hydrogen and a total cubic; The product containing initial hydrocarbons and toluene, which in the fourth zone of vapor-liquid separation, under conditions that provide separation, divides into the first parphase stream containing the initial hydrocarbons fed to the zone, dehydrocyclization reactions, and the fourth liquid stream containing toluene supplied together with the stream of the enriched absorption liquid and the first liquid product to the first distillation column, into which part of the initial hydrocarbons is fed as irrigation and which operates in catches that provide the separation of supplied hydrocarbons to the first total upper linear flow containing initial hydrocarbons and practically free of Cg-hydrocarbons, directed to the dehydrocyclodimerization reaction zone together with the rest of the initial C-C-hydrocarbons, and the first total bottoms a product containing C-Cg-aromatic hydrocarbons, which is in the second distillation column section-. are poured on the second total upper-. gonnogo flow, ssdarzhapschy benzene, output as a target blow-. JQ ta and the second total bottom stream containing toluene and Cg-aromatic hydrocarbons and practically free of benzene; part of which is output as target product; another {5 part of the second total bottom product is fed to the absorption zone as a depleted absorption liquid,
    2o The method according to 1, about tl and h and y - 20
    u and with the fact that, the second vapor-phase flow before feeding it into
    the second zone of vapor-liquid separation is cooled by indirect heat exchange with the liquid withdrawn from. bottom 25
    parts of the stripping column 3. The method according to p. 1, of which is the third liquid stream being fed to the stripping column above the feed point of the second liquid-JQ 1st stream in the stripper column,
    4o The method according to claim 1, about tl and h a - y and with the fact that the first cy fmapny
    n
    w1
    l
    281.3
    151.6
    27275.0
    580.8.
    14549.2
    14158.7
    256.7
    1677.1
    13898.4
    585.9
    10702.9
    193.0
    3068.2
    1.8
    9.0
    8.7
    the upper running stream before feeding to the dehydrocyclization zone is mixed with the rest of the initial C-C hydrocarbons
    . .. a b and c a 1
    Working conditions
    498 517 40 448 17 3599 -29 3344 -81 414 20 and -22 414 -16 207.
    bo214 861 152 83
    Table 2
    12339.8 523.4
    15
    1523052
    Flow rates. (Kg / h)
    16 Continuation of table 2
    Table3
    Continuation of table 3
    Continuation of table 3
    eleven
    V
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    引用文献:
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    申请号 | 申请日 | 专利标题
    US06/659,794|US4528412A|1984-10-11|1984-10-11|Dehydrocyclodimerization process|
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