CN108424345B - Ethylbenzene production device and process - Google Patents
Ethylbenzene production device and process Download PDFInfo
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- CN108424345B CN108424345B CN201710078808.5A CN201710078808A CN108424345B CN 108424345 B CN108424345 B CN 108424345B CN 201710078808 A CN201710078808 A CN 201710078808A CN 108424345 B CN108424345 B CN 108424345B
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- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 186
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 239000007789 gas Substances 0.000 claims abstract description 163
- 238000005336 cracking Methods 0.000 claims abstract description 100
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 52
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000005977 Ethylene Substances 0.000 claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 43
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000011084 recovery Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000000926 separation method Methods 0.000 claims abstract description 21
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 20
- 239000006227 byproduct Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 238000010791 quenching Methods 0.000 claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000007906 compression Methods 0.000 claims abstract description 16
- 230000006835 compression Effects 0.000 claims abstract description 15
- 230000000171 quenching effect Effects 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 16
- 238000001179 sorption measurement Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000000197 pyrolysis Methods 0.000 claims description 11
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 10
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 10
- 239000000446 fuel Substances 0.000 claims description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 10
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000005057 refrigeration Methods 0.000 claims description 7
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- -1 acetylene hydrocarbon Chemical class 0.000 claims description 2
- 239000002737 fuel gas Substances 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000001345 alkine derivatives Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/04—Ethylene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/067—C8H10 hydrocarbons
- C07C15/073—Ethylbenzene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of hydrocarbon processing, and particularly discloses an ethylbenzene production device and a process, wherein the device comprises a cracking unit, a quenching unit, a compression unit, a cold separation unit, an ethylbenzene synthesis unit and a tail gas recovery unit which are sequentially connected, and the tail gas recovery unit is also connected with the cracking unit; the cracking unit, the quenching unit, the compression unit and the cold separation unit are used for converting cracking raw materials to obtain dilute ethylene material flow; the tail gas recovery unit is used for separating ethylbenzene reaction tail gas generated by the ethylbenzene synthesis unit into by-product hydrogen, tail gas recovered methane and tail gas recovered ethane, and sending the tail gas recovered ethane back to the cracking unit. The device and the process can effectively reduce the equipment investment, and can reduce the consumption of the required cracking raw material by more than 20 percent and the consumption of fuel gas by about 50 percent when the same ethylbenzene productivity is maintained; meanwhile, by-product hydrogen with high added value can be obtained.
Description
Technical Field
The invention belongs to the field of hydrocarbon processing, and particularly relates to an ethylbenzene production device and an ethylbenzene production process.
Background
With the development of economy, the demand for hydrocarbon chemical raw materials is gradually rising, and the application market of ethylbenzene as an important chemical raw material is also continuously expanded. For a long time, the main production means of ethylbenzene is the reaction of refined ethylene and benzene to generate ethylbenzene, the reactor of the technical route has small size, and the requirement on the purity of ethylene is extremely high, so that a set of complete ethylene device is required to produce polymerization-grade ethylene as a reaction raw material. The ethylene device is used as a tap device of a chemical device, the flow is complex, the investment is high, and the economical efficiency of the technology for preparing ethylbenzene by a refined ethylene method is limited.
As technology advances, dilute ethylene processes have been developed that use ethylene-rich dry gas from refineries as the reaction feedstock, eliminating the need for ethylene plants. However, the technology needs to be built by depending on refineries, and meanwhile, because the components such as acid gas, propylene, alkyne and the like exist in the dry gas, the dry gas needs to be refined before entering the device, so that the device investment is increased, and meanwhile, the reaction tail gas has no good utilization means.
Currently, some of the technicians propose to use the products from ethylene cracking as raw material for ethylbenzene production by dilute ethylene process after separation, for example, CN1273575A proposes that the gas and fluid products of the cracking zone of an ethylene production plant be fractionated in a demethanizer to form a dilute ethylene stream. The dilute ethylene is sent to an ethylbenzene plant and reacted with impure benzene. CN1630700A proposes a process for a dilute ethylene stream and a dilute propylene stream, which can be used as a feedstock for the production of ethylbenzene.
However, the above solution has the following significant disadvantages: 1. the dilute ethylene method has a large amount of reaction tail gas, wherein components such as hydrogen, methane, ethane and the like have remarkable utilization value, but the scheme does not provide a utilization scheme for the components; 2. the technical key point of the dilute ethylene method is impurity control in the dilute ethylene gas, and the purity of the reaction product synthesized by the ethylbenzene can be influenced by acid gas, acetylene and more than three carbon components; none of the above solutions solves this problem. Therefore, it is desirable to provide a process for producing ethylbenzene with low investment, effective impurity control, and full byproduct utilization.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an ethylbenzene production device and a process, which can reasonably utilize byproducts in ethylbenzene production, reduce investment and reduce energy consumption.
According to a first aspect of the present invention, there is provided an ethylbenzene production apparatus, comprising a cracking unit, a quenching unit, a compressing unit, a cold separation unit, an ethylbenzene synthesis unit and a tail gas recovery unit, which are connected in sequence, wherein the tail gas recovery unit is further connected to the cracking unit; wherein,
the cracking unit, the quenching unit, the compression unit and the cold separation unit are used for converting cracking raw materials to obtain dilute ethylene material flow; the tail gas recovery unit is used for separating ethylbenzene reaction tail gas generated by the ethylbenzene synthesis unit into by-product hydrogen, tail gas recovered methane and tail gas recovered ethane, and sending the tail gas recovered ethane back to the cracking unit.
According to a second aspect of the present invention, there is provided a process for the production of ethylbenzene using an apparatus as hereinbefore described, the process comprising: removing acetylene and more than three carbon components from a cracking raw material through a cracking unit, a quenching unit, a compression unit and a cold separation unit to obtain a dilute ethylene material flow, allowing the dilute ethylene material flow to enter an ethylbenzene synthesis unit to react with benzene to obtain an ethylbenzene product and an ethylbenzene reaction tail gas, and separating the ethylbenzene reaction tail gas into by-product hydrogen, tail gas recovery methane and tail gas recovery ethane through a tail gas recovery unit; and the tail gas recovered ethane is recycled to the cracking unit to be used as a recycled cracking raw material, and the tail gas recovered methane is used as a fuel of the cracking unit for use.
The ethylbenzene production device and the process have the following advantages:
1. compared with the method for producing ethylbenzene by adopting an ethylene device and a device for preparing ethylbenzene by a dilute ethylene method, the ethylbenzene production device does not need to build a complete ethylene device, and dilute ethylene material flow does not need to be refined again before entering an ethylbenzene synthesis unit, so that the equipment investment is greatly reduced;
2. the ethylbenzene production process can reasonably utilize the ethylbenzene reaction tail gas of the ethylbenzene synthesis unit, wherein the recovered ethane tail gas is recycled as a cracking raw material, and the recovered methane tail gas is used as fuel of a cracking furnace, so that the raw material consumed by a cracking part is reduced by more than 20% and the fuel gas consumption can be reduced by about 50% while the same ethylbenzene productivity is maintained, the cracking raw material and fuel consumption are greatly reduced, and the ethylbenzene reaction tail gas can be treated to obtain the byproduct hydrogen gas with high added value, so that the economic benefit is remarkable.
Drawings
FIG. 1: a schematic diagram of an ethylbenzene production plant and process of an exemplary embodiment of the present invention.
Description of reference numerals:
u-01-a cleavage unit; u-02-quench unit; u-03-compression unit; U-04-Cold separation Unit; a U-05-ethylbenzene synthesis unit; u-06-tail gas recovery unit; f-001-cracking furnace; e-001-first heat exchanger; e-002-a second heat exchanger; c-202-quench water tower; k-301-primary booster compressor; k-302-secondary booster compressor; c-301-alkaline washing tower; DR-301-dryer; c-401-deethanizer; r-401-catalytic hydrogenation reactor; e-401-condenser; PR-401 propylene refrigeration system; r-501 ethylbenzene reaction system; a K-601-ethane supercharger; PSA-601-first pressure swing adsorption system; PSA-602-two-stage pressure swing adsorption systems;
s001-cyclic cracking of the raw material; s002-fresh cracking raw material; s101, cracking gas at an outlet of a cracking furnace; s102, cooling the cracked gas; s201, cracking gas at an inlet of a compressor; s301, cracking gas after acid gas removal by primary pressure increase; s302, cracking the gas after secondary pressure boosting; s401-deethanizer overhead gas; s402-a dilute ethylene stream; s403-more than three carbon components; s501-raw material benzene; s502-ethylbenzene production; s503-ethylbenzene reaction tail gas; s601-recovering ethane from tail gas; s602, recovering methane from tail gas; S603-Hydrogen is by-produced.
Detailed Description
In order that the invention may be more readily understood, the following detailed description of the invention is to be read in connection with the accompanying drawings and the embodiments which are given by way of illustration only and are not intended to be limiting of the invention.
According to a first aspect of the present invention, there is provided an ethylbenzene production apparatus, comprising a cracking unit, a quenching unit, a compressing unit, a cold separation unit, an ethylbenzene synthesis unit and a tail gas recovery unit, which are connected in sequence, wherein the tail gas recovery unit is further connected to the cracking unit; wherein,
the cracking unit, the quenching unit, the compression unit and the cold separation unit are used for converting cracking raw materials to obtain dilute ethylene material flow; the tail gas recovery unit is used for separating ethylbenzene reaction tail gas generated by the ethylbenzene synthesis unit into by-product hydrogen, tail gas recovered methane and tail gas recovered ethane, and sending the tail gas recovered ethane back to the cracking unit.
According to a preferred embodiment of the present invention, the tail gas recovery unit comprises a first pressure swing adsorption system, a second pressure swing adsorption system and an ethane booster connected in sequence.
According to the invention, the compression unit is used for removing acid gas, moisture and the like in the pyrolysis gas, and the treated pyrolysis gas is sent to the cold separation unit after being pressurized. Preferably, the compression unit comprises a primary booster compressor, an alkaline washing tower, a dryer and a secondary booster compressor which are connected in sequence.
Wherein the alkaline tower is used for removing acid gas (CO) in the cracked gas2、H2S), the dryer is used for dewatering.
Preferably, the primary booster compressor and the secondary booster compressor are units sharing a set of casing and rotor.
According to the invention, the cold separation unit comprises a deethanizer, a catalytic hydrogenation reactor and a condenser connected in sequence.
The deethanizer has the function of separating pyrolysis gas into more than three carbon components and less than two carbon components. The number of the deethanizer may be one or more.
The catalytic hydrogenation reactor is used for further removing alkyne in the following components. The number of the catalytic hydrogenation reactors can be one or more.
Preferably, the refrigeration capacity of the condenser is provided by a propylene refrigeration system.
In addition, the cracking unit and the quenching unit can be selected by referring to the existing dilute ethylene stream preparation technology.
Wherein, the cracking unit comprises a cracking furnace and a heat exchanger which are connected in sequence. The number of the cracking furnaces is n, wherein n is less than or equal to 8, and preferably n is less than or equal to 4.
Preferably, the cracking unit comprises two heat exchangers.
The quench unit includes a quench water tower.
According to a second aspect of the present invention, there is provided a process for the production of ethylbenzene using an apparatus as hereinbefore described, the process comprising: removing acetylene and more than three carbon components from a cracking raw material through a cracking unit, a quenching unit, a compression unit and a cold separation unit to obtain a dilute ethylene material flow, allowing the dilute ethylene material flow to enter an ethylbenzene synthesis unit to react with benzene to obtain an ethylbenzene product and an ethylbenzene reaction tail gas, and separating the ethylbenzene reaction tail gas into by-product hydrogen, tail gas recovery methane and tail gas recovery ethane through a tail gas recovery unit; and the tail gas recovered ethane is recycled to the cracking unit to be used as a recycled cracking raw material, and the tail gas recovered methane is used as a fuel of the cracking unit for use.
According to one embodiment, the ethylbenzene production process comprises the following steps:
1) cracking the circulating cracking raw material and the fresh cracking raw material in a cracking furnace of a cracking unit into cracking gas at the outlet of the cracking furnace, and cooling the cracking gas by a heat exchanger to obtain cooled cracking gas;
2) sending the cooled pyrolysis gas into a quenching unit for further cooling to obtain compressor inlet pyrolysis gas;
3) the method comprises the following steps that (1) after the cracked gas at the inlet of a compressor is boosted by a primary boosting compressor in a compression unit, acid gas is removed in an alkaline tower to obtain a primary boosted acid gas-removed cracked gas, the cracked gas is dried by a dryer and then sent to a secondary boosting compressor to be boosted again to obtain a secondary boosted cracked gas;
4) the cracked gas after secondary pressure rise is used for removing more than three carbon components in a deethanizer of a cold separation unit, the obtained deethanizer overhead gas is hydrogenated in a catalytic hydrogenation reactor to remove acetylene hydrocarbon, and then is condensed by a condenser, the obtained gas phase is a dilute ethylene stream (namely, cracked gas after removing three carbon components and hydrogenation) which is used as a raw material of an ethylbenzene synthesis reaction, and the liquid phase is used as reflux of the deethanizer;
5) reacting the dilute ethylene material flow with raw material benzene in an ethylbenzene synthesis unit to obtain an ethylbenzene product and ethylbenzene reaction tail gas;
6) the ethylbenzene reaction tail gas is treated by a first-stage pressure swing adsorption system and a second-stage pressure swing adsorption system of a tail gas recovery unit, hydrogen is obtained as a byproduct through separation, methane is recovered from the tail gas, and ethane is recovered from the tail gas, wherein the ethane is recovered from the tail gas and is sent into a cracking unit after being boosted by an ethane booster to serve as a cyclic cracking raw material, and the methane is recovered from the tail gas to serve as a fuel of a cracking furnace.
In the step 1), the volume content of ethane in the fresh cracking raw material can be 1-100%, and from the viewpoint of easy availability of the raw material, the volume content of ethane in the fresh cracking raw material is preferably 50-97%.
The volume ratio of the circulating cracking raw material to the fresh cracking raw material can be (0.1-100): 100.
The temperature of the cooled pyrolysis gas can be 100-500 ℃, and is preferably 150-350 ℃.
In the step 3), the pressure of the cracked gas after the primary pressure boosting and acid gas removal can be 0.5-4.0 MPaG, and preferably 1.2-2.0 MPaG; the concentration of the acid gas may be 0.1 to 5000ppm, preferably 1 to 20 ppm.
The pressure of the cracked gas after secondary pressure boosting can be 1.0-5.0 MPaG, and preferably 1.6-3.5 MPaG.
In the step 4), the operation pressure of the deethanizer can be 1.0-5.0 MPaG, and preferably 1.6-3.5 MPaG; the operating temperature of the tower kettle can be-60 ℃ to 150 ℃, and is preferably-40 ℃ to 100 ℃.
The catalyst adopted by the catalytic hydrogenation reactor is preferably a BC-H-21B type hydrogenation catalyst.
In the dilute ethylene material flow, the content of propylene can be 1-2000 ppm, preferably 50-300 ppm; the acetylene content can be 0.1-1000 ppm, preferably 1-5 ppm; the content of propyne and propadiene may be 0.1 to 1000ppm, preferably 1 to 5 ppm.
In the step 6), the volume content of ethane in the ethane recovered from the tail gas can be 40-100%, and preferably 80-95%.
The volume content of hydrogen in the by-product hydrogen can be 30-100%, and preferably 80-99.9%.
The device and the process for producing the ethylbenzene can effectively reduce the equipment investment, reduce the consumption of raw materials and fuel, can produce hydrogen by-product, and have obvious economic benefit.
The present invention will be described in detail below by way of examples.
Example 1
This example illustrates an ethylbenzene production plant and process according to the invention.
As shown in fig. 1, in this embodiment, the primary booster compressor K-301 and the secondary booster compressor K-302 of the compression unit U-03 are units sharing a set of casing and rotor.
The refrigeration for condenser E-401 in cold separation unit U-04 is provided by propylene refrigeration system PR-401.
The tail gas recovery unit U-06 comprises a first-stage pressure swing adsorption system PSA-601, a second-stage pressure swing adsorption system PSA-602 and an ethane supercharger K-601 which are connected in sequence.
Specifically, the ethylbenzene production process comprises the following steps:
1) cracking the circulating cracking raw material S001 and the fresh cracking raw material S002 in a cracking furnace F-001 to obtain cracking gas S101 at the outlet of the cracking furnace, and cooling the cracking gas S101 by a first heat exchanger E-001 and a second heat exchanger E-002 in sequence to obtain cooled cracking gas S102;
2) sending the cooled pyrolysis gas S102 into a quenching water tower C-202 for further cooling to obtain a compressor inlet pyrolysis gas S201;
3) after the compressor inlet cracked gas S201 is subjected to pressure boosting by a primary pressure boosting compressor K-301, acid gas (H) is removed by an alkaline tower C-3012S、CO2) Obtaining first-time pressure-boosting deacidified gas and then cracking gas S301 (the pressure is 1.6MPaG, and CO in the gas is2、H2The concentration of S is lower than 1ppm, the dried S is sent to a secondary booster compressor K-302 for boosting again after being dried by a dryer DR-301 to obtain secondary boosted pyrolysis gas S302 (S)Pressure 3.0 MPaG);
4) the cracked gas S302 after secondary pressure boosting is used for removing more than three carbon components S403 in a deethanizer C-401, the obtained deethanizer overhead gas S401 is hydrogenated in a catalytic hydrogenation reactor R-401 filled with a BC-H-21B type catalyst to remove alkyne, and then is condensed by a condenser E-401, the obtained gas phase is a dilute ethylene material flow S402 which is used as a raw material for ethylbenzene synthesis reaction, and the liquid phase is used as reflux of the deethanizer C-401; wherein the operation pressure of the deethanizer C-401 is 2.7MPaG, and the operation temperature of a tower kettle is 70 ℃; wherein the content of propylene in the dilute ethylene stream S402 is less than 250ppm, the content of acetylene, propyne and propadiene is less than 5ppm,
5) reacting the dilute ethylene material flow S402 with the raw material benzene S501 in an ethylbenzene reaction system R-501 to obtain an ethylbenzene product S502 and an ethylbenzene reaction tail gas S503;
6) the ethylbenzene reaction tail gas S503 is treated by a first-stage pressure swing adsorption system PSA-601 of a tail gas recovery unit U-06 to obtain a byproduct hydrogen gas S603, and then treated by a second-stage pressure swing adsorption system PSA-602 to obtain a tail gas recovery methane S602 and a tail gas recovery ethane S601, wherein the tail gas recovery ethane S601 is boosted by an ethane booster K-601 and then sent to a cracking furnace F-001 to serve as the cyclic cracking raw material S001, and the tail gas recovery methane S602 serves as a fuel of the cracking furnace F-001.
Wherein the parameters of the main streams are shown in table 1:
TABLE 1
By adopting the ethylbenzene production device and the process, on one hand, the equipment investment is greatly reduced as a complete ethylene device does not need to be built and the dilute ethylene material flow does not need to be refined again before entering the ethylbenzene synthesis unit; on the other hand, when the same ethylbenzene productivity is maintained, the recovered ethane tail gas in the ethylbenzene reaction tail gas is recycled as a cracking raw material, so that the raw material consumed by a cracking part is reduced by more than 20% (about 23%), the recovered methane tail gas is used as fuel of a cracking furnace, the fuel gas consumption can be reduced by about 50%, meanwhile, a byproduct hydrogen gas with a high added value is obtained, and the economic benefit is remarkable.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the illustrated embodiments.
Claims (13)
1. A process for producing ethylbenzene from ethane, the process comprising: removing acetylene and more than three carbon components from a cracking raw material ethane through a cracking unit, a quenching unit, a compression unit and a cold separation unit to obtain a dilute ethylene stream, allowing the dilute ethylene stream to enter an ethylbenzene synthesis unit to react with benzene to obtain an ethylbenzene product and an ethylbenzene reaction tail gas, and separating the ethylbenzene reaction tail gas into by-product hydrogen, tail gas recovery methane and tail gas recovery ethane through a tail gas recovery unit; and the tail gas recovered ethane is recycled to the cracking unit to be used as a recycled cracking raw material, and the tail gas recovered methane is used as a fuel of the cracking unit for use.
2. The process for the production of ethylbenzene using ethane as claimed in claim 1, wherein the process comprises the following scheme:
1) cracking the circulating cracking raw material and the fresh cracking raw material in a cracking furnace of a cracking unit into cracking gas at the outlet of the cracking furnace, and cooling the cracking gas by a heat exchanger to obtain cooled cracking gas;
2) sending the cooled pyrolysis gas into a quenching unit for further cooling to obtain compressor inlet pyrolysis gas;
3) the method comprises the following steps that (1) after the cracked gas at the inlet of a compressor is boosted by a primary boosting compressor in a compression unit, acid gas is removed in an alkaline tower to obtain a primary boosted acid gas-removed cracked gas, the cracked gas is dried by a dryer and then sent to a secondary boosting compressor to be boosted again to obtain a secondary boosted cracked gas;
4) the cracked gas after secondary pressure rise is subjected to carbon removal of more than three components in a deethanizer of a cold separation unit, the obtained deethanizer overhead gas is subjected to hydrogenation in a catalytic hydrogenation reactor to remove acetylene hydrocarbon, and then is condensed by a condenser, the obtained gas phase is a dilute ethylene stream which is used as a raw material of an ethylbenzene synthesis reaction, and the liquid phase is used as reflux of the deethanizer;
5) reacting the dilute ethylene material flow with raw material benzene in an ethylbenzene synthesis unit to obtain an ethylbenzene product and ethylbenzene reaction tail gas;
6) the ethylbenzene reaction tail gas is treated by a first-stage pressure swing adsorption system and a second-stage pressure swing adsorption system of a tail gas recovery unit, hydrogen is obtained as a byproduct through separation, methane is recovered from the tail gas, and ethane is recovered from the tail gas, wherein the ethane is recovered from the tail gas and is sent into a cracking unit after being boosted by an ethane booster to serve as a cyclic cracking raw material, and the methane is recovered from the tail gas to serve as a fuel of a cracking furnace.
3. The process for producing ethylbenzene using ethane as claimed in claim 2, wherein, in the step 3),
the pressure of the cracked gas after the primary pressure boosting and acid gas removal is 0.5-4.0 MPaG, wherein the concentration of the acid gas is 0.1-5000 ppm;
and the pressure of the cracked gas after secondary pressure boosting is 1.0-5.0 MPaG.
4. The process for producing ethylbenzene using ethane as claimed in claim 3, wherein, in the step 3),
the pressure of the cracked gas after the primary pressure boosting and acid gas removal is 1.2-2.0 MPaG, wherein the concentration of the acid gas is 1-20 ppm;
and the pressure of the cracked gas after secondary pressure boosting is 1.6-3.5 MPaG.
5. The process for producing ethylbenzene using ethane as claimed in claim 2, wherein, in the step 4),
the operating pressure of the deethanizer is 1.0-5.0 MPaG; the operation temperature of the tower kettle is-60 ℃ to 150 ℃;
the catalytic hydrogenation reactor adopts a BC-H-21B type hydrogenation catalyst;
in the dilute ethylene material flow, the content of propylene is 1-2000 ppm; the acetylene content is 0.1-1000 ppm; the content of propyne and propadiene is 0.1-1000 ppm.
6. The process for producing ethylbenzene using ethane as claimed in claim 5, wherein, in the step 4),
the operating pressure of the deethanizer is 1.6-3.5 MPaG; the operation temperature of the tower kettle is-40 ℃ to 100 ℃;
in the dilute ethylene material flow, the content of propylene is 50-300 ppm; the acetylene content is 1-5 ppm; the content of propyne and propadiene is 1-5 ppm.
7. The process for producing ethylbenzene using ethane as claimed in claim 2, wherein, in the step 6),
the volume content of ethane in the tail gas recovered ethane is 40-100%; the volume content of hydrogen in the by-product hydrogen is 30-100%.
8. The process for producing ethylbenzene using ethane as claimed in claim 7, wherein, in the step 6),
the volume content of ethane in the tail gas recovered ethane is 80-95%; the volume content of hydrogen in the by-product hydrogen is 80-99.9%.
9. A device for producing ethylbenzene by adopting ethane is characterized by comprising a cracking unit, a quenching unit, a compression unit, a cold separation unit, an ethylbenzene synthesis unit and a tail gas recovery unit which are connected in sequence, wherein the tail gas recovery unit is also connected with the cracking unit; wherein,
the cracking unit, the quenching unit, the compression unit and the cold separation unit are used for converting cracking raw materials to obtain dilute ethylene material flow; the tail gas recovery unit is used for separating ethylbenzene reaction tail gas generated by the ethylbenzene synthesis unit into by-product hydrogen, tail gas recovered methane and tail gas recovered ethane, and sending the tail gas recovered ethane back to the cracking unit;
the compression unit comprises a primary booster compressor, an alkaline washing tower, a dryer and a secondary booster compressor which are sequentially connected;
the cold separation unit comprises a deethanizer, a catalytic hydrogenation reactor and a condenser which are connected in sequence.
10. The apparatus for manufacturing ethylbenzene using ethane according to claim 9, wherein the tail gas recovery unit comprises a first pressure swing adsorption system, a second pressure swing adsorption system and an ethane booster connected in sequence.
11. The apparatus for ethylbenzene production using ethane as claimed in claim 9, wherein the primary booster compressor and the secondary booster compressor are a unit sharing a set of casing and rotor.
12. The apparatus for producing ethylbenzene using ethane as claimed in claim 9, wherein the refrigeration of the condenser is provided by a propylene refrigeration system.
13. The apparatus for manufacturing ethylbenzene using ethane as claimed in claim 9, wherein the cracking unit comprises a cracking furnace and a heat exchanger connected in series.
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| CN111320525A (en) * | 2020-03-02 | 2020-06-23 | 大连理工大学 | Non-low temperature separation process for ethylene-rich catalytic cracking gas |
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