CN115838315A - Process for producing tert-butyl ethylbenzene by low aromatic-to-olefin ratio and tert-butyl ethylbenzene - Google Patents
Process for producing tert-butyl ethylbenzene by low aromatic-to-olefin ratio and tert-butyl ethylbenzene Download PDFInfo
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- NKRAJTUTWBTQFT-UHFFFAOYSA-N 1-tert-butyl-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C(C)(C)C NKRAJTUTWBTQFT-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000008569 process Effects 0.000 title claims abstract description 32
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 245
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 72
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 53
- 230000029936 alkylation Effects 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- -1 di-tert-butyl ethylbenzene Chemical compound 0.000 claims abstract description 26
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims description 49
- 238000011084 recovery Methods 0.000 claims description 38
- 238000000926 separation method Methods 0.000 claims description 29
- 239000002994 raw material Substances 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 24
- 239000012535 impurity Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 238000003541 multi-stage reaction Methods 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- MUJPTTGNHRHIPH-UHFFFAOYSA-N 1-tert-butyl-3-ethylbenzene Chemical compound CCC1=CC=CC(C(C)(C)C)=C1 MUJPTTGNHRHIPH-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OYBFKZHDPTTWGE-UHFFFAOYSA-N 1-tert-butyl-4-ethylbenzene Chemical compound CCC1=CC=C(C(C)(C)C)C=C1 OYBFKZHDPTTWGE-UHFFFAOYSA-N 0.000 description 3
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- QTIAYNBMYSOJME-UHFFFAOYSA-N 1-butyl-2-ethylbenzene Chemical group CCCCC1=CC=CC=C1CC QTIAYNBMYSOJME-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VIDOPANCAUPXNH-UHFFFAOYSA-N 1,2,3-triethylbenzene Chemical compound CCC1=CC=CC(CC)=C1CC VIDOPANCAUPXNH-UHFFFAOYSA-N 0.000 description 1
- SZURZHQMGVKJLV-UHFFFAOYSA-N 1,2-ditert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1C(C)(C)C SZURZHQMGVKJLV-UHFFFAOYSA-N 0.000 description 1
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- WTFUTSCZYYCBAY-SXBRIOAWSA-N 6-[(E)-C-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-N-hydroxycarbonimidoyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C/C(=N/O)/C1=CC2=C(NC(O2)=O)C=C1 WTFUTSCZYYCBAY-SXBRIOAWSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a process for producing tert-butyl ethylbenzene by using a low aromatic-to-olefin ratio and tert-butyl ethylbenzene produced by using the process, and belongs to the technical field of chemical substance synthesis. The invention adopts a multistage reaction process, the discharge concentration of the tert-butyl ethylbenzene is high, the amount of the circulating ethylbenzene is small, the purpose of energy saving is achieved, meanwhile, the reaction process controls the feeding to be the alkylation reaction of the ethylbenzene and isobutene basically, the generation amount of the di-tert-butyl ethylbenzene is reduced, the low arene molar ratio of the ethylbenzene to the isobutene is 3.0-4.0, the concentration ratio of the di-tert-butyl ethylbenzene to the tert-butyl ethylbenzene in a reaction product is enabled to be below 0.2%, and a reverse alkylation reactor is not required to be arranged.
Description
Technical Field
The invention relates to the technical field of chemical substance preparation, in particular to a process for producing tert-butyl ethylbenzene by using a low arene ratio and tert-butyl ethylbenzene produced by using the process.
Background
Tert-butyl ethylbenzene is an important chemical raw material, is mainly used for producing monomer tert-butyl styrene for chemical materials through dehydrogenation, and is generally constructed together with a tert-butyl styrene device as a combined device. The main reaction principle is as follows: under a certain arene ratio condition, ethylbenzene and isobutene undergo primary alkylation reaction formulas (1) and (2) to generate tert-butyl ethylbenzene, including p-tert-butyl ethylbenzene and m-tert-butyl ethylbenzene, which is a strong exothermic reaction. In addition, the ratio of para-tert-butyl ethylbenzene to meta-tert-butyl ethylbenzene is controlled to be greater than 9 due to the polymeric material performance requirements of the downstream tert-butyl styrene.
C 8 H 10 +C 4 H 8 →P-C 12 H 18 Para-tert-butyl ethylbenzene (1)
C 8 H 10 +C 4 H 8 →M-C 12 H 18 M-tert-butyl ethylbenzene (2)
The generated tert-butyl ethylbenzene can also be continuously subjected to alkylation reaction with isobutene to generate di-tert-butyl ethylbenzene, and the speed of the secondary alkylation reaction is equivalent to that of the primary alkylation reaction. Therefore, in order to reduce material consumption, an anti-alkylation reactor of di-tert-butyl ethylbenzene is required to be arranged in the general process, and the di-tert-butyl ethylbenzene and ethylbenzene react to generate tert-butyl ethylbenzene. However, due to the existence of ethyl and methyl in the material, the product of the reverse alkylation reaction is very complex, including methyl ethyl benzene, butylbenzene, diethylbenzene, triethylbenzene, carbon nonaromatic hydrocarbon, p-tert-butyl ethyl benzene, m-tert-butyl ethyl benzene, di-tert-butyl benzene and other products, and the separation process is complex and difficult. Also important factors are: the ratio of the anti-alkylation control to the tert-butyl ethylbenzene and the m-tert-butyl ethylbenzene can be changed, which can cause that the requirement that the downstream ratio control is more than 9 cannot be met, so that the method for reducing the material consumption by arranging the anti-alkylation is difficult to realize.
In addition, in order to reduce the amount of di-tert-butyl ethylbenzene generated by the reaction, many processes are provided with a high arene ratio (molar ratio of ethylbenzene to isobutene) of about 10, and the high arene ratio brings the problems that a large amount of unreacted ethylbenzene needs to be recycled in a post system, and the energy consumption of the device is increased. Therefore, the reduction of the aromatic-to-olefin ratio becomes a research hotspot.
Disclosure of Invention
In view of the above, in order to solve the above-mentioned drawbacks in the background art, in one aspect, the present invention provides a process for producing tert-butyl ethylbenzene with a low arene ratio, wherein a multi-stage reaction process is adopted, the tert-butyl ethylbenzene discharge concentration is high, the amount of recycled ethylbenzene is small, and the purpose of energy saving is achieved, meanwhile, the reaction process controls the alkylation reaction of ethylbenzene and isobutylene as the feed material, reduces the generation amount of di-tert-butyl ethylbenzene, and makes the ethylbenzene/isobutylene low arene molar ratio be 3.0-4.0, so that the concentration ratio of di-tert-butyl ethylbenzene to tert-butyl ethylbenzene in the reaction product is below 0.2%, and no "anti-alkylation" reactor is required.
In order to achieve the purpose, the invention provides the following technical scheme:
a process for producing tert-butyl ethylbenzene by using a low aromatic olefin ratio comprises the following steps:
step 1, mixing ethylbenzene with a small amount of isobutene, then passing the mixture through a protective reactor, then mixing the mixture with a part of isobutene, entering a multi-stage alkylation reactor for alkylation reaction, carrying out ethylbenzene crude separation on a reaction discharge material in a multi-stage ethylbenzene crude separation tower, processing a material at the bottom of the tower in an ethylbenzene recovery tower, recovering ethylbenzene at the top of the tower to control the content of tert-butyl ethylbenzene to be less than 0.5%, returning the mixture to be mixed with a part of isobutene again, entering the multi-stage alkylation reactor for reaction, circulating for a plurality of times, and finally enabling the material of the alkylation reaction to flow out of the top of a liquid-phase alkylation reactor and enter the ethylbenzene recovery tower to process the reaction material;
step 2, the raw material ethylbenzene enters a separation system to process impurity components separately, and then returns to the multistage alkylation reactor circularly;
and 3, distilling ethylbenzene from the top of the ethylbenzene recovery tower, partially extracting and feeding the part of the ethylbenzene in a gas phase form into a light component removal tower to be used as a heat source of the tower to maintain the operation of the tower, removing C8 nonaromatic hydrocarbons accumulated in a system at the top of the light component removal tower, feeding materials at the bottom of the tower in a liquid phase form to a multi-stage alkylation reactor to be used as ethylbenzene serving as a raw material for alkylation reaction, extracting materials rich in tert-butyl ethylbenzene from the bottom of the ethylbenzene recovery tower and feeding the materials into a tert-butyl ethylbenzene recovery tower, wherein in the tert-butyl ethylbenzene recovery tower, distillate at the top of the tower is used as a refined tert-butyl ethylbenzene product of the unit, and residual oil of extracted materials at the bottom of the tower is sent to the outside.
Preferably, step 2 is specifically:
the raw material ethylbenzene is divided into two material flows, the first part enters the top of an ethylbenzene recovery tower after passing through an impurity adsorber B, the second part is used as the feed of a light component removal tower, and the dehydrated dry ethylbenzene enters the top of the ethylbenzene recovery tower through an impurity adsorber A and returns to a multistage alkylation reactor together with the first part to be used as the raw material.
Preferably, the number of reaction stages in the multistage alkylation reactor is from 2 to 12 stages, preferably from 4 to 8 stages, most preferably 8 stages.
Preferably, the number of the stages of the multistage ethylbenzene crude separation tower is 1-6 stages, preferably 2-4 stages, and most preferably 3 stages.
Preferably, a strongly acidic catalyst is used in the multistage alkylation reactor.
Preferably, the strongly acidic catalyst is an MCM series molecular sieve catalyst.
Preferably, the multistage alkylation reactor is operated at a pressure of from 0.8 to 3.0MPaG, preferably from 1.5 to 2.5MPaG.
Preferably, the operating temperature of the multistage alkylation reactor is between 90 and 180 ℃, preferably between 100 and 140 ℃, most preferably between 105 and 120 ℃.
Preferably, the flow ratio of the first portion of ethylbenzene feedstock to the second portion of ethylbenzene feedstock is in the range of 0 to 600, preferably 0.15 to 0.2.
On the other hand, the invention also provides tert-butyl ethylbenzene prepared by the process for producing the tert-butyl ethylbenzene by utilizing the low arene ratio.
Compared with the prior art, the invention has the following beneficial effects:
the process for producing the tert-butyl ethylbenzene by the low arene ratio provided by the invention has the advantages that a multi-stage reaction process is adopted, the discharge concentration of the tert-butyl ethylbenzene is high, the amount of the circulating ethylbenzene is small, the energy-saving purpose is achieved, meanwhile, the reaction process controls the feeding to be basically the alkylation reaction of the ethylbenzene and the isobutene, the generation amount of the di-tert-butyl ethylbenzene is reduced, the ethylbenzene/isobutene low arene molar ratio is 3.0-4.0, the concentration ratio of the di-tert-butyl ethylbenzene to the tert-butyl ethylbenzene in a reaction product is enabled to be below 0.2%, and an anti-alkylation reactor is not required.
Drawings
FIG. 1 is a production process flow chart of example 1 of the present invention;
in the figure, 1, a multi-stage alkylation reactor, 2, a multi-stage ethylbenzene crude separation tower, 21, a first stage ethylbenzene crude separation tower, 22, a second stage ethylbenzene crude separation tower, 23, a third stage ethylbenzene crude separation tower, 3, a protection reactor, 4, an ethylbenzene recovery tower, 5, a light component removal tower, 6, impurity adsorbers A,7, impurity adsorbers B,8, a tert-butyl ethylbenzene recovery tower and 9, an alkylation ethylbenzene booster pump.
Detailed Description
The invention provides a process for producing tert-butyl ethylbenzene by using low aromatic-to-olefin ratio, which comprises the following steps:
step 1, mixing ethylbenzene with a small amount of isobutene, then passing the mixture through a protective reactor 3, mixing the mixture with partial isobutene, and entering a multi-stage alkylation reactor 1 for alkylation reaction;
performing ethylbenzene crude separation on reaction discharge materials in a multistage ethylbenzene crude separation tower 2, treating materials at the bottom of the tower in an ethylbenzene recovery tower, recovering ethylbenzene from the top of the tower to control the content of tert-butyl ethylbenzene to be less than 0.5%, returning the ethylbenzene to be mixed with partial isobutene to enter a multi-stage alkylation reactor 1 for reaction, and after circulating for a plurality of times, finally enabling the materials of the alkylation reaction to flow out of the top of a liquid-phase alkylation reactor and enter an ethylbenzene recovery tower 4 for treating the reaction materials;
step 2, the raw material ethylbenzene enters a separation system to process impurity components separately, and then is circularly returned to the multistage alkylation reactor 1;
and 3, distilling ethylbenzene from the top of the ethylbenzene recovery tower 4, partially extracting and feeding a gas phase into a light component removal tower 5 to be used as a heat source of the tower to maintain the operation of the tower, removing C8 nonaromatic hydrocarbons accumulated in a system at the top of the light component removal tower 5, feeding a tower bottom material to the multistage alkylation reactor 1 in a liquid phase form to be used as raw material ethylbenzene of the alkylation reaction, extracting a material rich in tert-butyl ethylbenzene from the bottom of the ethylbenzene recovery tower 4 and feeding the material into a tert-butyl ethylbenzene recovery tower 8, wherein in the tert-butyl ethylbenzene recovery tower 8, a tower top distillate is used as a refined tert-butyl ethylbenzene product of the unit, and a tower bottom extract residual oil is sent to the outside.
In the present invention, the ethylbenzene feedstock is fed by an ethylbenzene hydrocarbonate booster pump 9.
In the invention, step 2 specifically comprises:
the raw material ethylbenzene is divided into two material flows, the first part of the raw material ethylbenzene enters the top of an ethylbenzene recovery tower 4 after passing through an impurity adsorber B7, the second part of the raw material ethylbenzene is used as the feeding material of a light component removal tower 5, and dehydrated dry ethylbenzene enters the top of the ethylbenzene recovery tower 4 through an impurity adsorber A6 and returns to the multistage alkylation reactor 1 together with the first part of the raw material ethylbenzene as the raw material.
In the present invention, the number of reaction stages of the multistage alkylation reactor 1 is 2 to 12 stages, preferably 4 to 8 stages, and most preferably 8 stages.
In the present invention, the number of stages of the multistage ethylbenzene crude separation column 2 is 1 to 6, preferably 2 to 4, and most preferably 3.
According to the invention, ethylbenzene can be roughly separated through the multistage ethylbenzene rough separation tower 2, the content of tert-butyl ethylbenzene at the tower top is controlled to be less than 0.5%, so that the probability of secondary alkylation of tert-butyl ethylbenzene in the material entering the next layer of catalyst is reduced, therefore, the content of di-tert-butyl ethylbenzene is reduced, after multi-stage reaction, the content of di-tert-butyl ethylbenzene entering the product tert-butyl ethylbenzene recovery tower 8 is controlled to be less than 0.2%, and di-tert-butyl ethylbenzene is discharged out of the system along with residual oil, so that no significant influence is caused on material consumption.
In the present invention, a strongly acidic catalyst is used in the multistage alkylation reactor 1.
In the invention, the strongly acidic catalyst is an MCM series molecular sieve catalyst, and the pore structure of the catalyst can control the proportion of p-tert-butyl ethylbenzene to m-tert-butyl ethylbenzene to be more than 9.
In the invention, regarding the treatment of the basic nitrogen, the catalyst in the multistage alkylation reactor 1 is considered to be an acid catalyst, the basic nitrogen is treated to meet the use requirement of the catalyst, an acid adsorbent is selected to be filled in an impurity adsorber A6 and an impurity adsorber B7, an acid beta molecular sieve catalyst is selected to be filled in a protection reactor, and the basic nitrogen in the feed of the protection reactor 3 is controlled to be 0.1PPM.
In the present invention, the multistage alkylation reactor 1 is operated at a pressure of 0.8 to 3.0MPaG, preferably 1.5 to 2.5MPaG.
In the present invention, the operating temperature of the multistage alkylation reactor 1 is 90 to 180 ℃, preferably 100 to 140 ℃, and most preferably 105 to 120 ℃.
In the present invention, the flow ratio of the first part of raw material ethylbenzene to the second part of raw material ethylbenzene is 0-600 (theoretical feasible value), preferably 0.15-0.2 (actual value), so that the water content in the circulating raw material ethylbenzene which returns to the alkylation reactor can be controlled to be 50-500 PPM, preferably 100-200 PPM, and because a small amount of water participates in the alkylation reaction process, the water content is controlled to be 100-200 PPM, and the operation requirement of the alkylation catalyst is selected to meet.
On the other hand, the invention also provides tert-butyl ethylbenzene prepared by the process for producing the tert-butyl ethylbenzene by utilizing the low arene ratio.
The technical solution of the present invention will be described in detail with reference to specific examples.
Example 1
The multistage alkylation reactor 1 is selected to be 8 stages, and the multistage ethylbenzene crude separation tower 2 is selected to be 3 stages which are respectively a first stage ethylbenzene crude separation tower 21, a second stage ethylbenzene crude separation tower 22 and a third stage ethylbenzene crude separation tower 23;
the specific production process comprises the following steps:
ethylbenzene from a rectification working section after recovery processing of impurities is pressurized by an alkylation ethylbenzene booster pump 9 and is completely mixed with a small amount of isobutene through a protective reactor 3 under the flow control, then the ethylbenzene is mixed with a part of isobutene and enters a first catalyst bed layer and a second catalyst bed layer of an alkylation reaction to enter the alkylation reaction, the isobutene completely reacts to generate tert-butyl ethylbenzene and a small amount of di-tert-butyl ethylbenzene, reaction discharge materials are subjected to ethylbenzene crude separation in a first-stage ethylbenzene crude separation tower 21, materials containing the ethylbenzene, the tert-butyl ethylbenzene and the small amount of di-tert-butyl ethylbenzene at the bottom of the tower are treated in an ethylbenzene recovery tower 4, the ethylbenzene is recovered at the top of the tower to control the tert-butyl ethylbenzene to be less than 0.5%, the ethyl benzene is returned again to be mixed with a part of isobutene and enters a third catalyst and a fourth catalyst for reaction, reaction discharge materials are subjected to ethylbenzene crude separation in a second-stage ethylbenzene crude separation tower 22, the materials containing the ethylbenzene, the ethylbenzene and the di-tert-butyl ethylbenzene are recovered at the top of the ethylbenzene recovery tower to control the tert-butyl ethylbenzene to be less than 0.5%, and are returned again mixed with a part of the isobutene and enter a fifth catalyst for reaction in a sixth catalyst reaction section. The reaction discharge is subjected to ethylbenzene crude separation in a third-stage ethylbenzene crude separation tower 23, the materials containing ethylbenzene, tert-butyl ethylbenzene and di-tert-butyl ethylbenzene at the tower bottom are treated in an ethylbenzene recovery tower 4, the ethylbenzene recovered at the tower top controls the tert-butyl ethylbenzene to be less than 0.5%, the materials are returned again to be mixed with partial isobutene to enter a seventh section and an eighth section of catalysts for reaction, and finally the alkylation reaction materials flow out of the reaction device from the top of the multistage alkylation reactor 1 and enter the ethylbenzene recovery tower 4 to treat the reaction materials;
the alkylation reaction raw material isobutene is divided into a plurality of strands, wherein the first strand of isobutene enters the protective reactor 3 to keep the protective catalyst in a reaction state, and the rest strands of isobutene respectively enter corresponding catalyst bed layers under the flow control to carry out alkylation reaction.
The raw material ethylbenzene firstly enters a separation system to treat impurity components separately and then circularly returns to a reaction system, fresh raw material ethylbenzene is divided into two material flows, wherein the first material flow enters the top of an ethylbenzene recovery tower 4 after passing through an impurity adsorber B7, the second material flow is used as a feed material for a light component removal tower 5, and dehydrated dry ethylbenzene enters the top of the ethylbenzene recovery tower 4 through an impurity adsorber A6 and is pressurized and returned to an alkylation reactor as a raw material together with the first part through an alkylation ethylbenzene pressurizing pump 9.
The ethyl benzene is distilled from the top of the ethyl benzene recovery tower 4, part of the ethyl benzene is extracted in a gas phase form and enters the light component removal tower 5 to be used as a heat source of the tower to maintain the operation of the tower, C8 non-aromatic hydrocarbons accumulated in a system are removed from the top of the light component removal tower 5, most of the bottom of the tower returns to a reaction working section in a liquid phase form to be used as raw material ethyl benzene for alkylation reaction, and a material rich in tert-butyl ethyl benzene is extracted from the bottom of the ethyl benzene recovery tower 4 and enters the tert-butyl ethyl benzene recovery tower 8. In a tert-butyl ethylbenzene recovery tower 8, the distillate at the top of the tower is used as a refined tert-butyl ethylbenzene product of the unit, and the residual oil of the extracted material at the bottom of the tower is sent to the outside;
wherein the molar ratio of ethylbenzene to isobutylene low arene is controlled to be 3.0.
Examples 2-6 differ from example 1 in the operating pressure, operating temperature and aromatics ratio of the alkylation reactor.
According to the process design, a device for producing 1 ten thousand tons of tertiary butyl ethylbenzene annually controls the water content of the raw material ethylbenzene to be 150PPM and the basic nitrogen to be 0.05PPM, adopts an 8-section reactor, has the reaction arene ratio of 3-4, the operating pressure of 1.5-2.5 MPaG and the operating temperature of a reactor inlet to be 105-120 ℃, and shows that the proportion of the di-tert-butyl ethylbenzene to the tertiary butyl ethylbenzene in the reaction material is 0.02-0.14 percent and is less than 0.2 percent, and the specific indexes are shown in the following table.
| Examples | Aryl to alkenyl ratio | Pressure of | Temperature of | Ratio of |
| Example 1 | 3 | 1.5 | 105 | 0.14 |
| Example 2 | 3.5 | 2 | 110 | 0.11 |
| Example 3 | 4 | 2.5 | 115 | 0.06 |
| Example 4 | 4 | 2.5 | 120 | 0.09 |
| Example 5 | 4 | 1.5 | 105 | 0.02 |
| Example 6 | 4 | 2 | 105 | 0.02 |
Note that: the ratio is di-tert-butyl ethylbenzene to tert-butyl ethylbenzene.
Claims (10)
1. A process for producing tert-butyl ethylbenzene by using a low aromatic olefin ratio is characterized by comprising the following steps:
step 1, mixing ethylbenzene with a small amount of isobutene, then passing the mixture through a protective reactor, then mixing the mixture with a part of isobutene, entering a multi-stage alkylation reactor for alkylation reaction, carrying out ethylbenzene crude separation on a reaction discharge material in a multi-stage ethylbenzene crude separation tower, processing a material at the bottom of the tower in an ethylbenzene recovery tower, recovering ethylbenzene at the top of the tower to control the content of tert-butyl ethylbenzene to be less than 0.5%, returning the mixture to be mixed with a part of isobutene again, entering the multi-stage alkylation reactor for reaction, circulating for a plurality of times, and finally enabling the material of the alkylation reaction to flow out of the top of a liquid-phase alkylation reactor and enter the ethylbenzene recovery tower to process the reaction material;
step 2, the ethylbenzene as a raw material enters a separation system to be subjected to impurity component treatment, and then the ethylbenzene is circularly returned to the multistage alkylation reactor;
and 3, distilling ethylbenzene from the top of the ethylbenzene recovery tower, partially extracting and feeding a gas phase into a light component removal tower to be used as a heat source of the tower to maintain the operation of the tower, removing C8 non-aromatic hydrocarbons accumulated in a system at the top of the light component removal tower, feeding a material at the bottom of the tower to a multistage alkylation reactor in a liquid phase form to be used as ethylbenzene serving as a raw material of an alkylation reaction, extracting a material rich in tert-butyl ethylbenzene from the bottom of the ethylbenzene recovery tower, feeding the material into a tert-butyl ethylbenzene recovery tower, feeding a distillate at the top of the tower in the tert-butyl ethylbenzene recovery tower as a refined tert-butyl ethylbenzene product of the unit, and feeding residual oil extracted from the bottom of the tower to the outside.
2. The process for producing tert-butyl ethylbenzene with low arene ratio as claimed in claim 1, wherein the step 2 is specifically as follows:
the raw material ethylbenzene is divided into two material flows, the first part enters the top of an ethylbenzene recovery tower after passing through an impurity adsorber B, the second part is used as the feed of a light component removal tower, and the dehydrated dry ethylbenzene enters the top of the ethylbenzene recovery tower through an impurity adsorber A and returns to a multistage alkylation reactor together with the first part to be used as the raw material.
3. The process for producing tert-butyl ethylbenzene according to claim 1, wherein the number of reaction stages in the multistage alkylation reactor is 2-12, preferably 4-8, and most preferably 8.
4. The process for producing tert-butyl ethylbenzene according to claim 3, wherein the number of stages of the multistage ethylbenzene crude separation column is 1-6 stages, preferably 2-4 stages, and most preferably 3 stages.
5. The process for producing tert-butyl ethylbenzene with low arene ratio as claimed in claim 1, wherein a strongly acidic catalyst is used in the multistage alkylation reactor.
6. The process for producing tert-butyl ethylbenzene according to claim 5, wherein the strongly acidic catalyst is an MCM series molecular sieve catalyst.
7. The process for producing tert-butyl ethylbenzene with low arene ratio according to claim 1, wherein the operating pressure of the multistage alkylation reactor is 0.8-3.0 MPaG, preferably 1.5-2.5 MPaG.
8. The process for producing tert-butyl ethylbenzene with low arene ratio according to claim 1, wherein the operating temperature of the multistage alkylation reactor is 90-180 ℃, preferably 100-140 ℃, and most preferably 105-120 ℃.
9. The process for producing tert-butyl ethylbenzene with low arene ratio according to claim 2, wherein the flow ratio of the first part of raw material ethylbenzene to the second part of raw material ethylbenzene is 0-600, preferably 0.15-0.2.
10. A tert-butyl ethylbenzene produced by a process for producing tert-butyl ethylbenzene with a low arene ratio as claimed in any one of claims 1 to 9.
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