CN117342909A - Co-production method and device for isopropylbenzene and alpha-methylstyrene - Google Patents
Co-production method and device for isopropylbenzene and alpha-methylstyrene Download PDFInfo
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- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 title claims abstract description 178
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 238000007327 hydrogenolysis reaction Methods 0.000 claims abstract description 93
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 88
- 239000000203 mixture Substances 0.000 claims abstract description 74
- 239000011259 mixed solution Substances 0.000 claims abstract description 67
- 239000003054 catalyst Substances 0.000 claims abstract description 62
- BDCFWIDZNLCTMF-UHFFFAOYSA-N 2-phenylpropan-2-ol Chemical compound CC(C)(O)C1=CC=CC=C1 BDCFWIDZNLCTMF-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000001257 hydrogen Substances 0.000 claims abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 41
- 230000018044 dehydration Effects 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012535 impurity Substances 0.000 claims abstract description 26
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 58
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 32
- 238000000926 separation method Methods 0.000 claims description 30
- 238000005191 phase separation Methods 0.000 claims description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000011973 solid acid Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 76
- 238000000034 method Methods 0.000 abstract description 62
- ARSRBNBHOADGJU-UHFFFAOYSA-N 7,12-dimethyltetraphene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)=C(C=CC=C1)C1=C2C ARSRBNBHOADGJU-UHFFFAOYSA-N 0.000 description 47
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 description 47
- GWESVXSMPKAFAS-UHFFFAOYSA-N Isopropylcyclohexane Chemical compound CC(C)C1CCCCC1 GWESVXSMPKAFAS-UHFFFAOYSA-N 0.000 description 38
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 38
- 230000008569 process Effects 0.000 description 32
- 229930195733 hydrocarbon Natural products 0.000 description 26
- 150000002430 hydrocarbons Chemical class 0.000 description 24
- 239000012071 phase Substances 0.000 description 24
- 239000000126 substance Substances 0.000 description 23
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 22
- 239000002994 raw material Substances 0.000 description 20
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 19
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 239000007788 liquid Substances 0.000 description 15
- 238000000605 extraction Methods 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 11
- 238000006735 epoxidation reaction Methods 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 230000009471 action Effects 0.000 description 7
- 238000005265 energy consumption Methods 0.000 description 7
- 238000007086 side reaction Methods 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- -1 methyl hydrocarbon Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229940009868 aluminum magnesium silicate Drugs 0.000 description 1
- WMGSQTMJHBYJMQ-UHFFFAOYSA-N aluminum;magnesium;silicate Chemical compound [Mg+2].[Al+3].[O-][Si]([O-])([O-])[O-] WMGSQTMJHBYJMQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (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
A method for coproducing isopropylbenzene and alpha-methylstyrene comprises the following sequential steps: 1) Hydrogenolysis reaction is carried out on the isopropylbenzene solution containing the alpha, alpha-dimethylbenzyl alcohol and hydrogen to obtain a mixture I-1, unreacted hydrogen, water and water-soluble impurities in the mixture I-1 are separated to obtain a mixed solution I-2 containing the isopropylbenzene and the unreacted alpha, alpha-dimethylbenzyl alcohol; 2) Carrying out dehydration reaction on the mixed solution I-2 to obtain a mixture II-1, and separating water and water-soluble impurities in the mixture II-1 to obtain a mixed solution II-2 containing isopropylbenzene and alpha-methylstyrene; 3) The cumene and alpha-methylstyrene in the mixture II-2 are separated. The method adopts the mode of first hydrogenolysis and then dehydration, can realize the efficient conversion and utilization of the alpha, alpha-dimethylbenzyl alcohol under the condition of a conventional catalyst, can obtain the isopropylbenzene and simultaneously can coproduce the alpha-methylstyrene with high selectivity, and has the characteristics of simplicity, high efficiency and flexibility.
Description
Technical Field
The invention belongs to the technical field of chemistry, and particularly relates to a method and a device for coproducing isopropylbenzene and alpha-methylstyrene.
Background
In the process of preparing propylene oxide by the cumene hydroperoxide process (CHPPO process), a large amount of alpha, alpha-dimethylbenzyl alcohol (DMBA) is simultaneously generated, so that efficient utilization of the DMBA is required to promote the economical efficiency of the CHPPO process. One of the existing treatment methods is to reduce DMBA to cumene for recycling, but this method also has some problems.
The method for preparing the isopropylbenzene by taking DMBA as a raw material through reduction mainly comprises two methods, namely a hydrogenolysis method and an indirect hydrogenolysis method. The hydrogenation method is to directly carry out substitution reaction on DMBA and hydrogen to obtain isopropylbenzene and water under the action of a catalyst, but the method has the defect that the hydrogenation conversion rate of DMBA is low, the catalyst is generally required to be modified or subjected to multistage hydrogenolysis under the conditions of high temperature and high pressure, and the cost and the energy consumption are high in order to improve the comprehensive conversion rate. For example, CN116023206A discloses a device and a method for preparing isopropylbenzene by hydrogenolysis of alpha, alpha-dimethylbenzyl alcohol, which uses Pd-A/SiO 2 -Al 2 O 3 As a first-stage catalyst, and adding organic acid in the first-stage hydrogenolysis process to cooperatively reduce the temperature of the first-stage hydrogenolysis to 120-140 ℃, but the pressure of the first-stage hydrogenolysis and the pressure of the second-stage hydrogenolysis are both more than 1.5MPa, and the introduced organic acid is unfavorable for the subsequent working section.
The indirect hydrogenation method is to dehydrate to obtain alpha-methyl styrene (AMS) under the action of a catalyst, and then hydrogenate to obtain isopropylbenzene. However, the conventional method requires a relatively high temperature and pressure in order to obtain a high conversion, and AMS generated after dehydration is liable to undergo polymerization side reactions and cause deactivation of the catalyst, etc. In order to increase the dehydration conversion of DMBA, an additional modification treatment may be performed on the catalyst, for example, CN115990469a discloses a modified alumina and a preparation method thereof, which reduces strong acid sites on the catalyst surface and improves hydrophilicity through an organic acid treatment, and increases the dehydration conversion of DMBA from 67.4% to 99.9% through a specific reaction condition in combination with the modified catalyst. In order to prevent AMS polymers from being produced, catalysts are also generally required to be optimized, for example, CN115178272a discloses a catalyst, a preparation method thereof and a cumene production method, which adopt a silica carrier to load nano-scale metallic copper and palladium catalysts, utilize the finite field effect of nano materials to affect the catalyst system structure and electron specificity, and avoid the formation of dimers in the AMS epoxy reaction process.
Therefore, if the comprehensive utilization efficiency of DMBA is improved in advance, the catalyst is modified or the temperature and pressure are required to be higher in the prior art, the method not only can increase the energy consumption burden, but also is relatively higher in catalyst cost, and the product produced by the process is single in form and low in production flexibility.
Disclosure of Invention
The invention provides a simple, efficient and flexible production process, which not only can realize efficient conversion and utilization of DMBA under the condition of a conventional catalyst, but also can coproduce cumene and alpha-methylstyrene, and can flexibly adjust the output proportion of a target product according to market demands.
The technical scheme adopted by the invention is as follows:
a method for coproducing isopropylbenzene and alpha-methylstyrene comprises the following sequential steps:
(1) Hydrogenolysis reaction is carried out on the isopropylbenzene solution containing the alpha, alpha-dimethylbenzyl alcohol and hydrogen to obtain a mixture I-1, unreacted hydrogen, water and water-soluble impurities in the mixture I-1 are separated to obtain a mixed solution I-2 containing the isopropylbenzene and the unreacted alpha, alpha-dimethylbenzyl alcohol;
(2) Carrying out dehydration reaction on the mixed solution I-2 to obtain a mixture II-1, and separating water and water-soluble impurities in the mixture II-1 to obtain a mixed solution II-2 containing isopropylbenzene and alpha-methylstyrene;
(3) Cumene and alpha-methylstyrene are separated from the mixture II-2, respectively.
The hydrogenolysis reaction in step (1) of the present invention may be carried out at lower temperature and pressure conditions, such as a temperature of 60 to 200 ℃, preferably 80 to 140 ℃, and a pressure of 0.05 to 1.4Mpa, preferably 0.2 to 1.0Mpa, with the catalyst being a conventional hydrogenolysis catalyst in the art. Typically, the hydrogenolysis catalysts in the art are supported, including a support and a supported active component, the active component may be selected from one or more of palladium (Pd), platinum (Pt), cobalt (Co), copper (Cu), zinc (Zn) or nickel (Ni), and the support may be selected from one or more of silica, alumina, activated carbon (C).
The invention can flexibly select the types of the hydrogenolysis catalyst according to different hydrogenolysis conversion rate requirements. The applicant found that when the conversion rate of alpha, alpha-dimethylbenzyl alcohol is too low to be less than 60%, the content of unreacted alpha, alpha-dimethylbenzyl alcohol in the mixed liquor I-2 is too high, which can negatively influence the subsequent dehydration reaction, and when the conversion rate of alpha, alpha-dimethylbenzyl alcohol is too high to be more than 89%, the local concentration of cumene in the step (1) can be too high, so that side reaction is increased. Accordingly, in step (1), the conversion of α, α -dimethylbenzyl alcohol is preferably 60 to 89%, and in order to obtain the above-mentioned suitable hydrogenolysis conversion, the hydrogenolysis catalyst of the present invention is preferably at least one of Pd/C, pd/alumina and Ni/alumina catalyst. Wherein, based on the total weight of the hydrogenolysis catalyst, the weight ratio of Pd element is 0.1 to 0.5 weight percent, and the weight ratio of Ni element is 10 to 60 weight percent.
The isopropylbenzene solution containing the alpha, alpha-dimethylbenzyl alcohol is obtained from a tower kettle material Z obtained after rectification and separation of an epoxidation reaction product of a CHPPO method, wherein the tower kettle material Z generally contains 30-70 wt% of alpha, alpha-dimethylbenzyl alcohol, 29-69.8 wt% of isopropylbenzene and less than or equal to 1.5wt% of other hydrocarbons, the other hydrocarbons comprise acetophenone, alpha-methylstyrene, phenol and the like, the temperature of the tower kettle material Z is generally about 120-180 ℃, and the tower kettle material Z can directly enter the step (1) without heat exchange, so that the heat energy in the CHPPO method process is fully utilized, and the energy consumption in the co-production process is further reduced.
To ensure that the reaction proceeds continuously and steadilyPreferably, the volume space velocity of the isopropylbenzene solution containing alpha, alpha-dimethylbenzyl alcohol in the step (1) of the invention is 1-15 h -1 The molar ratio of the hydrogen to the alpha, alpha-dimethylbenzyl alcohol is (0.8-15): 1, preferably (2 to 10): 1 to ensure that the α, α -dimethylbenzyl alcohol is converted within the correct range, thereby providing a suitable concentration of unreacted α, α -dimethylbenzyl alcohol in the mixture stream I-2.
After the raw materials with a specific proportion are subjected to hydrogenolysis reaction under the reaction condition of the step (1), a mixture I-1 containing isopropylbenzene, water, unreacted alpha, alpha-dimethylbenzyl alcohol, unreacted hydrogen, other hydrocarbons and the like is generally obtained, and the step (1) of the invention adopts lower temperature and pressure, so that hydrogenation side reaction in the hydrogenolysis process can be prevented, and the mixture I-1 does not contain the over-hydrogenated products such as isopropyl cyclohexane, cyclohexanol, cyclohexanone and the like. Unreacted hydrogen, water and water-soluble impurities can be removed from the mixture I-1 after gas-liquid two-phase separation and oil-water separation, so that a mixed solution I-2 is obtained, wherein the mixed solution I-2 contains isopropylbenzene, unreacted alpha, alpha-dimethylbenzyl alcohol and other hydrocarbon substances from a tower kettle material Z. The method for separating unreacted hydrogen, water and water-soluble impurities in the step (1) can be realized in various modes, as one implementation mode, the mixture I-1 is fully introduced into a phase-splitting tank, after the temperature is reduced and the mixture is kept still, gaseous substances in the mixture I-1 are discharged from the top of the phase-splitting tank, the rest substances are layered in oil and water phases, then water phase is discharged from the bottom of the phase-splitting tank, and the obtained oil phase substances are recorded as mixed liquid I-2. The phase-splitting tank can be a horizontal tank, and in a more preferred embodiment, the bottom of the phase-splitting tank is connected with a water splitting hopper so as to reduce liquid disturbance in the phase-splitting tank and further facilitate oil-water layering.
In the dehydration reaction of the step (2), namely, the process of dehydrating the alpha, alpha-dimethylbenzyl alcohol to form the alpha-methylstyrene, in order to reduce energy consumption in the dehydration reaction, the weight ratio of the unreacted alpha, alpha-dimethylbenzyl alcohol is preferably 3.3-28 wt% based on the total weight of the mixed liquor I-2. The temperature of the dehydration reaction is 170-320 ℃, the pressure of the dehydration reaction is 0-1.0 MPa, the reaction condition is mild, the conversion rate is high, and the unreacted alpha isIf the ratio of α -dimethylbenzyl alcohol is outside this range, higher temperatures and/or higher pressures may be required to achieve high conversion. The higher temperature and pressure can make the alpha, alpha-dimethylbenzyl alcohol more dehydrated to produce alpha-methylstyrene, but also the increased risk of side reactions such as polymerization of the alpha-methylstyrene and the like are accompanied by higher energy consumption, so that when the weight ratio of unreacted alpha, alpha-dimethylbenzyl alcohol is 3.3 to 28wt%, the dehydration temperature is more preferably 170 to 240 ℃ and the pressure is more preferably 0 to 0.6MPa. Preferably, the volume space velocity of the mixed solution I-2 is 1 to 10 hours -1 Preferably 3 to 8 hours -1 The mixed solution I-2 has proper residence time in the dehydration reactor, is favorable for the alpha-methyl styrene generated by the reaction to enter the subsequent process quickly on the premise of sufficient reaction, and avoids the polymerization reaction of the alpha-methyl styrene in the dehydration reactor and the deactivation of the catalyst.
The step (2) of the present invention may be performed using a dehydration catalyst conventional in the art, and may be selected from at least one of a solid acid catalyst such as alumina, titania, zirconia, silica, zeolite, a cation exchange resin, and an aluminum magnesium silicate molecular sieve, and more preferably, activated alumina, which has a low acid amount, a large pore diameter, and abundant mesopores, so as to avoid polymerization of α -methylstyrene due to an excessive amount of catalyst acid.
The mixture II-1 obtained after the dehydration reaction in the step (2) generally contains cumene, alpha-methylstyrene, water-soluble impurities, unreacted alpha, alpha-dimethylbenzyl alcohol, other hydrocarbons from the raw materials, a small amount of polymerization side reaction impurities and the like, and the water-soluble impurities in the mixture II-1 are separated to obtain a mixed solution II-2, so that the mixed solution II-2 contains the heavy component impurities such as unreacted alpha, alpha-dimethylbenzyl alcohol, other hydrocarbons from the raw materials, a small amount of polymerization side reaction impurities and the like in addition to the cumene and the alpha-methylstyrene. The method for separating water and water-soluble impurities in step (2) may be the same as that in step (1), or other conventional techniques in the art may be employed.
According to the invention, the separation of water and water-soluble impurities in the step (1) and the step (2) can improve the conversion efficiency of the reaction, and can avoid the reduction of the activity of the catalyst caused by the fact that water circulates back to the hydrogenolysis reactor along with the mixed flow.
The step (3) of the invention is a process of extracting and separating the isopropylbenzene and the alpha-methylstyrene in the mixed solution II-2, and the step of separating the isopropylbenzene and the alpha-methylstyrene is arranged after the hydrogenolysis reaction and the dehydration reaction, thereby being beneficial to obtaining the high-purity isopropylbenzene and the high-purity alpha-methylstyrene and simultaneously being beneficial to heat integration in the technical process. The separation in step (3) according to the invention is preferably carried out in a rectification column. The type of rectifying column may be of conventional specifications in the art, such as tray columns or packed columns, which are used primarily for separation purposes and may be any packing known in the art, such as wire mesh packing, structured packing, random packing, etc. The required condition parameters for rectification are conventional in the art, for example, the temperature of a tower kettle can be 150-170 ℃, and the pressure in the tower is more than 0MPa and less than 0.1MPa. Through rectification separation, the gas phase component cumene in the mixed liquor II-2 is discharged from the top of the rectification tower, the heavy components in the mixed liquor II-2, such as phenol, acetophenone, alpha-dimethylbenzyl alcohol, polymerization side reaction impurities and the like, are discharged from the bottom of the rectification tower, and the alpha-methylstyrene is discharged from a side collecting port of the rectification tower.
The invention further provides a device which can be used in the co-production method of the invention, and comprises a hydrogenolysis reactor A, a dehydration reactor B and a separation tower C, wherein the hydrogenolysis reactor A is positioned in front of the dehydration reactor B, a first phase separation tank is arranged between the hydrogenolysis reactor A and the dehydration reactor B, so that materials are subjected to hydrogenolysis reaction and phase separation and then subjected to dehydration reaction, the dehydration reactor B is positioned in front of the separation tower C, and a second phase separation tank is arranged between the dehydration reactor B and the separation tower C, so that materials are subjected to dehydration reaction and phase separation and then separated.
The type of reactor used in the present invention is conventional in the art, and a fixed bed reactor is preferably used. The present invention is not particularly limited to the feeding position of the raw material and the discharging position of the reaction product, as long as the functions of each unit and the continuity of the material transportation can be realized, for example, the gas-liquid two phases can flow downward in parallel, the gas-liquid two phases can flow upward in parallel, or the liquid phase enters from the upper part and flows downward, and the gas phase enters from the lower part and flows upward.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a simple, efficient and flexible production process, which adopts a mode of hydrogenolysis and dehydration, can realize the efficient conversion and utilization of alpha, alpha-dimethylbenzyl alcohol under the condition of a conventional catalyst, can obtain cumene and simultaneously can highly selectively co-produce alpha-methylstyrene, has the characteristics of simplicity, high efficiency and flexibility, and can flexibly adjust the output proportion of a target product according to market demands. Meanwhile, the invention adds the steps of separating water and water-soluble impurities in the follow-up of hydrogenolysis reaction and the follow-up of dehydration reaction respectively, thereby reducing the negative influence of water and water-soluble impurities on the follow-up procedure and ensuring the continuous and stable operation of the co-production process.
(1) The method has the advantages that the production process is simple, the conditions are mild, the raw materials and products do not need to be specially treated, other auxiliary agents do not need to be introduced, the efficient conversion and utilization of DMBA can be realized by using a conventional catalyst, the amount of new impurities such as over-hydrogenation, polymers and the like generated in the reaction process is small, and the cumene and the alpha-methylstyrene with high purity can be obtained;
(2) The preparation method can co-produce the isopropylbenzene and the alpha-methylstyrene, regulate and control the output proportion of the isopropylbenzene and the alpha-methylstyrene according to the supply and demand conditions of the product market, improve the added value of the product of the device and improve the process economy.
Drawings
FIG. 1 is a schematic diagram of a production plant employed in the co-production process of the present invention;
wherein A is a hydrogenolysis reactor, B is a dehydration reactor, C is a separation tower, E1 is a first phase separation tank, E2 is a second phase separation tank, 11 is a raw material inlet pipeline, 12 is a gas phase inlet pipeline, 13 is a mixture I-1 extraction pipeline, 14 is a water phase extraction pipeline, 15 is a gas phase extraction pipeline, 21 is a mixed liquid I-2 pipeline, 22 is a mixture II-1 pipeline, 23 is a water phase extraction pipeline, 31 is a mixed liquid II-2 pipeline, 32 is a gas phase component extraction pipeline, 33 is a heavy component extraction pipeline, and 34 is a side extraction pipeline.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples.
The raw materials used in the invention are all conventional materials and are all commercially available, wherein Pd/C catalyst is purchased from new materials of Siam Kaili, pd/alumina catalyst is purchased from Kaida chemical industry of Shaanxi, ni/alumina catalyst is purchased from Xinyu Hongzhou of Hubei, and active alumina is purchased from Basff.
In analysis of the process efficiency, the total conversion (%) of α, α -dimethylbenzyl alcohol= [ total weight of α, α -dimethylbenzyl alcohol consumed/weight of α, α -dimethylbenzyl alcohol in the feedstock ] ×100%, the total selectivity (%) of cumene= [ total weight of cumene produced/total weight of α, α -dimethylbenzyl alcohol consumed ] ×100%.
Example 1
As shown in figure 1, the production device adopted by the co-production method comprises a hydrogenolysis reactor A, a first phase separation tank E1, a pump, a dehydration reactor B, a second phase separation tank E2, a pump and a separation tower C which are connected in sequence, wherein the hydrogenolysis reactor is a fixed bed reactor filled with hydrogenolysis catalyst, the dehydration reactor is a fixed bed reactor filled with dehydration catalyst, the separation tower is a rectifying tower filled with structured packing, the first phase separation tank and the second phase separation tank are all horizontal tanks, and a water dividing hopper is connected to the bottom of the phase separation tank. The bottom of the hydrogenolysis reactor is provided with a material inlet which is connected with a raw material inlet pipeline 11 and a gas phase inlet pipeline 12, the top of the hydrogenolysis reactor is provided with a material outlet which is connected with a first phase-splitting tank E1 through a mixture I-1 extraction pipeline 13, the first phase-splitting tank E1 is provided with a water phase extraction pipeline 14, a gas phase extraction pipeline 15 and a mixed liquid I-2 pipeline 21, the other end of the mixed liquid I-2 pipeline 21 is connected with a pump, the other end of the pump is connected with the material inlet of the dehydration reactor B, the material outlet of the dehydration reactor B is connected with a second phase-splitting tank E2 through a mixture II-1 pipeline 22, the second phase-splitting tank E2 is provided with a water phase extraction pipeline 23 and a mixed liquid II-2 pipeline 31, the other end of the mixed liquid II-2 pipeline 31 is connected with a pump, the other end of the pump is connected with the material inlet of the separation tower C, the top of the separation tower C is provided with a gas phase component extraction pipeline 32, the bottom is provided with a heavy component extraction pipeline 33, and the side surface is provided with a side extraction pipeline 34.
When the hydrogenolysis device is used, cumene solution containing alpha, alpha-dimethylbenzyl alcohol enters a hydrogenolysis reactor A through a raw material inlet pipeline 11, meanwhile, hydrogen enters a hydrogenolysis reactor A through a gas phase inlet pipeline 12 to carry out hydrogenolysis reaction, a mixture I-1 is obtained after the reaction is finished, the mixture I-1 enters a first phase separation tank E1 through a mixture I-1 collecting pipeline 13, unreacted hydrogen in the mixture I-1 is collected from a gas phase collecting pipeline 15, water and water-soluble impurities are collected from a water phase collecting pipeline 14, a mixed liquid I-2 is collected from a mixed liquid I-2 pipeline 21 and pumped into a dehydration reactor B through a pump, after the dehydration reaction is finished, the mixture II-1 enters a second phase separation tank E2 through a mixture II-1 pipeline 22, water and water-soluble impurities are collected from the water phase collecting pipeline 23, the mixed liquid II-2 is collected from the mixed liquid II-2 pipeline 31 and pumped into a separation tower through a pump, after rectification separation, cumene is collected from a gas phase component collecting pipeline 32, unreacted alpha-dimethylbenzyl alcohol, alpha-dimethyl alcohol, alpha-hydrocarbon and other impurities from a small amount of methyl hydrocarbon and the like from a benzene side are collected from a gas phase component collecting pipeline 34, and a small amount of heavy impurities from a methyl hydrocarbon and the like.
Example 2
The column bottom material V-1 obtained after the rectification and separation of the CHPPO method epoxidation reaction product is used as the raw material, the column bottom material V-1 contains 30 weight percent of alpha, alpha-dimethylbenzyl alcohol, 68.7 weight percent of isopropylbenzene and 1.30 weight percent of other hydrocarbons (including acetophenone, alpha-methylstyrene, phenol and the like), and the temperature of the column bottom material V-1 is 180 ℃.
The preparation and results were as follows, using the apparatus shown in example 1:
hydrogenolysis reaction process: the tower kettle material V-1 is introduced into a hydrogenolysis reactor after heat exchange, and is contacted with hydrogen under the action of Pd/C catalyst with Pd content of 0.5 wt%. The hydrogenolysis reaction temperature is 200 ℃, the pressure is 1.4MPa, and the molar ratio of hydrogen to alpha, alpha-dimethylbenzyl alcohol is 10:1, the volume space velocity of the tower kettle material V-1 is 8h -1 After the reaction, a mixture I-1 was obtained, which did not contain isopropyl cyclohexane, cyclohexanol, cyclohexanone, and the conversion of DMBA in the hydrogenolysis reaction was 89%, and the cumene selectivity was 99.85%. Introducing the mixture I-1 into a phase separation tank, and separating unreacted hydrogen, water and water-soluble substances to obtain a mixed solution I-2, wherein the mixed solution I-2 contains 95.36wt% of isopropylbenzene, 3.3wt% of unreacted DMBA and 1.34wt% of other hydrocarbons based on the total weight of the mixed solution I-2.
Dehydration reaction process: the mixed solution I-2 is sent into a dehydration reaction unit to react in the presence of an active alumina catalyst, the dehydration reaction temperature is 170 ℃, the pressure is 0.1MPa, and the volume space velocity is 8h -1 After the reaction, a mixture II-1 was obtained, the conversion of DMBA during dehydration was 98.1%, and the selectivity of AMS was 99.97%. The mixture II-1 is completely introduced into a phase separation tank, and water-soluble substances are separated to obtain a mixed solution II-2 which does not contain 2, 3-dimethyl-2, 3-diphenyl butane.
The mixed solution II-2 was fed into a rectifying column, and cumene with a purity of 99.99% and AMS with a purity of 99.97% were separated, and isopropyl cyclohexane, cyclohexanol, cyclohexanone and 2, 3-dimethyl-2, 3-diphenylbutane were not contained.
Example 3
The column bottom material V-2 obtained after the rectification and separation of the product of the epoxidation reaction by the CHPPO method is used as the raw material of the invention, the column bottom material V-2 contains 50 weight percent of alpha, alpha-dimethylbenzyl alcohol, 49.2 weight percent of isopropylbenzene and 0.8 weight percent of other hydrocarbons (including acetophenone, alpha-methylstyrene, phenol and the like), and the temperature of the column bottom material V-2 is 140 ℃.
The preparation and results were as follows, using the apparatus shown in example 1:
hydrogenolysis reaction process: the column bottoms V-2 was directly fed to the hydrogenolysis reactor and contacted with hydrogen under the influence of a Pd/C catalyst having a Pd content of 0.3 wt%. The hydrogenolysis reaction temperature is 140 ℃, the pressure is 0.05MPa, and the molar ratio of hydrogen to alpha, alpha-dimethylbenzyl alcohol is 6:1, the volume space velocity of the tower kettle material V-2 is 15h -1 Obtaining a mixture I after the reaction1, wherein the catalyst does not contain isopropyl cyclohexane, cyclohexanol and cyclohexanone, the conversion rate of DMBA in the hydrogenolysis reaction is 80%, and the selectivity of cumene is 99.95%. Introducing the mixture I-1 into a phase separation tank, and separating unreacted hydrogen, water and water-soluble substances to obtain a mixed solution I-2, wherein the mixed solution I-2 contains 89.18wt% of isopropylbenzene, 10.0wt% of unreacted DMBA and 0.82wt% of other hydrocarbons based on the total weight of the mixed solution I-2.
Dehydration reaction process: the mixed solution I-2 is sent into a dehydration reaction unit to react in the presence of an active alumina catalyst, the dehydration reaction temperature is 190 ℃, the pressure is 0.6MPa, and the volume space velocity is 10h -1 After the reaction, a mixture II-1 was obtained, the conversion of DMBA during dehydration was 98.5%, and the selectivity of AMS was 99.95%. The mixture II-1 is completely introduced into a phase separation tank, and water-soluble substances are separated to obtain a mixed solution II-2 which does not contain 2, 3-dimethyl-2, 3-diphenyl butane.
The mixed solution II-2 was fed into a rectifying column, and cumene with a purity of 99.98% and AMS with a purity of 99.96% were separated, and isopropyl cyclohexane, cyclohexanol, cyclohexanone and 2, 3-dimethyl-2, 3-diphenylbutane were not contained.
Example 4
The tower material V-3 obtained after the rectification and separation of the product of the epoxidation reaction by the CHPPO method is used as the raw material of the invention, the tower material V-3 contains 60 weight percent of alpha, alpha-dimethylbenzyl alcohol, 38.5 weight percent of isopropylbenzene and 1.5 weight percent of other hydrocarbons (including acetophenone, alpha-methylstyrene, phenol and the like), and the temperature of the tower material V-3 is 120 ℃.
The preparation and results were as follows, using the apparatus shown in example 1:
hydrogenolysis reaction process: the tower kettle material V-3 is introduced into a hydrogenolysis reactor after heat exchange, and is contacted with hydrogen under the action of Pd/alumina catalyst with Pd content of 0.5 wt%. The hydrogenolysis reaction temperature is 80 ℃, the pressure is 0.6MPa, and the molar ratio of hydrogen to alpha, alpha-dimethylbenzyl alcohol is 0.8:1, the volume space velocity of the tower kettle material V-3 is 3h -1 After the reaction, a mixture I-1 is obtained, which does not contain isopropyl cyclohexane, cyclohexanol and cyclohexanone and is subjected to hydrogenolysisThe conversion of DMBA in the reaction was 75%, and the cumene selectivity was 99.81%. The mixture I-1 is completely introduced into a phase separation tank, unreacted hydrogen, water and water-soluble substances are separated to obtain a mixed solution I-2, wherein the mixed solution I-2 contains 83.41 weight percent of isopropylbenzene, 15.0 weight percent of unreacted DMBA and 1.59 weight percent of other hydrocarbons based on the total weight of the mixed solution I-2.
Dehydration reaction process: the mixed solution I-2 is sent into a dehydration reaction unit to react in the presence of an active alumina catalyst, the dehydration reaction temperature is 200 ℃, the pressure is 0MPa, and the volume space velocity is 3h -1 After the reaction, a mixture II-1 was obtained, the conversion of DMBA during dehydration was 99%, and the selectivity of AMS was 99.91%. The mixture II-1 was introduced into a phase-separating tank in its entirety, and water-soluble substances were separated to obtain a mixed solution II-2 in which the content of 2, 3-dimethyl-2, 3-diphenylbutane was 7ppm.
The mixed solution II-2 was fed into a rectifying column, and cumene with a purity of 99.97% and AMS with a purity of 99.95% were separated, and isopropyl cyclohexane, cyclohexanol, cyclohexanone and 2, 3-dimethyl-2, 3-diphenylbutane were not contained.
Example 5
The column bottom material V-4 obtained after the rectification and separation of the product of the epoxidation reaction by the CHPPO method is used as the raw material of the invention, the column bottom material V-4 contains 70 weight percent of alpha, alpha-dimethylbenzyl alcohol, 29.8 weight percent of isopropylbenzene and 0.2 weight percent of other hydrocarbons (including acetophenone, alpha-methylstyrene, phenol and the like), and the temperature of the column bottom material V-4 is 150 ℃.
The preparation and results were as follows, using the apparatus shown in example 1:
hydrogenolysis reaction process: the column bottoms V-4 was directly fed to the hydrogenolysis reactor and contacted with hydrogen under the influence of a Ni/alumina catalyst having a Ni content of 10 wt%. The hydrogenolysis reaction temperature is 150 ℃, the pressure is 1.2MPa, and the molar ratio of hydrogen to alpha, alpha-dimethylbenzyl alcohol is 8:1, the volume space velocity of the tower kettle material V-4 is 1h -1 After the reaction, a mixture I-1 was obtained, which did not contain isopropyl cyclohexane, cyclohexanol, and cyclohexanone, and the conversion of DMBA in the hydrogenolysis reaction was 60%, and the selectivity for cumene was 99.87%. Mixing the mixture I1 are all introduced into a phase separation tank, and unreacted hydrogen, water and water-soluble substances are separated to obtain a mixed solution I-2, wherein the mixed solution I-2 contains 71.75wt% of isopropylbenzene, 28wt% of unreacted DMBA and 0.25wt% of other hydrocarbons based on the total weight of the mixed solution I-2.
Dehydration reaction process: the mixed solution I-2 is sent into a dehydration reaction unit to react in the presence of zeolite, the dehydration reaction temperature is 180 ℃, the pressure is 0.4MPa, and the volume space velocity is 1h -1 After the reaction, a mixture II-1 was obtained, the conversion of DMBA during dehydration was 97.6%, and the selectivity of AMS was 99.79%. The mixture II-1 was introduced into a phase-separating tank in its entirety, and water-soluble substances were separated to obtain a mixed solution II-2 in which the content of 2, 3-dimethyl-2, 3-diphenylbutane was 56ppm.
The mixture II-2 was fed into a rectifying column, and cumene with a purity of 99.91% and AMS with a purity of 99.93% were separated, and isopropyl cyclohexane, cyclohexanol, cyclohexanone and 2, 3-dimethyl-2, 3-diphenylbutane were not contained.
Example 6
The column bottom material V-5 obtained after the rectification and separation of the product of the epoxidation reaction by the CHPPO method is used as the raw material, the column bottom material V-5 contains 40 weight percent of alpha, alpha-dimethylbenzyl alcohol, 59 weight percent of isopropylbenzene and 1.0 weight percent of other hydrocarbons (including acetophenone, alpha-methylstyrene, phenol and the like), and the temperature of the column bottom material V-5 is 120 ℃.
The preparation and results were as follows, using the apparatus shown in example 1:
hydrogenolysis reaction process: and (3) introducing the tower kettle material V-5 into a hydrogenolysis reactor after heat exchange, and contacting with hydrogen under the action of a Pd/C catalyst with the Pd content of 0.1 wt%. The hydrogenolysis reaction temperature is 60 ℃, the pressure is 1.0MPa, and the molar ratio of hydrogen to alpha, alpha-dimethylbenzyl alcohol is 2:1, the volume space velocity of the tower kettle material V-4 is 9h -1 After the reaction, a mixture I-1 was obtained, which did not contain isopropyl cyclohexane, cyclohexanol, and cyclohexanone, and the conversion of DMBA in the hydrogenolysis reaction was 65%, and the selectivity to cumene was 99.89%. Introducing the mixture I-1 into a phase-splitting tank, separating unreacted hydrogen, water and water-soluble substances to obtain a mixed solution I-2,wherein, based on the total weight of the mixed solution I-2, the mixed solution I-2 contains 84.97wt% of isopropylbenzene, 14.0wt% of unreacted DMBA and 1.03wt% of other hydrocarbons.
Dehydration reaction process: the mixed solution I-2 is sent into a dehydration reaction unit to react in the presence of an active alumina catalyst, the dehydration reaction temperature is 240 ℃, the pressure is 0.5MPa, and the volume space velocity is 9h -1 After the reaction, a mixture II-1 was obtained, the conversion of DMBA during dehydration was 99.5%, and the selectivity of AMS was 99.85%. The mixture II-1 was introduced into a phase-separating tank in its entirety, and water-soluble substances were separated to obtain a mixed solution II-2 in which the content of 2, 3-dimethyl-2, 3-diphenylbutane was 15ppm.
The mixed solution II-2 was fed into a rectifying column, and cumene with a purity of 99.96% and AMS with a purity of 99.94% were separated, and isopropyl cyclohexane, cyclohexanol, cyclohexanone and 2, 3-dimethyl-2, 3-diphenylbutane were not contained.
Example 7
The column bottom material V-6 obtained after the rectification and separation of the CHPPO method epoxidation reaction product is used as the raw material, the column bottom material V-6 contains 35 weight percent of alpha, alpha-dimethylbenzyl alcohol, 64.9 weight percent of isopropylbenzene and 0.1 weight percent of other hydrocarbons (including acetophenone, alpha-methylstyrene, phenol and the like), and the temperature of the column bottom material V-6 is 120 ℃.
The preparation and results were as follows, using the apparatus shown in example 1:
hydrogenolysis reaction process: the column bottoms V-6 was directly fed to the hydrogenolysis reactor and contacted with hydrogen under the influence of a Pd/alumina catalyst having a Pd content of 0.1 wt%. The hydrogenolysis reaction temperature is 120 ℃, the pressure is 0.8MPa, and the molar ratio of hydrogen to alpha, alpha-dimethylbenzyl alcohol is 5:1, the volume space velocity of the tower kettle material V-6 is 4h -1 After the reaction, a mixture I-1 was obtained, which did not contain isopropyl cyclohexane, cyclohexanol, cyclohexanone, and the conversion of DMBA in the hydrogenolysis reaction was 70%, and the selectivity to cumene was 99.91%. Introducing the mixture I-1 into a phase-splitting tank, and separating unreacted hydrogen, water and water-soluble substances to obtain a mixed solution I-2, wherein the mixed solution I-2 contains 89.3 based on the total weight of the mixed solution I-28wt% cumene, 10.5wt% unreacted DMBA,0.12wt% other hydrocarbons.
Dehydration reaction process: the mixed solution I-2 is sent into a dehydration reaction unit to react in the presence of zirconia, the dehydration reaction temperature is 320 ℃, the pressure is 1.0MPa, and the volume space velocity is 4h -1 After the reaction, a mixture II-1 was obtained, the conversion of DMBA during dehydration was 99.9%, and the selectivity of AMS was 99.5%. The mixture II-1 was introduced into a phase-separating tank in its entirety, and water-soluble substances were separated to obtain a mixed solution II-2 in which the content of 2, 3-dimethyl-2, 3-diphenylbutane was 74ppm.
The mixture II-2 was fed into a rectifying column, and cumene with a purity of 99.92% and AMS with a purity of 99.91% were separated, and isopropyl cyclohexane, cyclohexanol, cyclohexanone and 2, 3-dimethyl-2, 3-diphenylbutane were not contained.
Example 8
The tower material V-7 obtained after the rectification and separation of the product of the epoxidation reaction by the CHPPO method is used as the raw material of the invention, the tower material V-7 contains 55 weight percent of alpha, alpha-dimethylbenzyl alcohol, 44.5 weight percent of isopropylbenzene and 0.5 weight percent of other hydrocarbons (including acetophenone, alpha-methylstyrene, phenol and the like), and the temperature of the tower material V-7 is 120 ℃.
The preparation and results were as follows, using the apparatus shown in example 1:
hydrogenolysis reaction process: the column bottoms V-7 was directly fed to the hydrogenolysis reactor and contacted with hydrogen under the influence of a Ni/alumina catalyst having a Ni content of 60wt%. The hydrogenolysis reaction temperature is 110 ℃, the pressure is 0.2MPa, and the molar ratio of hydrogen to alpha, alpha-dimethylbenzyl alcohol is 15:1, the volume space velocity of the tower kettle material V-6 is 5h -1 After the reaction, a mixture I-1 was obtained, which did not contain isopropyl cyclohexane, cyclohexanol, cyclohexanone, and the conversion of DMBA in the hydrogenolysis reaction was 70%, and the selectivity to cumene was 99.94%. The mixture I-1 is completely introduced into a phase separation tank, unreacted hydrogen, water and water-soluble substances are separated to obtain a mixed solution I-2, wherein the mixed solution I-2 contains 82.98 weight percent of isopropylbenzene, 16.5 weight percent of unreacted DMBA and 0.52 weight percent of other hydrocarbons based on the total weight of the mixed solution I-2.
Dehydration reaction process: the mixed solution I-2 is sent into a dehydration reaction unit to react in the presence of a titanium dioxide catalyst, the dehydration reaction temperature is 280 ℃, the pressure is 0.8MPa, and the volume space velocity is 5h -1 After the reaction, a mixture II-1 was obtained, the conversion of DMBA during dehydration was 99.4%, and the selectivity of AMS was 99.6%. The mixture II-1 was introduced into a phase-separating tank in its entirety, and water-soluble substances were separated to obtain a mixed solution II-2 in which the content of 2, 3-dimethyl-2, 3-diphenylbutane was 75ppm.
The mixture II-2 was fed into a rectifying column, and cumene with a purity of 99.91% and AMS with a purity of 99.93% were separated, and isopropyl cyclohexane, cyclohexanol, cyclohexanone and 2, 3-dimethyl-2, 3-diphenylbutane were not contained.
Comparative example 1
The column bottom material V-1 obtained after the rectification and separation of the product of the epoxidation reaction by the CHPPO method is used as the raw material for the hydrogenolysis reaction, the column bottom material V-1 contains 30 weight percent of alpha, alpha-dimethylbenzyl alcohol, 68.7 weight percent of isopropylbenzene and 1.30 weight percent of other hydrocarbons (including acetophenone, alpha-methylstyrene, phenol and the like), and the temperature of the column bottom material V-1 is 180 ℃.
The preparation and results were as follows, using the apparatus shown in example 1:
hydrogenolysis reaction process: the tower kettle material V-1 is introduced into a hydrogenolysis reactor after heat exchange, and is contacted with hydrogen under the action of Pd/C catalyst with Pd content of 0.5 wt%. The hydrogenolysis reaction temperature is 230 ℃, the pressure is 2MPa, and the molar ratio of hydrogen to alpha, alpha-dimethylbenzyl alcohol is 10:1, the volume space velocity of the tower kettle material V-1 is 3h -1 After the reaction was completed, a mixture I-1 was obtained in which the total content of isopropyl cyclohexane, cyclohexyl alcohol and cyclohexanone was 1037ppm, the conversion of DMBA in the hydrogenolysis reaction was 95.7%, and the selectivity to cumene was 97.8%. The mixture I-1 is completely introduced into a phase separation tank, unreacted hydrogen, water and water-soluble substances are separated to obtain a mixed solution I-2, wherein the mixed solution I-2 contains 96.78wt% of isopropylbenzene, 1.29wt% of unreacted DMBA and 1.93wt% of other hydrocarbons based on the total weight of the mixed solution I-2.
Dehydration reaction process: feeding the mixed solution I-2The mixture is put into a dehydration reaction unit to react in the presence of an active alumina catalyst, the dehydration reaction temperature is 350 ℃, the pressure is 1.5MPa, and the volume space velocity is 8h -1 After the reaction, a mixture II-1 was obtained, the conversion of DMBA during dehydration was 99.9%, and the selectivity of AMS was 97.6%. The mixture II-1 was introduced into a phase-separating tank in its entirety, and water-soluble substances were separated to obtain a mixed solution II-2 having a 2, 3-dimethyl-2, 3-diphenylbutane content of 1317ppm.
The mixed solution II-2 was fed into a rectifying column, and cumene with a purity of 99.83% and AMS with a purity of 99.76% were separated, wherein the total content of isopropyl cyclohexane, cyclohexyl alcohol and cyclohexanone in cumene was 1094ppm.
Comparative example 2
The tower kettle material V-4 obtained after the rectification and separation of the epoxidation reaction product by the CHPPO method is used as the hydrogenolysis reaction raw material, the tower kettle material V-4 contains 70 weight percent of alpha, alpha-dimethylbenzyl alcohol, 29.8 weight percent of isopropylbenzene and 0.2 weight percent of other hydrocarbons (including acetophenone, alpha-methylstyrene, phenol and the like), and the temperature of the tower kettle material V-4 is 150 ℃.
The preparation and results were as follows, using the apparatus shown in example 1:
hydrogenolysis reaction process: and (3) introducing the tower kettle material V-4 into a hydrogenolysis reactor after heat exchange, and contacting with hydrogen under the action of a Pd/C catalyst with the Pd content of 0.05 wt%. The hydrogenolysis reaction temperature is 50 ℃, the pressure is 0.3MPa, and the molar ratio of hydrogen to alpha, alpha-dimethylbenzyl alcohol is 5:1, the volume space velocity of the tower kettle material V-4 is 9h -1 After the reaction was completed, a mixture I-1 was obtained in which the total content of isopropyl cyclohexane, cyclohexyl alcohol and cyclohexanone was 83ppm, the conversion of DMBA in the hydrogenolysis reaction was 51%, and the selectivity to cumene was 99.87%. The mixture I-1 is completely introduced into a phase separation tank, unreacted hydrogen, water and water-soluble substances are separated to obtain a mixed solution I-2, wherein the mixed solution I-2 contains 65.45wt% of isopropylbenzene, 34.3wt% of unreacted DMBA and 0.25wt% of other hydrocarbons based on the total weight of the mixed solution I-2.
Dehydration reaction process: feeding the mixed solution I-2 into a dehydration reaction unit to react in the presence of activated aluminaThe dehydration reaction temperature is 320 ℃, the pressure is 1MPa, and the volume space velocity is 4h -1 After the reaction, a mixture II-1 was obtained, the conversion of DMBA during dehydration was 98.1%, and the selectivity of AMS was 99.1%. The mixture II-1 was introduced into a phase-separating tank in its entirety, and water-soluble substances were separated to obtain a mixed solution II-2 in which the content of 2, 3-dimethyl-2, 3-diphenylbutane was 98ppm.
The mixed solution II-2 was fed into a rectifying column, and cumene with a purity of 99.88% and AMS with a purity of 99.82% were separated, wherein the total content of isopropyl cyclohexane, cyclohexyl alcohol and cyclohexanone in cumene was 101ppm.
In summary, comparative example 1 uses higher temperature and pressure to carry out the hydrogenolysis reaction, and the result shows that although the conversion rate of DMBA is improved, the selectivity of cumene is reduced, meanwhile, the content of unreacted DMBA in the mixed liquor I-2 is lower due to the excessively high conversion rate of the hydrogenolysis reaction, so that the local concentration of cumene is lower, the risk of over-hydrogenation is increased, and finally, the over-hydrogenation byproduct is generated. In addition, higher temperatures and pressures are used during the dehydration reaction, which results in higher DMBA conversion, but lower AMS selectivity and higher polymerization byproducts, higher production of new impurities during the preparation, and ultimately lower product purity.
Comparative example 2 employs a lower Pd content hydrogenolysis catalyst and uses a lower hydrogenolysis temperature and pressure, resulting in too low a DMBA conversion, the unreacted DMBA in the mixed liquor I-2 being over 28wt% and under this condition, the DMBA conversion is only 98.1% even if dehydration reaction conditions of 320℃and 1MPa are used, and it is seen that when the unreacted DMBA in the mixed liquor I-2 is higher in its content, a higher temperature and pressure need to be matched to increase the conversion, and thus the energy consumption is higher. Meanwhile, the selectivity of the isopropylbenzene and the AMS is slightly reduced, so that over-hydrogenation and polymerization impurities are generated, and finally, the purity of the product is reduced.
By adopting the technical scheme for coproducing the isopropylbenzene and the alpha-methylstyrene, the yield of the alpha-methylstyrene can be flexibly adjusted, the efficient conversion of the DMBA can be realized under the conditions of lower reaction temperature, reaction pressure and the like, in addition, the raw materials and the products do not need to be specially treated in the reaction, other auxiliary agents do not need to be introduced, the operation is simple, the reaction is stable, the energy consumption is lower, and the impurity amount generated in the whole preparation process is less.
The present invention was also evaluated for the effect after 500 hours of continuous operation, and the results are shown in table 1, wherein comparative example 3 differs from example 3 in that the first phase separation tank and the second phase separation tank were not used.
Table 1 evaluation results after 500 hours of continuous operation
Thus, when the split-phase tank is not arranged between the hydrogenolysis reactor and the dehydration reactor for dehydration, water enters the dehydration reactor to cause negative influence on the dehydration catalyst, the conversion rate of DMBA in the dehydration reaction is reduced after continuous operation for 500 hours, and the selectivity of AMS is reduced.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (8)
1. The co-production method of the isopropylbenzene and the alpha-methylstyrene is characterized by comprising the following sequential steps:
(1) Hydrogenolysis reaction is carried out on the isopropylbenzene solution containing the alpha, alpha-dimethylbenzyl alcohol and hydrogen to obtain a mixture I-1, unreacted hydrogen, water and water-soluble impurities in the mixture I-1 are separated to obtain a mixed solution I-2 containing the isopropylbenzene and the unreacted alpha, alpha-dimethylbenzyl alcohol;
(2) Carrying out dehydration reaction on the mixed solution I-2 to obtain a mixture II-1, and separating water and water-soluble impurities in the mixture II-1 to obtain a mixed solution II-2 containing isopropylbenzene and alpha-methylstyrene;
(3) The cumene and alpha-methylstyrene in the mixture II-2 are separated.
2. The co-production process according to claim 1, characterized in that in step (1) the temperature of the hydrogenolysis reaction is 60-200 ℃, preferably 80-140 ℃; the pressure is 0.05 to 1.4MPa, preferably 0.2 to 1.0MPa.
3. The co-production method according to claim 1, wherein in the step (1), the catalyst of the hydrogenolysis reaction is a supported hydrogenolysis catalyst, the active component of the supported hydrogenolysis catalyst is one or more of Pd, pt, co, cu, zn or Ni, and the carrier of the supported hydrogenolysis catalyst is one or more of silica, alumina and activated carbon; the hydrogenolysis catalyst is preferably at least one of Pd/C, pd/alumina and Ni/alumina catalyst. Wherein, based on the total weight of the hydrogenolysis catalyst, the weight ratio of Pd element is 0.1 to 0.5 weight percent, and the weight ratio of Ni element is 10 to 60 weight percent.
4. The co-production method according to claim 1, wherein in the step (1), the volume space velocity of the cumene solution containing α, α -dimethylbenzyl alcohol is 1 to 15 hours -1 The molar ratio of the hydrogen to the alpha, alpha-dimethylbenzyl alcohol is (0.8-15): 1, preferably (2 to 10): 1.
5. the co-production process according to claim 1, characterized in that the temperature of the dehydration reaction is 170-320 ℃, preferably 170-240 ℃; the dehydration reaction pressure is 0 to 1.0MPa, preferably 0 to 0.6MPa.
6. The co-production method according to claim 1, wherein the catalyst of the dehydration reaction is a solid acid catalyst.
7. The co-production process according to claim 1, wherein the separation is performed in step (1) and/or step (2) using a split-phase tank.
8. The apparatus for co-production process according to any one of claims 1 to 7, characterized by comprising a hydrogenolysis reactor a, a dehydration reactor B and a separation column C, wherein the hydrogenolysis reactor a is located in the front of the dehydration reactor B, a first phase separation tank is provided between the hydrogenolysis reactor a and the dehydration reactor B to allow the material to undergo the hydrogenolysis reaction and phase separation and then to undergo the dehydration reaction, the dehydration reactor B is located in the front of the separation column C, and a second phase separation tank is provided between the dehydration reactor B and the separation column C to allow the material to undergo the dehydration reaction and phase separation and then to undergo the separation.
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| CN202311273736.1A CN117342909A (en) | 2023-09-28 | 2023-09-28 | Co-production method and device for isopropylbenzene and alpha-methylstyrene |
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| CN202311273736.1A CN117342909A (en) | 2023-09-28 | 2023-09-28 | Co-production method and device for isopropylbenzene and alpha-methylstyrene |
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| CN202311273736.1A Pending CN117342909A (en) | 2023-09-28 | 2023-09-28 | Co-production method and device for isopropylbenzene and alpha-methylstyrene |
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