CN113651664B - Method for conversion of benzyl alcohol - Google Patents
Method for conversion of benzyl alcohol Download PDFInfo
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- CN113651664B CN113651664B CN202010394871.1A CN202010394871A CN113651664B CN 113651664 B CN113651664 B CN 113651664B CN 202010394871 A CN202010394871 A CN 202010394871A CN 113651664 B CN113651664 B CN 113651664B
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- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 title claims description 97
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 title claims description 48
- 235000019445 benzyl alcohol Nutrition 0.000 title claims description 16
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims abstract description 126
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- BDCFWIDZNLCTMF-UHFFFAOYSA-N 2-phenylpropan-2-ol Chemical compound CC(C)(O)C1=CC=CC=C1 BDCFWIDZNLCTMF-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000007327 hydrogenolysis reaction Methods 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000012071 phase Substances 0.000 claims description 82
- 229910052739 hydrogen Inorganic materials 0.000 claims description 42
- 239000001257 hydrogen Substances 0.000 claims description 42
- 239000007791 liquid phase Substances 0.000 claims description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 150000002431 hydrogen Chemical class 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 8
- 238000000066 reactive distillation Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 5
- 230000007717 exclusion Effects 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 38
- 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 19
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 description 19
- 239000007788 liquid Substances 0.000 description 10
- 230000007246 mechanism Effects 0.000 description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 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 3
- OIGWAXDAPKFNCQ-UHFFFAOYSA-N 4-isopropylbenzyl alcohol Chemical compound CC(C)C1=CC=C(CO)C=C1 OIGWAXDAPKFNCQ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- GWESVXSMPKAFAS-UHFFFAOYSA-N Isopropylcyclohexane Chemical compound CC(C)C1CCCCC1 GWESVXSMPKAFAS-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- -1 this step Chemical compound 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
- C07C1/24—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
-
- 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
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
-
- 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
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
- B01D3/322—Reboiler specifications
-
- 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
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
- B01D3/324—Tray constructions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
-
- 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
Landscapes
- 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
The invention relates to a method for converting benzyl alcohol, which mainly solves the problems of low catalyst activity, short service life, more byproducts and poor economy in the prior art. The invention solves the problem well by adopting a countercurrent three-phase process, and can be used in the industrial production of the isopropylbenzene by the hydrogenolysis of the alpha, alpha-dimethylbenzyl alcohol.
Description
Technical Field
The invention relates to a method for converting benzyl alcohol.
Background
Propylene oxide is an important basic organic chemical raw material, and the main production methods at present are a chlorohydrin method and a co-oxidation method, wherein the chlorohydrin method has poor economic benefit caused by environmental pollution and equipment corrosion, and is being eliminated. However, the co-oxidation method of tertiary butanol and ethylbenzene in the co-oxidation method is advanced, but the economic benefit fluctuates due to the fluctuation of the price of the co-production product, and the method has the defect of strong uncertainty for manufacturers. The cumene co-oxidation method is one of main research and development directions because of the advantages of no co-production, environmental friendliness and the like. The conversion of alpha, alpha-dimethylbenzyl alcohol into isopropylbenzene through hydrogenolysis is an important link of the process route, and the improvement of the conversion rate of the alpha, alpha-dimethylbenzyl alcohol and the selectivity of the isopropylbenzene has remarkable effects on enhancing the economy and the competitiveness of the process.
As a method for producing cumene and propylene oxide including this step, patent CN1860087A, CN100376520C reports a method for producing cumene by hydrogenolysis of cumyl alcohol or hydrogenation after dehydration, which includes using a palladium-based catalyst as a catalyst for hydrogenolysis or hydrogenation and using hydrogen having a carbon monoxide concentration of 0.1 to 10% by volume as hydrogen. CN1553886a reports a method for producing cumene, characterized in that a copper-based catalyst precursor containing copper in an oxidized state is reduced with hydrogen in liquid cumene to prepare a copper-based catalyst, and cumyl alcohol is hydrogenated in the presence of the copper-based catalyst. CN1852879a reports a process for producing cumene, which comprises producing cumene from cumyl alcohol and hydrogen with a dehydration catalyst and a hydrogenation catalyst, wherein the dehydration catalyst and the hydrogenation catalyst are alternately packed, thereby forming n layers (n is an integer of 3 or more), or a mixture thereof is packed into a reactor. However, no literature or patent is currently available that relates to a specific route or equipment connection for the hydrogenolysis of α, α -dimethylbenzyl alcohol to cumene.
Patent CN105294382a reports a method for separating and cracking carbon five by catalytic reaction distillation, which is characterized in that the reaction and distillation occur simultaneously, and similarly patent CN105801408A, CN109438179a. Through experiments, the invention discovers that the hydrogenolysis reaction of alpha, alpha-dimethylbenzyl alcohol is carried out in countercurrent three-phase reaction to obtain good conversion rate and selectivity, especially when the reactor exists in the form of a reactive rectifying tower.
Disclosure of Invention
There are two reaction mechanisms for the hydrogenolysis of alpha, alpha-dimethylbenzyl alcohol to cumene: indirect hydrogenolysis mechanisms and direct hydrogenolysis mechanisms.
(1) Indirect hydrogenolysis mechanism
The acid carrier is adopted to load a bifunctional catalyst of hydrogenation metal, and an indirect hydrogenolysis mechanism is adopted as the dominant hydrogenolysis reaction. The alpha, alpha-dimethylbenzyl alcohol firstly undergoes dehydration reaction on the acid center of the catalyst to produce alpha-methylstyrene, and then the alpha-methylstyrene undergoes hydrogenation reaction on the metal center of the catalyst to produce isopropylbenzene, wherein the reaction process is as follows:
(2) Direct hydrogenolysis mechanism
The surface hydrogen adsorbed by the catalyst active component is dissociated to directly "replace" the hydroxyl groups of DMBA to produce cumene and water, a mechanism typically occurring on metal or supported metal catalysts.
Whether an indirect hydrogenolysis mechanism or a direct hydrogenolysis mechanism, the overall alpha, alpha-dimethylbenzyl alcohol hydrogenolysis cumene is exothermic, and the gas and liquid should be separated during the discharge of the reaction in order to reduce the difficulty of the subsequent separation process. The heat released by the reaction can be effectively utilized by the reaction rectification; by continuously removing the product, the conversion and selectivity of the reaction can be increased while a purer product can be obtained.
The invention aims to solve the technical problems of low catalyst activity, short service life, more byproducts and poor economy of the prior art, and provides a novel benzyl alcohol conversion method which has the characteristics of high catalyst activity, low energy consumption and material consumption, high conversion rate of alpha, alpha-dimethyl benzyl alcohol hydrogenolysis reaction and high selectivity of cumene as a product.
In order to solve the technical problems, the invention adopts the following technical scheme: a method for conversion of benzyl alcohol, the method comprising the steps of:
a) Raw materials (1) containing alpha, alpha-dimethylbenzyl alcohol and isopropylbenzene obtained by the reaction of propylene and cumene hydroperoxide enter a 10% -30% position at the upper part of a countercurrent three-phase reactor I for reaction, a liquid phase product (2) mainly containing isopropylbenzene is obtained at the bottom of a tower, and a gas phase product (3) mainly containing hydrogen, isopropylbenzene and water is obtained at the top of the tower;
b) The cumene-containing liquid phase product (2) is divided into two strands by pressurization, wherein the first strand accounting for 0-100% by weight of the liquid phase product (4) is returned to the reaction zone in the step a), and the rest of the second strand of liquid phase product (5) is led to the downstream;
c) The gas phase product (3) mainly containing hydrogen, isopropylbenzene and water is cooled and separated to obtain a gas phase (7) containing hydrogen, an oil phase (9) containing isopropylbenzene and a water phase (8), and the gas phase (7) and fresh supplementary hydrogen (10) enter the 10% -30% of the lower part of the countercurrent three-phase reactor I after being pressurized.
In the above technical scheme, in the preferred technical scheme, the reaction zone in the countercurrent three-phase reactor can be a single-stage reaction zone or a reaction zone formed by connecting a plurality of reaction sections in series.
In the above technical scheme, preferably, in the raw material containing α, α -dimethylbenzyl alcohol and cumene, the content of α, α -dimethylbenzyl alcohol is 5-80% by weight, and the content of cumene is 20-95% by weight.
In the above technical scheme, preferably, the operating pressure of the countercurrent three-phase reactor is 0.5-4.0 MPa in terms of gauge pressure.
In the above technical scheme, preferably, the operation temperature of the countercurrent three-phase reactor is 80-250 ℃.
In the above technical scheme, preferably, the volume space velocity of the hydrocarbon raw material in the reaction zone in the countercurrent three-phase reactor is 0.5-20 hours -1.
In the above technical scheme, preferably, the mass flow of hydrogen in the reaction zone in the countercurrent three-phase reactor accounts for 1.0% -6.0% of the mass flow of the hydrocarbon raw material.
In the above technical scheme, preferably, the first liquid-phase product (4) pressurized by the pump II accounts for 20-80% of the weight of the liquid-phase product (2).
In the above technical scheme, optionally, the countercurrent three-phase reactor oil phase (9) and/or countercurrent three-phase reactor bottom liquid phase product (5) is taken as a product exclusion boundary or taken as a raw material to be taken to a two-stage hydrogenolysis reactor.
In the above technical solution, preferably, the catalyst packed in the countercurrent three-phase reactor is a palladium-based catalyst.
In the above technical solution, preferably, the countercurrent three-phase reactor is a reactive rectifying tower.
In the above technical scheme, preferably, the tower body part of the reactive distillation tower comprises three sections of a rectifying section, a reactive rectifying section and a stripping section from top to bottom in sequence,
Wherein the rectifying section is formed by 12 to 26 layers of tower plates or packing materials with corresponding heights;
the reaction rectifying section is composed of 20 to 40 layers of tower plates or filler with corresponding height;
The stripping section is composed of 15 to 30 layers of tower plates or fillers with corresponding heights.
The gas phase feeding position is the junction of the reactive rectifying section and the stripping section, and the liquid phase feeding position is the junction of the reactive rectifying section and the rectifying section.
In the above technical solution, preferably, the reaction rectifying tower includes a reboiler.
In the above technical scheme, preferably, the reflux ratio of the reactive distillation column is (1-3): 1.
The reflux ratio is the ratio of the volume flow of the material flow returned to the top of the tower to the volume flow of the material flow discharged from the oil phase (9) of the countercurrent three-phase reactor.
In the above technical scheme, preferably, when the reaction rectifying section of the reaction rectifying tower is composed of a tray, the catalyst is filled at the overflow port.
In the above technical scheme, preferably, when the reactive rectifying section of the reactive rectifying tower is composed of a filler, the filler and the catalyst are alternately filled according to the axial position of the tower.
The total conversion of α, α -dimethylbenzyl alcohol is expressed as the percentage of the molar flow of α, α -dimethylbenzyl alcohol in the feed to countercurrent three-phase reactor I, as reduced by the hydrogenolysis reaction, as shown in the following equation:
the total selectivity to cumene is expressed as the percentage of the molar flow of cumene added after passing through countercurrent three-phase reactor I to the molar flow of alpha, alpha-dimethylbenzyl alcohol reduced after the hydrogenolysis reaction, as shown in the following formula:
In the technical scheme of the invention, the hydrogenolysis reaction of the raw material containing the alpha, alpha-dimethylbenzyl alcohol and the isopropylbenzene and the hydrogen is completed in a countercurrent three-phase reaction mode, preferably in a reactive distillation mode, and most of water in the reaction product is discharged from the top of the reactor, so that the reduction of the catalyst activity caused by recycling the liquid-phase product in the tower kettle to the reaction inlet is avoided, and the conversion rate of DMBA is improved.
Drawings
FIG. 1 is a schematic diagram of a countercurrent three-phase reaction process.
FIG. 2 is a schematic diagram of a gas-liquid mixed feed reaction process.
In the countercurrent three-phase reaction process flow shown in the figure 1, a raw material (1) containing alpha, alpha-dimethylbenzyl alcohol and isopropylbenzene obtained by the reaction of propylene and cumene hydroperoxide enters a countercurrent three-phase reactor I for reaction, a liquid phase product (2) mainly containing the isopropylbenzene is obtained at the bottom, and a gas phase product (3) mainly containing hydrogen, the isopropylbenzene and water is obtained at the top; the liquid phase product (2) containing isopropylbenzene is pressurized by a pump II and divided into two streams, wherein the first stream of liquid phase product (4) accounting for 0-100% by weight is returned to a countercurrent three-phase reactor I, and the rest of liquid phase product (5) is led to the downstream; the gas phase product (3) mainly containing hydrogen, cumene and water is cooled to a required temperature through a device III, enters a gas-liquid separator V, separates out a gas phase (7) containing hydrogen, an oil phase (9) containing cumene and a water phase (8), the gas phase (7) and fresh make-up hydrogen (10) enter a circulating hydrogen booster IV for boosting, the oil phase (9) and the liquid phase product (5) are led to the downstream, and the water phase (8) is discharged outside the boundary for treatment; when the countercurrent three-phase reactor is a reactive rectifying tower, the countercurrent three-phase reactor also comprises a reboiler, which is omitted in the figure.
In the gas-liquid mixed feed reaction process flow shown in fig. 2, a raw material (1) containing alpha, alpha-dimethylbenzyl alcohol and cumene obtained by reacting propylene with cumene hydroperoxide and recycle hydrogen (11) enter a mixer VI to obtain a gas-liquid mixture (13), a material flow (13) enters a reactor I to react, a liquid phase product (2) mainly containing cumene is obtained at the bottom, and a gas phase product (3) mainly containing hydrogen, cumene and water is obtained at the top; pressurizing the liquid-phase product (2) containing the isopropylbenzene by a pump II to divide the liquid-phase product into two streams, wherein the first stream accounting for 0-100% by weight of the liquid-phase product (4) is recycled into the raw material (1) to obtain a stream (12), and the remaining second stream of liquid-phase product (5) is led to the downstream; the gas phase product (3) mainly containing hydrogen, cumene and water is cooled to a required temperature through a device III, enters a gas-liquid separator V, separates out a gas phase (7) containing hydrogen, an oil phase (9) containing cumene and a water phase (8), the gas phase (7) and fresh supplementary hydrogen (10) enter a circulating hydrogen booster IV for boosting, the oil phase (9) and the liquid phase product (5) are led to the downstream, and the water phase (8) is discharged outside for treatment.
The present invention is further illustrated by, but not limited to, the following examples.
Detailed Description
[ Example 1]
As shown in FIG. 1, a raw material containing alpha, alpha-dimethylbenzyl alcohol (DMBA concentration 56wt%, cumene concentration 44 wt%) was fed into a countercurrent three-phase reactor I at 55kg/h, and hydrogen raw material was fed into the countercurrent three-phase reactor I at 3kg/h for reaction, wherein 14kg of catalyst was packed in the reactor, and a palladium-based alumina catalyst developed for Shanghai petrochemical institute was developed, wherein palladium content was 0.8wt%, 50% by weight of the liquid phase product of the catalyst reaction was returned into the reactor, and the remaining 50% by weight of the liquid phase product was fed downstream; the inlet temperature of the countercurrent three-phase reactor is 150 ℃, the reaction pressure is 2.0MPaG, the DMBA conversion rate is 78.9%, and the selectivity of cumene is 92.4%.
[ Example 2]
Unlike example 1, the countercurrent three-phase reactor inlet temperature was 160 ℃, the reaction pressure was 2.0MPaG, the DMBA conversion was 82.1%, and the cumene selectivity was 86.5%.
[ Example 3]
As shown in FIG. 1, a raw material containing alpha, alpha-dimethylbenzyl alcohol (DMBA concentration 56wt%, cumene concentration 44 wt%) was fed at 55kg/h and a hydrogen raw material at 3kg/h into a countercurrent three-phase reactor I for reaction, which was a reaction rectifying column filled with 14kg of a catalyst, a palladium-based alumina catalyst developed for Shanghai petrochemical institute, wherein palladium content 0.8wt%, 50% by weight of a catalyst reaction liquid phase product was returned to the reactor, and the remaining 50% by weight of the liquid phase product was fed downstream. The number of tower plates of a rectifying section in the reaction rectifying tower is 20, the number of tower plates of the reaction rectifying section is 30, the number of tower plates of a stripping section is 25, and the reflux ratio is 1.2:1; the inlet temperature of the countercurrent three-phase reactor is 150 ℃, the reaction pressure is 2.0MPaG, the DMBA conversion rate is 84.4%, and the selectivity of cumene is 92.5%.
[ Example 4]
Unlike example 3, the countercurrent three-phase reactor inlet temperature was 160 ℃, the reaction pressure was 2.0MPaG, the DMBA conversion was 86.5%, and the cumene selectivity was 86%.
[ Example 5]
Unlike example 1, the hydrogen feed was 1kg/h, DMBA conversion 77.6% and cumene selectivity 90.7%.
[ Example 6]
Unlike example 1, the hydrogen feed was 6kg/h, DMBA conversion 91.1% and cumene selectivity 82.3%.
[ Example 7]
As shown in FIG. 1, a raw material containing alpha, alpha-dimethylbenzyl alcohol (DMBA concentration 56wt%, cumene concentration 44 wt%) was fed at 55kg/h and a hydrogen raw material at 3kg/h into a countercurrent three-phase reactor I for reaction, which was a reaction rectifying column filled with 14kg of a catalyst, a palladium-based alumina catalyst developed for Shanghai petrochemical institute, wherein palladium content 0.8wt%, 80% by weight of a catalyst reaction liquid-phase product was returned to the reactor, and the remaining 20% by weight of the liquid-phase product was fed downstream. The number of tower plates of a rectifying section in the reaction rectifying tower is 20, the number of tower plates of the reaction rectifying section is 30, the number of tower plates of a stripping section is 25, and the reflux ratio is 1.2:1; the inlet temperature of the hydrogenolysis reactor is 160 ℃, the reaction pressure is 2.4MPaG, the DMBA conversion rate is 79.6%, and the selectivity of cumene is 94.7%.
[ Example 8]
Unlike example 7, the countercurrent three-phase reactor inlet temperature was 170 ℃, the reaction pressure was 2.4MPaG, the DMBA conversion was 88.6%, and the cumene selectivity was 85.3%.
Comparative example 1
As shown in FIG. 2, 55kg/h of a raw material containing alpha, alpha-dimethylbenzyl alcohol (DMBA concentration 56wt%, cumene concentration 44 wt%) and 3kg/h of a hydrogen raw material are mixed and then enter a reactor I for reaction, 14kg of a catalyst is filled in the reactor, a palladium-based alumina catalyst developed for Shanghai petrochemical institute development is filled in the reactor, wherein the palladium content is 0.8wt%, 50% by weight of a liquid phase product of the catalyst reaction is returned to the reactor, and the rest 50% by weight of the liquid phase product is led to the downstream; the inlet temperature of the countercurrent three-phase reactor is 150 ℃, the reaction pressure is 2.0MPaG, the DMBA conversion rate is 60.3%, and the selectivity of cumene is 78.5%.
It can be seen that when the remaining conditions are the same, the reaction effect of the gas-liquid mixed feed is significantly inferior to the countercurrent three-phase reaction effect of the gas-liquid separate feed.
Comparative example 2
Unlike example 1, the hydrogen feed was 0.5kg/h, DMBA conversion 68.3% and cumene selectivity 84.4%.
It can be seen that when the remaining conditions are the same, the hydrogen flow is too low, which tends to result in incomplete DMBA conversion.
[ Comparative example 3]
Unlike example 1, the hydrogen feed was 8kg/h, DMBA conversion was 95.4% and cumene selectivity was 73.6%.
It can be seen that when the remaining conditions are the same, too high a hydrogen flow rate increases the DMBA conversion rate, but side reactions tend to occur to produce isopropyl cyclohexane or the like, resulting in lower selectivity. And the excessively high hydrogen amount can increase the difficulty of subsequent gas-liquid separation.
Claims (13)
1. A method of benzyl alcohol conversion comprising the steps of:
a) The raw material (1) containing alpha, alpha-dimethylbenzyl alcohol and isopropylbenzene enters the upper part of a countercurrent three-phase reactor I for reaction, a liquid phase product (2) mainly containing isopropylbenzene is obtained at the bottom of the tower, and a gas phase product (3) mainly containing hydrogen, isopropylbenzene and water is obtained at the top of the tower;
b) The liquid phase product (2) containing the isopropylbenzene is pressurized by a pump II and divided into two strands, wherein the first strand of liquid phase product (4) accounting for 0-100% by weight is returned to the reaction zone in the step a), and the rest of second strand of liquid phase product (5) is led to the downstream;
c) The gas phase product (3) mainly containing hydrogen, cumene and water is cooled and separated to obtain a gas phase (7) containing hydrogen, an oil phase (9) containing cumene and a water phase (8), and the gas phase (7) and fresh supplementary hydrogen (10) are pressurized and then enter the lower part of a countercurrent three-phase reactor I as a hydrogen feed stream (11);
the mass flow of hydrogen in the countercurrent three-phase reactor accounts for 1.0% -6.0% of the mass flow of the raw material (1);
the catalyst filled in the countercurrent three-phase reactor is a palladium-based catalyst; the countercurrent three-phase reactor is a reaction rectifying tower; the tower body part of the reactive distillation tower sequentially comprises a rectifying section, a reactive rectifying section and a stripping section from top to bottom.
2. The process for benzyl alcohol conversion as claimed in claim 1, wherein the raw material (1) containing α, α -dimethylbenzyl alcohol and cumene is introduced into the countercurrent three-phase reactor I at a height of 10% to 30% to conduct the reaction.
3. The process for benzyl alcohol conversion according to claim 1, characterized in that the gas phase (7) and fresh make-up hydrogen (10) are pressurized and fed as hydrogen feed stream (11) to a countercurrent three-phase reactor I at a level of from 70% to 90%.
4. The process of claim 1 wherein the reaction zone in the countercurrent three-phase reactor is either a single-stage reaction zone or a reaction zone comprising a plurality of reaction stages in series.
5. The method for benzyl alcohol conversion according to claim 1, wherein the raw material containing α, α -dimethylbenzyl alcohol and cumene comprises, by weight, 5 to 80% of α, α -dimethylbenzyl alcohol and 20 to 95% of cumene.
6. The benzyl alcohol conversion method according to claim 1, wherein the operating pressure of the countercurrent three-phase reactor is 0.5 to 4.0mpa in gauge; and/or the operation temperature of the countercurrent three-phase reactor is 80-250 ℃; and/or the volume space velocity of the raw material (1) in the reaction zone in the countercurrent three-phase reactor is 0.5-20 hours -1; and/or the mole ratio of the alpha, alpha-dimethylbenzyl alcohol in the hydrogen/raw material (1) of the countercurrent three-phase reactor is (5-20): 1.
7. The method for benzyl alcohol conversion according to claim 1, wherein the first liquid phase product (4) pressurized by the pump II accounts for 20-80% of the liquid phase product (2) in weight percent.
8. The process for benzyl alcohol conversion according to claim 1, characterized in that the countercurrent three-phase reactor oil phase (9) and/or countercurrent three-phase reactor bottom liquid phase product (5) are optionally removed as product exclusion limit or as feedstock to a two-stage hydrogenolysis reactor.
9. The process for benzyl alcohol conversion as set forth in claim 1, wherein said rectifying section is comprised of 12 to 26 layers of trays or packing of corresponding height;
the reaction rectifying section is composed of 20 to 40 layers of tower plates or filler with corresponding height;
the stripping section consists of 15 to 30 layers of tower plates or fillers with corresponding heights;
The gas phase feeding position is the junction of the reactive rectifying section and the stripping section, and the liquid phase feeding position is the junction of the reactive rectifying section and the rectifying section.
10. The method of benzyl alcohol conversion as set forth in claim 1, wherein the reactive distillation column comprises a reboiler.
11. The method for benzyl alcohol conversion according to claim 1, wherein the reflux ratio of the reactive distillation column is (1-3): 1.
12. The method for benzyl alcohol conversion according to claim 1, wherein the catalyst is packed at the overflow port when the reactive rectifying section of the reactive rectifying column is composed of trays.
13. The method for benzyl alcohol conversion as set forth in claim 1, wherein when the reactive distillation section of the reactive distillation column is composed of a filler, the filler and the catalyst are alternately packed at column axial positions.
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