CN113651664A - Method for conversion of benzyl alcohol - Google Patents
Method for conversion of benzyl alcohol Download PDFInfo
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- CN113651664A CN113651664A CN202010394871.1A CN202010394871A CN113651664A CN 113651664 A CN113651664 A CN 113651664A CN 202010394871 A CN202010394871 A CN 202010394871A CN 113651664 A CN113651664 A CN 113651664A
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- benzyl alcohol
- cumene
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 title claims description 89
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 title claims description 54
- 235000019445 benzyl alcohol Nutrition 0.000 title claims description 18
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims abstract description 128
- 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 21
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000012071 phase Substances 0.000 claims description 78
- 229910052739 hydrogen Inorganic materials 0.000 claims description 39
- 239000001257 hydrogen Substances 0.000 claims description 39
- 239000007791 liquid phase Substances 0.000 claims description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- 150000002431 hydrogen Chemical class 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 20
- 238000000066 reactive distillation Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 238000012856 packing Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 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 39
- 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
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 230000007246 mechanism Effects 0.000 description 7
- 238000004519 manufacturing process Methods 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
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-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
- 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
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 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
- 230000002378 acidificating effect Effects 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004821 distillation 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003208 petroleum Substances 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
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- 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
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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
The invention relates to a method for converting benzyl alcohol, which mainly solves the problems of low activity, short service life, more byproducts and poor economy of the catalyst in the prior art. The invention solves the problem well by adopting a counter-current three-phase process, and can be used in the industrial production of producing the isopropylbenzene by the hydrogenolysis of the alpha, alpha-dimethyl benzyl 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, the main production methods at present are a chlorohydrin method and an co-oxidation method, and the chlorohydrin method is eliminated because of poor economic benefit caused by environmental pollution and equipment corrosion. The tert-butyl alcohol and ethylbenzene co-oxidation method in the co-oxidation method is advanced, but has the defect of strong uncertainty for manufacturers because the economic benefit fluctuates due to the fluctuation of the price of co-produced products. The cumene co-oxidation method becomes one of the main research and development directions due to the advantages of no co-production, environmental protection and the like. The conversion of the alpha, alpha-dimethyl benzyl alcohol into the isopropylbenzene through hydrogenolysis is an important link of the process route, and the improvement of the conversion rate of the alpha, alpha-dimethyl benzyl alcohol and the selectivity of the isopropylbenzene has obvious effect on enhancing the economy and the competitiveness of the process.
As a method for producing cumene and propylene oxide including the step, patents CN1860087A, CN100376520C report a method for producing cumene by hydrogenolysis or hydrogenation of cumyl alcohol after dehydration, which comprises 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 process for producing cumene, which is characterized by reducing a copper-based catalyst precursor containing copper in an oxidized state with hydrogen in liquid cumene to prepare a copper-based catalyst, and decomposing cumyl alcohol by hydrogenation in the presence of the copper-based catalyst. CN1852879A reports a process for producing cumene, which comprises producing cumene from cumyl alcohol and hydrogen gas with a dehydration catalyst and a hydrogenation catalyst, wherein the dehydration catalyst and the hydrogenation catalyst are alternately packed so as to form n layers (n is an integer of 3 or more), or a mixture thereof is packed into a reactor. However, there is no literature or patent concerning a specific process route or device connection for the hydrogenolysis of α, α -dimethylbenzyl alcohol to cumene.
Patent CN105294382A reports a method for separating cracked carbon five by catalytic reaction rectification, which is characterized in that the reaction and rectification occur simultaneously, and similarly, patent CN105801408A and patent CN109438179A also refer to the method. Through experimentation, the present inventors have discovered that good conversion and selectivity can be obtained for the production of cumene by the hydrogenolysis of α, α -dimethylbenzyl alcohol in a counter-current three-phase reaction, particularly when the reactor is in the form of a reactive distillation column.
Disclosure of Invention
The hydrogenolysis of alpha, alpha-dimethylbenzyl alcohol to cumene has two reaction mechanisms: indirect and direct hydrogenolysis mechanisms.
(1) Mechanism of indirect hydrogenolysis
The bifunctional catalyst of hydrogenation metal loaded on an acidic carrier is adopted, and the indirect hydrogenolysis mechanism is used for leading the hydrogenolysis reaction. Alpha, alpha-dimethyl benzyl alcohol firstly generates dehydration reaction on an acid center of a catalyst to generate alpha-methyl styrene, and then the alpha-methyl styrene generates hydrogenation reaction on a metal center of the catalyst to generate isopropyl benzene, and the reaction process is as follows:
(2) mechanism of direct hydrogenolysis
The dissociation of surface hydrogen adsorbed by the active component of the catalyst directly "replaces" the hydroxyl groups of DMBA to produce cumene and water, a mechanism that typically occurs on metal or supported metal catalysts.
The overall hydrogenolysis of α, α -dimethylbenzyl alcohol to cumene is an exothermic reaction, either by an indirect or direct hydrogenolysis mechanism, and the gas and liquid should be separated during the reaction discharge in order to reduce the difficulty of the subsequent separation process. The heat released by the reaction can be effectively utilized through the reactive distillation; 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 in 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 hydrogenolysis reaction of alpha, alpha-dimethyl benzyl alcohol and high selectivity of cumene serving as a product.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for converting benzyl alcohol, the method comprising the steps of:
a) raw materials (1) containing alpha, alpha-dimethylbenzyl alcohol and cumene obtained by the reaction of propylene and cumene hydroperoxide enter 10-30% of the upper part of a countercurrent three-phase reactor I to react, a liquid-phase product (2) mainly containing the cumene is obtained at the tower bottom, and a gas-phase product (3) mainly containing hydrogen, the cumene and water is obtained at the tower top;
b) the liquid-phase product (2) containing the isopropyl benzene is divided into two parts by pressurization, the first part of the liquid-phase product (4) accounting for 0-100% of the weight is returned to the reaction zone in the step a), and the remaining second part of the 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 make-up hydrogen (10) enter 10-30% of the lower part of a countercurrent three-phase reactor I after being pressurized.
In the above technical solution, a preferable technical solution is that the reaction zone in the countercurrent three-phase reactor may be a single-stage reaction zone, or a reaction zone formed by connecting a plurality of reaction zones in series.
In the above technical solution, preferably, in the raw material containing α, α -dimethylbenzyl alcohol and cumene, the content of α, α -dimethylbenzyl alcohol is 5 to 80% by weight, and the content of cumene is 20 to 95% by weight.
In the above technical solution, preferably, the operating pressure of the countercurrent three-phase reactor is 0.5 to 4.0MPa in gauge pressure.
In the technical scheme, the operation temperature of the countercurrent three-phase reactor is preferably 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 solution, preferably, the mass flow rate of hydrogen in the reaction zone in the countercurrent three-phase reactor is 1.0-6.0% of the mass flow rate of the hydrocarbon raw material.
In the technical scheme, preferably, the first liquid-phase product (4) pressurized by the pump II accounts for 20-80% of the liquid-phase product (2) by weight.
In the above technical solution, optionally, the counter-current three-phase reactor oil phase (9) and/or the counter-current three-phase reactor bottom liquid phase product (5) are excluded as a product or used as a feedstock to a secondary hydrogenolysis reactor.
In the above technical solution, preferably, the catalyst filled in the countercurrent three-phase reactor is a palladium-based catalyst.
In the above technical solution, preferably, the countercurrent three-phase reactor is a reaction rectifying tower.
In the above technical solution, preferably, the tower body part of the reactive distillation tower comprises a distillation section, a reactive distillation section and a stripping section from top to bottom in sequence,
wherein the rectifying section consists of 12 to 26 layers of trays or packing materials with corresponding heights;
the reactive distillation section consists of 20-40 layers of tower plates or packing with corresponding height;
the stripping section consists of 15-30 layers of trays or packing materials with corresponding heights.
The gas phase feeding position is the junction of the reaction rectifying section and the stripping section, and the liquid phase feeding position is the junction of the reaction rectifying section and the rectifying section.
In the above technical solution, preferably, the reactive distillation column includes a reboiler.
In the technical scheme, the reflux ratio of the reactive distillation tower is preferably (1-3): 1.
The reflux ratio is the ratio of the volume flow of the material flow returned to the top of the tower in the oil phase (9) of the countercurrent three-phase reactor to the volume flow of the material flow discharged.
In the above technical solution, preferably, when the reactive distillation section of the reactive distillation column consists of trays, the catalyst is filled at the overflow port.
In the above technical solution, preferably, when the reactive distillation section of the reactive distillation column is composed of packing, the packing and the catalyst are alternately packed in the axial position of the column.
The overall conversion of α, α -dimethylbenzyl alcohol, as a percentage of the molar flow of α, α -dimethylbenzyl alcohol reduced by hydrogenolysis as a molar flow of α, α -dimethylbenzyl alcohol in the feed to the counter-current three-phase reactor i, is shown by the following equation:
the overall selectivity for cumene, as a percentage of the molar flow of cumene added after passing through the countercurrent three-phase reactor i to the molar flow of α, α -dimethylbenzyl alcohol reduced after the hydrogenolysis reaction, is shown by the following equation:
in the technical scheme of the invention, the hydrogenolysis reaction of the raw material containing alpha, alpha-dimethylbenzyl alcohol and cumene and hydrogen is completed in a countercurrent three-phase reaction mode, preferably in a reaction rectification mode, most of water in reaction products is discharged from the top of a reactor, the reduction of the activity of the catalyst caused by the circulation of liquid phase products in a tower kettle back to a 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 counter-current three-phase reaction process shown in fig. 1, a raw material (1) containing alpha, alpha-dimethylbenzyl alcohol and cumene obtained by the reaction of propylene and cumene hydroperoxide enters a counter-current three-phase reactor I for reaction, a liquid-phase product (2) mainly containing the cumene is obtained at the bottom, and a gas-phase product (3) mainly containing hydrogen, the cumene and water is obtained at the top; a liquid-phase product (2) containing the isopropylbenzene is pressurized by a pump II and divided into two parts, wherein the first part of the liquid-phase product (4) accounting for 0-100% of the weight of the liquid-phase product returns to the countercurrent three-phase reactor I, and the remaining second part of the liquid-phase product (5) is led to the downstream; cooling a gas-phase product (3) mainly containing hydrogen, cumene and water to a required temperature through equipment III, feeding the gas-phase product into a gas-liquid separator V, separating a gas phase (7) containing the hydrogen, an oil phase (9) containing the cumene and a water phase (8), feeding the gas phase (7) and fresh make-up hydrogen (10) into a circulating hydrogen supercharger IV for supercharging, leading the oil phase (9) and a liquid-phase product (5) to the downstream, and discharging the water phase (8) to be treated outside the room; when the countercurrent three-phase reactor is a reaction rectifying tower, the countercurrent three-phase reactor also comprises a reboiler, and the figure is omitted.
In the gas-liquid mixed feeding reaction process flow shown in fig. 2, a raw material (1) containing alpha, alpha-dimethylbenzyl alcohol and cumene obtained by the reaction of propylene and cumene hydroperoxide and circulating hydrogen (11) enter a mixer VI to obtain a gas-liquid mixture (13), the material flow (13) enters a reactor I for reaction, a liquid-phase product (2) mainly containing the cumene is obtained at the bottom, and a gas-phase product (3) mainly containing hydrogen, the cumene and water is obtained at the top; a liquid-phase product (2) containing the isopropylbenzene is pressurized by a pump II and divided into two parts, wherein the first part of the liquid-phase product (4) accounting for 0-100% of the weight of the isopropylbenzene circularly enters the raw material (1) to obtain a material flow (12), and the remaining second part of the liquid-phase product (5) is led to the downstream; a gas-phase product (3) mainly containing hydrogen, cumene and water is cooled to the required temperature through equipment III, enters a gas-liquid separator V, a gas phase (7) containing the hydrogen, an oil phase (9) containing the cumene and a water phase (8) are separated, the gas phase (7) and fresh make-up hydrogen (10) enter a circulating hydrogen supercharger IV for pressurization, the oil phase (9) and the liquid-phase product (5) are led to the downstream, and the water phase (8) is discharged to be treated outside.
The present invention will be further illustrated by the following examples, but is not limited to these examples.
Detailed Description
[ example 1 ]
As shown in figure 1, raw materials containing alpha, alpha-dimethyl benzyl alcohol (DMBA concentration 56 wt%, cumene concentration 44 wt%) are reacted in a countercurrent three-phase reactor I at 55kg/h and hydrogen raw material at 3kg/h, the reactor is filled with 14kg of catalyst, palladium-based alumina catalyst developed for Shanghai petroleum chemical research institute development, wherein the palladium content is 0.8 wt%, 50% of the liquid phase product of the catalyst reaction is returned to the reactor, and the other 50% of the liquid phase product is led to the downstream; the inlet temperature of the counter-current three-phase reactor is 150 ℃, the reaction pressure is 2.0MPaG, the conversion rate of DMBA is 78.9 percent, and the selectivity of cumene is 92.4 percent.
[ example 2 ]
Different from the example 1, the inlet temperature of the counter-current three-phase reactor is 160 ℃, the reaction pressure is 2.0MPaG, the conversion rate of DMBA is 82.1 percent, and the selectivity of isopropyl benzene is 86.5 percent.
[ example 3 ]
As shown in figure 1, raw material containing alpha, alpha-dimethyl benzyl alcohol (DMBA concentration 56 wt%, cumene concentration 44 wt%) is reacted in a countercurrent three-phase reactor I with 55kg/h and hydrogen raw material with 3kg/h, the reactor is a reaction rectifying tower filled with 14kg of catalyst, palladium-based alumina catalyst developed for Shanghai petrochemical institute, wherein the palladium content is 0.8 wt%, 50% of the liquid phase product of the catalyst reaction is returned to the reactor, and the other 50% of the liquid phase product is led to the downstream. The number of the tower plates of the rectifying section in the reactive rectifying tower is 20, the number of the tower plates of the reactive rectifying section is 30, the number of the tower plates of the stripping section is 25, and the reflux ratio is 1.2: 1; the inlet temperature of the counter-current three-phase reactor is 150 ℃, the reaction pressure is 2.0MPaG, the conversion rate of DMBA is 84.4 percent, and the selectivity of cumene is 92.5 percent.
[ example 4 ]
Unlike example 3, the inlet temperature of the countercurrent three-phase reactor was 160 ℃, the reaction pressure was 2.0MPaG, the DMBA conversion was 86.5%, and the cumene selectivity was 86%.
[ example 5 ]
In contrast to example 1, the flow rate of the hydrogen feed was 1kg/h, the DMBA conversion was 77.6% and the cumene selectivity was 90.7%.
[ example 6 ]
In contrast to example 1, the flow of the hydrogen feed was 6kg/h, the DMBA conversion was 91.1% and the cumene selectivity was 82.3%.
[ example 7 ]
As shown in figure 1, raw material containing alpha, alpha-dimethyl benzyl alcohol (DMBA concentration 56 wt%, cumene concentration 44 wt%) is reacted in a countercurrent three-phase reactor I with 55kg/h and hydrogen raw material with 3kg/h, the reactor is a reaction rectifying tower filled with 14kg of catalyst, palladium-based alumina catalyst developed for Shanghai petrochemical institute, wherein the palladium content is 0.8 wt%, 80% of the liquid phase product of the catalyst reaction is returned to the reactor, and the rest 20% of the liquid phase product is led to the downstream. The number of the tower plates of the rectifying section in the reactive rectifying tower is 20, the number of the tower plates of the reactive rectifying section is 30, the number of the tower plates of the 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 conversion rate of DMBA is 79.6 percent, and the selectivity of cumene is 94.7 percent.
[ example 8 ]
Unlike example 7, the inlet temperature of the counter-current three-phase reactor 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 raw material containing α, α -dimethylbenzyl alcohol (DMBA concentration 56 wt%, cumene concentration 44 wt%) and 3kg/h hydrogen raw material were mixed and fed into a reactor i for reaction, the reactor was filled with 14kg catalyst, palladium-based alumina catalyst developed for the research institute of petroleum chemical industry in shanghai, wherein palladium content was 0.8 wt%, 50% by weight of liquid phase product of catalyst reaction was returned to the reactor, and the remaining 50% by weight of liquid phase product was passed to the downstream; the inlet temperature of the counter-current three-phase reactor is 150 ℃, the reaction pressure is 2.0MPaG, the conversion rate of DMBA is 60.3 percent, and the selectivity of cumene is 78.5 percent.
It can be seen that when the other conditions are the same, the reaction effect of the gas-liquid mixed feeding is obviously inferior to the countercurrent three-phase reaction effect of the gas-liquid separated feeding.
Comparative example 2
In contrast to example 1, the flow rate of the hydrogen feed was 0.5kg/h, the DMBA conversion was 68.3% and the cumene selectivity was 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
In contrast to example 1, the flow of the hydrogen feed was 8kg/h, the DMBA conversion was 95.4% and the cumene selectivity was 73.6%.
It can be seen that, when the other conditions are the same, the hydrogen flow rate is too high, which increases the DMBA conversion rate, but side reactions are likely to occur to generate isopropylcyclohexane, etc., resulting in a lower selectivity. And too high hydrogen content can increase the difficulty of subsequent gas-liquid separation.
Claims (14)
1. A method of benzyl alcohol conversion comprising the steps of:
a) the raw material (1) containing alpha, alpha-dimethylbenzyl alcohol and cumene enters the upper part (preferably 10-30% of the height of a reactor) of a countercurrent three-phase reactor I to react, a liquid-phase product (2) mainly containing the cumene is obtained at the tower bottom, and a gas-phase product (3) mainly containing hydrogen, the cumene and water is obtained at the tower top;
b) the liquid-phase product (2) containing the isopropyl benzene is divided into two parts by pressurization, the first part of the liquid-phase product (4) accounting for 0-100% of the weight is returned to the reaction zone in the step a), and the remaining second part of the 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 make-up hydrogen (10) are pressurized and then enter the lower part (preferably 70-90% of the height of the reactor) of the countercurrent three-phase reactor I as a hydrogen feeding stream (11).
2. Benzyl alcohol conversion process according to claim 1, characterized in that the reaction zone in the counter-current three-phase reactor can be either a single-stage reaction zone or a reaction zone consisting of a plurality of reaction stages connected in series.
3. The method for converting benzyl alcohol according to claim 1, wherein the raw material containing α, α -dimethylbenzyl alcohol and cumene contains, by weight, 5 to 80% of α, α -dimethylbenzyl alcohol and 20 to 95% of cumene.
4. Benzyl alcohol conversion method according to claim 1, characterized in that the mass flow of hydrogen in the counter-current three-phase reactor is between 1.0% and 6.0% of the mass flow of the hydrocarbon feedstock.
5. Benzyl alcohol conversion method according to claim 1, characterized in that the operating pressure of the counter-current three-phase reactor is 0.5 to 4.0MPa in gauge pressure; and/or a countercurrent three-phase reactorThe operation temperature of (A) is 80-250 ℃; and/or 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(ii) a And/or the molar ratio of the alpha, alpha-dimethyl benzyl alcohol in the hydrogen/hydrocarbon raw material of the countercurrent three-phase reactor is (5-20): 1.
6. The method for converting benzyl alcohol according to claim 1, wherein the first stream of liquid phase product (4) pressurized by pump ii comprises 20-80% by weight of the liquid phase product (2).
7. Process for the conversion of benzyl alcohol according to claim 1, characterized in that the counter-current three-phase reactor oil phase (9) and/or the counter-current three-phase reactor bottom liquid phase product (5) are optionally excluded as products or passed as feedstock to a secondary hydrogenolysis reactor.
8. Benzyl alcohol conversion method according to claim 1, characterized in that the catalyst packed in the counter-current three-phase reactor is a palladium-based catalyst.
9. Benzyl alcohol conversion method according to claims 1 to 8, characterized in that the counter-current three-phase reactor is a reactive rectification column.
10. The method of benzyl alcohol conversion according to claim 9, wherein the body portion of the reactive distillation column comprises three sections, a rectifying section, a reactive distillation section and a stripping section, in order from top to bottom,
wherein the rectifying section consists of 12 to 26 layers of trays or packing materials with corresponding heights;
the reactive distillation section consists of 20-40 layers of tower plates or packing with corresponding height;
the stripping section consists of 15-30 layers of trays or packing materials with corresponding heights.
The gas phase feeding position is the junction of the reaction rectifying section and the stripping section, and the liquid phase feeding position is the junction of the reaction rectifying section and the rectifying section.
11. Benzyl alcohol conversion method according to claim 9, characterized in that the reactive rectification column comprises a reboiler.
12. Benzyl alcohol conversion method according to claim 9, characterized in that the reflux ratio of the reactive distillation column is (1-3): 1.
13. Benzyl alcohol conversion method according to claim 10, characterized in that the catalyst is filled at the overflow when the reactive distillation section of the reactive distillation column consists of trays.
14. The method for converting benzyl alcohol according to claim 10, wherein when the reactive distillation section of the reactive distillation column is composed of packing, the packing and the catalyst are alternately packed in the axial position of the column.
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| CN114874066A (en) * | 2022-06-16 | 2022-08-09 | 上海优铖工逸技术有限公司 | Method and device for preparing alpha-methyl styrene by dehydrating 2-phenyl-2-propanol |
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