CN114392706B - Microchannel reactor, coating method thereof and method for synthesizing 1, 3-propanediol - Google Patents
Microchannel reactor, coating method thereof and method for synthesizing 1, 3-propanediol Download PDFInfo
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- CN114392706B CN114392706B CN202210049951.2A CN202210049951A CN114392706B CN 114392706 B CN114392706 B CN 114392706B CN 202210049951 A CN202210049951 A CN 202210049951A CN 114392706 B CN114392706 B CN 114392706B
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- 238000000034 method Methods 0.000 title claims abstract description 84
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 title claims abstract description 60
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 title claims abstract description 58
- 229940035437 1,3-propanediol Drugs 0.000 title claims abstract description 58
- 229920000166 polytrimethylene carbonate Polymers 0.000 title claims abstract description 58
- 238000000576 coating method Methods 0.000 title claims abstract description 41
- 230000002194 synthesizing effect Effects 0.000 title abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 70
- 239000003960 organic solvent Substances 0.000 claims abstract description 47
- AKXKFZDCRYJKTF-UHFFFAOYSA-N 3-Hydroxypropionaldehyde Chemical compound OCCC=O AKXKFZDCRYJKTF-UHFFFAOYSA-N 0.000 claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 238000001704 evaporation Methods 0.000 claims abstract description 24
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 230000008020 evaporation Effects 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 8
- 230000009471 action Effects 0.000 claims abstract description 6
- 230000001681 protective effect Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 88
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 52
- 238000005984 hydrogenation reaction Methods 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 22
- 229920002301 cellulose acetate Polymers 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 7
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 239000007868 Raney catalyst Substances 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 230000008595 infiltration Effects 0.000 claims description 2
- 238000001764 infiltration Methods 0.000 claims description 2
- 238000012546 transfer Methods 0.000 abstract description 15
- 238000002791 soaking Methods 0.000 abstract description 11
- 239000006227 byproduct Substances 0.000 abstract description 6
- 239000007787 solid Substances 0.000 abstract description 4
- 208000012839 conversion disease Diseases 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 10
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005810 carbonylation reaction Methods 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 238000000855 fermentation Methods 0.000 description 3
- 230000004151 fermentation Effects 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- -1 polytrimethylene terephthalate Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- 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
- B01J19/002—Avoiding undesirable reactions or side-effects, e.g. avoiding explosions, or improving the yield by suppressing side-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
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/082—Controlling processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/22—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00718—Type of compounds synthesised
- B01J2219/0072—Organic compounds
Abstract
The invention provides a microchannel reactor, a coating method thereof and a method for synthesizing 1, 3-propanediol, wherein the coating method comprises the following steps: mixing the evaporation type organic solvent, the film-forming organic solvent and the protective gas, introducing the mixture into a microchannel reactor, introducing the catalyst and the evaporation type organic solvent into the microchannel reactor after the evaporation type organic solvent is evaporated to form an organic film, soaking, volatilizing the evaporation type organic solvent, and repeating for at least three times to obtain the microchannel reactor with the catalyst. The method for synthesizing the 1, 3-propanediol comprises the following steps: and introducing the 3-hydroxy propanal aqueous solution and hydrogen into a microchannel reactor, and carrying out catalytic hydrogenation reaction under the action of a catalyst coated on the inner wall of the microchannel reactor to prepare the 1, 3-propanediol. The invention can accelerate the gas-liquid-solid mass transfer efficiency, increase the heat transfer, reduce the generation of byproducts and improve the reaction conversion rate and selectivity.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a microchannel reactor, a coating method thereof and a method for synthesizing 1, 3-propanediol.
Background
1, 3-propanediol (1, 3-PDO for short) is a main raw material for producing polytrimethylene terephthalate (PTT), is also used as a raw material for synthesizing plasticizers, detergents, preservatives and emulsifying agents, particularly for producing PTT fibers with excellent performance, combines the softness of nylon, the fluffiness of acrylic fibers and the dirt resistance of terylene with the inherent elasticity, can be dyed at normal temperature and the like, integrates the excellent performances of various fibers, and has wide application prospect in the fields of clothing, industry, decoration, engineering plastics and the like. 1, 3-propanediol is used as a monomer which is not replaced by PTT and becomes the main raw material of new generation synthetic fiber and thermoplastic engineering plastics. Therefore, the development of synthetic routes for 1,3 propanediol has become an inevitable trend in industrial technology to meet the continuous development of new materials for polyesters.
The current industrialized method for synthesizing 1, 3-propylene glycol mainly comprises an ethylene oxide carbonylation hydrogenation method, a biological fermentation method and an acrolein hydration hydrogenation method. The 3-hydroxy-propionaldehyde is produced by the carbonylation reaction of ethylene oxide, and then the 1, 3-propanediol is produced by catalytic hydrogenation, but the whole reaction is carried out under high pressure, and the carbonylation reaction catalyst system is complex and the ligand is extremely toxic, so the technical equipment investment is the largest and the difficulty is the highest; although the research progress of the biological fermentation method in the synthesis field is rapid, the biological fermentation method still faces the problems of low conversion rate, poor selectivity, high technical difficulty and the like; the hydration hydrogenation method of the acrolein also needs to synthesize the 1, 3-propanediol through the step of catalytic hydrogenation of the 3-hydroxy propanal, but the hydration reaction condition is mild, the requirement on equipment is not high, the hydrogenation technology is more mature, compared with other methods, the method is easier to realize industrial application, and has wider industrial application prospect.
Although the acrolein hydration hydrogenation method for synthesizing the 1, 3-propanediol has higher conversion rate and selectivity, the problems of uneven heating, low gas-liquid-solid mass transfer efficiency and the like still exist for a gas-liquid-solid three-phase reaction system, the reaction rate is low, the byproducts are increased, and the conversion rate and the selectivity of the reaction system are further improved.
The prior art mostly adopts improved equipment or subsequent re-purification technology to improve the purity of the 1, 3-propanediol, but the essential problem of byproduct increase caused by poor mass transfer and heat transfer efficiency can not be solved.
Therefore, there is a need to develop a new method for synthesizing 1, 3-propanediol.
Disclosure of Invention
In order to solve the technical problems, the invention provides a microchannel reactor, a coating method thereof and a method for synthesizing 1, 3-propanediol, wherein the coating method can realize uniform and stable coating of a catalyst on the inner wall of the microchannel reactor, and the method for synthesizing 1, 3-propanediol has high inter-phase mass transfer efficiency and high heat transfer efficiency, reduces the generation of byproducts and improves the yield and selectivity of 1, 3-propanediol.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method of coating a catalyst in a microchannel reactor, the method comprising the steps of:
mixing the evaporation type organic solvent, the film-forming organic solvent and the protective gas, introducing the mixture into a microchannel reactor, introducing the catalyst and the evaporation type organic solvent into the microchannel reactor after the evaporation type organic solvent is evaporated to form an organic film, soaking, volatilizing the evaporation type organic solvent, and repeating for at least three times to obtain the microchannel reactor with the catalyst.
According to the method for coating the catalyst in the microchannel reactor, the solid catalyst can be uniformly coated on the inner wall of the reactor through the coordination of the evaporation type organic solvent and the film-forming organic solvent, and is effectively fixed on the inner wall of the reactor through the organic film.
Preferably, the inner wall of the microchannel reactor is made of stainless steel, for example, stainless steel 304.
Preferably, the catalyst comprises Raney nickel, pt/TiO 2 、Pt/C、Pd/C、Ni/Al 2 O 3 Or Ni/SiO 2 Any one or a combination of at least two of these, wherein typical but non-limiting combinations are Raney nickel and Pt/TiO 2 Combinations of Raney nickel and Pt/C, pt/C and Pt/TiO 2 In combination of Pd/C and Ni/SiO 2 Is Ni/Al 2 O 3 And Pt/TiO 2 Is a combination of (a) and (b).
The catalyst is preferably screened to a size of 100 to 200 mesh, for example, 100 mesh, 112 mesh, 123 mesh, 134 mesh, 145 mesh, 156 mesh, 167 mesh, 178 mesh, 189 mesh or 200 mesh, etc., but not limited to the recited values, other non-recited values within this range are equally applicable.
Preferably, the diameter of the microchannel reactor is 0.2-5 mm, for example, 0.2mm, 0.8mm, 1.3mm, 1.8mm, 2.4mm, 2.9mm, 3.4mm, 4mm, 4.5mm or 5mm, etc., but not limited to the recited values, other non-recited values within this range are equally applicable.
The diameter of the micro-channel reactor is preferably 0.2-5 mm, which is favorable for guaranteeing the mass transfer and heat transfer of the reaction and further improving the selectivity and conversion rate of the reaction.
Preferably, the length of the micro-channel reactor is 800-1200 mm, for example, 800mm, 840mm, 880mm, 930mm, 970mm, 1020mm, 1060mm, 1110mm, 1150mm or 1200mm, etc., but the present invention is not limited to the recited values, and other values not recited in the range are equally applicable.
Preferably, the microchannel reactor is a T-shaped circular channel.
Preferably, the T-shaped circular channel is provided with a first liquid phase feed inlet and a first gas phase feed inlet.
Preferably, the layout of the microchannel reactor comprises a continuous S-shape.
Preferably, the evaporative organic solvent comprises any one or a combination of at least two of acetone, chloroform or dichloromethane, wherein typical but non-limiting combinations are combinations of acetone and chloroform, combinations of chloroform and dichloromethane, and combinations of acetone and dichloromethane.
The present invention further preferably uses the solvent as an evaporation type solvent, and the solvent can be effectively mixed with a film-forming organic solvent such as cellulose acetate, and has the advantages of easy film formation and high film-forming strength.
Preferably, the film-forming organic solvent comprises cellulose acetate.
The invention further preferably adopts cellulose acetate as a film-forming organic solvent, can quickly form a film, and has the advantages of high viscosity and easy catalyst fixation.
Preferably, the mass ratio of the film-forming organic solvent to the evaporation-type organic solvent is 1:11 to 15, for example, 1:11, 1:12, 1:13, 1:14, or 1:15, etc., but the present invention is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the shielding gas comprises nitrogen.
The mass of the catalyst to be fed into the reactor is preferably 1 to 10g, for example, 1g, 2g, 3g, 4g, 5g, 6g, 7g, 8g, 9g or 10g, but the catalyst is not limited to the values recited, and other values not recited in the range are equally applicable.
The time for the infiltration is preferably 20 to 45s, and may be, for example, 20s, 23s, 26s, 29s, 32s, 34s, 37s, 40s, 43s, 45s, or the like, but is not limited to the recited values, and other values not recited in the range are equally applicable.
The temperature at which the catalyst and the evaporative organic solvent are introduced into the microchannel reactor is preferably 30 to 45 ℃, and may be, for example, 30 ℃, 32 ℃, 34 ℃, 35 ℃, 37 ℃, 39 ℃, 40 ℃, 42 ℃, 44 ℃, 45 ℃ or the like, but is not limited to the values recited, and other values not recited in the range are equally applicable.
In a second aspect, the present invention provides a microchannel reactor, wherein the microchannel reactor is obtained after coating by the method for coating a catalyst in the microchannel reactor according to the first aspect.
The microchannel reactor provided by the invention is coated by adopting the method of the first aspect, so that the catalyst coating is more uniform, the catalyst is more beneficial to be exposed on the surface of the membrane and can be firmly combined, and the microchannel reactor can be suitable for coating the catalyst for synthesizing 1, 3-propanediol. In a third aspect, the invention provides a method for synthesizing 1, 3-propanediol by hydrogenating a microchannel reactor, wherein the method is carried out by adopting the microchannel reactor coated by the method for coating the catalyst in the microchannel reactor in the second aspect.
The method for synthesizing the 1, 3-propanediol by hydrogenating the micro-channel reactor of the third aspect of the invention adopts the micro-channel reactor coated with the catalyst of the second aspect, so that the mass transfer and heat transfer efficiency is high, the continuous production can be realized, and the yield and the selectivity of the 1, 3-propanediol are improved.
Preferably, the method comprises the steps of: and introducing the 3-hydroxy propanal aqueous solution and hydrogen into a microchannel reactor, and carrying out catalytic hydrogenation reaction under the action of a catalyst coated on the inner wall of the microchannel reactor to prepare the 1, 3-propanediol.
Preferably, the flow pattern of the aqueous 3-hydroxypropanal solution with hydrogen in the microchannel reactor comprises any one or a combination of at least two of Taylor flow, transition flow, or turbulence, wherein typical but non-limiting combinations are combinations of Taylor flow and transition flow, combinations of Taylor flow and turbulence, and combinations of transition flow and turbulence.
The mass concentration of the aqueous 3-hydroxypropanal solution is preferably 8 to 20%, and may be, for example, 8%, 10%, 11%, 12%, 14%, 15%, 16%, 18%, 19%, 20%, or the like, but is not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the ratio of 3-hydroxypropanal to hydrogen is 2 to 6:1, for example, 2:1, 2.5:1, 2.9:1, 3.4:1, 3.8:1, 4.3:1, 4.7:1, 5.2:1, 5.6:1, or 6:1, etc., but not limited to the recited values, other non-recited values within the range are equally applicable.
Preferably, the catalytic hydrogenation reaction comprises a two-stage reaction.
The temperature of the first reaction in the two-stage reaction is preferably 30 to 70 ℃, and may be, for example, 30 ℃, 35 ℃, 39 ℃, 44 ℃, 48 ℃, 53 ℃, 57 ℃, 62 ℃, 66 ℃, or 70 ℃, etc., but is not limited to the values recited, and other values not recited in the range are equally applicable.
The second stage reaction in the two-stage reaction is preferably carried out at a temperature of 80 to 120℃and may be, for example, 80℃85℃89℃94℃98℃103℃107℃112℃116℃120℃or the like, but is not limited to the values recited, and other values not recited in the above range are equally applicable.
The invention further preferably carries out the staged reaction, and can better improve the conversion rate and selectivity of the reaction.
Preferably, the length ratio of the first stage reaction to the second stage reaction is 1 to 3:1, for example, 1:1, 1.3:1, 1.5:1, 1.7:1, 1.9:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1 or 3:1, etc., but not limited to the recited values, other non-recited values in the range are equally applicable.
The invention further preferably controls the ratio of the first-stage reaction to the second-stage reaction in the above range, thereby being more beneficial to controlling the residence time of materials in each stage and effectively guaranteeing the selectivity and the yield of the reaction.
The pressure of the catalytic hydrogenation reaction is preferably 1 to 5MPa, and may be, for example, 1MPa, 1.5MPa, 1.9MPa, 2.4MPa, 2.8MPa, 3.3MPa, 3.7MPa, 4.2MPa, 4.6MPa, or 5MPa, etc., but the present invention is not limited to the values recited, and other values not recited in the above range are equally applicable.
As a preferred technical scheme of the second aspect of the invention, the method for synthesizing 1, 3-propanediol by hydrogenation in the microchannel reactor comprises the following steps:
introducing a 3-hydroxypropionaldehyde aqueous solution with the mass concentration of 8-20% and hydrogen into a microchannel reactor, wherein the hydrogen-oil ratio of the 3-hydroxypropionaldehyde to the hydrogen is 2-6:1, and carrying out two-stage catalytic hydrogenation reaction under the conditions of the catalyst coated on the inner wall of the microchannel reactor and the pressure of 1-5 MPa, wherein the temperature of the first-stage reaction is 30-70 ℃, the temperature of the second-stage reaction is 80-120 ℃, and the length ratio of the first-stage reaction to the second-stage reaction is 1-3:1, so as to prepare the 1, 3-propanediol.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The method for coating the catalyst in the microchannel reactor can realize uniform and stable coating of the solid phase catalyst;
(2) According to the method for synthesizing the 1, 3-propanediol by hydrogenation in the microchannel reactor, provided by the invention, bubbles with a gas-liquid film can be formed in the microchannel by regulating and controlling the flow rate of gas-liquid phases, so that the mass transfer and heat transfer of reactants and the contact of the reactants with a tube wall catalyst are accelerated, the generation of byproducts is reduced, the yield and the selectivity of the 1, 3-propanediol are improved, wherein the conversion rate of 3-hydroxypropionaldehyde is preferably more than 99.3%, and the selectivity of the 1, 3-propanediol is preferably more than 99.6%;
(3) The method for synthesizing the 1, 3-propanediol by hydrogenation in the microchannel reactor provided by the invention is convenient to operate, can realize continuous production, has good safety and is beneficial to industrial production.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
As one embodiment of the present invention, there is provided a coating method of a catalyst in a microchannel reactor, the coating method comprising the steps of:
mixing the evaporation type organic solvent, the film forming organic solvent and the protective gas, wherein the mass ratio of the film forming organic solvent to the evaporation type organic solvent is 1:11-15, introducing the mixture into a microchannel reactor, after the evaporation of the evaporation type organic solvent to form an organic film, introducing 1-10 g of a catalyst with a screening size of 100-200 meshes and the evaporation type organic solvent into the microchannel reactor with a diameter of 0.2-5 mm at 30-45 ℃, soaking the mixture for 20-45 s, volatilizing the evaporation type organic solvent, and repeating the steps at least three times to obtain the microchannel reactor with the catalyst.
As another embodiment of the present invention, there is provided a method for synthesizing 1, 3-propanediol by hydrogenation in a microchannel reactor, the method for synthesizing 1, 3-propanediol by hydrogenation in the microchannel reactor comprising:
introducing a 3-hydroxypropionaldehyde aqueous solution with the mass concentration of 8-20% and hydrogen into a microchannel reactor, wherein the hydrogen-oil ratio of the 3-hydroxypropionaldehyde to the hydrogen is 2-6:1, and carrying out two-stage catalytic hydrogenation reaction under the conditions of the catalyst coated on the inner wall of the microchannel reactor and the pressure of 1-5 MPa, wherein the temperature of the first-stage reaction is 30-70 ℃, the temperature of the second-stage reaction is 80-120 ℃, and the length ratio of the first-stage reaction to the second-stage reaction is 1-3:1, so as to prepare the 1, 3-propanediol.
Specific examples are described below.
Example 1
The present embodiment provides a method for coating a catalyst in a microchannel reactor, the method comprising the steps of:
mixing 1g of cellulose acetate, 15g of acetone and nitrogen, introducing into a microchannel reactor until the solution is completely coated on the inner wall of the microchannel reactor, evaporating the evaporated organic solvent to form a cellulose acetate organic film, mixing 1.5g of Raney nickel catalyst with the size of 100-200 meshes with 4g of acetone at 35 ℃, introducing into the microchannel reactor with the diameter of 0.2mm and the length of 900mm, soaking for 30s, volatilizing the acetone, and repeating for three times to obtain the microchannel reactor with the catalyst.
The embodiment also provides a method for synthesizing 1, 3-propanediol by hydrogenation in a microchannel reactor, which comprises the following steps:
3-hydroxy-propionaldehyde aqueous solution with the mass concentration of 20% at 0.5mL/min and high-purity hydrogen with the mass concentration of 60mL/min are respectively introduced into the microchannel reactor through a metering pump, the hydrogen-oil ratio of the 3-hydroxy-propionaldehyde to the hydrogen is 2:1, two-stage catalytic hydrogenation reaction is carried out under the conditions of the action of a catalyst coated on the inner wall of the microchannel reactor and the pressure of 4MPa, the temperature of the first-stage reaction is 70 ℃, the temperature of the second-stage reaction is 100 ℃, the length ratio of the first-stage reaction to the second-stage reaction is 3:1, and two materials are circularly reacted for 4 times in Taylor flow patterns to prepare 1, 3-propanediol.
Example 2
The present embodiment provides a method for coating a catalyst in a microchannel reactor, the method comprising the steps of:
mixing 1.5g of cellulose acetate, 19.5g of acetone and nitrogen, introducing into a microchannel reactor until the solution is completely coated on the inner wall of the microchannel reactor, evaporating the evaporated organic solvent to form a cellulose acetate organic film, and then adding 3g of Pt/TiO with 100-200 meshes at 35 DEG C 2 Mixing the catalyst and 5g of acetone, introducing the mixture into a micro-channel reactor with the diameter of 2mm and the length of 1200mm, soaking the mixture for 30s, volatilizing the acetone, and repeating the steps for three times to obtain the micro-channel reactor with the catalyst.
The embodiment also provides a method for synthesizing 1, 3-propanediol by hydrogenation in a microchannel reactor, which comprises the following steps:
3-hydroxy-propionaldehyde aqueous solution with the mass concentration of 15% at 0.2mL/min and high-purity hydrogen with the mass concentration of 60mL/min are respectively introduced into the microchannel reactor through a metering pump, the hydrogen-oil ratio of the 3-hydroxy-propionaldehyde to the hydrogen is 5:1, two-stage catalytic hydrogenation reaction is carried out under the conditions of the catalyst coated on the inner wall of the microchannel reactor and the pressure of 5MPa, the temperature of the first-stage reaction is 60 ℃, the temperature of the second-stage reaction is 120 ℃, the length ratio of the first-stage reaction to the second-stage reaction is 2:1, and two materials are circularly reacted for 2 times in Taylor flow pattern to prepare 1, 3-propanediol.
Example 3
The present embodiment provides a method for coating a catalyst in a microchannel reactor, the method comprising the steps of:
mixing 2g of cellulose acetate, 22g of acetone and nitrogen, introducing the mixture into a microchannel reactor until the solution is completely coated on the inner wall of the microchannel reactor, evaporating the evaporated organic solvent to form a cellulose acetate organic film, mixing 5g of Pd/C catalyst with the size of 150-200 meshes with 4g of acetone at 35 ℃, introducing the mixture into the microchannel reactor with the diameter of 2mm and the length of 800mm, soaking for 30s, volatilizing the acetone, and repeating the process for three times to obtain the microchannel reactor with the catalyst.
The embodiment also provides a method for synthesizing 1, 3-propanediol by hydrogenation in a microchannel reactor, which comprises the following steps:
and (3) respectively introducing a 3-hydroxypropionaldehyde aqueous solution with the mass concentration of 8% at 0.4mL/min and 72mL/min of high-purity hydrogen into the microchannel reactor through a metering pump, wherein the hydrogen-oil ratio of the 3-hydroxypropionaldehyde to the hydrogen is 3:1, and carrying out two-stage catalytic hydrogenation reaction under the conditions of the catalyst coated on the inner wall of the microchannel reactor and the pressure of 1MPa, wherein the temperature of the first-stage reaction is 30 ℃, the temperature of the second-stage reaction is 80 ℃, the length ratio of the first-stage reaction to the second-stage reaction is 1:1, and the two materials are circularly reacted for 3 times in a transitional flow pattern to prepare the 1, 3-propanediol.
Example 4
The present embodiment provides a method for coating a catalyst in a microchannel reactor, the method comprising the steps of:
mixing 3g of cellulose acetate, 36g of acetone and nitrogen, introducing into a microchannel reactor until the solution is completely coated on the inner wall of the microchannel reactor, evaporating the evaporated organic solvent to form a cellulose acetate organic film, mixing 2.5g of Pt/C catalyst with the size of 100-150 meshes with 6g of acetone at 35 ℃, introducing into the microchannel reactor with the diameter of 5mm and the length of 1200mm, soaking for 30s, volatilizing the acetone, and repeating for three times to obtain the microchannel reactor with the catalyst.
The embodiment also provides a method for synthesizing 1, 3-propanediol by hydrogenation in a microchannel reactor, which comprises the following steps:
3-hydroxy-propionaldehyde aqueous solution with the mass concentration of 20% at 0.2mL/min and high-purity hydrogen with the mass concentration of 72mL/min are respectively introduced into the microchannel reactor through a metering pump, the hydrogen-oil ratio of the 3-hydroxy-propionaldehyde to the hydrogen is 6:1, two-stage catalytic hydrogenation reaction is carried out under the conditions of the action of a catalyst coated on the inner wall of the microchannel reactor and the pressure of 6MPa, the temperature of the first-stage reaction is 55 ℃, the temperature of the second-stage reaction is 90 ℃, the length ratio of the first-stage reaction to the second-stage reaction is 2:1, and two materials are circularly reacted for 3 times in a transitional flow pattern to prepare the 1, 3-propanediol.
Example 5
The present embodiment provides a method for coating a catalyst in a microchannel reactor, the method comprising the steps of:
mixing 2g of cellulose acetate, 26g of acetone and nitrogen, introducing into a microchannel reactor until the solution is completely coated on the inner wall of the microchannel reactor, evaporating the evaporated organic solvent to form a cellulose acetate organic film, mixing 1.5g of Raney nickel catalyst with the size of 150-200 meshes with 5g of acetone at 35 ℃, introducing into the microchannel reactor with the diameter of 3mm and the length of 1200mm, soaking for 30s, volatilizing the acetone, and repeating for three times to obtain the microchannel reactor with the catalyst.
The embodiment also provides a method for synthesizing 1, 3-propanediol by hydrogenation in a microchannel reactor, which comprises the following steps:
3-hydroxy-propionaldehyde aqueous solution with the mass concentration of 15% in 1mL/min and high-purity hydrogen with the mass concentration of 121mL/min are respectively introduced into the microchannel reactor through a metering pump, the hydrogen-oil ratio of 3-hydroxy-propionaldehyde to hydrogen is 2:1, and under the conditions of the catalyst coated on the inner wall of the microchannel reactor and the pressure of 5MPa, two-stage catalytic hydrogenation reaction is carried out, wherein the temperature of the first-stage reaction is 60 ℃, the temperature of the second-stage reaction is 90 ℃, the length ratio of the first-stage reaction to the second-stage reaction is 2:1, and the two materials are subjected to turbulent flow type circulation reaction for 3 times to prepare 1, 3-propanediol.
Example 6
The present embodiment provides a method for coating a catalyst in a microchannel reactor, the method comprising the steps of:
mixing 4g of cellulose acetate, 52g of acetone and nitrogen, introducing into a microchannel reactor until the solution is completely coated on the inner wall of the microchannel reactor, evaporating the evaporated organic solvent to form a cellulose acetate organic film, mixing 1.5g of Raney nickel catalyst with the size of 100-200 meshes with 7g of acetone at 35 ℃, introducing into the microchannel reactor with the diameter of 0.3mm and the length of 1200mm, soaking for 45s, volatilizing the acetone, and repeating for four times to obtain the microchannel reactor with the catalyst.
The embodiment also provides a method for synthesizing 1, 3-propanediol by hydrogenation in a microchannel reactor, which comprises the following steps:
and (3) respectively introducing a 3-hydroxypropionaldehyde aqueous solution with the mass concentration of 20% at 0.2mL/min and 48mL/min of high-purity hydrogen into the microchannel reactor through a metering pump, wherein the hydrogen-oil ratio of the 3-hydroxypropionaldehyde to the hydrogen is 4:1, and carrying out two-stage catalytic hydrogenation reaction under the conditions of the action of a catalyst coated on the inner wall of the microchannel reactor and the pressure of 2MPa, wherein the temperature of the first-stage reaction is 40 ℃, the temperature of the second-stage reaction is 80 ℃, the length ratio of the first-stage reaction to the second-stage reaction is 1:1, and the two materials are circularly reacted for 4 times in a Taylor flow pattern to prepare the 1, 3-propanediol.
Example 7
The present embodiment provides a method for coating a catalyst in a microchannel reactor, the method comprising the steps of:
mixing 3g of cellulose acetate, 33g of acetone and nitrogen, introducing into a microchannel reactor until the solution is completely coated on the inner wall of the microchannel reactor, evaporating the evaporated organic solvent to form a cellulose acetate organic film, and then adding 1.5g of Ni/SiO with the size of 100-150 meshes at 35 DEG C 2 Mixing the catalyst and 5g of acetone, introducing the mixture into a micro-channel reactor with the diameter of 0.2mm and the length of 1000mm, soaking the mixture for 20 seconds, volatilizing the acetone, and repeating the steps for five times to obtain the micro-channel reactor with the catalyst.
The embodiment also provides a method for synthesizing 1, 3-propanediol by hydrogenation in a microchannel reactor, which comprises the following steps:
3-hydroxy-propionaldehyde aqueous solution with the mass concentration of 20% at 0.2mL/min and 36mL/min of high-purity hydrogen are respectively introduced into the microchannel reactor through a metering pump, the hydrogen-oil ratio of the 3-hydroxy-propionaldehyde to the hydrogen is 3:1, and under the conditions of the catalyst coated on the inner wall of the microchannel reactor and the pressure of 4MPa, two-stage catalytic hydrogenation reaction is carried out, wherein the temperature of the first-stage reaction is 70 ℃, the temperature of the second-stage reaction is 100 ℃, the length ratio of the first-stage reaction to the second-stage reaction is 2:1, and the two materials are circularly reacted for 4 times in Taylor flow pattern to prepare the 1, 3-propanediol.
Example 8
The present example provides a method for synthesizing 1, 3-propanediol by hydrogenation in a microchannel reactor, which is the same as example 1 except that the flow rates of the 3-hydroxypropanal aqueous solution and the high-purity hydrogen gas are 30mL/min and 5mL/min, respectively, and the two materials are reacted in a bubble flow pattern.
Example 9
This example provides a process for the hydrogenation synthesis of 1, 3-propanediol in a microchannel reactor, which is the same as example 1 except that the two feeds are reacted only 1 time in the microchannel reactor.
Example 10
This example provides a method for synthesizing 1, 3-propanediol by hydrogenation in a microchannel reactor, which is the same as example 1 except that cellulose acetate is replaced with polyvinyl alcohol solution.
Example 11
The present example provides a method for synthesizing 1, 3-propanediol by hydrogenation in a microchannel reactor, wherein the temperature of the method is 100 ℃, and the rest is the same as example 1 except that no two-stage reaction is performed.
Comparative example 1
This comparative example provides a process for the hydrogenation synthesis of 1, 3-propanediol in a microchannel reactor, the process being the same as example 1 except that the catalyst coating process is a process in which the catalyst is introduced into the microchannel reactor along with a mixture of cellulose acetate and acetone.
The reaction mixtures of the above examples and comparative examples were subjected to chromatographic detection to calculate the conversion of 3-hydroxypropanal and the selectivity of 1, 3-propanediol as shown in Table 1.
TABLE 1
From table 1, the following points can be seen:
(1) As can be seen from comprehensive examples 1-7, the method for synthesizing 1, 3-propanediol by hydrogenation in the microchannel reactor provided by the invention is carried out by adopting the microchannel reactor coated with the catalyst, so that the conversion rate and selectivity of the reaction are improved, and continuous production can be realized, wherein the conversion rate of 3-hydroxypropionaldehyde is more than 99.3%, and the selectivity of 1, 3-propanediol is more than 99.6%;
(2) As can be seen from the combination of examples 1 and examples 9 to 10, in example 1, the reaction coating was repeated three times when the catalyst was coated on the inner wall of the microchannel reactor and the film forming organic solvent was preferably cellulose acetate, and compared with the reaction of example 9 only for 1 time, in example 10, the film forming organic solvent was polyvinyl alcohol solution, the conversion rate of 3-hydroxypropanal in example 1 was 99.1%, the 1, 3-propanediol selectivity was 99.8%, and the 3-hydroxypropanal conversion rates in examples 9 to 10 were 63.8% and 82.4%, respectively, and the 1, 3-propanediol selectivity was 99.6% and 96.7%, respectively, thereby indicating that the catalyst of this reaction could be better coated on the surface of the microchannel reactor by preferably using the film forming organic solvent and the coating times, and the conversion rate and selectivity of the subsequent reaction were improved;
(3) As can be seen from a combination of examples 1 and 8, the specific flow rate is specifically selected to achieve taylor flow pattern in example 1, and the conversion and selectivity of the reaction in example 1 are significantly higher than those of the bubble flow pattern reaction caused by the flow rate change in example 8, thereby indicating that the selectivity and conversion are significantly improved by the preference of the specific reaction flow pattern in the present invention in addition to the microchannel reactor using the coated catalyst;
(4) It can be seen from the combination of example 1 and example 11 that the staged reaction in example 1 has a selectivity of up to 99.8% for 1, 3-propanediol in example 1 and only 90.5% in example 11, compared to the case where the staged reaction is not performed in example 11, thus showing that the present invention significantly improves the selectivity of the reaction by optimizing the two-step staged reaction;
(5) As can be seen from the comprehensive example 1 and the comparative example 1, in the invention, the film-forming organic solvent is formed on the surface of the reactor, and then the catalyst is introduced for soaking and coating.
In summary, the microchannel reactor provided by the invention can accelerate the gas-liquid-solid mass transfer efficiency, increase the heat transfer, reduce the generation of byproducts, and improve the reaction conversion rate and selectivity.
The applicant states that the detailed process equipment and process flows of the present invention are described by the above examples, but the present invention is not limited to, i.e., does not mean that the present invention must be practiced in dependence upon, the above detailed process equipment and process flows. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (22)
1. A method of coating a catalyst in a microchannel reactor, the method comprising the steps of:
mixing a vaporized organic solvent, a film-forming organic solvent and a protective gas, introducing the mixture into a microchannel reactor, introducing a catalyst and the vaporized organic solvent into the microchannel reactor after the vaporized organic solvent forms an organic film, infiltrating, volatilizing the vaporized organic solvent, and repeating the steps at least three times to obtain the microchannel reactor with the catalyst;
the evaporation type organic solvent comprises any one or a combination of at least two of acetone, chloroform and dichloromethane;
the film-forming organic solvent comprises cellulose acetate;
the mass ratio of the film-forming organic solvent to the evaporation-type organic solvent is 1:11-15.
2. The method of claim 1, wherein the catalyst comprises raney nickel, pt/TiO 2 、Pt/C、Pd/C、Ni/Al 2 O 3 Or Ni/SiO 2 Any one or a combination of at least two of these.
3. The coating method according to claim 1, wherein the catalyst has a sieve size of 100 to 200 mesh.
4. The coating method according to claim 1 or 2, wherein the diameter of the microchannel reactor is 0.2-5 mm.
5. A coating method according to any one of claims 1 to 3, wherein the microchannel reactor is a T-shaped circular channel.
6. The coating method of claim 5, wherein the T-shaped round channel is provided with a first liquid phase feed port and a first gas phase feed port.
7. The coating process of claim 1, wherein the microchannel reactor layout comprises a continuous S-shape.
8. The coating method of claim 1, wherein the shielding gas comprises nitrogen.
9. The coating method according to claim 5, wherein the mass of the catalyst in one pass is 1-10 g.
10. The coating method according to claim 1, wherein the time of the infiltration is 20 to 45s.
11. The coating method according to claim 1, wherein the temperature at which the catalyst and the evaporative organic solvent are introduced into the microchannel reactor is 30-45 ℃.
12. A microchannel reactor, wherein the microchannel reactor is coated by the method for coating a catalyst in the microchannel reactor according to any one of claims 1 to 11.
13. A process for the hydrogenation synthesis of 1, 3-propanediol by a microchannel reactor, wherein the process is carried out using the microchannel reactor of claim 12.
14. The method according to claim 13, characterized in that it comprises the steps of: and introducing the 3-hydroxy propanal aqueous solution and hydrogen into a microchannel reactor, and carrying out catalytic hydrogenation reaction under the action of a catalyst coated on the inner wall of the microchannel reactor to prepare the 1, 3-propanediol.
15. The method of claim 14, wherein the flow pattern of the aqueous 3-hydroxypropanal solution and hydrogen in the microchannel reactor comprises any one or a combination of at least two of taylor flow, transitional flow, or turbulent flow.
16. The method according to claim 15, wherein the mass concentration of the 3-hydroxypropanal aqueous solution is 8 to 20%.
17. The method according to claim 15, wherein the hydrogen-to-oil ratio of the 3-hydroxypropanal to the hydrogen is 2-6:1.
18. The method of claim 14, wherein the catalytic hydrogenation reaction comprises a two-stage reaction.
19. The method of claim 18, wherein the temperature of the first of the two-stage reactions is 30-70 ℃.
20. The method of claim 18, wherein the second reaction stage of the two reaction stages is at a temperature of 80 to 120 ℃.
21. The method of claim 18, wherein the ratio of the length of the first stage reaction to the length of the second stage reaction is 1-3:1.
22. The method of claim 18, wherein the catalytic hydrogenation reaction is carried out at a pressure of 1 to 5mpa.
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