CN104478702B - A kind of method using micro passage reaction synthesizing adipic acid - Google Patents
A kind of method using micro passage reaction synthesizing adipic acid Download PDFInfo
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Abstract
A kind of method using micro passage reaction synthesizing adipic acid of the invention, it belongs to the technical field of organic synthesis application.Be one kind in Corning micro passage reactions, using KA oil and nitric acid as raw material, Cu and V are catalyst, in micro passage reaction in the tens seconds of short duration reaction time to a few minutes alcohol ketone oxidation synthesis of adipic acid new technology.Material is after measuring pump is passed through Corning micro passage reactions, by preheating, mixing, oxidation reaction post-processes to obtain adipic acid product, and this method has easy to operate and safe, high yield continuous production adipic acid product, in addition, the environmental pollution of the technique substantially reduces.
Description
Technical field
The invention belongs to organic synthesis applied technical field, and in particular to cyclohexanone and cyclohexanol（Alcohol ketone oil, is commonly called as KA
Oil）It is raw material with nitric acid, Cu and V are catalyst, and alcohol ketone oxidation reaction synthesizing adipic acid product is carried out in micro passage reaction.
In particular it is in the Corning micro passage reactions of high flux microchannel continuous stream, is synthesized using nitric acid oxidation KA oil
The technique of adipic acid.
Background technology
Adipic acid also known as adipic acid（Adipic Acid）, be most have in aliphatic dicarboxylic acid application value binary acid it
One, the reaction such as salt, esterification and amidatioon can occur into, mainly for the production of polyamide fibre 66 and nylon66 fiber engineering plastics, poly- ammonia
Ester foamed plastic and plasticizer, it additionally can be used for production senior lubricant, food additives, medicine intermediate, spices and essence
Controlling agent, new monocrystal material, plastics blowing agent, coating, insecticide, adhesive and dyestuff etc., purposes is quite varied.
At present, the industrial process of adipic acid is mainly hexamethylene method, and the process route accounts for global adipic acid at present
The 93% of total productive capacity.Hexamethylene route, i.e., generate hexamethylene by purified petroleum benzin catalytic hydrogenation, and hexamethylene generates through air oxidation again
Cyclohexanone and cyclohexanol（Alcohol ketone oil, it is commonly called as KA oil）, then by nitric acid oxidation synthesizing adipic acid.The route produces substantial amounts of " three
It is useless ", wherein main is caused waste liquid in alcohol ketone building-up process, the waste water and Nitric Acid Oxidation of alcohol ketone oxidation synthesis of adipic acid process
The waste gas such as caused nitrogen oxide during change KA oil.As environmental protection pressure is increasing, for existing in adipic acid production process
Using corrosivity nitric acid material and the problems such as produce the nitrogen oxides, nitric acid vapor and acid pickle of serious pollution environment, at present
Researching and developing cyclohexene oxide method, butadiene process and the process for cleanly preparing using adipic acids such as biological catalysis.
Cyclohexene oxide method：With 30% hydrogen peroxide as oxidant cyclohexene oxide obtaining adipic acid, condition temperature
With yield is about 93% ~ 95%.Technological advantage is high catalytic activity, and high selectivity, mild condition, etching apparatus, not pollution-free.
Shortcoming is reaction time length, and hydrogen peroxide consumption is high（1mol adipic acids are produced, consume 4mol hydrogen peroxide）.Japanese Scientists are opened
Send out with catalyst n a2WO4·2H2O is catalyst, [CH3N(n-C8H17)3]HSO4It is direct for phase transfer catalyst, hydrogen peroxide
Cyclohexene oxide prepares adipic acid.Cyclohexene：Na2WO4·2H2O：[CH3N(n-C8H17)3]HSO4=100:1:1,30%H2O2, 75 ~
90 DEG C, 8h, ADA yields reach 93%.Using the sulfate of Long carbon chain primary amine or tertiary amine as phase transfer catalyst, ADA is received Zhang Jinhui etc.
Rate reaches 94.1%.For Zhang etc. using benzyltriethylammoinium chloride as phase transfer catalyst, phosphotungstic acid is catalyst, and ADA yields reach
To 87%.Chinese Academy of Sciences's Lanzhou materialization develops peroxotungstate organic coordination compound and replaces phase transfer catalyst technique, catalyst [W
(O)(O2)L2]2-, when using oxalic acid as part, cyclohexene conversion rate reaches 100%, adipic acid yield 96.6%.Beam carbuncle etc. with
Sodium tungstate/L- (+)-ascorbic acid is catalyst system and catalyzing, and adds surfactant in right amount（Lauryl sodium sulfate PEG10M）, use
30%H2O2Cyclohexene oxide synthesizing adipic acid, n (hexene):n(H2O2):N (sodium tungstate):N [L (+) ascorbic acid]=1:4.4:
0.025:0.025, high-speed stirred, flow back 5h, and reaction solution is quiet overnight at 0 DEG C, adipic acid yield 86%.
Butadiene process：DuPont and BASF AG prepare the condition of adipic acid with butadiene carbonyl alkoxylate：100
DEG C, 128atm.Co2(CO)8It is catalyst system and catalyzing with pyridine, butadiene conversion is more than 98%, selectivity 88%.After DuPont
To use PdCl again2, triphenylphosphine, pyridine, sulfuric acid catalysis system, conversion ratio 100%, selectivity be more than 92%, catalyst Ni
(CO) complex or mantoquita complex, 100 ~ 140 DEG C, butadiene conversion is 84 ~ 89%.Intermediate product alkene cyanogen is again through carbonyl alcoxyl
Base or hydrocarboxylation generation adipic acid.Adipic acid is prepared using butadiene carbonyl process, raw material is relatively inexpensive, high income, and it is produced
Cost is lower than cyclohexane oxidation, and shortcoming is that technique owes maturation, and complex process, severe reaction conditions, byproduct is more, at present industry
On do not use generally.
Biological catalysis：Utilize D-Glucose living things catalysis synthesizing adipic acid.1990s, DuPont develop biology
Catalytic processes.D2 glucose is converted into using Escherichia coli suitable, cis- hexadienoic acid, is then hydrogenated to adipic acid.Later should
Company develops new bioprocess technology method again, and enzyme is compiled with a kind of gene a small bundle of straw, etc. for silkworms to spin cocoons on separated from aerobic denitration bacterial strain
Code, so as to obtain the synzyme that cyclohexanol converts adipic acid processed.The mutation chief cell of the synzyme is under suitable growth conditions
Cyclohexanol can optionally be changed into adipic acid.
The present invention is used with cyclohexanone and cyclohexanol（Alcohol ketone oil, it is commonly called as KA oil）It is raw material with nitric acid, Cu and V are catalysis
Agent, alcohol ketone oxidation reaction synthesizing adipic acid technique is carried out in micro passage reaction, is specifically reacted as shown in the equation below：
The reaction mechanism of nitric acid oxidation alcohol ketone production adipic acid is as follows：（1）In the presence of copper, vanadium catalyst and nitric acid,
Cyclohexanol in alcohol ketone mixed solution generates cyclohexanone by rapid oxidation, while produces HNO2.There is trace HNO2In the presence of, ring
The reaction rate that hexanol is oxidized to cyclohexanone is fast, caused HNO2It is the key substance that cyclohexanone further aoxidizes.（2）Cyclohexanone
Oxidation reaction.Cyclohexanone is in HNO2In the presence of, it is oxidized to intermediate product 6- oximido -6- nitro caproic acids（Abbreviation nitrol acid,
It is abbreviated as NA）.Concentration of nitric acid is relatively low, and cyclohexanone can form 1,2- cyclohexanedione semihydrates, abbreviation diketone.Oxidizing cyclohexanone
It is first order reaction to cyclohexanone, its reaction rate dramatically increases with the raising of concentration of nitric acid and reaction temperature into nitrol acid.This is anti-
Answer thermal discharge larger, account for 90% or so of total thermal discharge.（3）The decomposition reaction of nitrol acid.Under nitric acid effect, nitrol acid decomposes
Into adipic acid, this reaction is first order reaction, and reaction rate is relatively slow compared with oxidizing cyclohexanone is into the speed of nitrol acid, is whole anti-
The rate-determining steps of speed are answered, and thermal discharge is small, accounts for 10% or so of total thermal discharge.（4）In the presence of catalyst, diketone is then whole
It is converted into accessory substance, mainly succinic acid and low molecular weight product（Such as ethanedioic acid）.In the presence of vanadium, diketone can Partial Conversion
For adipic acid, while also generate a considerable amount of accessory substance binary acid.（5）At high temperature, when there is a large amount of HNO2In the presence of, more
Nitro functions can be introduced into intermediate product neighbour's nitrous pentylcyclohexanone, then form more nitrocyclohexanones, and then be converted into penta 2
Acid and succinic acid etc..Copper can effectively suppress the generation of above-mentioned reaction, improve adipic acid yield.
So far, there is not yet carrying out KA oil nitric acid oxidation synthesizing adipic acids in a manner of the continuous stream of Corning microchannels
Method research.The present invention provides a kind of oil of the nitric acid oxidation KA in a manner of continuous stream in Corning micro passage reactions
The process route of synthesizing adipic acid.
Carried out in Corning micro passage reactions when early stage, synthetic reaction condition screened, it is necessary to which reactant dosage is little, no
But the dosage of expensive, poisonous adverse reaction thing can be reduced, caused environmental contaminants are also few in course of reaction, laboratory base
This is pollution-free, is a kind of environment-friendly, study on the synthesis novel substance technology platform.In Corning in micro passage reaction
The matching analysis is carried out to product and modern age analytical instrument, such as GC, GC-MS, HPLC and NMR, can be used for modern age analytical instrument straight
The degree that on-line monitoring reaction is carried out is connect, substantially increases the speed of research synthetic route.
The type of the special glass functional module of Corning micro passage reactions has straight-through channel type, cardioid mixed structure
Type, there is one section of cardioid mixed structure to be followed by straight-through channel type, have one section of capillary mixed structure be followed by straight-through channel type etc..
The special glass functional module of Corning micro passage reactions have double charging aperture list discharging openings functional module and single charging aperture and
The functional module of single discharging opening.Its safe operating temperature range of Corning micro passage reactions is -25 DEG C ~ 200 DEG C, safety behaviour
It is 0 ~ 18bar to make pressure limit, and material pipeline is connected as PFA（Perfluoroalkoxy resin）Material.European patent WO2010/
037012A2, it is the module patent of Corning companies special construction design, has write out the spy of Corning productions in patent in detail
The structure of different module, the size of module and the arrangement of passage etc., it is indicated that the integrated and miniaturization of module is chemical process
The safer selection of amplification.
The content of the invention
It is an object of the present invention to provide a kind of nitric acid oxidation KA in a manner of continuous stream in Corning micro passage reactions oil
Synthesizing adipic acid product, compared with existing technique, there is the technique reaction condition accurately to control, and reduce the row of organic liquid waste
Put, the mode of continuous safety produces, and the KA oil conversion completely within the extremely short time, and adipic acid selectivity is high.
The present invention is a kind of method using micro passage reaction synthesizing adipic acid, it is characterised in that is entered as steps described below
OK：
（1）With cyclohexanone and cyclohexanol（Alcohol ketone oil, it is commonly called as KA oil）It is raw material with nitric acid, Cu and V are catalyst, micro- logical
Alcohol ketone oxidation reaction synthesizing adipic acid product is carried out in road reactor.Copper and vanadium catalyst are dissolved in nitric acid under agitation and being made into
Oxidation acid solution and KA oil are used as reaction mass, each lead into micro passage reaction through measuring pump and are carried out in advance in each channel module
Heat, design temperature are controlled by external heat exchanger, and heat transferring medium is conduction oil；Controlled again by flow and change KA oil:Oxidation
Acid solution mol ratio=1:10~1:20；Control KA oil flow rates：1mL/min ~ 5mL/min, control oxidizing acid solution flow rate：10mL/
min~20mL/min；Synchronously enter via respective measuring pump in mass transfer enhancement pattern block and carry out hybrid reaction, mixing temperature is same
It is controlled by external heat exchanger；
（2）Control the mol ratio of KA oil and oxidation acid solution by flow, it is blended in the module and after reacting,
Continue through a series of mass transfer enhancement type microchannel modules and once-through type microchannel module, after the completion of course of reaction, product from
The outlet outflow of reactor, into cooling last handling process；Course of reaction reaction time in micro passage reaction is
50s~100s, reaction temperature are 60~120 DEG C, and pressure is 0.1 ~ 1.5 MPa；
（3）The reaction solution that micro passage reaction is exported to obtain, catalyst is isolated through recrystallization, it is dry that adipic acid produces
Product, it is used for after the caused recovered concentration of spent acid in next oxidation reaction.KA oil total conversion is 100%, and adipic acid selectivity is about
85 ~ 90% or so, total yield of products about 85 ~ 90%.
Wherein step（1）Middle oxidation acid solution, wherein oxidation acid solution is copper and vanadium catalyst be dissolved in nitric acid prepare and
Into Cu2+Concentration 0.1% ~ 1.0%, VO2+Concentration 0.1% ~ 0.5%.
Wherein step（1）Middle KA oil:It is preferably 1 to aoxidize acid solution mol ratio:15~1:17, nitric acid mass concentration be 40%~
80%。
Wherein step（1）Middle KA oil flow rates are preferably：2mL/min ~ 3mL/min, control oxidizing acid solution flow rate are preferably：
14mL/min~16mL/min。
Wherein step（1）Aoxidize Cu in acid solution2+Concentration preferably 0.3% ~ 0.5%, VO2+Concentration preferably 0.2% ~
0.3%, nitric acid mass concentration is preferably 50~60%.
Wherein step（2）In in micro passage reaction reaction time be preferably 70~85s, reaction temperature is preferably
85~90 DEG C, pressure is preferably 0.4 ~ 0.6 MPa.
The Corning for high flux microchannel continuous stream used in the present invention（It is healthy and free from worry）Micro passage reaction, the reaction system
System formed by polylith module assembled, intermodule can assembled in parallel or assembled in series, module by exchange heat path with react path integrate
With one, or containing only reaction path, and it is immersed in temperature control heat-conducting medium.It is furnished with thermoelectricity in heat exchange path or heat-conducting medium
It is even, available for the actual temperature of heat transferring medium or extraneous heat-conducting medium in measure heat exchange path.In heat exchange path or heat-conducting medium
In be furnished with thermocouple, available for measure exchange heat path in the actual temperature of heat transferring medium or extraneous heat-conducting medium.The material of the module
Matter is monocrystalline silicon, special glass, ceramics, the stainless steel for scribbling corrosion resistant coating or metal alloy, polytetrafluoroethylene (PTFE) etc..Reaction system
Can anti-corrosion it is pressure-resistant, it is different and different that voltage endurance capability regards material.MCA divides once-through type channel design and enhancing mixed in module
Two kinds of mould assembly channel design, once-through type passage are tubular structure, and enhancing mixed type channel design is heart-shaped structure, and passage waterpower is straight
Footpath is 0.5mm ~ 10mm.
The mass transfer enhancement type micro channel reactor system that the present invention carries out KA oil nitric acid oxidations is anti-including the preheating of KA oil, mixing
Answer, oxidizing process three parts, it is therefore desirable to raw material preheating module, mixing module and a number of reaction module, particular number
Determined by reaction time.
The present invention has following main feature compared with prior art：
1. the present invention uses the Corning microchannels continuous flow reactor of continuous stream, reaction time from traditional a few hours
Tens seconds are shortened to a few minutes, significantly improves reaction efficiency.
2. because raw material mixes splendid in microchannel, temperature accurately controls, and in course of reaction, the dosage of nitric acid can be big
It is big to reduce, reduce the generation of spent acid, and the selectivity of product significantly improves.
3. the Corning micro passage reactions material used in the present invention is special glass, the material of measuring pump is poly- four
PVF and titanium, excellent corrosion resistance, avoid the problem of etching apparatus is serious in conventional reactor.
4. in micro passage reaction, react, avoid for continuous stream from charging, preheating, mixing and course of reaction whole process
Need the leakage occurred in extra configuration device and transfer in Conventional batch reaction, Environmental Safety, production efficiency is high.
Brief description of the drawings
Fig. 1 is KA oil nitric acid oxidation synthesizing adipic acid product process flow figure of the present invention；
Fig. 2 is Corning micro passage reactions module used in the present invention and structure chart：1- straight channel functional modules,
2- " cardioid " structure function module, 3- " cardioid " structural representation；
Fig. 3 is Corning micro passage reactions schematic flow sheet used in the present invention：1st, 2- head tanks, 3,4- raw materials
Pump, 5,6- pressure gauges, 7-Corning straight trip channel modules, 8,9-Corning enhancing mixing " cardioid " modules, 10- products are received
Collection.
Embodiment
The technological process of the present invention of reference picture 1, using Fig. 3 installation drawing, as steps described below：（1）First by 1,2 storage tanks
And KA oil and oxidation acid solution pass through 3,4 measuring pumps respectively, squeeze into straight channel module 7 according to certain proportioning（Straight channel knot
Structure is referring to No. 1 in Fig. 2）Preheated, whole process passes through 5,6 pressure gauge inspection system pressure；（2）KA oil and oxidation acid solution
It is passed through micro-mixer heart mixing module 8 again after preheating（Heart-shaped structure is referring to 2, No. 3 in Fig. 2）Inside mixed；（3）It is mixed
The raw material got togather, which is entered back into the following group heart mixing module 9, to be reacted；（4）The product that should be obtained by microchannel plate, through weight
Crystallization Separation goes out catalyst, dry adipic acid product, is used for after the caused recovered concentration of spent acid in next oxidation reaction.
The present invention is further illustrated below by embodiment, but content not thereby limiting the invention.
Embodiment 1
（1）Equipment therefor：Corning high flux micro passage reactions（Corning straight trip channel module+Corning cardioid
Channel module）, reference picture 3 determines micro passage reaction connection mode, when hybrid reaction number of modules stops according to flow velocity with reaction
Between determine, heat transferring medium is conduction oil.
（2）Head tank 1,2 has configured KA oil, aoxidizes acid solution（Nitric acid mass concentration is 40%, Cu2+Concentration 0.1%, VO2 +Concentration 0.1%）.Set each measuring pump 3, the flow control of pump 4 changes KA oil:Aoxidize acid solution mol ratio=1:10, control KA
Oil flow rate：1mL/min, control oxidizing acid solution flow rate：10mL/min, material is squeezed into respectively in each straight channel warm-up block,
It is 60 DEG C to control reaction temperature, pressure 0.1MPa；KA oil and oxidation acid solution squeeze into micro-mixer with measuring pump 3,4 respectively
Mixed in heart-shaped mixing module 8, the raw material mixed, which is entered back into the following group heart mixing module 9, to be reacted.Reaction stops
It is 50s to stay the time, after reaction product is by cooling coil ice-water bath, is connected freewheeling state outflow reactor with high dispersive（See attached
Fig. 3）.
（3）Reaction solution isolates catalyst through recrystallization, dry adipic acid product, after the caused recovered concentration of spent acid
For in next oxidation reaction.KA oil total conversion is 100%, adipic acid selectivity about 85.5%, total yield of products about 85.5%.
Embodiment 2
（1）Equipment therefor：Corning high flux micro passage reactions（Corning straight trip channel module+Corning cardioid
Channel module）, reference picture 3 determines micro passage reaction connection mode, when hybrid reaction number of modules stops according to flow velocity with reaction
Between determine, heat transferring medium is conduction oil.
（2）Head tank 1,2 has configured KA oil, aoxidizes acid solution（Nitric acid mass concentration is 40%, Cu2+Concentration 0.2%, VO2 +Concentration 0.1%）.Set each measuring pump 3, the flow control of pump 4 changes KA oil:Aoxidize acid solution mol ratio=1:12, control KA
Oil flow rate：2mL/min, control oxidizing acid solution flow rate：12mL/min, material is squeezed into respectively in each straight channel warm-up block,
It is 80 DEG C to control reaction temperature, pressure 0.2MPa；KA oil and oxidation acid solution squeeze into micro-mixer with measuring pump 3,4 respectively
Mixed in heart-shaped mixing module 8, the raw material mixed, which is entered back into the following group heart mixing module 9, to be reacted.Reaction stops
It is 60s to stay the time, after reaction product is by cooling coil ice-water bath, is connected freewheeling state outflow reactor with high dispersive（See attached
Fig. 3）.
（3）Reaction solution isolates catalyst through recrystallization, dry adipic acid product, after the caused recovered concentration of spent acid
For in next oxidation reaction.KA oil total conversion is 100%, adipic acid selectivity about 87.5%, total yield of products about 87.5%.
Embodiment 3
（1）Equipment therefor：Corning high flux micro passage reactions（Corning straight trip channel module+Corning cardioid
Channel module）, reference picture 3 determines micro passage reaction connection mode, when hybrid reaction number of modules stops according to flow velocity with reaction
Between determine, heat transferring medium is conduction oil.
（2）Head tank 1,2 has configured KA oil, aoxidizes acid solution（Nitric acid mass concentration is 50%, Cu2+Concentration 0.3%, VO2 +Concentration 0.2%）.Set each measuring pump 3, the flow control of pump 4 changes KA oil:Aoxidize acid solution mol ratio=1:15, control KA
Oil flow rate：2mL/min, control oxidizing acid solution flow rate：14mL/min, material is squeezed into respectively in each straight channel warm-up block,
It is 85 DEG C to control reaction temperature, pressure 0.4MPa；KA oil and oxidation acid solution squeeze into micro-mixer with measuring pump 3,4 respectively
Mixed in heart-shaped mixing module 8, the raw material mixed, which is entered back into the following group heart mixing module 9, to be reacted.Reaction stops
It is 70s to stay the time, after reaction product is by cooling coil ice-water bath, is connected freewheeling state outflow reactor with high dispersive（See attached
Fig. 3）.
（3）Reaction solution isolates catalyst through recrystallization, dry adipic acid product, after the caused recovered concentration of spent acid
For in next oxidation reaction.KA oil total conversion is 100%, adipic acid selectivity about 90%, total yield of products about 90%.
Embodiment 4
（1）Equipment therefor：Corning high flux micro passage reactions（Corning straight trip channel module+Corning cardioid
Channel module）, reference picture 3 determines micro passage reaction connection mode, when hybrid reaction number of modules stops according to flow velocity with reaction
Between determine, heat transferring medium is conduction oil.
（2）Head tank 1,2 has configured KA oil, aoxidizes acid solution（Nitric acid mass concentration is 50%, Cu2+Concentration 0.4%, VO2 +Concentration 0.3%）.Set each measuring pump 3, the flow control of pump 4 changes KA oil:Aoxidize acid solution mol ratio=1:16, control KA
Oil flow rate：3mL/min, control oxidizing acid solution flow rate：15mL/min, material is squeezed into respectively in each straight channel warm-up block,
It is 90 DEG C to control reaction temperature, pressure 0.6MPa；KA oil and oxidation acid solution squeeze into micro-mixer with measuring pump 3,4 respectively
Mixed in heart-shaped mixing module 8, the raw material mixed, which is entered back into the following group heart mixing module 9, to be reacted.Reaction stops
It is 80s to stay the time, after reaction product is by cooling coil ice-water bath, is connected freewheeling state outflow reactor with high dispersive（See attached
Fig. 3）.
（3）Reaction solution isolates catalyst through recrystallization, dry adipic acid product, after the caused recovered concentration of spent acid
For in next oxidation reaction.KA oil total conversion is 100%, adipic acid selectivity about 89.8%, total yield of products about 89.8%.
Embodiment 5
（1）Equipment therefor：Corning high flux micro passage reactions（Corning straight trip channel module+Corning cardioid
Channel module）, reference picture 3 determines micro passage reaction connection mode, when hybrid reaction number of modules stops according to flow velocity with reaction
Between determine, heat transferring medium is conduction oil.
（2）Head tank 1,2 has configured KA oil, aoxidizes acid solution（Nitric acid mass concentration is 60%, Cu2+Concentration 0.5%, VO2 +Concentration 0.3%）.Set each measuring pump 3, the flow control of pump 4 changes KA oil:Aoxidize acid solution mol ratio=1:17, control KA
Oil flow rate：3mL/min, control oxidizing acid solution flow rate：16mL/min, material is squeezed into respectively in each straight channel warm-up block,
It is 95 DEG C to control reaction temperature, pressure 0.8MPa；KA oil and oxidation acid solution squeeze into micro-mixer with measuring pump 3,4 respectively
Mixed in heart-shaped mixing module 8, the raw material mixed, which is entered back into the following group heart mixing module 9, to be reacted.Reaction stops
It is 85s to stay the time, after reaction product is by cooling coil ice-water bath, is connected freewheeling state outflow reactor with high dispersive（See attached
Fig. 3）.
（3）Reaction solution isolates catalyst through recrystallization, dry adipic acid product, after the caused recovered concentration of spent acid
For in next oxidation reaction.KA oil total conversion is 100%, adipic acid selectivity about 89.7%, total yield of products about 89.7%.
Embodiment 6
（1）Equipment therefor：Corning high flux micro passage reactions（Corning straight trip channel module+Corning cardioid
Channel module）, reference picture 3 determines micro passage reaction connection mode, when hybrid reaction number of modules stops according to flow velocity with reaction
Between determine, heat transferring medium is conduction oil.
（2）Head tank 1,2 has configured KA oil, aoxidizes acid solution（Nitric acid mass concentration is 70%, Cu2+Concentration 0.8%, VO2 +Concentration 0.4%）.Set each measuring pump 3, the flow control of pump 4 changes KA oil:Aoxidize acid solution mol ratio=1:18, control KA
Oil flow rate：4mL/min, control oxidizing acid solution flow rate：18mL/min, material is squeezed into respectively in each straight channel warm-up block,
It is 100 DEG C to control reaction temperature, pressure 1.0MPa；KA oil and oxidation acid solution squeeze into microring array with measuring pump 3,4 respectively
Mixed in device heart mixing module 8, the raw material mixed, which is entered back into the following group heart mixing module 9, to be reacted.Reaction
Residence time is 90s, after reaction product is by cooling coil ice-water bath, is connected freewheeling state outflow reactor with high dispersive（See
Accompanying drawing 3）.
（3）Reaction solution isolates catalyst through recrystallization, dry adipic acid product, after the caused recovered concentration of spent acid
For in next oxidation reaction.KA oil total conversion is 100%, adipic acid selectivity about 85.4%, total yield of products about 85.4%.
Embodiment 7
（1）Equipment therefor：Corning high flux micro passage reactions（Corning straight trip channel module+Corning cardioid
Channel module）, reference picture 3 determines micro passage reaction connection mode, when hybrid reaction number of modules stops according to flow velocity with reaction
Between determine, heat transferring medium is conduction oil.
（2）Head tank 1,2 has configured KA oil, aoxidizes acid solution（Nitric acid mass concentration is 80%, Cu2+Concentration 1.0%, VO2 +Concentration 0.5%）.Set each measuring pump 3, the flow control of pump 4 changes KA oil:Aoxidize acid solution mol ratio=1:20, control KA
Oil flow rate：5mL/min, control oxidizing acid solution flow rate：20mL/min, material is squeezed into respectively in each straight channel warm-up block,
It is 120 DEG C to control reaction temperature, pressure 1.5MPa；KA oil and oxidation acid solution squeeze into microring array with measuring pump 3,4 respectively
Mixed in device heart mixing module 8, the raw material mixed, which is entered back into the following group heart mixing module 9, to be reacted.Reaction
Residence time is 100s, after reaction product is by cooling coil ice-water bath, is connected freewheeling state outflow reactor with high dispersive（See
Accompanying drawing 3）.
（3）Reaction solution isolates catalyst through recrystallization, dry adipic acid product, after the caused recovered concentration of spent acid
For in next oxidation reaction.KA oil total conversion is 100%, adipic acid selectivity about 87.9%, total yield of products about 87.9%.
Claims (2)
- A kind of 1. method using micro passage reaction synthesizing adipic acid, it is characterised in that carry out as steps described below：（1）Equipment therefor：Corning high flux micro passage reactions are that Corning straight trips channel module+Corning cardioid is led to Road module, micro passage reaction connection mode is determined as steps described below：First will（1）、（2）KA oil and oxidizing acid in storage tank is molten Liquid passes through respectively（3）、（4）Measuring pump, straight channel module is squeezed into according to certain proportioning（7）Preheated, whole process passes through （5）、（6）Pressure gauge inspection system pressure；KA oil and oxidation acid solution are passed through micro-mixer heart hybrid guided mode again after preheating Block（8）Inside mixed；The raw material mixed enters back into the following group heart mixing module（9）In reacted；By microchannel plate The product that should be obtained, catalyst is isolated through recrystallization, dry adipic acid product, be used for after the caused recovered concentration of spent acid In next oxidation reaction；Hybrid reaction number of modules determines that heat transferring medium is conduction oil according to flow velocity and reaction time；（2）Head tank 1,2 has configured KA oil, aoxidizes acid solution, is dissolved in wherein oxidation acid solution is copper and vanadium catalyst in nitric acid It is formulated, nitric acid mass concentration is 40%, Cu2+Concentration 0.1%, VO2+Concentration 0.1%, set each measuring pump 3, the stream of pump 4 Amount control changes KA oil:Aoxidize acid solution mol ratio=1:10, control KA oil flow rates：1mL/min, control oxidizing acid solution flow rate： 10mL/min, material is squeezed into respectively in each straight channel warm-up block, it is 60 DEG C to control reaction temperature, pressure 0.1MPa； KA oil and oxidation acid solution are squeezed into micro-mixer heart mixing module 8 with measuring pump 3,4 mixed respectively, the original mixed Material, which is entered back into the following group heart mixing module 9, to be reacted；Reaction time is 50s, and reaction product passes through cooling coil ice After water-bath, it is connected freewheeling state outflow reactor with high dispersive；（3）Reaction solution isolates catalyst through recrystallization, dry adipic acid product, is used for after the caused recovered concentration of spent acid In next oxidation reaction；KA oil total conversion is 100%, adipic acid selectivity about 85.5%, total yield of products about 85.5%.
- A kind of 2. method using micro passage reaction synthesizing adipic acid, it is characterised in that or carry out as steps described below：（1）Equipment therefor：Corning high flux micro passage reactions are that Corning straight trips channel module+Corning cardioid is led to Road module, micro passage reaction connection mode is determined as steps described below：First will（1）、（2）KA oil and oxidizing acid in storage tank is molten Liquid passes through respectively（3）、（4）Measuring pump, straight channel module is squeezed into according to certain proportioning（7）Preheated, whole process passes through （5）、（6）Pressure gauge inspection system pressure；KA oil and oxidation acid solution are passed through micro-mixer heart hybrid guided mode again after preheating Block（8）Inside mixed；The raw material mixed enters back into the following group heart mixing module（9）In reacted；By microchannel plate The product that should be obtained, catalyst is isolated through recrystallization, dry adipic acid product, be used for after the caused recovered concentration of spent acid In next oxidation reaction；Hybrid reaction number of modules determines that heat transferring medium is conduction oil according to flow velocity and reaction time；（2）Head tank 1,2 has configured KA oil, aoxidizes acid solution, is dissolved in wherein oxidation acid solution is copper and vanadium catalyst in nitric acid It is formulated, nitric acid mass concentration is 40%, Cu2+Concentration 0.2%, VO2+Concentration 0.1%；Set each measuring pump 3, the stream of pump 4 Amount control changes KA oil:Aoxidize acid solution mol ratio=1:12, control KA oil flow rates：2mL/min, control oxidizing acid solution flow rate： 12mL/min, material is squeezed into respectively in each straight channel warm-up block, it is 80 DEG C to control reaction temperature, pressure 0.2MPa； KA oil and oxidation acid solution are squeezed into micro-mixer heart mixing module 8 with measuring pump 3,4 mixed respectively, the original mixed Material, which is entered back into the following group heart mixing module 9, to be reacted；Reaction time is 60s, and reaction product passes through cooling coil ice After water-bath, it is connected freewheeling state outflow reactor with high dispersive；（3）Reaction solution isolates catalyst through recrystallization, dry adipic acid product, is used for after the caused recovered concentration of spent acid In next oxidation reaction；KA oil total conversion is 100%, adipic acid selectivity about 87.5%, total yield of products about 87.5%.
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