CN104478702A - Method for synthesizing adipic acid by adopting microchannel reactor - Google Patents
Method for synthesizing adipic acid by adopting microchannel reactor Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/27—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with oxides of nitrogen or nitrogen-containing mineral acids
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention provides a method for synthesizing adipic acid by adopting a microchannel reactor, belonging to the technical field of organic synthesis application. The method is a new process for synthesizing adipic acid by using KA (alcohol ketone) oil and nitric acid as raw materials and Cu and V as catalysts to oxidize KA in a short reaction time from tens of seconds to several minutes in the Corning microchannel reactor. The method is characterized by carrying out preheating, mixing and oxidation reaction on the materials after the materials are pumped into the Corning microchannel reactor by a metering pump and then treating the product, thus obtaining the adipic acid product. The method is simple, convenient and safe to operate and is used for continuously producing the adipic acid product at high yield. In addition, the environmental pollution of the process is greatly reduced.
Description
Technical field
The invention belongs to organic synthesis applied technical field, being specifically related to pimelinketone and hexalin (alcohol ketone oil, is commonly called as KA oil) and nitric acid is raw material, Cu and V is catalyzer, carries out alcohol ketone oxidizing reaction synthesizing adipic acid product in micro passage reaction.Be in particular in the Corning micro passage reaction of high-throughput microchannel Continuous Flow, utilize the technique of nitric acid oxidation KA oil synthesizing adipic acid.
Background technology
Hexanodioic acid has another name called adipic acid (Adipic Acid), it is one of diprotic acid having using value most in aliphatic dicarboxylic acid, the reactions such as salify, esterification and amidation can be there is, mainly for the production of polyamide fibre 66 and nylon66 fiber engineering plastics, urethane foam and softening agent, can be used in addition producing senior lubricant, foodstuff additive, medicine intermediate, spices and essence control agent, novel monocrystal material, plastics blowing agent, coating, sterilant, tackiness agent and dyestuff etc., purposes is very extensive.
At present, the industrial process mainly hexanaphthene method of hexanodioic acid, this operational path accounts for 93% of global hexanodioic acid overall throughput at present.Hexanaphthene route, namely generates hexanaphthene by purified petroleum benzin shortening, and hexanaphthene generates pimelinketone and hexalin (alcohol ketone oil, is commonly called as KA oil) through atmospheric oxidation again, then by nitric acid oxidation synthesizing adipic acid.This route produces a large amount of " three wastes ", and wherein main is the waste gas such as the nitrogen oxide produced in waste liquid, the waste water of alcohol ketone oxidation synthesis of adipic acid process and the nitric acid oxidation KA oil process produced in alcohol ketone building-up process.Along with environmental protection pressure is increasing, for the use corrodibility nitric acid material existed in hexanodioic acid production process with produce the problems such as the oxynitride of serious environment pollution, nitric acid vapor and spent acid solution, researching and developing cyclohexene oxide method, butadiene process at present and utilizing the process for cleanly preparing of the hexanodioic acids such as biological catalysis.
Cyclohexene oxide method: with the hydrogen peroxide as oxidant cyclohexene oxide obtaining adipic acid of 30%, condition is gentleer, and yield is about 93% ~ 95%.Technological advantage is high catalytic activity, highly selective, mild condition, not etching apparatus, pollution-free.Shortcoming is long reaction time, and hydrogen peroxide consumes high (produce 1mol hexanodioic acid, consume 4mol hydrogen peroxide).Japanese Scientists develops with catalyst n a
2wO
42H
2o is catalyzer, [CH
3n (n-C
8h
17)
3] HSO
4for phase-transfer catalyst, hexanodioic acid prepared by hydrogen peroxide direct oxidation tetrahydrobenzene.Tetrahydrobenzene: Na
2wO
42H
2o:[CH
3n (n-C
8h
17)
3] HSO
4=100:1:1,30%H
2o
2, 75 ~ 90 DEG C, 8h, ADA yield reaches 93%.Zhang Jinhui etc. are with the vitriol of Long carbon chain primary amine or tertiary amine for phase-transfer catalyst, and ADA yield reaches 94.1%.Zhang etc. take benzyltriethylammoinium chloride as phase-transfer catalyst, and phospho-wolframic acid is catalyzer, and ADA yield reaches 87%.Chinese Academy of Sciences's Lanzhou materialization develops peroxotungstate organic coordination compound and replaces phase-transfer catalyst technique, catalyzer [W (O) (O
2) L
2]
2-, when taking oxalic acid as part, cyclohexene conversion rate reaches 100%, adipic acid yield 96.6%.Beam carbunclies etc. for catalyst system, and add tensio-active agent (sodium lauryl sulphate PEG10M) with sodium wolframate/L-(+)-xitix in right amount, use 30%H
2o
2cyclohexene oxide synthesizing adipic acid, n (hexene): n (H
2o
2): n (sodium wolframate): n [L (+) xitix]=1:4.4:0.025:0.025, high-speed stirring, backflow 5h, reaction solution is quiet at 0 DEG C to spend the night, and adipic acid yield is 86%.
Butadiene process: the condition of hexanodioic acid is prepared with divinyl carbonyl alkoxylate by DuPont company and BASF AG: 100 DEG C, 128atm.Co
2(CO)
8be catalyst system with pyridine, butadiene conversion is greater than 98%, selectivity 88%.DuPont company used PdCl again afterwards
2, triphenylphosphine, pyridine, sulfuric acid catalysis system, transformation efficiency 100%, selectivity is greater than 92%, and catalyzer is Ni (CO) title complex or mantoquita title complex, 100 ~ 140 DEG C, and butadiene conversion is 84 ~ 89%.Intermediate product alkene cyanogen generates hexanodioic acid through carbonyl alkoxylate or hydrocarboxylation again.Adopt divinyl carbonyl process to prepare hexanodioic acid, raw material is comparatively cheap, and yield is high, and its production cost is lower than cyclohexane oxidation, and shortcoming is that technique owes ripe, complex process, severe reaction conditions, and byproduct is more, does not industrially at present generally use.
Biological catalysis: utilize D-Glucose biocatalysis synthesizing adipic acid.1990s, DuPont company develops biocatalysis technique.Utilize intestinal bacteria to be suitable by D2 conversion of glucose, cis-Sorbic Acid, then hydrogenation generates hexanodioic acid.The said firm developed again new bioprocess technology method afterwards, encoded to enzyme with a kind of gene a small bundle of straw, etc. for silkworms to spin cocoons on separated from aerobic denitration bacterial strain, thus obtained the synthetic enzyme that hexalin transforms hexanodioic acid processed.Hexalin optionally can be changed into hexanodioic acid by the mutation chief cell of this synthetic enzyme under suitable growth conditions.
It is raw material that the present invention adopts with pimelinketone and hexalin (alcohol ketone oil, is commonly called as KA oil) and nitric acid, Cu and V is catalyzer, carries out alcohol ketone oxidizing reaction synthesizing adipic acid technique in micro passage reaction, specifically reacts as shown in following equation:
The reaction mechanism that nitric acid oxidation alcohol ketone produces hexanodioic acid is as follows: (1), under the effect of copper, vanadium catalyst and nitric acid, the hexalin in alcohol ketone mixing solutions is generated pimelinketone by rapid oxidation, produces HNO simultaneously
2.There iing trace HNO
2under existence, cyclohexanol becomes the speed of reaction of pimelinketone fast, the HNO of generation
2it is the key substance that pimelinketone is oxidized further.(2) oxidizing reaction of pimelinketone.Pimelinketone is at HNO
2effect under, be oxidized to intermediate product 6-oximido-6-nitro caproic acid (be called for short nitrol acid, be abbreviated as NA).Concentration of nitric acid is lower, and pimelinketone can form 1,2-cyclohexanedione semihydrate, is called for short diketone.Oxidizing cyclohexanone becomes nitrol acid, and be first order reaction to pimelinketone, its speed of reaction significantly increases with the raising of concentration of nitric acid and temperature of reaction.This exothermic heat of reaction amount is comparatively large, accounts for about 90% of total thermal discharge.(3) decomposition reaction of nitrol acid.Under nitric acid effect, hexanodioic acid is resolved in nitrol acid, and this reaction for first order reaction, compared with the speed that speed of reaction and oxidizing cyclohexanone become nitrol acid slowly, be the rate-determining steps of whole speed of reaction, and thermal discharge is little, is accounted for about 10% of total thermal discharge.(4) when catalyst-free exists, diketone is then all converted into by product, mainly succinic acid and low molecular weight product (as oxalic acid).Under the effect of vanadium, diketone can be partially converted into hexanodioic acid, also generates a considerable amount of by product diprotic acid simultaneously.(5) at high temperature, when there being a large amount of HNO
2when existing, more nitro functions can be introduced into the adjacent nitroso-group pimelinketone of intermediate product, then form many nitrocyclohexanones, and then be converted into pentanedioic acid and succinic acid etc.Copper effectively can suppress the generation of above-mentioned reaction, and adipic acid yield is improved.
Up to now, there is not yet the research of the method for carrying out KA oil nitric acid oxidation synthesizing adipic acid in the mode of Corning microchannel Continuous Flow.The invention provides a kind of in Corning micro passage reaction with the mode nitric acid oxidation KA of Continuous Flow oil synthesizing adipic acid operational path.
When carrying out synthetic reaction condition screening in early stage in Corning micro passage reaction, need reactant consumption very micro-, not only can reduce the consumption of costliness, poisonous, adverse reaction thing, the environmental pollutant produced in reaction process are also few, laboratory is substantially pollution-free, is the technology platform of a kind of environmental friendliness, study on the synthesis novel substance.Corning obtain in micro passage reaction product and modern age analytical instrument, as GC, GC-MS, HPLC and NMR carry out the matching analysis, make modern age analytical instrument can be used for direct-on-line monitoring and react the degree of carrying out, substantially increase the speed of research synthetic route.
The type of the special glass functional module of Corning micro passage reaction has straight-through channel type, cardioid hybrid junctions configuration, connects straight-through channel type after having one section of cardioid mixed structure, connect after having one section of kapillary mixed structure straight-through channel type etc.The special glass functional module of Corning micro passage reaction has two functional module of opening for feed list discharge port and the functional module of single opening for feed and single discharge port.Its safe operating temperature range of Corning micro passage reaction is-25 DEG C ~ 200 DEG C, and safe working pressure scope is 0 ~ 18bar, and material pipeline connects for PFA(perfluoroalkoxy resin) material.European patent WO2010/037012A2, it is the module patent of Corning company special construction design, the structure of the special module that Corning produces has been write out in detail in patent, the size of module and the arrangement of passage etc., indicate module integrated and microminiaturized be that chemical process amplifies safer selection.
Summary of the invention
The object of the invention be to provide a kind of in Corning micro passage reaction with the mode nitric acid oxidation KA of Continuous Flow oil synthesizing adipic acid product, compared with existing technique, this technique has reaction conditions and accurately controls, reduce the discharge of organic liquid waste, continuous safe mode is produced, and KA oil transforms completely within the extremely short time, hexanodioic acid selectivity is high.
The present invention is a kind of method adopting micro passage reaction synthesizing adipic acid, it is characterized in that carrying out according to following step:
(1) be raw material with pimelinketone and hexalin (alcohol ketone oil, is commonly called as KA oil) and nitric acid, Cu and V is catalyzer, carries out alcohol ketone oxidizing reaction synthesizing adipic acid product in micro passage reaction.Under agitation copper and vanadium catalyst are dissolved in nitric acid be made into oxidizing acid solution and KA oil as reaction mass, pass into respectively in micro passage reaction through volume pump and carry out preheating in each channel module, design temperature is controlled by external heat exchanger, and heat transferring medium is thermal oil; KA oil is changed again: oxidizing acid solution mol ratio=1:10 ~ 1:20 by flow control; Control KA oil flow velocity: 1mL/min ~ 5mL/min, controlled oxidization acid solution flow velocity: 10mL/min ~ 20mL/min; Synchronously enter in mass transfer enhancement pattern block via respective volume pump and carry out hybrid reaction, mixing temperature is controlled by external heat exchanger equally;
(2) by flow control KA oil and the mol ratio of oxidizing acid solution, in this module after the raw reaction of hybrid concurrency, continue through a series of mass transfer enhancement type microchannel module and once-through type microchannel module, after reaction process completes, product flows out from the outlet of reactor, enters cooling last handling process; This reaction process reaction time in micro passage reaction is 50s ~ 100s, and temperature of reaction is 60 ~ 120 DEG C, and pressure is 0.1 ~ 1.5 MPa;
(3) micro passage reaction is exported the reaction solution obtained, isolates catalyzer through recrystallization, dry adipic acid product, the spent acid of generation through reclaim concentrated after in next oxidizing reaction.KA oil total conversion rate is 100%, hexanodioic acid selectivity about about 85 ~ 90%, total yield of products about 85 ~ 90%.
Wherein oxidizing acid solution in step (1), wherein oxidizing acid solution is that copper and vanadium catalyst are dissolved in nitric acid formulated, Cu
2+concentration 0.1% ~ 1.0%, VO
2+concentration 0.1% ~ 0.5%.
Wherein KA oil in step (1): oxidizing acid solution mol ratio is preferably 1:15 ~ 1:17, and nitric acid mass concentration is 40% ~ 80%.
Wherein in step (1), KA oil flow velocity is preferably: 2mL/min ~ 3mL/min, controlled oxidization acid solution flow velocity is preferably: 14mL/min ~ 16mL/min.
Wherein Cu in step (1) oxidizing acid solution
2+concentration preferably 0.3% ~ 0.5%, VO
2+concentration preferably 0.2% ~ 0.3%, nitric acid mass concentration is preferably 50 ~ 60%.
Wherein in step (2), in micro passage reaction, reaction time is preferably 70 ~ 85s, and temperature of reaction is preferably 85 ~ 90 DEG C, and pressure is preferably 0.4 ~ 0.6 MPa.
The Corning(of high-throughput microchannel Continuous Flow that what the present invention was used is is healthy and free from worry) micro passage reaction, this reactive system is formed by polylith module assembled, intermodule can assembled in parallel or assembled in series, module by heat exchange path with reaction path integrated with one, or only containing reaction path, and be immersed in temperature control heat-conducting medium.In heat exchange path or heat-conducting medium, be furnished with thermopair, can be used for the actual temperature measuring heat transferring medium or extraneous heat-conducting medium in heat exchange path.In heat exchange path or heat-conducting medium, be furnished with thermopair, can be used for the actual temperature measuring heat transferring medium or extraneous heat-conducting medium in heat exchange path.The material of this module is silicon single crystal, special glass, pottery, the stainless steel scribbling corrosion resistant coating or metal alloy, tetrafluoroethylene etc.Reactive system can be anticorrosion withstand voltage, and it is different and different that voltage endurance capability looks material.In module, Micro Channel Architecture is divided once-through type channel architecture and strengthens mixed type channel architecture two kinds, and once-through type passage is tubular structure, and strengthening mixed type channel architecture is heart-shaped structure, and passage hydraulic diameter is 0.5mm ~ 10mm.
The mass transfer enhancement type micro channel reactor system that the present invention carries out KA oil nitric acid oxidation comprises the preheating of KA oil, hybrid reaction, oxidising process three part, therefore need the reaction module of raw material preheating module, mixing module and some amount, concrete quantity is determined by reaction time.
The present invention has following principal feature compared with prior art:
1. the present invention adopts the Corning microchannel continuous flow reactor of Continuous Flow, and reaction times from traditional a few hours shorten to tens seconds to several minutes, significantly improve reaction efficiency.
2. because raw material mixes splendid in microchannel, temperature accurately controls, and in reaction process, the consumption of nitric acid can greatly reduce, and decreases the generation of spent acid, and the selectivity of product significantly improves.
3. the Corning micro passage reaction material used in the present invention is special glass, and the material of volume pump is tetrafluoroethylene and titanium, and excellent corrosion resistance, avoids the problem that etching apparatus in conventional reactor is serious.
4., in micro passage reaction, omnidistance from charging, preheating, mixing and reaction process is Continuous Flow reaction, and avoid the leakage needing in Conventional batch reaction to occur in additional configuration device and transfer, Environmental Safety, production efficiency is high.
Accompanying drawing explanation
Fig. 1 is KA of the present invention oil nitric acid oxidation synthesizing adipic acid product process flow figure;
Fig. 2 is Corning micro passage reaction module used in the present invention and structure iron: 1-straight channel functional module, 2-" cardioid " structure function module, 3-" cardioid " structural representation;
Fig. 3 is Corning micro passage reaction schematic flow sheet used in the present invention: 1,2-head tank, 3,4-feedstock pump, 5,6-tensimeter, and 7-Corning craspedodrome channel module, 8,9-Corning strengthens mixing " cardioid " module, 10-product-collecting.
Embodiment
With reference to Fig. 1 technical process of the present invention, utilize the setting drawing of Fig. 3, according to following step: (1) first by 1,2 storage tanks with KA oil and oxidizing acid solution respectively through 3,4 volume pumps, according to certain proportioning squeeze into straight channel module 7(straight passage structures see in Fig. 2 No. 1) carry out preheating, whole process is by 5,6 tensimeter inspection system pressure; (2) KA oil and oxidizing acid solution pass into again after preheating micro mixer heart mixing module 8(heart-shaped structure see in Fig. 22, No. 3) in mix; (3) raw material mixed enters in lower group heart-shaped mixing module 9 again and reacts; (4) product be obtained by reacting through microchannel, isolates catalyzer through recrystallization, dry adipic acid product, the spent acid of generation through reclaim concentrated after in next oxidizing reaction.
Make a nearly step below by embodiment to the present invention to illustrate, but content not thereby limiting the invention.
embodiment 1
(1) equipment therefor: Corning high-throughput micro passage reaction (Corning craspedodrome channel module+Corning cardioid channel module), with reference to Fig. 3 determination micro passage reaction connection mode, hybrid reaction number of modules is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil.
(2) head tank 1,2 configures KA oil, and (nitric acid mass concentration is 40%, Cu to oxidizing acid solution
2+concentration 0.1%, VO
2+concentration 0.1%).Set the flow control change KA oil of each volume pump 3, pump 4: oxidizing acid solution mol ratio=1:10, control KA oil flow velocity: 1mL/min, controlled oxidization acid solution flow velocity: 10mL/min, squeezes in each straight channel warm-up block respectively by material, temperature of reaction of controlling well is 60 DEG C, and pressure is 0.1MPa; KA oil and oxidizing acid solution are squeezed in the heart-shaped mixing module 8 of micro mixer with volume pump 3,4 respectively and are mixed, and the raw material mixed enters in lower group heart-shaped mixing module 9 again and reacts.Reaction time is 50s, and reaction product, by after spiral coil cooling tube ice-water bath, to be connected freewheeling state outflow reactor (see accompanying drawing 3) with high dispersive.
(3) reaction solution isolates catalyzer through recrystallization, dry adipic acid product, the spent acid of generation through reclaim concentrated after in next oxidizing reaction.KA oil total conversion rate is 100%, hexanodioic acid selectivity about 85.5%, total yield of products about 85.5%.
embodiment 2
(1) equipment therefor: Corning high-throughput micro passage reaction (Corning craspedodrome channel module+Corning cardioid channel module), with reference to Fig. 3 determination micro passage reaction connection mode, hybrid reaction number of modules is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil.
(2) head tank 1,2 configures KA oil, and (nitric acid mass concentration is 40%, Cu to oxidizing acid solution
2+concentration 0.2%, VO
2+concentration 0.1%).Set the flow control change KA oil of each volume pump 3, pump 4: oxidizing acid solution mol ratio=1:12, control KA oil flow velocity: 2mL/min, controlled oxidization acid solution flow velocity: 12mL/min, squeezes in each straight channel warm-up block respectively by material, temperature of reaction of controlling well is 80 DEG C, and pressure is 0.2MPa; KA oil and oxidizing acid solution are squeezed in the heart-shaped mixing module 8 of micro mixer with volume pump 3,4 respectively and are mixed, and the raw material mixed enters in lower group heart-shaped mixing module 9 again and reacts.Reaction time is 60s, and reaction product, by after spiral coil cooling tube ice-water bath, to be connected freewheeling state outflow reactor (see accompanying drawing 3) with high dispersive.
(3) reaction solution isolates catalyzer through recrystallization, dry adipic acid product, the spent acid of generation through reclaim concentrated after in next oxidizing reaction.KA oil total conversion rate is 100%, hexanodioic acid selectivity about 87.5%, total yield of products about 87.5%.
embodiment 3
(1) equipment therefor: Corning high-throughput micro passage reaction (Corning craspedodrome channel module+Corning cardioid channel module), with reference to Fig. 3 determination micro passage reaction connection mode, hybrid reaction number of modules is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil.
(2) head tank 1,2 configures KA oil, and (nitric acid mass concentration is 50%, Cu to oxidizing acid solution
2+concentration 0.3%, VO
2+concentration 0.2%).Set the flow control change KA oil of each volume pump 3, pump 4: oxidizing acid solution mol ratio=1:15, control KA oil flow velocity: 2mL/min, controlled oxidization acid solution flow velocity: 14mL/min, squeezes in each straight channel warm-up block respectively by material, temperature of reaction of controlling well is 85 DEG C, and pressure is 0.4MPa; KA oil and oxidizing acid solution are squeezed in the heart-shaped mixing module 8 of micro mixer with volume pump 3,4 respectively and are mixed, and the raw material mixed enters in lower group heart-shaped mixing module 9 again and reacts.Reaction time is 70s, and reaction product, by after spiral coil cooling tube ice-water bath, to be connected freewheeling state outflow reactor (see accompanying drawing 3) with high dispersive.
(3) reaction solution isolates catalyzer through recrystallization, dry adipic acid product, the spent acid of generation through reclaim concentrated after in next oxidizing reaction.KA oil total conversion rate is 100%, hexanodioic acid selectivity about 90%, total yield of products about 90%.
embodiment 4
(1) equipment therefor: Corning high-throughput micro passage reaction (Corning craspedodrome channel module+Corning cardioid channel module), with reference to Fig. 3 determination micro passage reaction connection mode, hybrid reaction number of modules is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil.
(2) head tank 1,2 configures KA oil, and (nitric acid mass concentration is 50%, Cu to oxidizing acid solution
2+concentration 0.4%, VO
2+concentration 0.3%).Set the flow control change KA oil of each volume pump 3, pump 4: oxidizing acid solution mol ratio=1:16, control KA oil flow velocity: 3mL/min, controlled oxidization acid solution flow velocity: 15mL/min, squeezes in each straight channel warm-up block respectively by material, temperature of reaction of controlling well is 90 DEG C, and pressure is 0.6MPa; KA oil and oxidizing acid solution are squeezed in the heart-shaped mixing module 8 of micro mixer with volume pump 3,4 respectively and are mixed, and the raw material mixed enters in lower group heart-shaped mixing module 9 again and reacts.Reaction time is 80s, and reaction product, by after spiral coil cooling tube ice-water bath, to be connected freewheeling state outflow reactor (see accompanying drawing 3) with high dispersive.
(3) reaction solution isolates catalyzer through recrystallization, dry adipic acid product, the spent acid of generation through reclaim concentrated after in next oxidizing reaction.KA oil total conversion rate is 100%, hexanodioic acid selectivity about 89.8%, total yield of products about 89.8%.
embodiment 5
(1) equipment therefor: Corning high-throughput micro passage reaction (Corning craspedodrome channel module+Corning cardioid channel module), with reference to Fig. 3 determination micro passage reaction connection mode, hybrid reaction number of modules is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil.
(2) head tank 1,2 configures KA oil, and (nitric acid mass concentration is 60%, Cu to oxidizing acid solution
2+concentration 0.5%, VO
2+concentration 0.3%).Set the flow control change KA oil of each volume pump 3, pump 4: oxidizing acid solution mol ratio=1:17, control KA oil flow velocity: 3mL/min, controlled oxidization acid solution flow velocity: 16mL/min, squeezes in each straight channel warm-up block respectively by material, temperature of reaction of controlling well is 95 DEG C, and pressure is 0.8MPa; KA oil and oxidizing acid solution are squeezed in the heart-shaped mixing module 8 of micro mixer with volume pump 3,4 respectively and are mixed, and the raw material mixed enters in lower group heart-shaped mixing module 9 again and reacts.Reaction time is 85s, and reaction product, by after spiral coil cooling tube ice-water bath, to be connected freewheeling state outflow reactor (see accompanying drawing 3) with high dispersive.
(3) reaction solution isolates catalyzer through recrystallization, dry adipic acid product, the spent acid of generation through reclaim concentrated after in next oxidizing reaction.KA oil total conversion rate is 100%, hexanodioic acid selectivity about 89.7%, total yield of products about 89.7%.
embodiment 6
(1) equipment therefor: Corning high-throughput micro passage reaction (Corning craspedodrome channel module+Corning cardioid channel module), with reference to Fig. 3 determination micro passage reaction connection mode, hybrid reaction number of modules is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil.
(2) head tank 1,2 configures KA oil, and (nitric acid mass concentration is 70%, Cu to oxidizing acid solution
2+concentration 0.8%, VO
2+concentration 0.4%).Set the flow control change KA oil of each volume pump 3, pump 4: oxidizing acid solution mol ratio=1:18, control KA oil flow velocity: 4mL/min, controlled oxidization acid solution flow velocity: 18mL/min, squeezes in each straight channel warm-up block respectively by material, temperature of reaction of controlling well is 100 DEG C, and pressure is 1.0MPa; KA oil and oxidizing acid solution are squeezed in the heart-shaped mixing module 8 of micro mixer with volume pump 3,4 respectively and are mixed, and the raw material mixed enters in lower group heart-shaped mixing module 9 again and reacts.Reaction time is 90s, and reaction product, by after spiral coil cooling tube ice-water bath, to be connected freewheeling state outflow reactor (see accompanying drawing 3) with high dispersive.
(3) reaction solution isolates catalyzer through recrystallization, dry adipic acid product, the spent acid of generation through reclaim concentrated after in next oxidizing reaction.KA oil total conversion rate is 100%, hexanodioic acid selectivity about 85.4%, total yield of products about 85.4%.
embodiment 7
(1) equipment therefor: Corning high-throughput micro passage reaction (Corning craspedodrome channel module+Corning cardioid channel module), with reference to Fig. 3 determination micro passage reaction connection mode, hybrid reaction number of modules is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil.
(2) head tank 1,2 configures KA oil, and (nitric acid mass concentration is 80%, Cu to oxidizing acid solution
2+concentration 1.0%, VO
2+concentration 0.5%).Set the flow control change KA oil of each volume pump 3, pump 4: oxidizing acid solution mol ratio=1:20, control KA oil flow velocity: 5mL/min, controlled oxidization acid solution flow velocity: 20mL/min, squeezes in each straight channel warm-up block respectively by material, temperature of reaction of controlling well is 120 DEG C, and pressure is 1.5MPa; KA oil and oxidizing acid solution are squeezed in the heart-shaped mixing module 8 of micro mixer with volume pump 3,4 respectively and are mixed, and the raw material mixed enters in lower group heart-shaped mixing module 9 again and reacts.Reaction time is 100s, and reaction product, by after spiral coil cooling tube ice-water bath, to be connected freewheeling state outflow reactor (see accompanying drawing 3) with high dispersive.
(3) reaction solution isolates catalyzer through recrystallization, dry adipic acid product, the spent acid of generation through reclaim concentrated after in next oxidizing reaction.KA oil total conversion rate is 100%, hexanodioic acid selectivity about 87.9%, total yield of products about 87.9%.
Claims (6)
1. adopt a method for micro passage reaction synthesizing adipic acid, it is characterized in that carrying out according to following step:
(1) be raw material with pimelinketone and hexalin (alcohol ketone oil, is commonly called as KA oil) and nitric acid, Cu and V is catalyzer, carries out alcohol ketone oxidizing reaction synthesizing adipic acid product in micro passage reaction;
Under agitation copper and vanadium catalyst are dissolved in nitric acid be made into oxidizing acid solution and KA oil as reaction mass, pass into respectively in micro passage reaction through volume pump and carry out preheating in each channel module, design temperature is controlled by external heat exchanger, and heat transferring medium is thermal oil; KA oil is changed again: oxidizing acid solution mol ratio=1:10 ~ 1:20 by flow control; Control KA oil flow velocity: 1mL/min ~ 5mL/min, controlled oxidization acid solution flow velocity: 10mL/min ~ 20mL/min; Synchronously enter in mass transfer enhancement pattern block via respective volume pump and carry out hybrid reaction, mixing temperature is controlled by external heat exchanger equally;
(2) by flow control KA oil and the mol ratio of oxidizing acid solution, in this module after the raw reaction of hybrid concurrency, continue through a series of mass transfer enhancement type microchannel module and once-through type microchannel module, after reaction process completes, product flows out from the outlet of reactor, enters cooling last handling process; This reaction process reaction time in micro passage reaction is 50s ~ 100s, and temperature of reaction is 60 ~ 120 DEG C, and pressure is 0.1 ~ 1.5 MPa;
(3) micro passage reaction is exported the reaction solution obtained, isolates catalyzer through recrystallization, dry adipic acid product, the spent acid of generation through reclaim concentrated after in next oxidizing reaction;
KA oil total conversion rate is 100%, hexanodioic acid selectivity about 85 ~ 90%, total yield of products about 85 ~ 90%.
2. a kind of method adopting micro passage reaction synthesizing adipic acid according to claim 1, it is characterized in that the wherein middle oxidizing acid solution of step (1), wherein oxidizing acid solution is that copper and vanadium catalyst are dissolved in nitric acid formulated, Cu
2+concentration 0.1% ~ 1.0%, VO
2+concentration 0.1% ~ 0.5%.
3. a kind of method adopting micro passage reaction synthesizing adipic acid according to claim 1, is characterized in that the wherein middle KA oil of step (1): oxidizing acid solution mol ratio is preferably 1:15 ~ 1:17, and nitric acid mass concentration is 40% ~ 80%.
4. a kind of method adopting micro passage reaction synthesizing adipic acid according to claim 1, it is characterized in that wherein step (1) middle KA oil flow velocity is preferably: 2mL/min ~ 3mL/min, controlled oxidization acid solution flow velocity is preferably: 14mL/min ~ 16mL/min.
5. a kind of method adopting micro passage reaction synthesizing adipic acid according to claim 1, is characterized in that wherein Cu in step (1) oxidizing acid solution
2+concentration preferably 0.3% ~ 0.5%, VO
2+concentration preferably 0.2% ~ 0.3%, nitric acid mass concentration is preferably 50 ~ 60%.
6. a kind of method adopting micro passage reaction synthesizing adipic acid according to claim 1, it is characterized in that wherein in step (2) in micro passage reaction reaction time be preferably 70 ~ 85s, temperature of reaction is preferably 85 ~ 90 DEG C, and pressure is preferably 0.4 ~ 0.6 MPa.
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| CN106380375A (en) * | 2016-08-22 | 2017-02-08 | 常州大学 | A method of continuously synthesizing hexanedioic acid through a microchannel reactor |
| CN107501050A (en) * | 2017-08-28 | 2017-12-22 | 常州大学 | A kind of method that phenol is prepared using micro passage reaction |
| CN109456167A (en) * | 2018-12-20 | 2019-03-12 | 福州大学 | A method of using micro passage reaction by cyclohexanone synthesizing adipic acid |
| CN112191217A (en) * | 2020-11-10 | 2021-01-08 | 中国平煤神马能源化工集团有限责任公司 | Novel continuous flow tube type reaction system and process for synthesizing adipic acid |
| CN113200842A (en) * | 2021-05-08 | 2021-08-03 | 中石油吉林化工工程有限公司 | Adipic acid preparation method and system |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380375A (en) * | 2016-08-22 | 2017-02-08 | 常州大学 | A method of continuously synthesizing hexanedioic acid through a microchannel reactor |
| CN106380375B (en) * | 2016-08-22 | 2018-12-04 | 常州大学 | A kind of method of the continuous synthesizing adipic acid of micro passage reaction |
| CN107501050A (en) * | 2017-08-28 | 2017-12-22 | 常州大学 | A kind of method that phenol is prepared using micro passage reaction |
| CN109456167A (en) * | 2018-12-20 | 2019-03-12 | 福州大学 | A method of using micro passage reaction by cyclohexanone synthesizing adipic acid |
| CN112191217A (en) * | 2020-11-10 | 2021-01-08 | 中国平煤神马能源化工集团有限责任公司 | Novel continuous flow tube type reaction system and process for synthesizing adipic acid |
| CN113200842A (en) * | 2021-05-08 | 2021-08-03 | 中石油吉林化工工程有限公司 | Adipic acid preparation method and system |
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