CN109456200A - A kind of preparation method of m-xylene diamine - Google Patents
A kind of preparation method of m-xylene diamine Download PDFInfo
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- CN109456200A CN109456200A CN201811402472.4A CN201811402472A CN109456200A CN 109456200 A CN109456200 A CN 109456200A CN 201811402472 A CN201811402472 A CN 201811402472A CN 109456200 A CN109456200 A CN 109456200A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/02—Preparation of carboxylic acid nitriles by reaction of nitrogen oxide with organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
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Abstract
The present invention provides a kind of preparation method of m-xylene diamine.In the method, meta-xylene is changed by isophthalodinitrile by ammoxidation.Resulting isophthalodinitrile is extracted using N- alkyl pyrazole.Isophthalodinitrile solution is obtained by extraction and obtains m-xylene diamine reaction solution into hydrogenator hydrogenation reaction after resin decarboxylation acid.The m-xylene diamine of the last isolated high-purity of rectifying (> 99.9%).This method has the characteristics that reaction process is simple, low energy consumption, easy to operate, m-xylene diamine high income and m-xylene diamine are with high purity.
Description
Technical field
The invention belongs to organic amines to synthesize field, be related to a kind of preparation method of high-purity m-xylene diamine.
Background technique
M-xylene diamine (abbreviation MXDA) is colourless transparent liquid, is dissolved in water and organic solvent, is mainly used as epoxy resin
Curing agent and modified nylon polymer monomer.The epoxy curing agent curing performance made from MXDA is excellent, heat resistance, resistance to
Aqueous and chemical corrosion resistance is good, the extremely smooth solidified resin in the surface that can be made transparent；Using MXDA as modified monomer system
Novel nylon resin-meta-xylene the nylon resin obtained has good anti-oxygen permeability and resistant to carbon dioxide leachability.MXDA is also
It can be used to monomer-meta-xylene dicyanate (abbreviation MXDI) of synthesis of polyurethane, with currently used diphenyl methane two
Isocyanates (abbreviation MDI) is compared, and product is not easy yellowing, and drying time is short, the paint film that available hardness is high, stability is good.
In addition, MXDA is in rubber product, pesticide, fibre trimmer, antirust agent, chelating agent, lubricant, paper and electronic product industry
There is application.
In method disclosed in patent JP2002-105035A, the gaseous product that ammoxidation of m-xylene is obtained directly with
Isophthalodinitrile (IPN) is extracted into organic solvent by organic solvent exposure.Use methyl-benzonitrile for extractant, extractant
Without isolation, liquefied ammonia is added and carries out hydrogenation reaction.Using methyl-benzonitrile as extractant in the patent, but methyl-benzonitrile is adding
Hydrogenation reaction can occur under hydrogen condition and generate methylbenzylamine, be unable to effective recycling.Therefore, methyl-benzonitrile cannot effectively be made
For the extractant in the patent.
In method disclosed in patent CN1972896B, the gaseous product that ammoxidation of m-xylene is obtained is using methyl benzyl
After nitrile extraction, methyl-benzonitrile and isophthalodinitrile are isolated by rectifying.In isophthalodinitrile after isolation be added solvent and
Liquefied ammonia carries out liquid-phase hydrogenatin again.When separating isophthalodinitrile and methyl-benzonitrile, rectifying tower reactor temperature is up to 165 DEG C or more, should
At a temperature of isophthalodinitrile by thermally labile, be easy to decompose.It is high additionally, due to isophthalodinitrile fusing point, when rectifying for prevent its
Rectifying column crystallizes and rectifying column is caused all to be filled in, and when distillation operation needs strict control to bottom temperature and pressure.In this method plus
Also needing to be added another solvent stable under hydroconversion condition and a large amount of liquefied ammonia in hydrogen step, (liquefied ammonia accounts for reaction in embodiment
The 84% of system quality), in later separation, energy consumption is very high, and step is more, complicated for operation.
In method disclosed in patent US20070088179A1, the gaseous product that ammoxidation of m-xylene is obtained directly with
Organic solvent N-Methyl pyrrolidone (NMP) contact, isophthalodinitrile is extracted into organic solvent, extraction temperature is preferably
80-120 DEG C, extract liquor separates water outlet and light component by rectifying, adds a large amount of liquefied ammonia and carries out hydrogenation reaction, liquid in embodiment
Ammonia additive amount is 1.75-5 times of isophthalodinitrile quality.It needs to add a large amount of liquefied ammonia in the patent and makees auxiliary agent, and extraction temperature is high,
It is easy to cause isophthalodinitrile to be lost.
In patent US6646163B2, ammoxidation organic gas preferably uses methyl-benzonitrile to absorb, the methyl-benzonitrile after absorption
Solution is washed at lower than 140 DEG C with alkaline aqueous solution, and removal ammoxidation carboxylic acids (such as itrile group benzoic acid, methyl benzoic acid) is secondary
It produces, then organic phase and water phase split-phase, organic phase distills isolated benzene dicarbonitrile.This method operation sequence is complicated, control strip
Part is harsh, and in addition to having the shortcomings that in above-mentioned patent CN1972896B, there is also methyl-benzonitriles and benzene dicarbonitrile at high temperature in alkali
The defects of hydrolyzing in aqueous solution although strict control alkali cleaning temperature, but still has more benzene dicarbonitrile product hydrolysis loss.This is specially
The problems such as benefit is more there is also alkaline waste water.
For in above-mentioned patent by meta-xylene prepare in the technique of m-xylene diamine extraction step and plus hydrogen and etc. deposit
The problem of, it is complicated for operation if step is more, isophthalodinitrile loss is big, energy consumption is very high and the three wastes mostly etc., it is new to need exploitation
Preparation process is insufficient to improve these.
Summary of the invention
The present invention is to solve the above deficiencies in the existing technologies, provides a kind of preparation of the m-xylene diamine of high-purity
Method synthesizes isophthalodinitrile by ammoxidation of m-xylene first, then adds hydrogen to prepare m-xylene diamine by isophthalodinitrile.We
A kind of excellent extractant alkyl pyrazole is specifically provided in method, using such solvent, is separated without solvent, in conjunction with this hair
The preprocess method of central bay benzene dicarbonitrile, has that reaction process is simple, low energy consumption, easy to operate, MXDA purity is high (>
99.9%), the features such as high income.
The present invention to achieve the above object, the technical solution adopted is as follows:
A kind of preparation method of m-xylene diamine, step include:
1) ammoxidation reaction: in the presence of a catalyst, meta-xylene reacts in the gas phase with ammonia and oxygen, is made and contains isophthalic
The gas of dimethoxy nitrile；
2) solvent extraction: gas of the organic solvent with step 1) containing isophthalodinitrile contacts, and extracts isophthalodinitrile, must contain
The solution of isophthalodinitrile；
3) resin adsorption: the solution by step 2) containing isophthalodinitrile is adsorbed by basic resin, removes carboxylic acids impurity；
4) hydrogenation reaction: the liquefied ammonia of 0~1 times of isophthalodinitrile quality is added in step 3) treated solution, is being catalyzed
In the presence of agent, the solution containing m-xylene diamine is made in hydrogenation reaction；
5) separating-purifying: solution of the step 4) containing m-xylene diamine separates to obtain m-xylene diamine by rectifying.
Further, during step 1) ammoxidation reaction:
The oxide of the catalyst at least four metallic elements in containing vanadium, chromium, molybdenum, phosphorus and iron；
The oxygen, source are preferably air；
The molar ratio of the meta-xylene and ammonia, oxygen is 1:2~10:2~10, preferably 1:4~6:4~6；Feed space velocities
0.02~0.2g/gCat./h, preferably 0.05~0.1g/gCat./h are calculated as with meta-xylene.
The reaction, temperature are 300~500 DEG C, preferably 350~480 DEG C；Pressure is 0.01~0.5MPa (gauge pressure), excellent
Select 0.02~0.2MPa (gauge pressure)；At reaction conditions, the residence time of unstrpped gas be 0.1~50s, preferably 0.1~20s,
Particularly preferred 0.2~10s；
The reactor of the reaction, use is selected from fixed bed, fluidized bed or moving bed.
Further, in step 2) solvent extraction process:
The organic solvent is alkyl pyrazole；It is preferred that N- methylpyrazole, N- ethylpyrazol, N- n-propyl pyrazoles, N- isopropyl
At least one of base pyrazoles, N- normal-butyl pyrazoles, N- isobutyl group pyrazoles and N- t-butylpyrazol；Further preferred N- methyl pyrrole
At least one of azoles, N- ethylpyrazol and N- isopropylpyrazol.
The consumption of organic solvent is 1~20 times, preferably 2~5 times of isophthalodinitrile quality.
The extraction, pressure (gauge pressure) are 0.2~4Bar, preferably 0.5~2Bar；Temperature is 30~50 DEG C.
The device of the extraction, use is selected from film condensation device, injection apparatus or extraction tower, preferably extraction tower.It is extracting
Tower, the gas containing isophthalodinitrile preferably enter from tower bottom, and organic solvent enters from tower top.To increase contact surface area, preferably
Tower tray, or filling structured packing or random packing are installed in extraction tower.
Organic solvent used in this step answers isophthalodinitrile solubility with higher, and not with isophthalodinitrile
Reaction, does not add hydrogen imine intermediate to react under hydrogenation conditions with ammonia, MXDA and isophthalodinitrile.In extraction process, contain
The gas and organic solvent of isophthalodinitrile can be by being directly blown into the appearance equipped with extractant for the gas containing isophthalodinitrile
Device, or by organic gas be sprayed onto the gas containing isophthalodinitrile carry out.Pass through gas and organic solvent containing isophthalodinitrile
Contact, ammoxidation product isophthalodinitrile is extracted into organic solvent, and with unreacted ammonia, hydrogen cyanide, carbon dioxide, an oxygen
Change the fixed gases such as carbon, nitrogen, oxygen to separate.
Further, during step 3) resin adsorption:
The basic resin is selected from the T series plastics or triumphant auspicious basic resin of Dandong jewel；The T series of Dandong jewel
Resin is T300, T300s or T200, and the triumphant auspicious basic resin is 201 systems, D201, D202 or D254；The basic resin is excellent
It is selected as T300 or D201.
The absorption, temperature are 30~50 DEG C；Solution flow velocity containing isophthalodinitrile is 0.5~10 times of resin volume/
Hour, preferably 1~5 times/hour.Bottom in and top out and upper entering and lower leaving, preferably bottom in and top out can be used in solution containing isophthalodinitrile.
The carboxylic acids impurity includes benzoic acid, 3- yl benzoic acid, 3- itrile group benzoic acid, M-phthalic acid, 4- methylbenzene
At least one of formic acid and 2- methyl benzoic acid.
Follow-up hydrogenation reaction can be directly entered by the solution containing isophthalodinitrile that resin adsorption is handled.
Further, in step 4) hydrogenation process:
The catalyst is selected from the catalyst containing nickel and/or cobalt, preferably Raney's nickel, thunder Buddhist nun cobalt, nickel-loaded and Supported Co
At least one of.The preferred aluminium oxide of the carrier of the nickel-loaded and Supported Co, silica, titanium oxide, magnesia or active carbon.
Preferably, the catalyst is changed by one of addition Cu, Cr, Ru, Fe, Mo, Sn, Mn and Zn or a variety of
Property.
The reactor of the hydrogenation reaction, use is selected from reaction kettle, fixed bed or slurry bed system, preferably fixed bed；It is described to add
Hydrogen reaction can be carried out using intermittently or serially mode, preferably continuation mode.
The hydrogenation reaction, temperature are 40~200 DEG C, preferably 60~150 DEG C；Pressure be 3~20MPa (gauge pressure), preferably 5
~12MPa (gauge pressure)；
Feed space velocities are calculated as 0.05~2g/gCat./h, preferably 0.1~0.5g/gCat./h with isophthalodinitrile.
In view of downstream application has very high demand to MXDA quality, unreacted nitrile should try to control in hydrogenation reaction solution
The content of base benzylamine, preferably smaller than 0.2wt%, more preferably in 0.05wt% or less.
In hydrogenation reaction of the present invention, liquefied ammonia is controlled in 1:1 with isophthalodinitrile mass ratio hereinafter, not adding even, public affairs
Know, liquefied ammonia is added to reaction system and makees auxiliary agent or solvent, MXDA yield can be effectively improved.Such as above, existing patent
CN1972896B and US20070088179A1 etc. is both needed to add a large amount of liquefied ammonia as auxiliary agent to improve MXDA yield, or
Using liquefied ammonia as solvent, liquefied ammonia additive amount is at least 1.75 times of isophthalodinitrile quality or more, even up to 14 times or more.And
Hydrogenation reaction solvent is made using extraction agent alkyl pyrazole of the invention, liquefied ammonia usage amount substantially reduces, or even in not annex solution
Also there is preferable yield when ammonia, can effectively save the energy consumption of ammonia separation recycling.
In hydrogenation reaction of the present invention, the hydroxide and alkoxide for not needing addition alkali or alkaline earth metal make auxiliary agent, can
It avoids these auxiliary agents from being precipitated in later separation in rectifying column, blocks rectifying column and respective lines.
Further, during step 5) separating-purifying:
The rectifying, operating pressure are 1~20kPa (absolute pressure), and preferably 1~10kPa (absolute pressure), tower bottom of rectifying tower temperature is
80~180 DEG C, preferably 100~160 DEG C.The rectifying is carried out using intermittently or serially mode, and rectifying column is packed tower or board-like
Tower.
The m-xylene diamine purity that the method for the present invention is prepared is greater than 99.9%.
The organic solvent alkyl pyrazole of the preparation method of m-xylene diamine of the present invention, use has the advantage that
(1) isophthalodinitrile solubility in N- alkyl pyrazole is very big, when being extracted, when not needing to keep extract liquor long
Between in high-temperature storage, extract liquor temperature is maintained at 30~50 DEG C, can be effective far below in the prior art 80~200 DEG C
It avoids isophthalodinitrile from being thermally decomposed, improves isophthalodinitrile utilization rate, reduce the impurity for decomposing and generating, improve isophthalodinitrile
Quality；
(2) N- alkyl pyrazole had both been used as ammoxidation reaction extractant, but also as the solvent of hydrogenation reaction.Resulting extraction
Take liquid to need not move through the separation of solvent and isophthalodinitrile before entering the reactor, under hydrogenation conditions not with intermediate
Or reaction product reacts, and after selecting suitable ratio, does not need additionally to add solvent before the reaction, can not only simplify behaviour
Make process, avoids the energy consumption of separation solvent, moreover it is possible to isophthalodinitrile be avoided to be thermally decomposed during the separation process；
(3) using N- alkyl pyrazole is solvent in hydrogenation reaction, greatly reduces auxiliary agent liquefied ammonia dosage or does not add,
Reach preferable reaction effect.
In existing method, decarboxylation acid by-product is needed by the processes such as high temperature washing, split-phase, desolventizing, extract liquor of the present invention
It is had the advantage that using resin adsorption processing decarboxylation acid by-product
(1) resin adsorption depickling uses organic solvent system, does not need to contact with water, isophthalodinitrile water can be effectively reduced
Solution；
(2) resin adsorption depickling temperature is low, less than 50 DEG C, can further decrease isophthalodinitrile hydrolysis and decomposition rate.
(3) resin adsorption depickling only needs a step to adsorb, and process flow is simple, and operating quantity is greatly decreased, and simplifies stream
Journey；The carboxylic acid by-product in ammoxidation reaction can not only effectively be sloughed, moreover it is possible to effectively reduce isophthalodinitrile loss, the proportion of goods damageds are lower than
0.5%.
M-xylene diamine preparation method of the present invention, compared with prior art, with reaction process is simple, low energy consumption, operation
Simply, the features such as MXDA purity is high, high income.
Specific embodiment
For a better understanding of the technical solution of the present invention, below with reference to the embodiment content that the present invention is further explained,
But the contents of the present invention are not limited only to following embodiment.
In following embodiments, chemical composition is determined by gas chromatographic analysis.The condition of gas chromatographic analysis are as follows: Agilent
HP-5 chromatographic column (specification is 5%Phenyl Methyl Siloxan30m × 0.32mm × 0.25mm), fid detector.Sample introduction
Device and detector temperature are 280 DEG C；Column temperature is controlled using temperature programming: initial 50 DEG C of column temperature are kept for 1 minute；10 DEG C/min liter
Temperature is kept for 0 minute to 200 DEG C；15 DEG C/min is warming up to 260 DEG C, is kept for 5 minutes.Column pressure 7.0126psi, flow velocity 1.5mL/
Min, the residence time 1.8551 minutes.Sample volume: 0.2 μ L.Conversion ratio and yield are calculated using area normalization method.
Heretofore described pressure is gauge pressure unless otherwise specified.
Embodiment 1
1) ammoxidation reaction:
Ammoxidation uses catalyst using aluminium oxide as carrier, and vector contg accounts for the 55% of catalyst weight, other compositions by
V, Cr, Mo and P are formed with the ratio of 1:1:0.1:0.1.The 5kg catalyst is loaded into fluidized-bed reactor, reaction raw materials exist
400 DEG C are preheating to before entering reactor, reacts 450 DEG C of hot(test)-spot temperature, oxygen sources are air, meta-xylene: ammonia: air
Molar ratio is 3:20:77.Reaction pressure is in 0.02~0.05MPa.Gas residence time is controlled in 0.5s.Diformazan containing isophthalic is made
The gas of nitrile, on the basis of the meta-xylene for being added to reaction system, IPN molar yield is 85.1%, and methyl-benzonitrile yield is
2.5%.
2) solvent extraction:
Gas containing isophthalodinitrile is added in extraction tower from extraction tower tower bottom.Extraction tower internal diameter 100mm is highly
850mm, deposit 3*3 θ ring in tower.Extraction tower operating pressure is 0.8Bar.Extraction agent N- methylpyrazole from tower top with
The flow velocity of 0.8kg/h is added, and ammoxidation gas is continuously passed through from tower bottom with the flow velocity of 3.5kg/h and is contacted with solvent, tower bottom extraction
Liquid temperature is kept for 45 DEG C, obtains the solution containing isophthalodinitrile, chemical composition is the IPN of 27.1wt%, the N- first of 71.5wt%
Base pyrazoles, the methyl-benzonitrile of 0.8wt% and the heavy constituent of 0.6wt%.
3) resin adsorption:
Solution containing isophthalodinitrile is entered into adsorption tower from resin adsorption tower tower bottom.Adsorption tower internal diameter 50mm is highly
300mm, deposit 3*3 θ ring in tower.Basic resin uses Dandong jewel T300.Adsorption temp is kept for 45 DEG C.Extraction solution into
The flow velocity for entering resin is 2.5 times/hour of basic resin volume.Isophthalodinitrile loss late is 0.21%.
4) hydrogenation reaction:
Adsorption liquid obtained by resin adsorption is directly entered hydrogenator, and hydrogenator is fixed bed reactors.Hydrogen is added to urge
Agent is Raney's nickel catalyst, consisting of: nickel content about 51wt%, aluminium content about 45wt%, molybdenum doped with 2wt% and
2% chromium.It is auxiliary agent that liquefied ammonia is added in solution, and liquefied ammonia additive amount and IPN mass ratio are 1:1.Hydrogenation reaction temperature is 80 DEG C, instead
Answering pressure is 8MPa, and IPN air speed is 0.2g/gCat./h.The solution that m-xylene diamine must be contained, based on IPN, MXDA yield is
96.5%, the complete itrile group benzylamine content of unreacted is 0.009%, and heavy constituent content is 2.1%, MXDA benzene ring hydrogenation product assay
It is 1.3%.
5) separating-purifying:
Solution containing m-xylene diamine uses packed tower rectifying, and rectifying tower plates number is 15.First in 0.5MPa (absolute pressure),
Ammonia is isolated in rectifying at 135 DEG C of bottom temperature.Then by remaining liquid in normal pressure, 152 DEG C of rectifying desolventizing N- of bottom temperature
Methylpyrazole.Finally in 2KPa (absolute pressure), the isolated high-purity m-xylene diamine of 155 DEG C of rectifying of bottom temperature.By analysis,
MXDA purity is 99.97%, contains 0.01% methyl-benzonitrile and 0.02% other components.
Embodiment 2
1) ammoxidation reaction:
Ammoxidation uses catalyst using aluminium oxide as carrier, and vector contg accounts for the 55% of catalyst weight, other compositions by
V, Cr, Mo and Fe are formed with the ratio of 1:1:0.1:0.1.The 5kg catalyst is loaded into fluidized-bed reactor, reaction raw materials exist
Enter 480 DEG C of hot(test)-spot temperature of preheating reaction before reactor, oxygen sources are air, meta-xylene: ammonia: the volume ratio of air is
1:6:28.Reaction pressure is in 0.02~0.05MPa.Gas residence time is controlled in 1s.The gas containing isophthalodinitrile is made, with
It is added on the basis of the meta-xylene of reaction system, IPN molar yield is 85.3%, and methyl-benzonitrile yield is 2.5%.
2) solvent extraction:
Gas containing isophthalodinitrile is added in extraction tower from extraction tower tower bottom.Extraction tower internal diameter 100mm is highly
850mm, deposit 3*3 θ ring in tower.Extraction tower operating pressure is 1Bar.Extraction agent N- ethylpyrazol is from tower top with 2kg/h
Flow velocity be added, ammoxidation gas is continuously passed through from tower bottom with the flow velocity of 3.6kg/h and contacted with solvent, and tower bottom Produced Liquid temperature is protected
50 DEG C to be held, obtains the solution containing isophthalodinitrile, chemical composition is the IPN of 15.6wt%, the N- ethylpyrazol of 83.5wt%,
The methyl-benzonitrile of 0.48wt% and the heavy constituent of 0.36wt%.
3) resin adsorption
Solution containing isophthalodinitrile is entered into adsorption tower from resin adsorption tower tower bottom.Adsorption tower internal diameter 50mm is highly
300mm, deposit 3*3 θ ring in tower.Basic resin uses triumphant auspicious D201.Adsorption temp is kept for 50 DEG C.Extraction solution enters tree
The flow velocity of rouge is 1 times/hour of resin volume.Isophthalodinitrile loss late is 0.34%.
4) hydrogenation reaction:
Adsorption liquid obtained by resin adsorption is directly entered hydrogenator.Hydrogenator is fixed bed reactors.Hydrogen is added to urge
Agent is thunder Buddhist nun Co catalysts, consisting of: cobalt content about 51wt%, aluminium content about 45wt%, copper doped with 2wt% and
2% manganese.It is auxiliary agent that liquefied ammonia is added in solution, and liquefied ammonia additive amount and IPN mass ratio are 1:1.Hydrogenation reaction temperature is 100 DEG C,
Reaction pressure is 12MPa, and IPN air speed is 0.5g/gCat./h.The solution that m-xylene diamine must be contained, based on IPN, MXDA yield
It is 96.9%, the complete itrile group benzylamine content of unreacted is 0.003%, and heavy constituent content is that 1.1%, MXDA benzene ring hydrogenation product contains
Amount is 1.9%.
5) separating-purifying:
Solution containing m-xylene diamine uses packed tower rectifying, and rectifying tower plates number is 15.First in 0.5MPa (absolute pressure),
Ammonia is isolated in rectifying at 140 DEG C of bottom temperature.Then by remaining liquid in normal pressure, 158 DEG C of rectifying desolventizing N- of bottom temperature
Methylpyrazole.Finally in 2KPa (absolute pressure), the isolated high-purity m-xylene diamine of 155 DEG C of rectifying of bottom temperature.By analysis,
MXDA purity is 99.98%, contains 0.01% methyl-benzonitrile and 0.01% other components.
Embodiment 3
1) ammoxidation reaction:
Ammoxidation uses catalyst using aluminium oxide as carrier, and vector contg accounts for the 55% of catalyst weight, other compositions by
V, Cr, Fe and P are formed with the ratio of 1:1:0.1:0.1.The 5kg catalyst is loaded into fluidized-bed reactor, reaction raw materials exist
Enter 350 DEG C of hot(test)-spot temperature of preheating reaction before reactor, oxygen sources are air, meta-xylene: ammonia: the molar ratio of air is
1:4:20.Reaction pressure is in 0.02~0.05MPa.Gas residence time is controlled in 1s.The gas containing isophthalodinitrile is made, with
It is added on the basis of the meta-xylene of reaction system, IPN molar yield is 84.9%, and methyl-benzonitrile yield is 2.5%.
2) solvent extraction:
Gas containing isophthalodinitrile is added in extraction tower from extraction tower tower bottom.Extraction tower internal diameter 100mm is highly
850mm, deposit 3*3 θ ring in tower.Extraction tower operating pressure is 2Bar.Extraction agent N- isopropylpyrazol from tower top with
The flow velocity of 1.5kg/h is added, and ammoxidation gas is continuously passed through from tower bottom with 3kg/h flow velocity and is contacted with solvent, tower bottom Produced Liquid temperature
Degree is kept for 30 DEG C, obtains the solution containing isophthalodinitrile, chemical composition is the IPN of 21.1wt%, the N- isopropyl of 77.8wt%
Pyrazoles, the methyl-benzonitrile of 0.61wt% and the heavy constituent of 0.35wt%.
3) resin adsorption
Solution containing isophthalodinitrile is entered into adsorption tower from resin adsorption tower tower bottom.Adsorption tower internal diameter 50mm is highly
300mm, deposit 3*3 θ ring in tower.Basic resin uses Dandong jewel T300.Adsorption temp is kept for 30 DEG C.Extraction solution into
The flow velocity for entering resin is 5 times/hour of resin volume.Isophthalodinitrile loss late 0.11%.
4) hydrogenation reaction:
Solvent extraction: gained extract liquor is directly entered hydrogenator reaction.Hydrogenator is fixed bed reactors.Add
Hydrogen catalyst is alumina load Co catalysts, consisting of: cobalt content about 50wt%, Zn content be 2wt%'s and iron content
1wt%.Liquefied ammonia auxiliary agent is not added in solution.Hydrogenation reaction temperature is 60 DEG C, and reaction pressure 10MPa, IPN air speed is 0.1g/
gCat./h.The solution that m-xylene diamine must be contained, based on IPN, MXDA yield is 95.5%, and the complete itrile group benzylamine of unreacted contains
Amount is 0.01%, and heavy constituent content is that 1.5%, MXDA benzene ring hydrogenation product assay is 2.3%.
5) separating-purifying:
Solution containing m-xylene diamine uses packed tower rectifying, and rectifying tower plates number is 15.First in 0.5MPa (absolute pressure),
Ammonia is isolated in rectifying at 138 DEG C of bottom temperature.Then by remaining liquid in normal pressure, 150 DEG C of rectifying desolventizing N- of bottom temperature
Isopropylpyrazol.Finally in 2KPa (absolute pressure), the isolated high-purity m-xylene diamine of 155 DEG C of rectifying of bottom temperature.Through excessive
Analysis, MXDA purity are 99.98%, contain 0.01% methyl-benzonitrile and 0.01% other components.
Embodiment 4
1) ammoxidation reaction:
Ammoxidation uses catalyst using aluminium oxide as carrier, and vector contg accounts for the 55% of catalyst weight, other compositions by
V, Cr, Fe and Mo are formed with the ratio of 1:1:0.1:0.1.The 5kg catalyst is loaded into fluidized-bed reactor, reaction raw materials exist
Enter 400 DEG C of hot(test)-spot temperature of preheating reaction before reactor, oxygen sources are air, meta-xylene: ammonia: the volume ratio of air is
1:5:22.Reaction pressure is in 0.02~0.05MPa.Gas residence time is controlled in 0.5s.The gas containing isophthalodinitrile is made,
On the basis of the meta-xylene for being added to reaction system, IPN molar yield is 84.9%, and methyl-benzonitrile yield is 2.5%.
2) solvent extraction:
Gas containing isophthalodinitrile is added in extraction tower from extraction tower tower bottom.Extraction tower internal diameter 100mm is highly
850mm, deposit 3*3 θ ring in tower.Extraction tower operating pressure is 1Bar.Extraction agent N- isopropylpyrazol from tower top with
The flow velocity of 1kg/h is added, and ammoxidation gas is continuously passed through from tower bottom with 3.3kg/h flow velocity and is contacted with solvent, tower bottom Produced Liquid temperature
Degree is kept for 40 DEG C, obtains the solution containing isophthalodinitrile, chemical composition is the IPN of 30.1wt%, the N- isopropyl of 68.1wt%
Pyrazoles, the methyl-benzonitrile of 0.9wt% and the heavy constituent of 0.6wt%.
3) resin adsorption:
Solution containing isophthalodinitrile is entered into adsorption tower from resin adsorption tower tower bottom.Adsorption tower internal diameter 50mm is highly
300mm, deposit 3*3 θ ring in tower.Basic resin uses Dandong jewel T300.Adsorption temp is kept for 40 DEG C.Extraction solution into
The flow velocity for entering resin is 2 times/hour of resin volume, and isophthalodinitrile loss late is 0.24%.
4) hydrogenation reaction:
Liquefied ammonia is not only added and makees auxiliary agent, and other conditions are the same as embodiment 2.Solution obtained containing m-xylene diamine is based on IPN
Meter, MXDA yield are 95.2%, and the complete itrile group benzylamine content of unreacted is 0.01%, and heavy constituent content is 3.3%, MXDA phenyl ring
Hydrogenation products content is 2.1%.Reaction when not adding liquefied ammonia, MXDA yield can also reach considerable level.
5) separating-purifying:
Solution containing m-xylene diamine is separated by rectifying, and condition obtains high-purity m-xylene diamine with embodiment 1, is passed through
Analysis, MXDA purity are 99.98%, contain 0.01% methyl-benzonitrile and 0.01% other components.
Comparative example 1
1) ammoxidation reaction:
With embodiment 3.
2) solvent extraction:
Only change extraction agent into NMP, other conditions are the same as embodiment 3.The solution of isophthalodinitrile, chemical composition must be contained
It is the IPN of 15.4wt%, the methyl-benzonitrile of the NMP of 83.7wt%, 0.6wt% and the heavy constituent of 0.3wt%.There is part isophthalic two
Formonitrile HCN fails effectively to extract.
3) resin adsorption:
With embodiment 3.
4) hydrogenation reaction:
With embodiment 3, based on IPN, MXDA yield is 75.2%, and the complete itrile group benzylamine content of unreacted is 3.2%, weight
Constituent content is that 20.5%, MXDA benzene ring hydrogenation product assay is 1.1%.
5) separating-purifying:
Solution containing m-xylene diamine is separated by rectifying, and condition obtains m-xylene diamine with embodiment 1, through analyzing,
MXDA purity is 99.38%, contains 0.48% methyl-benzonitrile and 0.14% other components.
Comparative example 2
1) ammoxidation reaction:
With embodiment 3.
2) solvent extraction:
Only change extraction agent into methyl-benzonitrile, other conditions are the same as embodiment 3.The solution of isophthalodinitrile must be contained, extracted
Isophthalodinitrile content is only 8.1% in liquid.Most of isophthalodinitrile fails effectively to extract.Extraction and separation solvent under this condition
Need to consume a large amount of energy consumption.It needs for extraction temperature to be promoted to 150 DEG C or more and gets to preferable effect of extracting.But such as
At a temperature of this is high, when extracting and separating isophthalodinitrile, benzene dicarbonitrile is easy to decompose by thermally labile.Additionally, due to isophthalic
Dimethoxy nitrile fusing point is high, causes rectifying column all to be filled in prevent it from crystallizing in rectifying column when rectifying, to bottom temperature when distillation operation
Strict control is needed with pressure
Comparative example 3
Ammoxidation reaction and solvent extraction are the same as embodiment 2.
Ammoxidation gas does not use resin adsorption after adsorbing using N- methylpyrazole, and is washed at 50 DEG C with alkaline aqueous solution
Wash, after after isolating solvent and isophthalodinitrile enter hydrogenator react.By alkali cleaning, there is 2.4% isophthalic diformazan
Nitrile hydrolysis loss.By split-phase, water content is 1.2% in organic phase.
The resulting organic phase of split-phase is directly entered hydrogenator reaction.Reaction condition is with embodiment 2, based on IPN,
MXDA yield is 88.9%, and the complete itrile group benzylamine content of unreacted is 0.004%, and heavy constituent content is that 3.1%, MXDA phenyl ring adds
Hydrogen product assay is that 1.9%, IPN hydrolysate benzene methanamine formamide content is 3.5%, and phenyl-diformyl amine content is 2.4%.
By alkali cleaning, there is about 2.4%IPN hydrolysis loss, the lye into system can still promote under hydrogenation conditions
IPN hydrolysis, causes IPN waste about 5.9%.Generally speaking alkali cleaning causes the IPN greater than 8% to lose.
Comparative example 4
Ammoxidation gas does not use resin suction to be directly entered hydrogenator reaction after adsorbing using N- methylpyrazole, other
With embodiment 1.Based on IPN, MXDA yield is 85.2%, and the complete itrile group benzylamine content of unreacted is 2.5%, heavy constituent content
It is 1.1% for 11.2%, MXDA benzene ring hydrogenation product assay.
Solution containing m-xylene diamine is separated by rectifying, and condition obtains high-purity m-xylene diamine with embodiment 1, is passed through
Analysis, MXDA purity are 99.51%, contain 0.38% methyl-benzonitrile and 0.11% other components.
By above embodiments as it can be seen that using method of the present invention, with reaction process is simple, low energy consumption, operation letter
The features such as list, MXDA high income and MXDA with high purity.
Claims (10)
1. a kind of preparation method of m-xylene diamine, which is characterized in that comprise the steps of:
1) in the presence of a catalyst, meta-xylene reacts in the gas phase with ammonia and oxygen, and the gas containing isophthalodinitrile is made；
2) gas of the organic solvent with step 1) containing isophthalodinitrile contacts, and extracts isophthalodinitrile, obtains containing isophthalodinitrile
Solution；
3) solution by step 2) containing isophthalodinitrile is adsorbed by basic resin, removes carboxylic acids impurity；
4) liquefied ammonia that 0~1 times of isophthalodinitrile quality is added in step 3) treated solution adds hydrogen in the presence of a catalyst
The solution containing m-xylene diamine is made in reaction；
5) solution of the step 4) containing m-xylene diamine separates to obtain m-xylene diamine by rectifying.
2. preparation method as described in claim 1, which is characterized in that in step 1), the catalyst be selected from containing vanadium, chromium,
The oxide of at least four metallic elements in molybdenum, phosphorus and iron；
The molar ratio of the meta-xylene and ammonia, oxygen is 1:2~10:2~10, preferably 1:4~6:4~6；Feed space velocities with
Dimethylbenzene is calculated as 0.02~0.2g/gCat./h, preferably 0.05~0.1g/gCat./h.
3. preparation method as described in claim 1, which is characterized in that in step 1), the reaction, temperature is 300~500
DEG C, preferably 350~480 DEG C；Pressure is 0.01~0.5MPa (gauge pressure), preferably 0.02~0.2MPa (gauge pressure)；In reaction condition
Under, the residence time of unstrpped gas is 0.1~50s, preferably 0.1~20s, particularly preferred 0.2~10s；
Preferably, the reactor used that reacts is fixed bed, fluidized bed or moving bed.
4. preparation method as described in claim 1, which is characterized in that in step 2), the organic solvent is alkyl pyrazole；It is excellent
Select N- methylpyrazole, N- ethylpyrazol, N- n-propyl pyrazoles, N- isopropylpyrazol, N- normal-butyl pyrazoles, N- isobutyl group pyrazoles and
At least one of N- t-butylpyrazol；In further preferred N- methylpyrazole, N- ethylpyrazol and N- isopropylpyrazol extremely
Few one kind；The consumption of organic solvent is 1~20 times, preferably 2~5 times of isophthalodinitrile quality.
5. preparation method as described in claim 1, which is characterized in that in step 2), the extraction, pressure (gauge pressure) is 0.2
~4Bar, preferably 0.5~2Bar；Temperature is 30~50 DEG C；
Preferably, the device used that extracts is film condensation device, injection apparatus or extraction tower, preferably extraction tower.
6. preparation method as described in claim 1, which is characterized in that in step 3), the basic resin is selected from Dandong jewel
T series plastics or triumphant auspicious basic resin；Preferably, the T series plastics of Dandong jewel are T300, T300s or T200, institute
Stating triumphant auspicious basic resin is 201 systems, D201, D202 or D254；The basic resin is more preferably T300 or D201.
7. preparation method as described in claim 1, which is characterized in that in step 3), the absorption, temperature is 30~50 DEG C；
Solution flow velocity containing isophthalodinitrile is 0.5~10 times/hour of resin volume, preferably 1~5 times/hour.
8. preparation method as described in claim 1, which is characterized in that in step 4), the catalyst be selected from containing nickel and/or
At least one of the catalyst of cobalt, preferably Raney's nickel, thunder Buddhist nun cobalt, nickel-loaded and Supported Co；The nickel-loaded and Supported Co
The preferred aluminium oxide of carrier, silica, titanium oxide, magnesia or active carbon；
Preferably, the catalyst is modified by one of addition Cu, Cr, Ru, Fe, Mo, Sn, Mn and Zn or a variety of.
9. preparation method as described in claim 1, which is characterized in that in step 4), the hydrogenation reaction, temperature be 40~
200 DEG C, preferably 60~150 DEG C；Pressure is 3~20MPa (gauge pressure), preferably 5~12MPa (gauge pressure)；
Feed space velocities are calculated as 0.05~2g/gCat./h, preferably 0.1~0.5g/gCat./h with isophthalodinitrile；
Preferably, the content that unreacted itrile group benzylamine is controlled in hydrogenation reaction solution is less than 0.2wt%, more preferably in 0.05wt%
Below.
10. preparation method as described in claim 1, which is characterized in that in step 5), the rectifying, operating pressure be 1~
20kPa (absolute pressure), preferably 1~10kPa (absolute pressure), tower bottom of rectifying tower temperature are 80~180 DEG C, preferably 100~160 DEG C.
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| CN111377820A (en) * | 2020-04-23 | 2020-07-07 | 中国天辰工程有限公司 | Preparation method of 2-methylpentanediamine |
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| CN112934226A (en) * | 2019-12-11 | 2021-06-11 | 中国科学院大连化学物理研究所 | Preparation method and application of hydrogenation catalyst for producing m-xylylenediamine |
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