CN103360266B - Method for co-production of aramid fiber scale m-phenylenediamine and resorcinol - Google Patents
Method for co-production of aramid fiber scale m-phenylenediamine and resorcinol Download PDFInfo
- Publication number
- CN103360266B CN103360266B CN201310304733.XA CN201310304733A CN103360266B CN 103360266 B CN103360266 B CN 103360266B CN 201310304733 A CN201310304733 A CN 201310304733A CN 103360266 B CN103360266 B CN 103360266B
- Authority
- CN
- China
- Prior art keywords
- mphenylenediamine
- resorcinol
- water
- hydrolyzed
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 229920006231 aramid fiber Polymers 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title abstract description 28
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 title abstract description 9
- 229940018564 m-phenylenediamine Drugs 0.000 title abstract 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 80
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 238000002425 crystallisation Methods 0.000 claims abstract description 40
- 230000008025 crystallization Effects 0.000 claims abstract description 35
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 24
- 238000011084 recovery Methods 0.000 claims abstract description 23
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 12
- 239000012065 filter cake Substances 0.000 claims abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 66
- 238000000605 extraction Methods 0.000 claims description 46
- 239000000284 extract Substances 0.000 claims description 28
- 230000007062 hydrolysis Effects 0.000 claims description 22
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 238000004821 distillation Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000007701 flash-distillation Methods 0.000 claims description 11
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000004064 recycling Methods 0.000 claims description 10
- 239000008346 aqueous phase Substances 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 9
- 239000003337 fertilizer Substances 0.000 claims description 9
- 239000012071 phase Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000003672 processing method Methods 0.000 claims 4
- 239000012452 mother liquor Substances 0.000 abstract description 17
- 239000000047 product Substances 0.000 abstract description 5
- 238000004939 coking Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 abstract 4
- 239000000413 hydrolysate Substances 0.000 abstract 3
- LDXYDHGRKFMULJ-UHFFFAOYSA-N (3-azaniumylphenyl)azanium;sulfate Chemical compound OS(O)(=O)=O.NC1=CC=CC(N)=C1 LDXYDHGRKFMULJ-UHFFFAOYSA-N 0.000 abstract 2
- 238000001704 evaporation Methods 0.000 abstract 2
- 230000008020 evaporation Effects 0.000 abstract 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 abstract 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 229960001755 resorcinol Drugs 0.000 description 44
- 239000002904 solvent Substances 0.000 description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000010413 mother solution Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 229920004933 Terylene® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000012938 design process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000004223 radioprotective effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a method for co-production of aramid fiber scale m-phenylenediamine and resorcinol. The method includes: cooling a m-phenylenediamine aqueous solution in a crystallization pot, precipitating part of m-phenylenediamine and trace o-phenylenediamine and p-phenylenediamine crystals, conducting filtration, and preparing aramid fiber scale m-phenylenediamine from a filter cake; adding sulfuric acid into a filtrated stock diluted by water, letting the filtrated stock react with sulfuric acid to generate m-phenylenediamine sulfate, continuously sending the m-phenylenediamine sulfate to a heater to undergo heating and sending it into a hydrolysis reaction kettle, subjecting the hydrolysate from the hydrolysis reaction kettle to flash evaporation to recover part of water for preparing the m-phenylenediamine aqueous solution, and adding ammonia water into the hydrolysate undergoing flash evaporation to perform neutralization; extracting the neutralized hydrolysate with butyl acetate, recovering butyl acetate from the extracted liquid in a butyl acetate recovery tower, and distilling the butyl acetate recovered rough resorcinol, thus obtaining the finished product resorcinol. According to the invention, the crystallization mother liquor has no need for concentration, the crystallization process is simple, and the co-production of the aramid fiber scale m-phenylenediamine and resorcinol is free of the coking problem in a crystallization mother liquor concentration process, and secondary pollution can be avoided.
Description
Technical field
The invention belongs to Chemicals technical field of producing, more particularly relate to aramid fiber level mphenylenediamine and Resorcinol co-production.
Background technology
Aramid fiber 1313 is a kind of tynex.For the tire window line of radioprotective dress material processed, space flight dress material, particular requirement.Also for the manufacture of high temperature resistant dress material, honeycomb product, high temperature spool, fuel tanker, fireproof brickwork, reverse osmosis membrane or tubular fibre etc.
Aramid fiber 1313 is a kind of soft pure white, very thin fluffy, rich glossiness fiber, outward appearance and common chemical fibre there is no difference, but collecting crowd is longer than all over the body, have unusual specific function: the thermostability that (1) is lasting, can under 220 DEG C of high temperature life-time service and not aging, its electric property and mechanical property keep 10 years, and excellent dimensional stability, be only 1% at the percent thermal shrinkage of about 250 DEG C, the short period of time be exposed in 300 DEG C of high temperature also can not shrink, brittle, softening or melting.(2) good flame resistance, belongs to fire-retardant fibre, so can not burn in atmosphere, also not combustion-supporting, has self-extinguishing; This natural characteristics coming from molecular structure own makes aramid fiber 1313 permanent fire retardant, therefore has the laudatory title of " tFlame Retardant Fibers ".(3) splendid electrical insulating property, the insulation paper prepared with aramid fiber 1313 is breakdown voltage resistant reaches 100,000 volts/mm
2, be the best insulating material that the whole world is generally acknowledged.(4) outstanding chemical stability, the chemical structure exceptional stability of aramid fiber 1313, can the burn into resistant to hydrolysis effect of the dense mineral acid of resistance to most height and other chemical and steam corrosion.(5) excellent mechanical characteristics, aramid fiber 1313 is flexible high molecular material, and Low rigidity high drawing characteristic makes it to possess the spinning property identical with general fibre.(6) superpower radiation resistance,
]the performance of aramid fiber 1313 resistance to α, β, χ ray and ultraviolet light radiation is very excellent, and with the χ x radiation x 100 hours of 50Kv, its fibre strength still keeps original 73%, and terylene has now become powder already.
Resorcinol is important industrial chemicals.Resorcinol is commonly called as resorcin, is a kind of important meticulous Organic Chemicals, is widely used in the fields such as agricultural, dyestuff, coating, medicine, plastics, rubber, electronic chemical product.For the synthesis of the m-first tacky resin of reinforcing rubber class, wood adhesive, automobile cord fabrics and additives for plastics.
Aramid fiber 1313 forms through solvent spinning by after mphenylenediamine and m-phthaloyl chloride polycondensation.Aramid fiber has above-mentioned numerous advantage, but its manufacturing technology and ingredient requirement are all very high.Wherein, require that mass content is greater than 99.9% to the mphenylenediamine of one of main raw material, impurity sub-indicator requires extremely strict: ortho para diamine contents is less than 50ppm respectively separately.Raw material mphenylenediamine is usually containing isomers O-Phenylene Diamine and Ursol D.Mphenylenediamine, O-Phenylene Diamine are similar with Ursol D physics and chemistry character, and rectification process does not reach the ingredient requirement of aramid fiber level mphenylenediamine, usually also need to carry out secondary purification by crystallization processes.Because the surfusion of mphenylenediamine is serious, fusion-crystallization method is industrially difficult to carry out.
The industrial method obtaining aramid fiber level mphenylenediamine mainly adopts the technique of solution crystallization now.In solution crystallization technique, be dissolved in solvent by thick mphenylenediamine, solvent can be the organic solvents such as methyl alcohol, ethanol, acetone, chloroform.Solution is cooled to certain temperature, the mphenylenediamine that in solution, content is higher first crystallization, a small amount of O-Phenylene Diamine and Ursol D are stayed in mother liquor, obtaining highly purified aramid fiber level mphenylenediamine, removing the mphenylenediamine in the solvent recuperation mother liquor in mother liquor by filtering.In crystallisation process, the concentration how controlling mother liquor is one of key factor obtaining aramid fiber level mphenylenediamine.Mother liquid concentration is too low, and be not easy the mphenylenediamine obtaining high-quality, mother liquid concentration is too high, easily obtains the mphenylenediamine of high-quality, but the utilization ratio of mphenylenediamine is low.In order to the purity of the utilization ratio and aramid fiber level product that improve mphenylenediamine, usually secondary even three crystallizations are needed, repeatedly need Repeat-heating and cooling station phenylenediamine solution in crystallisation process, need to consume a large amount of energy, the mphenylenediamine reclaimed in mother liquor needs to remove solvents a large amount of in mother liquor, and also require the expenditure of energy, energy consumption is higher, the solvent simultaneously removed in mother liquor can produce tar in tower reactor, causes the loss of mphenylenediamine.From crystallization processes, in mother liquor, concentration more high being more conducive to obtains highly purified target product.If the mother liquor in solution crystal process directly can be utilized, then do not need the recycled solvent mphenylenediamine removed in mother liquor, under higher mother liquid concentration, crystallization can obtain the mphenylenediamine of high-quality simultaneously, reduce the technological operation difficulty in crystallisation process.
Resorcinol is main in the past to be produced with benzene process for sulfonation, and in recent years along with the raw-material rise in price of the basic chemical industry such as sulfuric acid, caustic soda, sulfonation method technique is eliminated.At present, the main method of producing Resorcinol is mphenylenediamine hydrolysis process.Mphenylenediamine, water, sulfuric acid are made into and consist of mphenylenediamine by hydrolysis process: sulfuric acid: water is the aqueous solution of 4-15:7.33-27.5:88.67-57.5.The above-mentioned aqueous solution is hydrolyzed at high temperature under high pressure and obtains Resorcinol.
We see that manufacturing aramid fiber level mphenylenediamine needs a large amount of mother liquor of process and repeatedly crystallization, and the hydrolysis process producing Resorcinol needs the mphenylenediamine solution that the mphenylenediamine compound concentration of buying solid is lower, if aramid fiber level mphenylenediamine and production process for resorcinol combine the joint process that just can form energy-conserving and environment-protective.
Summary of the invention
The object of the invention is to: a kind of aramid fiber level mphenylenediamine and Resorcinol co-production are provided, aramid fiber level mphenylenediamine and production process for resorcinol are combined, adopt water as recrystallisation solvent, crystalline mother solution is for the manufacture of Resorcinol, the solvent in mother liquor need not be removed in aramid fiber level mphenylenediamine manufacturing process, adopt the method for primary crystallization, avoid the generation of energy expenditure in recycling design process and tar, improve the concentration of mphenylenediamine in mother liquor in crystallisation process simultaneously, suitable raising Tc, reduce crystallization operation difficulty, be beneficial to manufacture the aramid fiber level mphenylenediamine of more high-quality.
Technical solution of the present invention is: the certain density mphenylenediamine aqueous solution is cooled in crystallizing pan the temperature of specifying, wherein part mphenylenediamine and micro-O-Phenylene Diamine and Ursol D crystallization, filtered by above-mentioned solution, filter cake goes to prepare aramid fiber level mphenylenediamine; Water and sulfuric acid is added in filtrated stock, mphenylenediamine in mother liquor and sulfuric acid reaction generate metaphenylenediamine sulphate, by above-mentioned metaphenylenediamine sulphate interval or deliver to heater heats continuously to certain temperature with certain flow and enter continuously in hydrolytic reaction pot, from hydrolytic reaction pot hydrolyzed solution out through flash distillation recovery part water for preparing the mphenylenediamine aqueous solution, the hydrolyzed solution after flash distillation adds ammonia neutralization; Hydrolyzed solution N-BUTYL ACETATE after neutralization extracts, and extraction liquid is recovery of acetic acid butyl ester in N-BUTYL ACETATE recovery tower, and the thick Resorcinol after recovery of acetic acid butyl ester obtains finishing room dihydroxy-benzene after simple distillation; The O-Phenylene Diamine that in crystalline mother solution, richness is long-pending and Ursol D are hydrolyzed generation pyrocatechol and Resorcinol is dissolved in extracting mother liquid, without the need to other refinement treatment.
the present invention specifically comprises the following steps:
(1) crystallization: thick mphenylenediamine and water being made into mass concentration is the 20-70% mphenylenediamine aqueous solution, is cooled to 5-20 DEG C under whipped state, part mphenylenediamine crystallization, has the O-Phenylene Diamine of trace and Ursol D to separate out simultaneously;
(2) filter: filtered by the above-mentioned cooled mphenylenediamine aqueous solution, filter cake is for the preparation of aramid fiber level mphenylenediamine;
(3) water distribution solution stock liquid: add appropriate sulfuric acid and water in filtrated stock, filtrated stock is mixed with quality group becomes mphenylenediamine: sulfuric acid: the hydrolysis material liquid of water=4-15:7.33-27.5:88.67-57.5;
(4) be hydrolyzed: said hydrolyzed stock liquid is heated to 200-280 DEG C and interval or deliver to continuously in autoclave, in the reaction of said temperature Water Under solution, generates the hydrolyzed solution of Resorcinol and monoammonium sulfate, hydrolysis time 2-8 hour;
(5) flash distillation: by said hydrolyzed liquid by vacuum flashing to normal pressure recovery part water for (1) or (3) step;
(6) neutralize: in the hydrolyzed solution after above-mentioned recovery part water, drip ammoniacal liquor, the pH value of hydrolyzed solution is adjusted to 3-5;
(7) extract: the hydrolyzed solution N-BUTYL ACETATE after above-mentioned neutralization extracts Resorcinol wherein; Aqueous phase after extraction distills out water wherein for (1) or (3) step, and distillation residue are monoammonium sulfate or ammonium chloride, makees fertilizer and uses;
(8) extraction agent reclaims: the extraction phase after above-mentioned extraction reclaims extraction agent by rectifying and extracts for (7) step, obtains thick Resorcinol after recycling design;
(9) Resorcinol is refined: above-mentioned thick Resorcinol carries out underpressure distillation, and tower top obtains finishing room dihydroxy-benzene.
The present invention has the following advantages: 1, energy-conservation, and crystalline mother solution is without the need to concentrated; 2, crystallization processes is simple, and namely primary crystallization obtains aramid fiber level mphenylenediamine; 3, aramid fiber level mphenylenediamine and Resorcinol coproduction, reduces the manufacture difficulty of aramid fiber level mphenylenediamine; 4, environmental protection, the coking problem in nodeless mesh mother liquor concentrations process take water as recrystallisation solvent, does not use the secondary pollution problem of other solvents.
Accompanying drawing explanation
Fig. 1 is technological process block-diagram of the present invention.
Embodiment
In further detail the present invention is described below in conjunction with specific embodiment.Should be understood that these examples just in order to demonstrate the invention, but not limit the scope of the invention by any way.Succinct in order to describe; this specification sheets omits the setting such as valve, instrument conventional on pipeline; the those of ordinary skill of the industry can carry out designing, adjust or improving according to specification, also can adjust number of devices and arrangement form, and these adjustment, improvement all should be considered as protection scope of the present invention.
Embodiment 1: produce aramid fiber level mphenylenediamine and Resorcinol according to following steps
(1) crystallization: thick mphenylenediamine and water being made into mass concentration is the 20% mphenylenediamine aqueous solution, is cooled to 5 DEG C under whipped state, part mphenylenediamine crystallization has the O-Phenylene Diamine of trace and Ursol D to separate out simultaneously;
(2) filter: filtered by the above-mentioned cooled mphenylenediamine aqueous solution, filter cake is for the preparation of aramid fiber level mphenylenediamine;
(3) water distribution solution stock liquid: add appropriate sulfuric acid and water in filtrated stock, filtrated stock is mixed with quality group becomes mphenylenediamine: sulfuric acid: the hydrolysis material liquid of water=4:7.33:88.67;
(4) be hydrolyzed: said hydrolyzed stock liquid is heated to 200 DEG C and interval or deliver to continuously in autoclave, in the reaction of said temperature Water Under solution, generates the hydrolyzed solution of Resorcinol and monoammonium sulfate, hydrolysis time 8 hours;
(5) flash distillation: by said hydrolyzed liquid by vacuum flashing to normal pressure recovery part water for (1) or (3) step;
(6) neutralize: in the hydrolyzed solution after above-mentioned recovery part water, drip ammoniacal liquor, the pH value of hydrolyzed solution is adjusted to 3;
(7) extract: the hydrolyzed solution N-BUTYL ACETATE after above-mentioned neutralization extracts Resorcinol wherein; Aqueous phase after extraction distills out water wherein for (1) or (3) step, and distillation residue are monoammonium sulfate or ammonium chloride, can make fertilizer and use;
(8) extraction agent reclaims: the extraction phase after above-mentioned extraction reclaims extraction agent by rectifying and extracts for (7) step, obtains thick Resorcinol after recycling design;
(9) Resorcinol is refined: above-mentioned thick Resorcinol carries out underpressure distillation, and tower top obtains finishing room dihydroxy-benzene.
Embodiment 2: produce aramid fiber level mphenylenediamine and Resorcinol according to following steps:
(1) crystallization: thick mphenylenediamine and water being made into mass concentration is the 50% mphenylenediamine aqueous solution, is cooled to 10 DEG C under whipped state, part mphenylenediamine crystallization has the O-Phenylene Diamine of trace and Ursol D to separate out simultaneously;
(2) filter: filtered by the above-mentioned cooled mphenylenediamine aqueous solution, filter cake is for the preparation of aramid fiber level mphenylenediamine;
(3) water distribution solution stock liquid: add appropriate sulfuric acid and water in filtrated stock, filtrated stock is mixed with quality group becomes mphenylenediamine: sulfuric acid: the hydrolysis material liquid of water=6:11:83;
(4) be hydrolyzed: said hydrolyzed stock liquid is heated to 220 DEG C and interval or deliver to continuously in autoclave, in the reaction of said temperature Water Under solution, generates the hydrolyzed solution of Resorcinol and monoammonium sulfate, hydrolysis time 6 hours;
(5) flash distillation: by said hydrolyzed liquid by vacuum flashing to normal pressure recovery part water for (1) or (3) step;
(6) neutralize: in the hydrolyzed solution after above-mentioned recovery part water, drip ammoniacal liquor, the pH value of hydrolyzed solution is adjusted to 4;
(7) extract: the hydrolyzed solution N-BUTYL ACETATE after above-mentioned neutralization extracts Resorcinol wherein; Aqueous phase after extraction distills out water wherein for (1) or (3) step, and distillation residue are monoammonium sulfate or ammonium chloride, can make fertilizer and use;
(8) extraction agent reclaims: the extraction phase after above-mentioned extraction reclaims extraction agent by rectifying and extracts for (7) step, obtains thick isophthalic two after recycling design;
(9) Resorcinol is refined: above-mentioned thick Resorcinol carries out underpressure distillation, and tower top obtains finishing room dihydroxy-benzene.
Embodiment 3: produce aramid fiber level mphenylenediamine and Resorcinol according to following steps
(1) crystallization: thick mphenylenediamine and water being made into mass concentration is the 70% mphenylenediamine aqueous solution, is cooled to 20 DEG C under whipped state, part mphenylenediamine crystallization has the O-Phenylene Diamine of trace and Ursol D to separate out simultaneously;
(2) filter: filtered by the above-mentioned cooled mphenylenediamine aqueous solution, filter cake is for the preparation of aramid fiber level mphenylenediamine;
(3) water distribution solution stock liquid: add appropriate sulfuric acid and water in filtrated stock, filtrated stock is mixed with quality group becomes mphenylenediamine: sulfuric acid: the hydrolysis material liquid of water=15:27.5:57.5;
(4) be hydrolyzed: said hydrolyzed stock liquid is heated to 280 DEG C and interval or deliver to continuously in autoclave, in the reaction of said temperature Water Under solution, generates the hydrolyzed solution of Resorcinol and monoammonium sulfate, hydrolysis time 2 hours;
(5) flash distillation: by said hydrolyzed liquid by vacuum flashing to normal pressure recovery part water for (1) or (3) step;
(6) neutralize: in the hydrolyzed solution after above-mentioned recovery part water, drip ammoniacal liquor, the pH value of hydrolyzed solution is adjusted to 5;
(7) extract: the hydrolyzed solution N-BUTYL ACETATE after above-mentioned neutralization extracts Resorcinol wherein; Aqueous phase after extraction distills out water wherein for (1) or (3) step, and distillation residue are monoammonium sulfate or ammonium chloride, can make fertilizer and use;
(8) extraction agent reclaims: the extraction phase after above-mentioned extraction reclaims extraction agent by rectifying and extracts for (7) step, obtains thick Resorcinol after recycling design;
(9) Resorcinol is refined: above-mentioned thick Resorcinol carries out underpressure distillation, and tower top obtains finishing room dihydroxy-benzene.
Embodiment 4: produce aramid fiber level mphenylenediamine and Resorcinol according to following steps
(1) crystallization: thick mphenylenediamine and water being made into mass concentration is the 50% mphenylenediamine aqueous solution, is cooled to 5 DEG C under whipped state, part mphenylenediamine crystallization has the O-Phenylene Diamine of trace and Ursol D to separate out simultaneously;
(2) filter: filtered by the above-mentioned cooled mphenylenediamine aqueous solution, filter cake is for the preparation of aramid fiber level mphenylenediamine;
(3) water distribution solution stock liquid: add appropriate sulfuric acid and water in filtrated stock, filtrated stock is mixed with quality group becomes mphenylenediamine: sulfuric acid: the hydrolysis material liquid of water=8:14.66:77.34;
(4) be hydrolyzed: said hydrolyzed stock liquid is heated to 250 DEG C and interval or deliver to continuously in autoclave, in the reaction of said temperature Water Under solution, generates the hydrolyzed solution of Resorcinol and monoammonium sulfate, hydrolysis time 4 hours;
(5) flash distillation: by said hydrolyzed liquid by vacuum flashing to normal pressure recovery part water for (1) or (3) step;
(6) neutralize: in the hydrolyzed solution after above-mentioned recovery part water, drip ammoniacal liquor, the pH value of hydrolyzed solution is adjusted to 4;
(7) extract: the hydrolyzed solution N-BUTYL ACETATE after above-mentioned neutralization extracts Resorcinol wherein; Aqueous phase after extraction distills out water wherein for (1) or (3) step, and distillation residue are monoammonium sulfate or ammonium chloride, can make fertilizer and use;
(8) extraction agent reclaims: the extraction phase after above-mentioned extraction reclaims extraction agent by rectifying and extracts for (7) step, obtains thick Resorcinol after recycling design;
(9) Resorcinol is refined: above-mentioned thick Resorcinol carries out underpressure distillation, and tower top obtains finishing room dihydroxy-benzene.
Claims (4)
1. the processing method of aramid fiber level mphenylenediamine and Resorcinol coproduction, is characterized in that this co-production specifically comprises the following steps:
(1) crystallization: thick mphenylenediamine and water being made into mass concentration is the 20% mphenylenediamine aqueous solution, is cooled to 5 DEG C under whipped state, part mphenylenediamine crystallization has the O-Phenylene Diamine of trace and Ursol D to separate out simultaneously;
(2) filter: filtered by the above-mentioned cooled mphenylenediamine aqueous solution, filter cake is for the preparation of aramid fiber level mphenylenediamine;
(3) water distribution solution stock liquid: add appropriate sulfuric acid and water in filtrated stock, filtrated stock is mixed with quality group becomes mphenylenediamine: sulfuric acid: the hydrolysis material liquid of water=4:7.33:88.67;
(4) be hydrolyzed: said hydrolyzed stock liquid is heated to 200 DEG C and interval or deliver to continuously in autoclave, in the reaction of said temperature Water Under solution, generates the hydrolyzed solution of Resorcinol and monoammonium sulfate, hydrolysis time 8 hours;
(5) flash distillation: by said hydrolyzed liquid by vacuum flashing to normal pressure recovery part water for (1) or (3) step;
(6) neutralize: in the hydrolyzed solution after above-mentioned recovery part water, drip ammoniacal liquor, the pH value of hydrolyzed solution is adjusted to 3;
(7) extract: the hydrolyzed solution N-BUTYL ACETATE after above-mentioned neutralization extracts Resorcinol wherein; Aqueous phase after extraction distills out water wherein for (1) or (3) step, and distillation residue are monoammonium sulfate, makees fertilizer and uses;
(8) extraction agent reclaims: the extraction phase after above-mentioned extraction reclaims extraction agent by rectifying and extracts for (7) step, obtains thick Resorcinol after recycling design;
(9) Resorcinol is refined: above-mentioned thick Resorcinol carries out underpressure distillation, and tower top obtains finishing room dihydroxy-benzene.
2. the processing method of aramid fiber level mphenylenediamine and Resorcinol coproduction, is characterized in that this co-production specifically comprises the following steps:
(1) crystallization: thick mphenylenediamine and water being made into mass concentration is the 50% mphenylenediamine aqueous solution, is cooled to 10 DEG C under whipped state, part mphenylenediamine crystallization has the O-Phenylene Diamine of trace and Ursol D to separate out simultaneously;
(2) filter: filtered by the above-mentioned cooled mphenylenediamine aqueous solution, filter cake is for the preparation of aramid fiber level mphenylenediamine;
(3) water distribution solution stock liquid: add appropriate sulfuric acid and water in filtrated stock, filtrated stock is mixed with quality group becomes mphenylenediamine: sulfuric acid: the hydrolysis material liquid of water=6:11:83;
(4) be hydrolyzed: said hydrolyzed stock liquid is heated to 220 DEG C and interval or deliver to continuously in autoclave, in the reaction of said temperature Water Under solution, generates the hydrolyzed solution of Resorcinol and monoammonium sulfate, hydrolysis time 6 hours;
(5) flash distillation: by said hydrolyzed liquid by vacuum flashing to normal pressure recovery part water for (1) or (3) step;
(6) neutralize: in the hydrolyzed solution after above-mentioned recovery part water, drip ammoniacal liquor, the pH value of hydrolyzed solution is adjusted to 4;
(7) extract: the hydrolyzed solution N-BUTYL ACETATE after above-mentioned neutralization extracts Resorcinol wherein; Aqueous phase after extraction distills out water wherein for (1) or (3) step, and distillation residue are monoammonium sulfate, makees fertilizer and uses;
(8) extraction agent reclaims: the extraction phase after above-mentioned extraction reclaims extraction agent by rectifying and extracts for (7) step, obtains thick Resorcinol after recycling design;
(9) Resorcinol is refined: above-mentioned thick Resorcinol carries out underpressure distillation, and tower top obtains finishing room dihydroxy-benzene.
3. the processing method of aramid fiber level mphenylenediamine and Resorcinol coproduction, is characterized in that this co-production specifically comprises the following steps:
(1) crystallization: thick mphenylenediamine and water being made into mass concentration is the 70% mphenylenediamine aqueous solution, is cooled to 20 DEG C under whipped state, part mphenylenediamine crystallization has the O-Phenylene Diamine of trace and Ursol D to separate out simultaneously;
(2) filter: filtered by the above-mentioned cooled mphenylenediamine aqueous solution, filter cake is for the preparation of aramid fiber level mphenylenediamine;
(3) water distribution solution stock liquid: add appropriate sulfuric acid and water in filtrated stock, filtrated stock is mixed with quality group becomes mphenylenediamine: sulfuric acid: the hydrolysis material liquid of water=15:27.5:57.5;
(4) be hydrolyzed: said hydrolyzed stock liquid is heated to 280 DEG C and interval or deliver to continuously in autoclave, in the reaction of said temperature Water Under solution, generates the hydrolyzed solution of Resorcinol and monoammonium sulfate, hydrolysis time 2 hours;
(5) flash distillation: by said hydrolyzed liquid by vacuum flashing to normal pressure recovery part water for (1) or (3) step;
(6) neutralize: in the hydrolyzed solution after above-mentioned recovery part water, drip ammoniacal liquor, the pH value of hydrolyzed solution is adjusted to 5;
(7) extract: the hydrolyzed solution N-BUTYL ACETATE after above-mentioned neutralization extracts Resorcinol wherein; Aqueous phase after extraction distills out water wherein for (1) or (3) step, and distillation residue are monoammonium sulfate, makees fertilizer and uses;
(8) extraction agent reclaims: the extraction phase after above-mentioned extraction reclaims extraction agent by rectifying and extracts for (7) step, obtains thick Resorcinol after recycling design;
(9) Resorcinol is refined: above-mentioned thick Resorcinol carries out underpressure distillation, and tower top obtains finishing room dihydroxy-benzene.
4. the processing method of aramid fiber level mphenylenediamine and Resorcinol coproduction, is characterized in that this co-production specifically comprises the following steps:
(1) crystallization: thick mphenylenediamine and water being made into mass concentration is the 50% mphenylenediamine aqueous solution, is cooled to 5 DEG C under whipped state, part mphenylenediamine crystallization has the O-Phenylene Diamine of trace and Ursol D to separate out simultaneously;
(2) filter: filtered by the above-mentioned cooled mphenylenediamine aqueous solution, filter cake is for the preparation of aramid fiber level mphenylenediamine;
(3) water distribution solution stock liquid: add appropriate sulfuric acid and water in filtrated stock, filtrated stock is mixed with quality group becomes mphenylenediamine: sulfuric acid: the hydrolysis material liquid of water=8:14.66:77.34;
(4) be hydrolyzed: said hydrolyzed stock liquid is heated to 250 DEG C and interval or deliver to continuously in autoclave, in the reaction of said temperature Water Under solution, generates the hydrolyzed solution of Resorcinol and monoammonium sulfate, hydrolysis time 4 hours;
(5) flash distillation: by said hydrolyzed liquid by vacuum flashing to normal pressure recovery part water for (1) or (3) step;
(6) neutralize: in the hydrolyzed solution after above-mentioned recovery part water, drip ammoniacal liquor, the pH value of hydrolyzed solution is adjusted to 4;
(7) extract: the hydrolyzed solution N-BUTYL ACETATE after above-mentioned neutralization extracts Resorcinol wherein; Aqueous phase after extraction distills out water wherein for (1) or (3) step, and distillation residue are monoammonium sulfate, makees fertilizer and uses;
(8) extraction agent reclaims: the extraction phase after above-mentioned extraction reclaims extraction agent by rectifying and extracts for (7) step, obtains thick Resorcinol after recycling design;
(9) Resorcinol is refined: above-mentioned thick Resorcinol carries out underpressure distillation, and tower top obtains finishing room dihydroxy-benzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310304733.XA CN103360266B (en) | 2013-07-19 | 2013-07-19 | Method for co-production of aramid fiber scale m-phenylenediamine and resorcinol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310304733.XA CN103360266B (en) | 2013-07-19 | 2013-07-19 | Method for co-production of aramid fiber scale m-phenylenediamine and resorcinol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103360266A CN103360266A (en) | 2013-10-23 |
| CN103360266B true CN103360266B (en) | 2015-04-22 |
Family
ID=49362622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310304733.XA Active CN103360266B (en) | 2013-07-19 | 2013-07-19 | Method for co-production of aramid fiber scale m-phenylenediamine and resorcinol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103360266B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104529712B (en) * | 2015-01-13 | 2016-09-28 | 青岛科技大学 | A kind of method using preparing resorcin by hydrolyzing m-phenylenediamine |
| CN110511150A (en) * | 2019-09-17 | 2019-11-29 | 四川北方红光特种化工有限公司 | A method of preparing high-purity polymer grade m-phenylene diamine (MPD) |
| CN113998824B (en) * | 2021-10-11 | 2023-08-29 | 金能科技股份有限公司 | Production method and equipment for reducing salt content and solid waste of p-methylphenol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1927795A (en) * | 2006-06-13 | 2007-03-14 | 老河口市华润化工有限公司 | Method of preparing resorcin by hydrolyzing m-phenylenediamine |
| CN101139261A (en) * | 2007-09-29 | 2008-03-12 | 南京大学 | Meta-dihydroxybenzene solid-phase fractional distillation refining process |
| CN101497558A (en) * | 2008-02-01 | 2009-08-05 | 浙江龙盛化工研究有限公司 | Method for preparing resorcinol by hydrolyzing m-phenylenediamine |
-
2013
- 2013-07-19 CN CN201310304733.XA patent/CN103360266B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1927795A (en) * | 2006-06-13 | 2007-03-14 | 老河口市华润化工有限公司 | Method of preparing resorcin by hydrolyzing m-phenylenediamine |
| CN101139261A (en) * | 2007-09-29 | 2008-03-12 | 南京大学 | Meta-dihydroxybenzene solid-phase fractional distillation refining process |
| CN101497558A (en) * | 2008-02-01 | 2009-08-05 | 浙江龙盛化工研究有限公司 | Method for preparing resorcinol by hydrolyzing m-phenylenediamine |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103360266A (en) | 2013-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105111047B (en) | Production method of Grade-99 pentaerythritol | |
| CN103360266B (en) | Method for co-production of aramid fiber scale m-phenylenediamine and resorcinol | |
| CN104193961B (en) | A kind of preparation method of hydrogenated bisphenol A epoxy resin | |
| CN103319538A (en) | Preparation method of hexaphenoxy cyclotriphosphazene | |
| CN105254544A (en) | Preparing method for bisphenol S | |
| CN110028542A (en) | The clean preparation method of canrenone | |
| CN105541604A (en) | Separation method for acetic acid in acylation reaction liquid | |
| CN102964270B (en) | Method for reducing hydrazine synthesized by diazonium salt by utilizing sodium sulphite | |
| CN110903207A (en) | Method for producing aminopropionic acid and sodium sulfate by using β -formylaminopropionitrile and application of aminopropionic acid and sodium sulfate | |
| CN113120925B (en) | Method for recovering iodide from isophorone cracking material | |
| CN105601496A (en) | Preparation method of 3,4-dimethoxy phenylpropionic acid | |
| CN103420833B (en) | A kind of dimethyl malonate synthetic method of Catalyzed by p-Toluenesulfonic Acid | |
| CN104959002A (en) | Method for removing hydrogen chloride by continuously recycling glyphosate hydrolyzed tail gas | |
| CN102775443B (en) | The synthetic method of Chlorpyrifos 94 | |
| CN102199073A (en) | Method for preparing 4,4'-dihydroxydiphenylmethane | |
| CN103724191A (en) | Dimethyl malonate preparation method | |
| CN110372496A (en) | A kind of method of electrodialysis purification neopentyl glycol sodium formate mixed liquor | |
| CN100410239C (en) | Simplified production technology of bisultap | |
| CN103910659A (en) | Refining method for 2-nitro-4-methylsulfonyl benzoic acid, and intermediate thereof | |
| CN104140360B (en) | Prepare the method for ortho-methyl phenol | |
| CN103360235A (en) | Preparation method of barium acetate | |
| CN103664654A (en) | Industrial production method of high-purity sulfuric acid terbutaline | |
| CN102285874A (en) | Method for crystallizing dibenzoyl methane | |
| CN103848768A (en) | Application method of methylamino formyl chloride decomposition tail gas hydrogen chloride in cartap synthesis | |
| CN102139893A (en) | Method for preparing potassium carbonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 223002 Huaian City, Jiangsu province Qingpu District West Road No. 40 Patentee after: Jiangsu Kesheng Intelligent Equipment Co.,Ltd. Address before: 223002 Huaian City, Jiangsu province Qingpu District West Road No. 40 Patentee before: JIANGSU KESHENG CHEMICAL MACHINERY Co.,Ltd. |
|
| CP03 | Change of name, title or address |