CN101857550B - Method for producing 6-aminocaproic acid hydrochloride and 6-aminocaproic acid by using nylon-6 waste through depolymerization - Google Patents
Method for producing 6-aminocaproic acid hydrochloride and 6-aminocaproic acid by using nylon-6 waste through depolymerization Download PDFInfo
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- CN101857550B CN101857550B CN200910097550.9A CN200910097550A CN101857550B CN 101857550 B CN101857550 B CN 101857550B CN 200910097550 A CN200910097550 A CN 200910097550A CN 101857550 B CN101857550 B CN 101857550B
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- AENOKLOQCCSDAZ-UHFFFAOYSA-N 6-aminohexanoic acid;hydrochloride Chemical compound Cl.NCCCCCC(O)=O AENOKLOQCCSDAZ-UHFFFAOYSA-N 0.000 title abstract 4
- 229960002684 aminocaproic acid Drugs 0.000 title abstract 4
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- MSWZFWKMSRAUBD-UHFFFAOYSA-N 2-Amino-2-Deoxy-Hexose Chemical compound NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 23
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 5
- 208000032843 Hemorrhage Diseases 0.000 description 4
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
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- QVGURAHKOZSVQR-UHFFFAOYSA-N 3-cyanopentanoic acid Chemical compound CCC(C#N)CC(O)=O QVGURAHKOZSVQR-UHFFFAOYSA-N 0.000 description 1
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 description 1
- SKUPALMUTWEAPI-UHFFFAOYSA-N 5-cyanopentanoic acid Chemical compound OC(=O)CCCCC#N SKUPALMUTWEAPI-UHFFFAOYSA-N 0.000 description 1
- CFEYBLWMNFZOPB-UHFFFAOYSA-N Allylacetonitrile Natural products C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
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- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
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- ZLHYDRXTDZFRDZ-UHFFFAOYSA-N epsilon-aminocaproamide Chemical compound NCCCCCC(N)=O ZLHYDRXTDZFRDZ-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
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- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 208000030208 low-grade fever Diseases 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/14—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with steam or water
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for producing 6-aminocaproic acid hydrochloride and 6-aminocaproic acid by using nylon-6 waste through depolymerization. The method is characterized by comprising the following steps of: depolymerizing the nylon-6 waste at the temperature of between 100 and 110 DEG C under constant pressure by using 10 to 20 percent solution of hydrochloric acid so as to obtain acidolysis solution, and filtering, separating, purifying, and drying to obtain refined 6-aminocaproic acid hydrochloride; and introducing ammonia into the solution of 6-aminocaproic acid hydrochloride to neutralize the solution to the pH of between 3 and 9, adding industrial alcohol in a volume 3 to 5 times that of the solution, and recrystallizing to obtain the refined 6-aminocaproic acid. The method has the advantages of simple technical process, low production cost, a few by-products, high yield of the aminocaproic acid, and safe production process.
Description
Technical field
The present invention relates to a kind of suitability for industrialized production that is suitable for comes depolymerization nylon-6 waste to produce the method for 6-aminocaprolc acid hydrochloride and 6-aminocaprolc acid with acid.
Background technology
6-aminocaprolc acid is called for short 6-ACA, generally adopts direct chemical synthesis, hexanolactam or caprolactam polymerization thing (frit of nylon-6, waste silk, discarded fabric, fishing net etc.) are hydrolyzed rear making with extra care and make.6-aminocaprolc acid (6-ACA) is for the synthesis of hexanolactam, and subsequently to the production of nylon-6,6-ACA can also directly be used as the starting material of producing nylon-6.In addition, 6-aminocaprolc acid the purposes of wide model be to be applied in medical field to have positive effect as hemostatic agent to increase some severe haemorrhage that causes because of the cellulose protein hemolytic activity.The acute illnesss such as the oozing of blood when being applicable to multiple surgical operation or local hemorrhage, Obstetric and Gynecologic Department are hemorrhage, digestive tract hemorrhage.
At present, the method for manufacture 6-aminocaprolc acid has following two kinds substantially:
One, take hexanolactam as starting material, make the 6-aminocaprolc acid hydrochloride through hydrochloric acid hydrolysis, then, with its dilution, adsorb by storng-acid cation exchange resin, then through purifying, the refining 6-aminocaprolc acid that obtains.The method length consuming time, schedule of operation is loaded down with trivial details, and production cost increases.Another kind method is that the 6-aminocaprolc acid hydrochloride solid that obtains is water-soluble, processes with aluminium hydroxide and the oxidation silver powder of yellow lead powder, new system successively, then removes halogen ion and metal ion with hydrogen sulfide treatment, obtains 6-aminocaprolc acid through crystallization, drying.The method obviously increases production cost, and operation is more loaded down with trivial details, and uses the hydrogen sulfide of toxicity, the dangerous increase.Patent CN101125821A has invented a kind of method for preparing the hemostatic agent 6-aminocaprolc acid.Take hexanolactam as starting material, make the 6-aminocaprolc acid hydrochloride through hydrochloric acid hydrolysis, utilize spherical polystyrene weak base anion-exchange resin to neutralize, obtain 6-aminocaprolc acid through aftertreatment.This invention condition is gentleer, is difficult for the tramp m. ion, and is simple to operate, reduces production costs, and still, its shortcoming is exactly consuming time longer, and efficient is low.
Two, prepare 6-aminocaprolc acid by the organic chemical synthesis method.For example, U.S. E.I. Du Pont De Nemours ﹠ Co. is the patent at China's application preparation 6-aminocaprolc acid in calendar year 2001, publication number is CN1505606A, this invention generates 3-, 4-and 5-formylvaleronitriles (FVN mixture) by the 3 pentene nitrile hydroformylation, the FVN mixture generates 3-, 4-and 5-cyanopentanoic acid through oxidation, then obtains 6-aminocaprolc acid through over hydrogenation; Holland DSM N. V. has applied for a kind of patent for preparing ε-caprolactam, 6-aminocaprolc acid and 6-aminocaproamide mixture in China, and publication number is CN1216529A; Holland DSM IP Assets BV disclosed the patent that a kind of biological chemistry synthetic method prepares 6-aminocaprolc acid in 2007, this invention has α by use, the enzyme of β-olefin(e) acid ester reductase activity removes to process α, and β-olefin(e) acid ester group and primary amine groups molecule are realized.Above-mentionedly prepare by the organic chemical synthesis method shortcoming that 6-aminocaprolc acid exists and mainly contain: a large amount of chemical reaction step of needs is completed, the material cost of reaction use is high, dangerous large, the by product that the target product that generates produces is many, difficulty is separated, yield is low, is not suitable for suitability for industrialized production.
For the above-mentioned existing shortcoming of method for preparing 6-aminocaprolc acid, the present invention adopts hydrochloric acid to come depolymerization nylon-6 waste to produce 6-aminocaprolc acid hydrochloride and 6-aminocaprolc acid.The nylon-6 waste is dropped into the hydrochloric acid soln depolymerization obtain thick 6-aminocaprolc acid hydrochloride solution, obtain refining 6-aminocaprolc acid hydrochloride through purifying, then, it is concentrated, pass into ammonia solution is neutralized to pH3-9, the industrial alcohol that adds 3-5 times of volume, crystallize out, the refining 6-aminocaprolc acid that obtains.This is invented, and compared with prior art technological process is simple, does not adopt Zeo-karb to separate, and saves the production time, enhances productivity; Preparation condition is gentle, does not need complicated chemical reaction step and harsh test conditions, reduces production costs; The 6-aminocaprolc acid purity that makes is high, productive rate is large; Take discarded nylon-6 as material cost is low, solved simultaneously the recycling problem of nylon 6 wastes.The method is science, reasonable more, meets the current environmental protection theory of advocating, and is suitable for the commercial scale production 6-aminocaprolc acid.
Summary of the invention
The technical problem to be solved in the present invention is: for the recycling problem of nylon-6 waste, and the existing preparation procedure of current preparation 6-aminocaprolc acid is more loaded down with trivial details, production cost is higher, product yield is lower, by product is more, difficult problem of separating, a kind of method of producing 6-aminocaprolc acid hydrochloride and 6-aminocaprolc acid with the nylon-6 waste through depolymerization is provided, its technological process is simple, do not adopt Zeo-karb to separate, save the production time, enhance productivity; Preparation condition is gentle, does not need complicated chemical reaction step and harsh test conditions, reduces production costs, and the 6-aminocaprolc acid purity that makes is high, productive rate is large.
The present invention solves the technical scheme that its technical problem takes: a kind of method of producing 6-aminocaprolc acid hydrochloride and 6-aminocaprolc acid with the nylon-6 waste through depolymerization, it is characterized in that including acidolysis workshop section, the 6-aminocaprolc acid hydrochloride separates and purifying workshop section, 6-aminocaprolc acid prepare workshop section, each workshop section's step is as described below:
(1), acidolysis workshop section, mass concentration 10-20% aqueous hydrochloric acid is added in the enamel reaction still of top with condensation reflux unit and hydrogen chloride gas absorption unit, mass ratio 100 according to nylon-6 and hydrogenchloride: 25-35 adds nylon-6, reacted 6～12 hours under the condition of normal pressure and 100-110 ℃, obtain acid hydrolysis solution;
(2), the 6-aminocaprolc acid hydrochloride separates and purifying workshop section, and reactor is slowly vacuumized, and treats that absolute pressure kept later on 20-30 minute less than 10KPa, the acid hydrolysis solution in step (1) is cooled to 30-40 ℃, uses activated carbon decolorizing after filtration residue; The thick 6-aminocaprolc acid hydrochloride solution that obtains, reduction vaporization is concentrated into the 30-40% of cumulative volume, is cooled to 30-45 ℃, filters the thick 6-aminocaprolc acid hydrochloride of separating out, and obtains refining 6-aminocaprolc acid hydrochloride with industrial ethyl alcohol recrystallization, drying;
(3), 6-aminocaprolc acid prepares workshop section, pass into ammonia in thick 6-aminocaprolc acid hydrochloride solution after concentrated in step (2) solution is neutralized to pH3-9, the industrial alcohol that adds 3-5 times of volume, fully stirring and low-grade fever are after 50-70 ℃, naturally cool to room temperature, the 6-aminocaprolc acid that filtration is separated out must be made with extra care 6-aminocaprolc acid after the washing with alcohol drying.
The described reaction times is dependent on the property of raw material of nylon-6 waste, when common nylon-6 carpet wool is done raw material, and preferred 8 hours.
Gac is adopted in decolouring described in step (2), and add-on is the 2-5% of thick 6-aminocaprolc acid hydrochloride solution total mass.
Vaporized distillate fluid described in vacuum Extract described in hydrogen chloride gas absorption liquid described in step (1), step (2), step (2) and filtrate merge, and after mensuration acidity, reuse is to step (1).
Be neutralized to the process of pH value of solution 3-9 with ammonia described in step (3), add strong aqua (22-25% if adopt, mass concentration, the industry first grade) be neutralized to pH value of solution 3-9, with the extremely near state of doing of solution evaporation, add while hot the industrial alcohol of 1-3 times of volume, filter the crystallization of separating out, dry with washing with alcohol, get refining 6-aminocaprolc acid.
The used ethanol of recrystallization described in step (2), or after in step (3), in used ethanol or strong aqua N-process, used ethanol merges, through reuse after the rectifying tower distillation.
Produce in the method for 6-aminocaprolc acid, in ethanol distillation is recycled, the ethanol distillation raffinate till needing this moment continuation evaporation concentration to ammonium chloride to begin to separate out, gets by-product ammonium chloride because containing the not directly waste treatment of a large amount of ammonium chlorides after the naturally cooling filtration drying.
The present invention compared with prior art has the following advantages and benefit:
1, come depolymerization to discard nylon-6 with the 10-20% aqueous hydrochloric acid, the temperature of hydrolysis is lower and can carry out under normal pressure, facilitates suitability for industrialized production, and transformation efficiency is higher; And the filtrate that obtains after depolymerization is completed and vaporized distillate fluid merge, and can be recycled after mensuration acidity;
2, with in ammonia and 6-aminocaprolc acid hydrochloride solution to pH3-9, then add the industrial alcohol recrystallization, the refining 6-aminocaprolc acid that obtains.Or adopt and to add strong aqua to be neutralized to pH value of solution 3-9, solution evaporation to the nearly state of doing, is added the industrial alcohol of 1-3 times of volume while hot, filter the crystallization of separating out, dry with washing with alcohol, get refining 6-aminocaprolc acid.So just avoided employing ion exchange resin to carry out the separation consumes time longer, the shortcoming that schedule of operation is many is enhanced productivity;
3, with the nylon-6 waste as starting material, reduced production cost, solved the recycling problem of nylon 6 wastes, the theory that meets recycling economy and Sustainable development, and production process safety, substantially pollution-free to environment, the by product that produces in production process is less, be convenient to separation and purification, improved 6-aminocaprolc acid purity.
Description of drawings
Fig. 1 process flow diagram;
Fig. 2 reaction process schematic diagram.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment 1
(1) add the 30% industrial by-product hydrochloric acid of 1000Kg in the enamel reaction still of top with condensation reflux unit and hydrogen chloride gas absorption unit, add again 750Kg water, the limit heating edge adds 1000Kg waste material nylon-6, and reaction is 10 hours under the condition of normal pressure and 100-110 ℃, obtains acid hydrolysis solution;
(2) reactor is evacuated to absolute pressure and kept later on 30 minutes less than 10KPa, acid hydrolysis solution is cooled to 35 ℃, remove by filter residue, then, add the 80Kg gac to decolour, obtain thick 6-aminocaprolc acid hydrochloride solution;
The thick 6-aminocaprolc acid hydrochloride solution decompression evaporation concentration that (3) will obtain is to the 30-40% of cumulative volume, be cooled to 30-45 ℃, the thick 6-aminocaprolc acid hydrochloride that filtration is separated out obtains refining 6-aminocaprolc acid hydrochloride with industrial alcohol recrystallization, the drying of 2 times of volumes;
(4) pass into ammonia in the thick 6-aminocaprolc acid hydrochloride solution that obtains in (2) step solution is neutralized to the pH=7 left and right, the industrial alcohol that adds 3-5 times of volume, after fully stirring and being heated to 60 ℃, naturally cool to room temperature, the 6-aminocaprolc acid that filtration is separated out, obtain refining 6-aminocaprolc acid white powder with the absolute ethanol washing drying, yield is greater than 90%, purity 98%.
Embodiment 2
Step (1) (2) is with embodiment 1.
(3) add commercially available strong aqua that solution is neutralized to the pH=7 left and right in the thick 6-aminocaprolc acid hydrochloride solution that obtains in (2) step, reduction vaporization is concentrated into 20% of the rear overall solution volume of neutralization, the industrial alcohol that adds while hot 4 times of residual volumes, after fully stirring, naturally cool to room temperature, filter the 6-aminocaprolc acid of separating out, obtain refining 6-aminocaprolc acid white powder with the absolute ethanol washing drying, yield is greater than 90%, purity 98%.
(4) ethanol of the ethanol filtrate in step (3) and washing step being used merges, rectifying in rectifying tower, and the cut of collecting 75-80 ℃ obtains 95% aqueous ethanolic solution, recycles.Continue to distill out part water to bottom product and begin to occur crystallization and stop, bottom product is expelled to cooling tank, natural cooling crystallization, filtration drying gets the by-product ammonium chloride white powder.
Claims (7)
1. method of producing 6-aminocaprolc acid hydrochloride and 6-aminocaprolc acid with the nylon-6 waste through depolymerization, it is characterized in that including acidolysis workshop section, the 6-aminocaprolc acid hydrochloride separates and purifying workshop section, 6-aminocaprolc acid prepare workshop section, each workshop section's step is as described below:
(1), acidolysis workshop section, mass concentration 10-20% aqueous hydrochloric acid is added in the enamel reaction still of top with condensation reflux unit and hydrogen chloride gas absorption unit, mass ratio 100 according to nylon-6 and hydrogenchloride: 25-35 adds nylon-6, reacted 6～12 hours under the condition of normal pressure and 100-110 ℃, obtain acid hydrolysis solution;
(2), the 6-aminocaprolc acid hydrochloride separates and purifying workshop section, and reactor is vacuumized, and treats that absolute pressure kept later on 20-30 minute less than 10KPa, the acid hydrolysis solution in step (1) is cooled to 30-40 ℃, uses activated carbon decolorizing after filtration residue; The thick 6-aminocaprolc acid hydrochloride solution that obtains, reduction vaporization is concentrated into the 30-40% of cumulative volume, is cooled to 30-45 ℃, filters the thick 6-aminocaprolc acid hydrochloride of separating out, and obtains refining 6-aminocaprolc acid hydrochloride with industrial ethyl alcohol recrystallization, drying;
(3), 6-aminocaprolc acid prepares workshop section, pass into ammonia in thick 6-aminocaprolc acid hydrochloride solution after concentrated in step (2) solution is neutralized to pH3-9, the industrial alcohol that adds 3-5 times of volume, after stirring and being heated to 50-70 ℃, naturally cool to room temperature, the hexosamine that filtration is separated out must be made with extra care 6-aminocaprolc acid after the washing with alcohol drying.
2. a kind of method of producing 6-aminocaprolc acid hydrochloride and 6-aminocaprolc acid with the nylon-6 waste through depolymerization according to claim 1, it is characterized in that the reaction times described in step (1) is dependent on the property of raw material of nylon-6 waste, when common nylon-6 carpet wool is done raw material, selected 8 hours.
3. a kind of method of producing 6-aminocaprolc acid hydrochloride and 6-aminocaprolc acid with the nylon-6 waste through depolymerization according to claim 1, it is characterized in that the decolouring employing gac described in step (2), add-on is the 2-5% of thick 6-aminocaprolc acid hydrochloride solution total mass.
4. a kind of method of producing 6-aminocaprolc acid hydrochloride and 6-aminocaprolc acid with the nylon-6 waste through depolymerization according to claim 1, the vaporized distillate fluid that produces in the vacuum Extract that it is characterized in that obtaining in the vacuum described in the resulting hydrogen chloride gas absorption liquid of the hydrogen chloride gas absorption unit described in step (1), step (2), the reduction vaporization concentration process described in step (2) and filtrate merge, measure acidity after reuse to step (1).
5. a kind of method of producing 6-aminocaprolc acid hydrochloride and 6-aminocaprolc acid with the nylon-6 waste through depolymerization according to claim 1, it is characterized in that being neutralized to the process of pH value of solution 3-9 with ammonia described in step (3), to adopt to add the strong aqua of mass concentration 22-25% to be neutralized to pH value of solution 3-9, and with the extremely near state of doing of solution evaporation, the industrial alcohol that adds while hot 1-3 times of volume, the crystallization that filtration is separated out, dry with washing with alcohol, get refining 6-aminocaprolc acid.
6. a kind of method of producing 6-aminocaprolc acid hydrochloride and 6-aminocaprolc acid with the nylon-6 waste through depolymerization according to claim 1, it is characterized in that the used ethanol of recrystallization described in step (2), or after in step (3), in the strong aqua N-process of used ethanol or 22-25%, used ethanol merges, through reuse after the rectifying tower distillation.
7. a kind of method of producing 6-aminocaprolc acid hydrochloride and 6-aminocaprolc acid with the nylon-6 waste through depolymerization according to claim 6, it is characterized in that vinasse after described ethanol is through the rectifying tower distillation is because containing the not directly waste treatment of a large amount of ammonium chlorides, till needing this moment continuation evaporation concentration to ammonium chloride to begin to separate out, get by-product ammonium chloride after the naturally cooling filtration drying.
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| CN102491913A (en) * | 2011-11-28 | 2012-06-13 | 江南大学 | Method for recovering alcoholysis products with catalytic alcoholysis of waste nylon 6 by using binuclear ionic liquid |
| US10239823B2 (en) * | 2017-08-25 | 2019-03-26 | Vitaworks Ip, Llc | Process for purifying long chain amino acids |
| CN114166982B (en) * | 2021-11-15 | 2023-11-10 | 北京百奥药业有限责任公司 | Method for simultaneously determining dimer, trimer and caprolactam in aminocaproic acid injection |
| CN114195663A (en) * | 2021-12-20 | 2022-03-18 | 昌德新材科技股份有限公司 | Preparation method of 6-aminocaproic acid |
| CN115710198A (en) * | 2022-11-11 | 2023-02-24 | 聊城鲁西聚酰胺新材料科技有限公司 | Method for preparing 6-aminocapronitrile |
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