CN1257880C - Process for producing adipic acid and hexanediamine by depolymerization of nylon-66 - Google Patents
Process for producing adipic acid and hexanediamine by depolymerization of nylon-66 Download PDFInfo
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- CN1257880C CN1257880C CN 200310102234 CN200310102234A CN1257880C CN 1257880 C CN1257880 C CN 1257880C CN 200310102234 CN200310102234 CN 200310102234 CN 200310102234 A CN200310102234 A CN 200310102234A CN 1257880 C CN1257880 C CN 1257880C
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Abstract
The present invention relates to a process for preparing adipic acid and hexamethylene diamine by depolymerization with nylon-66, which is composed of the working sections of acidolysis, crystallization by cooling, virgin acid separation, recrystallization, neutralization and refining., wherein firstly, the working section of acidolysis is carried out to obtain the adipic acid; then, alkali is added to carry out neutralization reaction and obtain the hexamethylene diamine. Acid used in the working section of acidolysis is sulphuric acid, and the alkali for neutralization is lime milk. The process is suitable for industrial mass production, solves the problem of high operating cost in the industrial production of monomers produced by depolymerization with waste nylon-66, and obtains high-purity adipic acid and high-purity hexamethylene diamine without new pollution, so the process has high economical and social benefits.
Description
Technical field
The present invention relates to a kind of technology of producing hexanodioic acid, hexanediamine, relate in particular to a kind of technology of producing hexanodioic acid, hexanediamine with nylon-66 disaggregation that is applicable to industrialized production with nylon-66 disaggregation.
Background technology
Macromolecular material excellent function and practicality have been brought a lot of convenience to the mankind.Plastics are ubiquitous in current people life, and usage quantity increases year by year, but meanwhile, has also caused serious environmental problem, and the depleted high molecular polymer is difficult to degraded at nature, and some even hundreds of years are all non-degradable.This is caused already the concern in the whole world, many countries make laws, and require the depleted high molecular polymer is recycled.
High molecular polymer reclaims and mainly contains following certain methods at present: melt pelletization regeneration; Chemical recovery; Energy recovery; Landfill disposal etc.But because the poor heat stability of nylon-66, melt pelletization regeneration back mechanical property descends significantly, can not repeatedly repeat.Energy recovery is meant plastics oil refining and the recovered energy that directly burns, and not only utility value is low, and atmosphere pollution.Landfill then takies a large amount of limited soils.Chemical recovery is that polymkeric substance is carried out depolymerization with chemical process, returns to the starting monomer of producing polymkeric substance.After purifying, can aggregate into new plastic once more, or make other manufacturing raw materials.Thereby reach resource recovery, ecological circulation is used, and is a kind of useless preferably high molecular polymerization substance treating method.
Chemical recycling has many companies, research department to carry out long research and test at home and abroad, tests in 1971 as light industry chemical research place, Shanxi Province, adopts the poly-legal system of alkaline hydrolysis to get hexanodioic acid, hexanediamine.Yingkou, Liaoning Province goods and materials reclaim the patent that a kind of hydrochloric acid hydrolysis nylon-66 has been declared in June, 1987 by company, and the patent No. is 87104224.U.S. DuPont company has carried out adopting the test of nitric acid depolymerization nylon-66, with hydrogenation method nitric acid hydrogenation ammonification is made hexanediamine.The patent that adopts the poly-nylon-66 of alkaline hydrolysis is declared in China by Holland DSM N. V. in July, 1998: publication number CN1205330A.U.S. Pat-A-5302756 has described a kind of at high temperature by ammonia, is with or without the technology of depolymerization nylon-66 under the phosphatic participation.U.S. Patent number 5233021, inventor Sikorski adopts the CO2 supercritical extraction, separates the recirculation of polycomponent polymeric material.But these technology all also rest on experimental stage, do not have the industrial applications example.DSM and Allied Signal have established Evergreen Nylon Recycling company jointly, handle carpet nylon with the large-scale recovery that goes into operation in November, 1999, but because the process cost of device is higher than predictable cost, this is installed on and stops production September calendar year 2001.And the nylon-66 carpet of separating, the said firm can not reclaim monomer, only uses the mechanical process melt pelletization, and this particle physics poor performance, application person is seldom.Causes both at home and abroad and can not industrially greatly reclaim the nylon-66 monomer, and the quantity-produced reason mainly contains:
1, reclaim the monomeric big industrial production poor operability of nylon-66, running cost is too high;
2, secondary pollution is serious;
3, the impurity of nylon waste material is many;
4, production security is poor;
5, the poor quality of product.
Summary of the invention
The objective of the invention is to overcome defective of the prior art, a kind of big industrial processing method of producing hexanodioic acid, hexanediamine with nylon-66 disaggregation that adapts to is provided.
The present invention is a kind of to produce hexanodioic acid, hexanediamine with nylon-66 disaggregation, by acidolysis workshop section, crystallisation by cooling workshop section, thick sour centrifugal station, recrystallization workshop section, in and workshop section and refining workshop section form, it is characterized in that at first carrying out acidolysis obtains hexanodioic acid, adding alkali then carries out neutralization reaction and obtains hexanediamine, used acid is sulfuric acid in the acidolysis workshop section, and the used alkali that neutralizes is milk of lime.This nylon-66 disaggregation is produced the technology of hexanodioic acid, hexanediamine, comprises the steps:
(1), sulfuric acid and water are joined in the reactor, add catalyzer, add nylon-66, under the condition of maintenance pressure, reacted 6～16 hours, obtain acid hydrolysis solution at 0.1～0.6MPA while heat then;
(2), acid hydrolysis solution is entered crystallisation by cooling workshop section and carries out crystallisation by cooling through coarse filter, separate obtaining thick adipic acid crystals and hexanediamine sulfate liquor then;
(3), the thick adipic acid crystals that obtains in the step (2) decolour, recrystallization, oven dry obtain refined adipic acid.
(4), in and add the milk of lime of capacity in the still, and then add the hexanediamine sulfate liquor that step (2) obtains, fully stir to make and react completely, the pH value of neutralization back solution filters to isolate the solution and the moist CaSO that contain hexanediamine greater than 12
42H
2O;
(5), the solution that contains hexanediamine that obtains in the step (4) is steamed with vacuum follow the example of or extraction process obtains the thick solution of hexanediamine;
(6), the CaSO of humidity in the recycling step (4)
42H
2Hexanediamine among the O: with the CaSO of the humidity that obtains in the step (4)
42H
2The O oven dry obtains exsiccant CaSO
42H
2The thick solution of O and hexanediamine;
(7), the thick solution of hexanediamine that obtains in step (5) and the step (6) is concentrated the refining purified hexanediamine that obtains;
Wherein used catalyzer is phosphoric acid or phosphoric acid salt; Separate thick hexanodioic acid chamber filter press; Described extraction process in the step (5) is: with the extraction of benzene, pure mixed solution, get organic phase then and carry out azeotropic and obtain the thick solution of hexanediamine; Oven dry in the step (6) adopts vacuum-drying and temperature to be lower than 170 ℃; Oven dry in the step (3) adopts vacuum-drying and temperature to be lower than 80 ℃.The waste water that produces in the technology of the present invention can be back to acidolysis workshop section and reuse.
A kind of technology of producing hexanodioic acid, hexanediamine with nylon-66 disaggregation of the present invention adapts to industrialized production, has solved the too high problem of the process cost on the industrial production; The used raw material of the present invention can be useless nylon-66, has solved the problem of the recovery difficulty of useless nylon-66; And the purity of hexanodioic acid that obtains and hexanediamine is higher, can reach 99.7%; Technology of the present invention is little to the pollution of environment, and waste water can reach zero release, and the solid by-product that produces in the technology is CaSO
42H
2O, and CaSO
42H
2O can obtain anhydrous or semi-hydrated gypsum through temperature oven dry more than 250 ℃, can be used as cement auxiliary material, also can be used as plasterboard for building, gypsum decorative board raw material; Can also be with CaSO
42H
2O is converted into SO through 1300 ℃ of pyrolytic decompositions
3And CaO, the former can be used to make sulfuric acid for the acidolysis use, and the latter can use for neutralization.
Embodiment
Below by embodiment the present invention is further detailed:
Embodiment: sulfuric acid 1100kg, water 2000kg and the catalyzer phosphoric acid 30kg of adding 98% in reactor, add useless nylon-66 1200kg while heating then, stir, reaction is about 10 hours under the condition of maintenance pressure at 0.1～0.6MPA, make to react completely, obtain acid hydrolysis solution; Then acid hydrolysis solution is filtered by coarse filter and carry out freezing and crystallizing again, chilling rate should not be too fast, and at room temperature natural cooling crystallization also can adopt the cooling of bleeding, and present embodiment adopts natural cooling crystallization, need not stop to stir when cooling.After crystallization is finished, separate thick hexanodioic acid and hexanediamine sulfate liquor with chamber filter press.Thick hexanodioic acid wherein obtains refining hexanodioic acid through decolouring, recrystallization, oven dry, when hexanodioic acid decolours, the water in the still of will decolouring earlier is heated to 〉=and 90 ℃, progressively add thick hexanodioic acid with respect to water weight percent 50%, the gac of the decolouring usefulness of weight ratio 4% is dropped in the dissolving back, stirs decolouring, and destainer separates gac and other undissolved impurity with plate filter, filtrate is wanted the recirculation press filtration, till can not detecting gac; And then crystallisation by cooling, use centrifuge dewatering after the crystallization again, place the vacuum drum dryer to dry then, bake out temperature is lower than 80 ℃, obtains the product hexanodioic acid, and its purity is greater than 99.7%; The hexanediamine sulfate liquor that obtains is above neutralized with milk of lime (lime suspension): at first in the neutralization reaction still, add milk of lime, and then add the hexanediamine sulfate liquor and (can prevent excessive sulfuric acid and calcium carbonate reaction like this and material takes place to dash, and minimizing equipment corrosion), stir, Deng pH value greater than 12 o'clock termination reactions, filter, obtain containing the solution and the moist CaSO of hexanediamine
42H
2O.The solution that contains hexanediamine that obtains is followed the example of steaming with the vacuum steaming obtain the thick solution of hexanediamine; CaSO with humidity
42H
2O places the vacuum drum dryer to dry, and temperature is lower than 170 ℃ of steamings and gets the thick solution of hexanediamine, slips by smart that tower is smart to slip together with the thick solution of the hexanediamine that obtains previously then, obtains purity greater than 99.7% hexanediamine.
Claims (4)
1, a kind of technology of producing hexanodioic acid, hexanediamine with nylon-66 disaggregation, by acidolysis workshop section, crystallisation by cooling workshop section, thick sour centrifugal station, recrystallization workshop section, in and workshop section and refining workshop section form, it is characterized in that each workshop section is as described below:
(1), sulfuric acid and water are joined in the reactor, add phosphoric acid or phosphoric acid salt, add nylon-66, under the condition of maintenance pressure, reacted 6～16 hours, obtain acid hydrolysis solution at 0.1～0.6MPA while heat then as catalyzer;
(2), acid hydrolysis solution is entered crystallisation by cooling workshop section and carries out crystallisation by cooling through coarse filter, separate obtaining thick adipic acid crystals and hexanediamine sulfate liquor then;
(3), the thick adipic acid crystals that obtains in the step (2) decolour, recrystallization, oven dry obtain refined adipic acid;
(4), in and add the milk of lime of capacity in the still, and then add the hexanediamine sulfate liquor that step (2) obtains, fully stir to make and react completely, the pH value of neutralization back solution filters to isolate the solution and the moist CaSO that contain hexanediamine greater than 12
42H
2O;
(5), the solution that contains hexanediamine that obtains in the step (4) is steamed with vacuum follow the example of or extraction process obtains the thick solution of hexanediamine;
(6), the CaSO of humidity in the recycling step (4)
42H
2Hexanediamine among the O: with the CaSO of the humidity that obtains in the step (4)
42H
2The O oven dry obtains exsiccant CaSO
42H
2The thick solution of O and hexanediamine;
(7), the thick solution of hexanediamine that obtains in step (5) and the step (6) is concentrated the refining purified hexanediamine that obtains.
2, a kind of nylon-66 disaggregation according to claim 1 is produced the technology of hexanodioic acid, hexanediamine, it is characterized in that the described extraction process in the step (5) is: with benzene, the extraction of pure mixed solution, get organic phase then and carry out azeotropic and obtain the thick solution of hexanediamine.
3, the technology of a kind of nylon-66 disaggregation production hexanodioic acid according to claim 1, hexanediamine is characterized in that the oven dry in the step (6) adopts vacuum-drying and temperature to be lower than 170 ℃.
4, the technology of a kind of nylon-66 disaggregation production hexanodioic acid according to claim 1, hexanediamine is characterized in that the oven dry in the step (3) adopts vacuum-drying and temperature to be lower than 80 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310102234 CN1257880C (en) | 2003-10-29 | 2003-10-29 | Process for producing adipic acid and hexanediamine by depolymerization of nylon-66 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310102234 CN1257880C (en) | 2003-10-29 | 2003-10-29 | Process for producing adipic acid and hexanediamine by depolymerization of nylon-66 |
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| Publication Number | Publication Date |
|---|---|
| CN1611477A CN1611477A (en) | 2005-05-04 |
| CN1257880C true CN1257880C (en) | 2006-05-31 |
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| CN 200310102234 Expired - Fee Related CN1257880C (en) | 2003-10-29 | 2003-10-29 | Process for producing adipic acid and hexanediamine by depolymerization of nylon-66 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423623B (en) * | 2007-11-02 | 2011-05-11 | 宁波大学 | Depolymerization and recovery method of high temperature resistant nylon poly-para-phenylene diformyl hexane diamine |
| CN101423478B (en) * | 2007-11-02 | 2012-05-23 | 宁波大学 | Method for producing hexane diacid and hexanediamine by using nylon-66 disaggregation |
| CN101857540B (en) * | 2009-04-09 | 2013-04-17 | 宁波大学 | Method for producing adipic acid, hexamethylenediamine hydrochloride and polyhexamethylene (di)guanidine chloride from nylon-66 through depolymerization |
| CN101857539B (en) * | 2009-04-09 | 2013-04-17 | 宁波大学 | Method for producing adipic acid, hexamethylenediamine sulfate and polyhexamethylene (di)guanidine sulfate from nylon-66 through depolymerization |
| CN106905139B (en) * | 2017-02-20 | 2020-10-02 | 苏州博洋化学股份有限公司 | Process for extracting high-purity adipic acid |
| CN107056624B (en) * | 2017-04-19 | 2019-04-16 | 青岛科技大学 | A kind of alcoholysis recovery method of nylon 66 material |
| CN107056625B (en) * | 2017-06-07 | 2019-04-23 | 巢湖市鼎盛渔具有限公司 | A kind of recovery method of -66 fishing net waste material of polyamide |
| CN114671768B (en) * | 2022-04-22 | 2023-09-12 | 上海东庚化工技术有限公司 | Industrial purifying method for hexamethylenediamine |
| WO2024090534A1 (en) * | 2022-10-27 | 2024-05-02 | 東レ株式会社 | Diamine or diamine composition, polyamide, molded article, fibers, film, sheet, method for producing diamine and/or dicarboxylic acid, method for producing diamine and/or diamine composition, and method for producing polyamide |
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