CN101857540B - Method for producing adipic acid, hexamethylenediamine hydrochloride and polyhexamethylene (di)guanidine chloride from nylon-66 through depolymerization - Google Patents
Method for producing adipic acid, hexamethylenediamine hydrochloride and polyhexamethylene (di)guanidine chloride from nylon-66 through depolymerization Download PDFInfo
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Abstract
The invention discloses a method for producing adipic acid, hexamethylenediamine hydrochloride and polyhexamethylene (di)guanidine chloride from waste nylon-66 serving as a raw amerial through depolymerization, which is characterized by comprising the following steps of: depolymerizing the waste nylon-66 by using hydrochloric acid to obtain refined adipic acid and hexamethylenediamine hydrochloride; polymerizing the hexamethylenediamine hydrochloride and dicyandiamide (in a molar ratio of 1:1) at the temperature of between 170 and 190DEG C for 1 to 3 hours to obtain a white or pale yellow solid polyhexamethylene diguanidine chloride; and adding dicyandiamide and ammonium chloride powder in a molar ratio of 1:2 into a reactor, performing reaction at high temperature for 1 to 3 hours, slowly adding hexamethylenediamine hydrochloride powder, continuously reacting for 3 to 7 hours to obtain a white or pale yellow solid polyhexamethylene guanidine chloride. The method improves production efficiency, reduces production cost, and solves the problems of difficult separation of the product hexamethylenediamine due to depolymerization, low yield and poor benefit; and the technological process is environment-friendly, simple and convenient, and is suitable for industrial production.
Description
Technical field
The present invention relates to utilize the nylon-66 waste through depolymerization to produce the novel method of hexanodioic acid, hexamethylene-diamine hydrochloride and polyhexamethylene list (two) guanidinesalt hydrochlorate sterilizing agent, especially introduced the novel method of a kind of suitable suitability for industrialized production polyhexamethylene list (two) guanidinesalt hydrochlorate.
Background technology
Nylon-66 is the macromolecular material that is formed by hexanodioic acid and hexanediamine polycondensation, in the synthetic and course of processing, can produce unacceptable product and tankage at it.Simultaneously, various nylon 66 goods are difficult to process after being used, and not only cause waste, and to environment.Therefore, recycle the extensive concern that waste and old nylon-66 has caused society.How it is turned waste into wealth, brings into play the focus that its economic benefit that has and social benefit become research.Nylon reclaims main method at present has: melt pelletization regeneration; Chemical recovery; Energy recovery; Landfill disposal etc.Chemical recycling is adopted widely, and for example: Minte Nylon Industry Co., Ltd., Ningbo has applied for a kind ofly producing the Chinese patent of the technique of hexanodioic acid, hexanediamine with nylon-66 disaggregation, and the patent No. is CN1611477; Sky, Liaoning becomes chemical industry company limited to declare a kind of Chinese patent of production method of useless nylon recycling, and the patent No. is CN1569802.Also have some to utilize the nylon-66 of chemical recycling disaggregation of waste and old.Yet, when the depolymerization nylon-66 is produced hexanodioic acid and hexanediamine monomer, exist still that productive rate is low, separation difficulty, problem that purity is not high.
The application of guanidine class sterilizing agent has had the history in more than 50 year, and what the initial stage used mainly is poly hexamethylene biguanide class sterilizing agent, such as 1,6-two (just-to the chlorobenzene biguanides) hexane (having another name called chlorhexidine, Tubulicid).In recent years, find that in the world polyhexamethylene list guanidine class sterilizing agent has higher fungicidal effectiveness, and fungicidal spectrum is wide, minimum inhibitory concentration (MIC) is low, speed of action is fast, the photo-thermal stable chemical performance, soluble in water, have no side effect, the characteristics such as non-corrosiveness, toxicity are low, meet in the international community requirement to the sterilization and disinfection product, receive much attention, become sterilizing agent most popular on the Vehicles Collected from Market, the trend that replaces gradually biguanides disinfectant is arranged greatly.That has developed has two kinds of polyhexamethylene list guanidine phosphoric acid salt and polyhexamethylene list guanidinesalt hydrochlorates, and polyhexamethylene guanidine phosphoric acid salt is because the existence of phosphate radical, toxicity is larger, eyes and skin mucosa had pungency, also can produce destroy environment simultaneously, thereby be careful, with good conditionsi in the world to its use.Polyhexamethylene list guanidinesalt hydrochlorate has become the nonpoisonous and tasteless sterilised products that is widely used.Had multiple process for producing method for Polyhaxemethylenguanidine Hydrochloride salt, for example the Polyhaxemethylenguanidine Hydrochloride salt sold of Vehicles Collected from Market is that to adopt publication number be that the described preparation technology of CN02135317 produces; Publication number be CN1390876A patent Introduction a kind of sterilant Polyhaxemethylenguanidine Hydrochloride salt and preparation method thereof for preparing; A kind of Polyhaxemethylenguanidine Hydrochloride salt and preparation method thereof has been invented by Tongling Biological High Polymer Technology Co., Ltd., and publication number is CN101245141A, and it is by Guanidinium hydrochloride and triethylenediamine and add initiator and at high temperature be polymerized; Publication number be CN101289536A patented invention by Guanidinium hydrochloride and 1,6-, the two amido hexanes method that Polyhaxemethylenguanidine Hydrochloride salt is produced in polymerization under hot conditions.
The above-mentioned method for preparing Polyhaxemethylenguanidine Hydrochloride salt respectively has relative merits because preparation technology is different.The present invention is on existing patent of invention basis, success to the depolymerized product exploitation that makes the transition, the technique of recycling the nylon-66 waste is improved, utilized depolymerization product hexamethylene-diamine hydrochloride direct production sterilizing agent polyhexamethylene list (two) guanidinesalt hydrochlorate.Both overcome the shortcoming that yield is low, separation is difficult that the intimate diacid of depolymerization nylon-66 manufacture order, hexanediamine exist, solved again the problem that productivity effect is poor, cost is high.The industrialized producing technology for preparing polyhexamethylene list (two) guanidinesalt hydrochlorate take the waste material nylon-66 as starting material was not reported in other documents or patent.
Summary of the invention
Purpose of the present invention mainly is to provide a kind of for the existing problem of present nylon-66 recycling to produce hexanodioic acid with nylon-66 disaggregation, the method of hexamethylene-diamine hydrochloride and polyhexamethylene list (two) guanidinesalt hydrochlorate, it is on existing technical foundation, nylon-66 disaggregation is produced hexanodioic acid, the technological process of hexanediamine is improved, adopt hydrochloric acid to come the depolymerization nylon-66, and with its depolymerization product hexamethylene-diamine hydrochloride for the preparation of polyhexamethylene list (two) guanidinesalt hydrochlorate, both solved and had the difficult separation of hexanediamine in the nylon-66 removal process, yield is low, problem of poor benefits has solved again the problem of production sterilizing agent polyhexamethylene list (two) guanidinesalt hydrochlorate raw material sources.
The technical scheme that the present invention is directed to above-mentioned technical problem employing is: a kind of method of producing hexanodioic acid, hexamethylene-diamine hydrochloride and polyhexamethylene list (two) guanidinesalt hydrochlorate with nylon-66 disaggregation, it is characterized in that including acidolysis workshop section, hexanodioic acid and separate and separate with recrystallization workshop section, hexamethylene-diamine hydrochloride and purifying workshop section, polyhexamethylene list (two) guanidinesalt hydrochlorate prepare workshop section, each workshop section's step is as described below:
(1), acidolysis workshop section, mass concentration 18-25% aqueous hydrochloric acid is added the top to be equipped with in the reactor of reflux exchanger and hydrogen chloride gas absorption unit, then add nylon-66 while heating, under the condition of normal pressure and 100-110 ℃, reacted 8～12 hours, obtain acid hydrolysis solution;
(2), hexanodioic acid separates and recrystallization workshop section, reactor is slowly vacuumized, treat that absolute pressure kept later on 20-30 minute less than 10KPa, acid hydrolysis solution in the step (1) is cooled to 30-40 ℃, separate to obtain thick adipic acid crystals with coarse filter, decolour again, recrystallization, oven dry obtain refining hexanodioic acid;
(3), hexamethylene-diamine hydrochloride separates and purifying workshop section, the 30-40% of the thick hexamethylene-diamine hydrochloride solution decompression evaporation concentration that obtains in the step (2) to cumulative volume, be cooled to 30-40 ℃, the industrial alcohol that adds 3-5 times of volume is separated out thick hexamethylene-diamine hydrochloride crystal, more after filtration, decolouring, recrystallization, drying obtain refining hexamethylene-diamine hydrochloride;
(4), polyhexamethylene list (two) guanidinesalt hydrochlorate prepares workshop section, the hexamethylene-diamine hydrochloride and the technical grade Dyhard RU 100 that obtain in the step (3) are roughly 1: 1 add-on input reactor according to mol ratio, nitrogen protection, stirred 10-30 minute, be warming up to 170-190 ℃, stirring reaction 3-7 hour, obtain hexamethylene and ammonium chloride mixt, slowly be pressed in the separating tank that fills industrial alcohol with the reaction solution of nitrogen with molten state while hot, filter after fully stirring, filter residue gets byproduct of reaction ammonium chloride behind the water recrystallization purifying, ethanol is removed in the underpressure distillation of hexamethylene ethanolic soln, obtained white or faint yellow solid hexamethylene; Calculate productive rate greater than 95% with hexamethylene-diamine hydrochloride.
(5), polyhexamethylene list (two) guanidinesalt hydrochlorate prepares workshop section, in reactor, drop into mol ratio and be roughly 1: 2 Dyhard RU 100 and ammonium chloride powder, nitrogen protection, stirred 10-30 minute, be warming up to 170-190 ℃, stirring reaction 1-3 hour, slowly add the hexamethylene-diamine hydrochloride powder (hexamethylene-diamine hydrochloride: the mol ratio of ammonium chloride 1: 1) that obtains in the step (3), continue reaction 3-7 hour, obtain polyhexamethylene list guanidinesalt hydrochlorate and ammonium chloride mixt, slowly be pressed in the separating tank that fills industrial alcohol with the reaction solution of nitrogen with molten state while hot, filter after fully stirring, filter residue gets byproduct of reaction ammonium chloride behind the water recrystallization purifying, with polyhexamethylene list guanidinesalt hydrochlorate ethanol filtrate, ethanol is removed in underpressure distillation, obtains white or faint yellow solid polyhexamethylene list guanidinesalt hydrochlorate; Calculate productive rate greater than 95% with hexamethylene-diamine hydrochloride.
Step (4) or step (5) can be choice for uses.
(6), recycle step, with used ethanol reuse after the rectifying tower weight steams in the ethanol filtrate of step (3) and step (4) or the step (5), tower reactor residue refrigerated separation, in the lump reuse step of evaporation dilute hydrochloric acid solution (1) in filtrate and step (2) and the step (3), the filter residue in filter residue and step (4) or the step (5) merge to be processed.
Evaporation concentration described in the step (3) is to the 30-40% of cumulative volume, preferred 35%; The industrial alcohol that adds 3-5 times of volume, preferred 4 times.
Gac is adopted in decolouring described in the step (3), and add-on is the 3-5% of thick hexamethylene-diamine hydrochloride crystal mass.
Temperature of reaction described in step (4) or the step (5) and reaction times determine that according to end-use the reaction times, molecular weight longer, the higher then polyhexamethylene of temperature of reaction list (two) guanidinesalt hydrochlorate was higher.
Tower reactor residue treatment process described in the step (6) need to be after 5-7 production cycle, as offal treatment.
The involved equipment configurations such as reactor, mechanical stirring and pipeline in step (4) or the step (5) all need to adopt high temperature resistant non-metallic material and the reaction system isolation such as enamel.
During adding hexamethylene-diamine hydrochloride powder described in the step (5), according to hexamethylene-diamine hydrochloride: the ammonium chloride powder is roughly 1: 1 mol ratio and feeds intake, and control evenly added in 30 minutes under the agitation condition.
Filter residue described in the step (5), the ammonium chloride reuse that obtains behind the water recrystallization purifying is to step (5).
Compare with technique with prior art, advantage of the present invention and effect are:
The present invention mainly be for present waste material nylon-66 disaggregation produce hexanodioic acid, hexanediamine productive rate lower, separate difficulty, the poor problem of productivity effect.On existing technical foundation, nylon-66 disaggregation is produced the technological process of hexanodioic acid, hexanediamine and improved, to the exploitation that makes the transition of its depolymerized product.Adopt hydrochloric acid to come the depolymerization nylon-66, and its depolymerization product hexamethylene-diamine hydrochloride is directly used in preparation polyhexamethylene list (two) guanidinesalt hydrochlorate, both solved the problem of nylon-66 recycling, solve again the problem of production sterilizing agent polyhexamethylene list (two) guanidinesalt hydrochlorate raw material sources, improved comprehensive productivity effect and profit margin.The waste that produces in the production process is few, and pollution on the environment is little, has reduced production cost, has improved production efficiency, and production technique is suitable for suitability for industrialized production.In addition, prepared polyhexamethylene list (two) guanidinesalt hydrochlorate can be made into stable solid powdery, is convenient to like this transportation, uses, can be in field widespread uses such as weaving, daily use chemicals, water treatments.
Description of drawings
Fig. 1 correlated response process flow diagram;
Fig. 2 chemical reaction process synoptic diagram of being correlated with.
Embodiment
Embodiment is described in further detail the present invention below in conjunction with accompanying drawing.
Embodiment 1
(1) depolymerization workshop section: the 30% industrial by-product hydrochloric acid that adds 1500Kg in the reactor of reflux exchanger and hydrogen chloride gas absorption unit is housed at the top, add 500Kg water, heating, add while stirring useless nylon-66 fragment 1000Kg, the control temperature of reaction is at 100-110 ℃, normal pressure, time 8h, reaction conversion ratio reaches more than 90%, obtains acid hydrolysis solution.Acid hydrolysis solution filters by coarse filter and is pressed into crystallizer, accelerate crystallisation by cooling speed by the top decompression of bleeding, froth breaking is collected in the liquid of carrying secretly in the pumping process screen filtration surge tank externally, passes into recirculated cooling water tank temperature to be crystallized and be down to till 30-40 ℃ in chuck.After finishing, crystallization separates thick crystallization of adipic acid and thick hexamethylene-diamine hydrochloride solution with chamber filter press.
(2) the refining workshop section of hexanodioic acid: in the still that will decolour more than the water temp. heating to 90 ℃, progressively add the thick hexanodioic acid solid that is equivalent to water yield weight ratio 50% this moment, wait the gac that dissolves rear adding and be equivalent to weight ratio 4%, stir decolouring, use plate filter isolating active charcoal and insoluble impurities, again crystallisation by cooling, filtration, oven dry obtains the hexanodioic acid sterling of purity more than 99.7%, 490Kg, yield 76%.
(3) the refining workshop section of hexamethylene-diamine hydrochloride: the liquid merging reduction vaporization of collecting in the thick hexamethylene-diamine hydrochloride solution that depolymerization operation (1) is obtained and the screen filtration surge tank is concentrated into 35% of cumulative volume, be cooled to 35 ℃, the industrial alcohol that adds 3-5 times of volume is separated out thick hexamethylene-diamine hydrochloride crystal, again after filtration, add the activated carbon decolorizing, recrystallization, the drying that are equivalent to weight ratio 4% and obtain refining hexamethylene-diamine hydrochloride, purity is greater than 99%, 610Kg, yield 73%.
(4) polyhexamethylene list (two) guanidinesalt hydrochlorate prepares workshop section; the hexamethylene-diamine hydrochloride and the technical grade Dyhard RU 100 that obtain in the hexamethylene-diamine hydrochloride refining step are dropped into reactor according to 1: 1 add-on of mol ratio; nitrogen protection; stir 30min; be warming up to 180 ℃; stirring reaction 5h; obtain hexamethylene and ammonium chloride mixt; slowly be pressed in the separating tank that fills industrial alcohol with the reaction solution of nitrogen with molten state while hot; filter after fully stirring; filter residue gets byproduct of reaction ammonium chloride behind the water recrystallization purifying; ethanol is removed in the underpressure distillation of hexamethylene ethanolic soln; obtain the white solid hexamethylene, yield is greater than 95%, with its crushing packing.
Depolymerization workshop section (1), the refining workshop section (2) of hexanodioic acid and the refining workshop section (3) of hexamethylene-diamine hydrochloride are with embodiment 1.
(4) polyhexamethylene list (two) guanidinesalt hydrochlorate prepares workshop section; the input mol ratio is 1: 2 Dyhard RU 100 and ammonium chloride powder in reactor; nitrogen protection; stir 25min; be warming up to 180 ℃; stirring reaction 2h; slowly add the hexamethylene-diamine hydrochloride powder that obtains in the refining workshop section (3) of hexamethylene-diamine hydrochloride; continue reaction 5h; obtain polyhexamethylene list guanidinesalt hydrochlorate and ammonium chloride mixt; slowly be pressed in the separating tank that fills industrial alcohol with the reaction solution of nitrogen with molten state while hot, filter after fully stirring, with polyhexamethylene list guanidinesalt hydrochlorate ethanol filtrate; ethanol is removed in underpressure distillation; obtain light yellow solid polyhexamethylene list guanidinesalt hydrochlorate, yield is greater than 92%, with its crushing packing.
Embodiment 3
Depolymerization workshop section (1), the refining workshop section (2) of hexanodioic acid, the refining workshop section (3) of hexanediamine vitriol and polyhexamethylene list (two) guanidine sulfate prepare workshop section (4) with embodiment 2.
With the thick ammonium chloride white powder that obtains after the above-mentioned filtration, add 300Kg hot water (80 ± 5 ℃), stirring and dissolving is filtered, reduction vaporization is concentrated into just to be had till the crystallization, and cooling is filtered, vacuum-drying gets 150Kg POV ammonium solid, and yield is more than 86%.According to the reaction equivalent ratio, suitably replenish fresh ammonium chloride, reuse to polyhexamethylene list (two) guanidinesalt hydrochlorate prepares workshop section (4).
This paper substantially mol ratio refers to allow mol ratio to fluctuate 10% on equivalent reaction basis.
Claims (6)
1. method of producing hexanodioic acid, hexamethylene-diamine hydrochloride and polyhexamethylene list or biguanide hydrochloride with nylon-66 disaggregation, it is characterized in that it includes acidolysis workshop section, hexanodioic acid and separates and separate with recrystallization workshop section, hexamethylene-diamine hydrochloride and purifying workshop section and polyhexamethylene list or biguanide hydrochloride prepare workshop section, each workshop section's step is as described below:
(1), acidolysis workshop section, mass concentration 18-25% aqueous hydrochloric acid is added the top to be equipped with in the reactor of reflux exchanger and hydrogen chloride gas absorption unit, then in heat-processed, add nylon-66, press the mass ratio 100: 40～60 of nylon and hydrogenchloride, under the condition of normal pressure and 100-110 ℃, reacted 8～12 hours, obtain acid hydrolysis solution;
(2), hexanodioic acid separates and recrystallization workshop section, reactor is vacuumized, treat that absolute pressure kept later on 20-30 minute less than 10KPa, acid hydrolysis solution in the step (1) is cooled to 30-40 ℃, separate to obtain thick adipic acid crystals with coarse filter, decolour again, recrystallization, oven dry obtain refining hexanodioic acid;
(3), hexamethylene-diamine hydrochloride separates and purifying workshop section, the 30-40% of the thick hexamethylene-diamine hydrochloride solution decompression evaporation concentration that obtains in the step (2) to cumulative volume, be cooled to 30-40 ℃, the industrial alcohol that adds 3-5 times of volume is separated out thick hexamethylene-diamine hydrochloride crystal, more after filtration, decolouring, recrystallization, drying obtain refining hexamethylene-diamine hydrochloride;
(4), hexamethylene prepares workshop section, be that 1: 1 add-on drops into reactor with the hexamethylene-diamine hydrochloride that obtains in the step (3) and technical grade Dyhard RU 100 according to mol ratio, nitrogen protection, stirred 10-30 minute, be warming up to 170-190 ℃, stirring reaction 3-7 hour, obtain hexamethylene and ammonium chloride mixt, reaction solution with molten state is pressed in the separating tank that fills industrial alcohol while hot, filter after stirring, ethanol is removed in the underpressure distillation of hexamethylene ethanolic soln, obtained white or faint yellow solid hexamethylene;
(5), polyhexamethylene list guanidinesalt hydrochlorate prepares workshop section, the input mol ratio is 1: 2 Dyhard RU 100 and ammonium chloride powder in reactor, nitrogen protection, stirred 10-30 minute, be warming up to 170-190 ℃, stirring reaction 1-3 hour, slowly add the hexamethylene-diamine hydrochloride powder that obtains in the step (3), continue reaction 3-7 hour, obtain polyhexamethylene list guanidinesalt hydrochlorate and ammonium chloride mixt, the reaction solution with molten state is pressed in the separating tank that fills industrial alcohol while hot, filter after stirring, with polyhexamethylene list guanidinesalt hydrochlorate ethanol filtrate, ethanol is removed in underpressure distillation, obtains white or faint yellow solid polyhexamethylene list guanidinesalt hydrochlorate;
Step (4) or step (5) choice for use.
2. method according to claim 1, it is characterized in that workshop section's step also includes step (6) and recycles step, with used ethanol reuse after the rectifying tower weight steams in the ethanol filtrate of step (3) and step (4) or the step (5), tower reactor residue refrigerated separation, in the lump reuse step of evaporation dilute hydrochloric acid solution (1) in filtrate and step (2) and the step (3), the filter residue in filter residue and step (4) or the step (5) merge to be processed.
3. method according to claim 2 is characterized in that in step (3), and thick hexamethylene-diamine hydrochloride solution decompression evaporation concentration is to 35% of cumulative volume; The industrial alcohol that adds 4 times of volumes is separated out thick hexamethylene-diamine hydrochloride crystal.
4. method according to claim 2 is characterized in that the decolouring employing gac described in the step (3), and add-on is the 3-5% of thick hexamethylene-diamine hydrochloride crystal mass.
5. method according to claim 2 is characterized in that involved reactor, mechanical stirring and pipeline in step (4) or the step (5), all adopts the isolation of enamel and reaction system.
6. method according to claim 2, when it is characterized in that the adding hexamethylene-diamine hydrochloride powder described in the step (5), according to hexamethylene-diamine hydrochloride: the ammonium chloride powder is that 1: 1 mol ratio feeds intake, and control evenly added in 30 minutes under the agitation condition.
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| CN 200910097552 CN101857540B (en) | 2009-04-09 | 2009-04-09 | Method for producing adipic acid, hexamethylenediamine hydrochloride and polyhexamethylene (di)guanidine chloride from nylon-66 through depolymerization |
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| CN 200910097552 CN101857540B (en) | 2009-04-09 | 2009-04-09 | Method for producing adipic acid, hexamethylenediamine hydrochloride and polyhexamethylene (di)guanidine chloride from nylon-66 through depolymerization |
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| CN103145981B (en) * | 2011-12-07 | 2015-04-01 | 上海高聚生物科技有限公司 | Polyhexamethylene guanidine phosphate and synthetic method thereof |
| CN103396546B (en) * | 2013-08-01 | 2015-09-30 | 湖南利洁科技有限公司 | The method of hexamethylene is prepared in a kind of suspension polymerization |
| TWI626229B (en) * | 2016-09-22 | 2018-06-11 | 中國石油化學工業開發股份有限公司 | Synthesis of biguanid phosphate and bactericide |
| CN107056624B (en) * | 2017-04-19 | 2019-04-16 | 青岛科技大学 | A kind of alcoholysis recovery method of nylon 66 material |
| CN108069880A (en) * | 2017-12-04 | 2018-05-25 | 辽宁科技大学 | A kind of polyhexamethylene list guanidine nitrate preparation method |
| CN108084434B (en) * | 2017-12-04 | 2020-07-03 | 辽宁科技大学 | Method for preparing polyhexamethylene guanidine hydrochloride from waste acid alkali liquor |
| CN110746595B (en) * | 2019-11-01 | 2023-12-22 | 吉林师范大学 | Preparation method of poly (propylene glycol) guanidine hydrochloride |
| WO2022240822A1 (en) * | 2021-05-14 | 2022-11-17 | Research Triangle Institute | Depolymerization of polymers with ammonia and amines |
| CN114181430A (en) * | 2021-11-29 | 2022-03-15 | 江苏志成新材料科技有限公司 | Process system for chemically regenerating waste polyester and waste polyamide into PBAT |
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