CN1032043A - The catalyst of hydrolysis of adipamide waste material and method thereof - Google Patents
The catalyst of hydrolysis of adipamide waste material and method thereof Download PDFInfo
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- CN1032043A CN1032043A CN87104224A CN87104224A CN1032043A CN 1032043 A CN1032043 A CN 1032043A CN 87104224 A CN87104224 A CN 87104224A CN 87104224 A CN87104224 A CN 87104224A CN 1032043 A CN1032043 A CN 1032043A
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- hydrolysis
- catalyst
- polyamide fibre
- hydrochloric acid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
A kind of catalyst and method thereof of hydrolysis polyamide fibre 66 waste materials, it is the comprehensive utilization of relevant polyamide fibre 66 waste materials.
The present invention when hydrolysis polyamide fibre 66 waste materials prepare adipic acid and hexamethylene-diamine hydrochloride in hydrochloric acid medium, adds an amount of phosphoric acid as catalyst, the time of hydrolysis was only used about 4 hours, and the concentration of raw material hydrochloric acid also therefore reduces to 15～20%.
Description
The invention relates to polyhexamethylene adipamide is the comprehensive utilization of polyamide fibre 66 waste materials.
The method of polyamide fibre 66 comprehensive utilization of waste material is a lot, adopts hydrolysis polyamide fibre 66 waste materials to prepare in the method for adipic acid and hexamethylene-diamine hydrochloride at present, and reaction is generally carried out in alkaline medium or acid medium.Domestic publication disclose in " in 1981 first phase of synthetic fiber " a kind of in hydrochloric acid medium the method for hydrolysis polyamide fibre 66 waste materials, its hydrolysis time is longer, and concentration of hydrochloric acid is had relatively high expectations.
The purpose of this invention is to provide and a kind ofly shorten the hydrolysis polyamide fibre catalyst in 66 waste material reaction time, and the preparation method when this catalyst exists.
A kind of catalyst and method thereof of hydrolysis polyamide fibre 66 waste materials, especially for preparation adipic acid and hexamethylene-diamine hydrochloride, this reaction is to carry out in hydrochloric acid medium, it is characterized in that adopting phosphoric acid as catalyst, its use amount be polyamide fibre 66 heavy 0.02～0.5%, its optimum quantum of utilization is 0.05～0.1%.(purity is in 100%) polyamide fibre 66 in 15%～20% hydrochloric acid medium, refluxes under boiling temperature under the condition that above-mentioned phosphoric acid catalyst exists, and reaction 4 hours is hydrolyzed.
The present invention is when hydrolysis polyamide fibre 66 waste materials prepare adipic acid and hexamethylene-diamine hydrochloride in hydrochloric acid medium, add an amount of phosphoric acid as catalyst, the time of hydrolysis was only used about 4 hours, and the concentration of raw material hydrochloric acid also therefore reduce to 15%～20%.
The hydrolysis of polyamide fibre 66 polymer is back reactions of adipic acid and hexamethylene diamine polycondensation reaction, and its reaction equation is as follows:
H
HN-（CH
2）
6-NHOC（CH
2）
4CO
OH+（n-1）H
2O ()/() nH
2N-（CH
2）
6-NH
2+nHOOC-（CH
2）
4-COOH
When carrying out in being reflected at hydrochloric acid, along with the generation of hydrolysis, hydrochloric acid constantly generates hexamethylene-diamine hydrochloride with the hexamethylene diamine effect that generates, and above-mentioned reaction is carried out to the depolymerization direction.Concentration of hydrochloric acid can influence hydrolysis speed, and the high hydrolysis speed of concentration of hydrochloric acid is fast, but because of the hydrochloric acid concentration of limitting itself can not be too high, the concentration of hydrochloric acid height makes the impurity that produces in the hydrolysis more simultaneously.
The present invention ties up in the acid medium, adopts the catalyst of phosphoric acid as hydrolysis, adds 0.02%～0.5%(weight ratio of relative polyamide fibre 66 raw material weights) phosphoric acid 0.05%～0.1%(weight ratio preferably) (phosphoric acid purity is all in 100%).As can be seen from Table 1, other condition is all identical, and reaction the 1, the 2nd does not add the hydrolysis of phosphoric acid, although the concentration of hydrochloric acid is higher 25～27%, and still very long need of reaction time 7～8 hours, the degree that reaction is carried out only can reach 90～92%.React 3,4,5 when adding phosphoric acid when being hydrolyzed such as in the table 1, though concentration of hydrochloric acid reduces to 15～20%, because of adding 0.02%～0.1% phosphoric acid, shortened in the reaction time, reaction is carried out more fully.Wherein, the phosphoric acid addition is few as 0.02% catalytic effect is weaker, be reflected in required concentration of hydrochloric acid higher as 20%, reaction time of carrying out is longer is 6 hours; Otherwise the addition of phosphoric acid is some more as 0.1% catalytic effect is obvious, though only be 15% hydrochloric acid with concentration, the reaction time still only needs 4 hours, and the degree of reaction reaches more than 95%.If but catalyst amount is too many, can influence the purity of products obtained therefrom.
The technology of hydrolysis of the present invention at first is to add in the reactor with polyamide fibre 66, hydrochloric acid, phosphoric acid, by suitable proportioning to carry out pre-reaction, removes the impurity in cleaning polyamide fibre 66 waste materials.The molecular weight of general polyamide fibre 66 polymer is about 14000, when at an amount of hydrochloric acid, when phosphoric acid exists, under boiling temperature, reflux 20～40 minutes the time, the molecular weight of polymer is dropped to about 1000～1500, though this moment, polyamide fibre 66 was in a liquid state, but do not have adipic acid to generate, (time of pre-reaction can not surpass 40 minutes, otherwise the part adipic acid that will make local reaction stop generating is removed together; Can not be lower than 20 minutes, otherwise the big titanium dioxide sedimentation of liquid viscosity do not get off, influence product quality.) titanium dioxide delustering agent and other impurity that polyamide fibre 66 adds in producing, can remove by filter by sedimentation.(titanium dioxide reclaims after with the alkali neutralisation treatment, still can do the usefulness of delustering agent for chemical fibre.) satisfactory for result for removing, filtrate can be repeated sedimentation and filter.
With filtrate back flow reaction 4 hours under boiling temperature, in the process of cooling naturally, have crystallization of adipic acid to separate out then, filter the adipic acid crude product.For improve yield can with filtrate more repeatedly sedimentation cross its crystal of leaching.(the middle control of reaction, be about to filtrate back flow reaction 1 hour, whether cooling is observed has crystallization to separate out, if not having crystallization of adipic acid separates out, reaction is terminal point) with filtrate distillation, preferably decompression distillation, steam hydrochloric acid and make filtrate concentrating, the amount of liquid that generally steams be filtrate 70～80% for well, naturally there is the hexamethylene-diamine hydrochloride crystal to separate out after the cooling, filters hexamethylene-diamine hydrochloride is separated.Can be for improving yield with the filtrate distill repeatedly, concentrate, filter, reclaim the hexamethylene-diamine hydrochloride crystal.
Thick product refining is to adopt the normal temperature mode of washing, and crystallization of adipic acid adopts the deionized water washing, to remove water-soluble substance, filters then, dries, drying, gets product.Be to improve purity, washing times can increase, as washs three product purities and can reach 99%, but total water consumption can not surpass 4 times of crystallization of adipic acid weight during washing.Because of adipic acid about 2.5 grams of solubility/100 gram water in the water at normal temperatures, water consumption can reduce yield too much.The ethanol washing is then adopted in the crystallization of hexamethylene-diamine hydrochloride, to remove adipic acid and other impurity.Wash used amount of alcohol and also be 4 times that are no more than hexamethylene-diamine hydrochloride crystallization weight, other operation is the same.
The present invention is that hydrolysis polyamide fibre 66 waste materials prepare in adipic acid and the hexamethylene-diamine hydrochloride process in hydrochloric acid medium, adopted phosphoric acid as catalyst, make the reaction time shorten to 4 hours by original 12 hours, both saved the energy, improve production efficiency again, just on same equipment, can increase production one times of product.While also decreases the raw material salt acid concentration of employing because of the adding of catalyst again, and not only raw material is easy to get, and has reduced cost.
Embodiment 1
In 10 liter reactors of reflux condenser are housed, add hydrochloric acid (20%) 7.5 liter, polyamide fibre 66 2 kilograms in no oily waste silk and 2.35 milliliters of phosphoric acid (85%) were warming up to 115～118 ℃ in 30 minutes, and back flow reaction is 20 minutes under this fluidized state.After stopping heating, put to cooler and cool off naturally, left standstill 6 hours.With the clear liquid sucking-off 80% after the sedimentation layering, remainder filters.The clear liquid of sucking-off and filtrate are merged, refund and continue heating in the aforesaid reaction vessel, and back flow reaction four hours.Put to the cooler cooling naturally and filter it after 6 hours, the crystallization of adipic acid crude product of separating out is separated.Filtrate is poured in the distillation still, adds thermal distillation, when distillate be filtrate volume 65% the time, stop the heating, put to cooler and cool off, after the cooling crystallization is leached, be the hexamethylene-diamine hydrochloride crystal crude product.Filtrate continue to concentrate, cooling, isolated by filtration.
After the crystallization of adipic acid crude product dried with centrifuge, water consumption is one times of crystallization of adipic acid weight deionized water washing, filters, dries, and in hothouse predrying 8 hours then, makes moisture reach at 2% o'clock, with vacuum dehydrating at lower temperature three hours, sample analysis purity was 95%.Wash once with quadrat method, purity is 99% again.Use two times of water washings more once with quadrat method, its purity can reach 99.9%, yield 87.4%.
The process for purification of hexamethylene-diamine hydrochloride crystal crude product is the same, just adopts ethanol to wash, and washing back purity is 95.5% for the first time, and purity is that 98%, three two times of ethanol washing back purity can reach 98.6%, yield 90% after the secondary washing.
Embodiment 2
Under the condition of embodiment 1, hydrochloric acid 7 liters with 18%, phosphatase 11 .17 milliliter (85%).Back flow reaction is 15 minutes for the first time, back flow reaction is 4 hours for the second time, when distillate liquid measure be filtrate 70% the time, through refining with quadrat method, with one times of deionized water washing, gained adipic acid purity is 92%, washing secondary purity is 98%, clean with two times of water, its purity can reach 99.7～99.9%, yield 86.5% again.The washing of hexamethylene-diamine hydrochloride crude product, its purity of washing back is 95% for the first time, when purity was 97.5% 3 two times of ethanol washing after the secondary washing, purity can reach 98.5%, yield 89.2%.
Example 3
In 500 liter pre-reactors of reflux condenser are housed, add hydrochloric acid (20%) 380 liter, polyamide fibre 66 no oily waste silk 120 kgs and phosphoric acid 70.6 grams (85%) and in 2 hours, be warmed up to 118～120 ℃, back flow reaction is 30 minutes under fluidized state, puts to cooler after stopping to heat and cools off naturally.Leave standstill after 8 hours the clear liquid sucking-off 75% after the sedimentation layering, remainder filters, filtrate is left standstill again, part sucking-off clear liquid refilters, the clear liquid of sucking-off is reinstated pump with filtrate one squeeze in the reactor of 1000 liters, heat 3 hours to boiling, and refluxed 3 hours, put to the cooler cooling naturally after 8 hours, with the clear liquid sucking-off 80% of sedimentation layering, remainder filters, and the crystallization of adipic acid crude product of separating out is told, dried.Filter pump is squeezed in the distillation still of 500 liters, decompression (500mmHg) distillation, when being 370 liters, liquid measure stops heating when distillating, put to cooler and cooled off 8 hours naturally, after the cooling crystallization is leached, dries, be the hexamethylene-diamine hydrochloride crystal crude product, filtrate is returned in the distillation still again and to be concentrated, cooling, isolated by filtration.
The crystallization of adipic acid crude product adopts deionized water washing three times, and the total water amount is no more than 4 times of crystallization weight, and the washing back dries, and is drying to obtain finished product, its purity 99.86%, yield 87%.
The hexamethylene-diamine hydrochloride crystal crude product adopts ethanol washing three times, and total consumption of ethanol is no more than 4 times of crystallization weight, and its operation is the same, its purity 98.37% of gained finished product, yield 89%.
Table 1
| Project | 1 | 2 | 3 | 4 | 5 |
| The inventory kilogram | 2 | 2 | 2 | 2 | 2 |
| Concentration of hydrochloric acid % | 27 | 25 | 20 | 18 | 15 |
| Phosphoric acid addition % | 0 | 0 | 0.02 | 0.05 | 0.1 |
| The hydrochloric acid ratio | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 |
| Reaction time hour | 7 | 8 | 6 | 4 | 4 |
| Extent of reaction % | 90 | 92 | 95 | 95 | 96 |
Annotate:
1. the addition of phosphoric acid is the percentage of material.
2. the hydrochloric acid ratio is an aqueous hydrochloric acid solution and the ratio of material.
3. the extent of reaction is an actual recovery and the ratio of theoretical yield.
Claims (3)
1, a kind of catalyst and method thereof of hydrolysis polyamide fibre 66 waste materials, especially for preparation hexanedioic acid and hexamethylene-diamine hydrochloride, this reaction is to carry out in hydrochloric acid medium, it is characterized in that: adopt phosphoric acid as catalyst.
2, the catalyst and the method thereof of hydrolysis polyamide fibre 66 waste materials according to claim 1 is characterized in that: the use amount of phosphoric acid catalyst be polyamide fibre 66 heavy 0.02～0.5%, its optimum quantum of utilization is 0.05～0.1%.(purity is in 100%.）
3, the catalyst and the method thereof of described hydrolysis polyamide fibre 66 waste materials of claim 1, be that polyamide fibre 66 is in hydrochloric acid medium, boiling temperature next time stream carry out hydrolysis, it is characterized in that: under the condition that above-mentioned phosphoric acid catalyst exists, hydrolysis is 4 hours in 15%～20% hydrochloric acid medium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87104224A CN1032043A (en) | 1987-06-12 | 1987-06-12 | The catalyst of hydrolysis of adipamide waste material and method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87104224A CN1032043A (en) | 1987-06-12 | 1987-06-12 | The catalyst of hydrolysis of adipamide waste material and method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1032043A true CN1032043A (en) | 1989-03-29 |
Family
ID=4814784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87104224A Pending CN1032043A (en) | 1987-06-12 | 1987-06-12 | The catalyst of hydrolysis of adipamide waste material and method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1032043A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017205A (en) * | 2014-06-11 | 2014-09-03 | 李兆顺 | Method for regenerating nylon |
-
1987
- 1987-06-12 CN CN87104224A patent/CN1032043A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017205A (en) * | 2014-06-11 | 2014-09-03 | 李兆顺 | Method for regenerating nylon |
| CN104017205B (en) * | 2014-06-11 | 2017-01-18 | 李兆顺 | Method for regenerating nylon |
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