CN108084434A - A kind of method that polyhexamethylene list guanidine hydrochloride is prepared by spent acid lye - Google Patents
A kind of method that polyhexamethylene list guanidine hydrochloride is prepared by spent acid lye Download PDFInfo
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- CN108084434A CN108084434A CN201711260588.4A CN201711260588A CN108084434A CN 108084434 A CN108084434 A CN 108084434A CN 201711260588 A CN201711260588 A CN 201711260588A CN 108084434 A CN108084434 A CN 108084434A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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Abstract
The present invention relates to a kind of methods that polyhexamethylene list guanidine hydrochloride is prepared by spent acid lye, comprise the following steps：Prepare ammonium chloride：The concentration of waste ammonia liquor and waste hydrochloric acid is surveyed, in molar ratio 1:1, waste ammonia liquor solution is poured slowly into abraum salt acid solution；Ammonium chloride solution is stirred to get, ammonia chloride crystal is precipitated, is filtered, it is dry；Ammonium chloride and dicyandiamide, hexamethylene diamine are in molar ratio (1.75 2):1:2 feed intake in reaction kettle, and stirring reacts at 150 200 DEG C, obtains white polyhexamethylene list guanidine hydrochloride powder.Advantage is：The spent acid lye that raw material is generated in being produced using enterprise, it is cheap, the recycle value of waste liquid is realized, reduces the processing of waste liquid, reduces pollution；It is simple for process to prepare polyhexamethylene list guanidine, technology maturation, it is easy to industrialized production.The technology path has the features such as at low cost, economic value is high.
Description
Technical field
Polymer preparation field more particularly to one kind the invention belongs to be used to sterilize prepare poly- six methylene by spent acid lye
The method of base list guanidine hydrochloride.
Background technology
Bulk pharmaceutical chemicals polyhexamethylene list guanidine hydrochloride is current internationally recognized new generation of green environment-friendly high-efficiency disinfectant,
It is classified as by national standard body of China within 2010 and leads to available for food, environment and article surface, human body, air and central air conditioning
In the disinfectant resourcing manifest of wind system, security obtains U.S. FDA and EPA accreditations.Industrial, agriculture, medical and daily
There is extremely extensive purposes in life.Its preparation method is long-standing, in the various polyhexamethylene list guanidine hydrochlorides of preparing
In method, can all there be the generation of exhaust gas ammonia.
Ammonia cannot be discharged directly, and a kind of water, which absorbs, generates ammonium hydroxide waste liquid, and another kind is absorbed with dilute hydrochloric acid, generates chlorination
Waste liquor of ammonium.In the production technology of existing polyhexamethylene list guanidine hydrochloride, a large amount of above-mentioned waste liquids can be all generated, are enterprise
The discharge of waste liquid, post processing bring heavy financial burden.Waste liquid such as handles bad, can bring serious environmental pollution.
The content of the invention
For overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of simple for process, easily operated by spent acid
The method that lye prepares polyhexamethylene list guanidine hydrochloride, the spent acid lye generated in being produced by enterprise are starting material, are synthesized
Polyhexamethylene list guanidine hydrochloride, realizes recycling for waste liquid, it is ensured that the bactericidal property of polyhexamethylene list guanidine hydrochloride.
To achieve the above object, the invention is realized by the following technical scheme：
A kind of method that polyhexamethylene list guanidine hydrochloride is prepared by spent acid lye, comprises the following steps：
1) ammonium chloride is prepared：With hydrochloric acid standard solution and standard solution of sodium hydroxide to waste liquid ammonium hydroxide and abraum salt acid solution into
Row acid base titration measures the concentration of waste ammonia liquor and waste hydrochloric acid, and then in molar ratio 1:1, waste ammonia liquor solution is poured slowly into abraum salt
In acid solution；Stir to get ammonium chloride solution；
2) ammonium chloride solution of generation is placed under sunlight and be exposed to the sun several days；Or ammonium chloride solution is put on hot plate
Ammonia chloride crystal is precipitated in heating evaporation, filters, and dry, purity is by Formaldehyde Absorption Method for Determination of Low；
3) by the ammonium chloride of generation and dicyandiamide, hexamethylene diamine in molar ratio (1.75-2):1:2 feed intake in reaction kettle,
Heat temperature raising under mechanical agitation reacts at 150-200 DEG C, is released up to no ammonia and stops reaction, given birth to through melt polycondensation reaction
It into thick solid, takes out, drying pulverizes, obtains white polyhexamethylene list guanidine hydrochloride powder；The ammonia generated in reaction
It collects and is absorbed by step 1) method, realize recycling, polyhexamethylene list guanidine hydrochloride is prepared using it.
The ammonia exhaust gas that waste ammonia liquor described in step 1) generates in being produced by enterprise is absorbed with deionized water to be prepared；It is described
Waste hydrochloric acid produced by enterprise in produce hydrogen chloride emission with deionized water absorb prepare.
Polyhexamethylene list guanidine hydrochloride solid described in step 3) is dissolved in water, filtering, and it is molten that a few drop concentrated hydrochloric acids are added dropwise
Liquid is tuned into neutrality, is configured to the polyhexamethylene list guanidine hydrochloride aqueous solution of 25% concentration.
Compared with prior art, the beneficial effects of the invention are as follows：
1st, for raw material of the invention using the spent acid lye generated in enterprise's production, source is more, cheap, realizes waste liquid
Recycle value, reduce the processing of waste liquid, reduce pollution, and the utilization rate of raw material can be improved.
2nd, it is starting material one-step method with the two kinds of industrial chemicals of ammonium chloride and dicyandiamide and hexamethylene diamine prepared by spent acid lye
Prepare polyhexamethylene list guanidine, simple for process, technology maturation, it is easy to industrialized production.The technology path has at low cost, warp
The features such as Ji value is high.
3rd, the polyhexamethylene list guanidine hydrochloride prepared proves there is good bactericidal effect after testing.
Specific embodiment
The present invention is described in detail below, it should be noted that the implementation of the present invention is not limited to following embodiment party
Formula.
The method that polyhexamethylene list guanidine hydrochloride is prepared by spent acid lye, comprises the following steps：
1) ammonium chloride is prepared：With hydrochloric acid standard solution and standard solution of sodium hydroxide to waste liquid ammonium hydroxide and abraum salt acid solution into
Row acid base titration measures the concentration of waste ammonia liquor and waste hydrochloric acid, and then in molar ratio 1:1, waste ammonia liquor solution is poured slowly into abraum salt
In acid solution；Stir to get ammonium chloride solution；The ammonia exhaust gas deionized water that the waste ammonia liquor generates in being produced by enterprise
It absorbs and prepares；The hydrogen chloride emission that the waste hydrochloric acid produces in being produced by enterprise is absorbed with deionized water to be prepared.
2) ammonium chloride solution of generation is placed under sunlight and be exposed to the sun several days；Or ammonium chloride solution is put on hot plate
Ammonia chloride crystal is precipitated in heating evaporation, filters, dry, and purity is by Formaldehyde Absorption Method for Determination of Low, is qualification if purity is more than 99%；
If purity is inadequate, then recrystallizes；
3) by the ammonium chloride of generation and dicyandiamide, hexamethylene diamine in molar ratio (1.75-2):1:2 feed intake in reaction kettle,
Heat temperature raising under mechanical agitation when reaction response 1-3 is small at 150-200 DEG C, releases up to no ammonia and stops reaction, through melting
Polycondensation reaction generates thick solid, takes out, and drying pulverizes, obtains white polyhexamethylene list guanidine hydrochloride powder；In reaction
The ammonia of generation is collected by connection tail gas reception device, then ammonia is absorbed by step 1) method, is realized recycling, is utilized
It prepares polyhexamethylene list guanidine hydrochloride.
In use, polyhexamethylene list guanidine hydrochloride solid is dissolved in water, filtering, during a few drop concentrated hydrochloric acid solutions of dropwise addition are tuned into
Property is configured to the polyhexamethylene list guanidine hydrochloride aqueous solution of 25% concentration of mass percent.It is i.e. commercially available, in use, needing
It is diluted to mass percent 0.1%-0.5% concentration and carries out sterilization use.
During inspection, compound concentration is the polyhexamethylene list guanidine hydrochloride aqueous solution of 0.1%-0.5%, common for four kinds
The Bactericidal tests of pathogenic species (Escherichia coli, pseudomonas aeruginosa, staphylococcus aureus, staphylococcus albus) grind
Study carefully, show that there is good bactericidal property by polyhexamethylene list guanidine hydrochloride prepared by the starting of spent acid lye.
Embodiment 1
The measure of the concentration of spent acid lye
1) first with 0.5mol/L hydrochloric acid standard solutions and standard solution of sodium hydroxide to waste liquid ammonium hydroxide and abraum salt acid solution
Acid base titration is carried out, measures waste ammonia liquor concentration as 1.756mol/L, abraum salt acid concentration is 0.872mol/L.Wherein, waste ammonia liquor by
The ammonia exhaust gas generated in enterprise's production is absorbed with deionized water to be prepared；The hydrogen chloride emission that waste hydrochloric acid produces in being produced by enterprise
It is absorbed and prepared with deionized water.
2) preparation of ammonium chloride
By volume 1:2, that is, take waste liquid ammonium hydroxide 100mL, abraum salt acid solution 200mL that waste ammonia liquor solution is poured into waste hydrochloric acid
In solution, stirring is placed under sunlight and is exposed to the sun several days；Or solution is put into heating evaporation on hot plate, it is brilliant that ammonium chloride is precipitated
Body filters, dry, obtains about 9 grams of solid ammonium chloride, purity is by Formaldehyde Absorption Method for Determination of Low, purity 99.2%.
3) polycondensation
Homemade ammonium chloride and dicyandiamide, hexamethylene diamine are pressed 2:1:2 molar ratio is added in 100mL there-necked flasks, will
The ammonium chloride of 3.210g, the dicyandiamide of 2.520g, the hexamethylene diamine of 7.067g are put into reaction kettle, connect mechanical stirring device,
Tail gas reception device is connected, stirring when the reaction 2 that heats up at 180 DEG C is small, stops stirring, obtains thick solid, takes out, drying,
It pulverizes, obtains white polyhexamethylene list guanidine hydrochloride powder.
4) solution is prepared
0.1g, 0.2g, 0.3g, 0.4g are weighed respectively, and 0.5g polyhexamethylene list guanidine hydrochlorides are dissolved in water, and are configured to matter
It is respectively 0.1%, 0.2%, 0.3%, 0.4% to measure concentration, and dense salt is added dropwise in 0.5% polyhexamethylene list guanidine hydrochloride solution
Several drops of acid, the pH for adjusting solution is 7.0, and inhibition zone sterilization experiment is used for after filtering.
5) Bactericidal test
By the polyhexamethylene list guanidine hydrochloride solution of above-mentioned preparation, respectively to Escherichia coli, pseudomonas aeruginosa, white
Staphylococcus and staphylococcus aureus these four common pathogens do inhibition zone test.Experimental result is shown in Table 1.By table 1 as it can be seen that
Antibacterial circle diameter is all higher than 7mm, meets《Disinfection technology standard》Bactericidal property requirement in handbook.Illustrate what is prepared by spent acid lye
Polyhexamethylene list guanidine hydrochloride has good bactericidal property.
1 Bactericidal test of table
Embodiment 2
The method that polyhexamethylene list guanidine hydrochloride is prepared by spent acid lye, comprises the following steps：
1) ammonium chloride is prepared：With hydrochloric acid standard solution and standard solution of sodium hydroxide to waste liquid ammonium hydroxide and abraum salt acid solution into
Row acid base titration measures the concentration of waste ammonia liquor and waste hydrochloric acid, and then in molar ratio 1:1, waste ammonia liquor solution is poured slowly into abraum salt
In acid solution；Stir to get ammonium chloride solution；The ammonia exhaust gas that waste ammonia liquor generates in being produced by enterprise is absorbed with deionized water to be made
It is standby；The hydrogen chloride emission that waste hydrochloric acid produces in being produced by enterprise is absorbed with deionized water to be prepared.
2) ammonium chloride solution of generation is placed under sunlight and be exposed to the sun several days；Or ammonium chloride solution is put on hot plate
Ammonia chloride crystal is precipitated in heating evaporation, filters, and dry, purity is by Formaldehyde Absorption Method for Determination of Low, purity 99.0%；
3) by the ammonium chloride of generation and dicyandiamide, hexamethylene diamine in molar ratio 1.75:1:2 feed intake in reaction kettle, in machinery
The lower heat temperature raising of stirring, when reaction response 3 is small at 150 DEG C, releases up to no ammonia and stops reaction, given birth to through melt polycondensation reaction
It into thick solid, takes out, drying pulverizes, obtains white polyhexamethylene list guanidine hydrochloride powder；The ammonia generated in reaction
It is collected by connection tail gas reception device, then ammonia is absorbed by step 1) method, realized recycling, poly- six are prepared using it
Methylene list guanidine hydrochloride.
Polyhexamethylene list guanidine hydrochloride solid is dissolved in water, filtering, and a few drop concentrated hydrochloric acid solutions are added dropwise and are tuned into neutrality, prepare
Into the polyhexamethylene list guanidine hydrochloride aqueous solution of 25% concentration.It can be diluted during use.
Embodiment 3
The method that polyhexamethylene list guanidine hydrochloride is prepared by spent acid lye, comprises the following steps：
1) ammonium chloride is prepared：Soda acid is carried out to ammonium hydroxide and hydrochloric acid solution with hydrochloric acid standard solution and standard solution of sodium hydroxide
Titration measures the concentration of ammonium hydroxide and hydrochloric acid, and then in molar ratio 1:1, waste ammonia liquor solution is poured slowly into abraum salt acid solution；It stirs
It mixes to obtain ammonium chloride solution；
2) ammonium chloride solution is put into heating evaporation on hot plate, ammonia chloride crystal is precipitated, filtered, it is dry, purity by
Formaldehyde Absorption Method for Determination of Low, purity 99.1%；
3) by the ammonium chloride of generation and dicyandiamide, hexamethylene diamine in molar ratio 1.85:1:2 feed intake in reaction kettle, in machinery
The lower heat temperature raising of stirring, the reaction response at 200 DEG C release up to no ammonia and stop reaction, generated through melt polycondensation reaction viscous
Thick shape solid takes out, and drying pulverizes, obtains white polyhexamethylene list guanidine hydrochloride powder；The ammonia generated in reaction is by even
The collection of tail gas reception device is connect, then ammonia is absorbed by step 1) method, recycling is realized, poly- six methylene is prepared using it
Base list guanidine hydrochloride.
Polyhexamethylene list guanidine hydrochloride solid is dissolved in water, filtering, and a few drop concentrated hydrochloric acid solutions are added dropwise and are tuned into neutrality, prepare
Into the polyhexamethylene list guanidine hydrochloride aqueous solution of 25% concentration.It can be diluted during use.
Claims (3)
- A kind of 1. method that polyhexamethylene list guanidine hydrochloride is prepared by spent acid lye, which is characterized in that comprise the following steps：1) ammonium chloride is prepared：Acid is carried out to waste liquid ammonium hydroxide and abraum salt acid solution with hydrochloric acid standard solution and standard solution of sodium hydroxide Alkalimetric titration measures the concentration of waste ammonia liquor and waste hydrochloric acid, and then in molar ratio 1:1, it is molten that waste ammonia liquor solution is poured slowly into waste hydrochloric acid In liquid；Stir to get ammonium chloride solution；2) ammonium chloride solution of generation is placed under sunlight and be exposed to the sun several days；Or ammonium chloride solution is put and is heated on hot plate Ammonia chloride crystal is precipitated in evaporation, filters, and dry, purity is by Formaldehyde Absorption Method for Determination of Low；3) by the ammonium chloride of generation and dicyandiamide, hexamethylene diamine in molar ratio (1.75-2):1:2 feed intake in reaction kettle, in machinery The lower heat temperature raising of stirring, reacts at 150-200 DEG C, is released up to no ammonia and stop reaction, generated through melt polycondensation reaction viscous Thick shape solid takes out, and drying pulverizes, obtains white polyhexamethylene list guanidine hydrochloride powder；The ammonia generated in reaction is collected And absorbed by step 1) method, it realizes recycling, polyhexamethylene list guanidine hydrochloride is prepared using it.
- 2. a kind of method that polyhexamethylene list guanidine hydrochloride is prepared by spent acid lye according to claim 1, feature It is, the ammonia exhaust gas that the waste ammonia liquor described in step 1) generates in being produced by enterprise is absorbed with deionized water to be prepared；Described The hydrogen chloride emission that waste hydrochloric acid produces in being produced by enterprise is absorbed with deionized water to be prepared.
- 3. a kind of method that polyhexamethylene list guanidine hydrochloride is prepared by spent acid lye according to claim 1, feature It is, the polyhexamethylene list guanidine hydrochloride solid described in step 3) is dissolved in water, filtering, and a few drop concentrated hydrochloric acid solution tune are added dropwise Into neutrality, the polyhexamethylene list guanidine hydrochloride aqueous solution of 25% concentration is configured to.
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| CN201711260588.4A CN108084434B (en) | 2017-12-04 | 2017-12-04 | Method for preparing polyhexamethylene guanidine hydrochloride from waste acid alkali liquor |
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| CN201711260588.4A CN108084434B (en) | 2017-12-04 | 2017-12-04 | Method for preparing polyhexamethylene guanidine hydrochloride from waste acid alkali liquor |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000035861A1 (en) * | 1998-12-18 | 2000-06-22 | Alcon Laboratories, Inc. | Bis-amido polybiguanides and the use thereof to disinfect contact lenses and preserve pharmaceutical compositions |
| CN101857540A (en) * | 2009-04-09 | 2010-10-13 | 宁波大学 | Method for producing adipic acid, hexamethylenediamine hydrochloride and polyhexamethylene (di)guanidine chloride from nylon-66 through depolymerization |
| CN104650352A (en) * | 2013-11-20 | 2015-05-27 | 青岛水世界环保科技有限公司 | Poly-hexamethylene biguanide hydrochloride sterilizing and disinfecting agent |
| CN105217693A (en) * | 2015-08-26 | 2016-01-06 | 昆明理工大学 | A kind of method preparing iron oxide yellow and ammonium chloride |
-
2017
- 2017-12-04 CN CN201711260588.4A patent/CN108084434B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000035861A1 (en) * | 1998-12-18 | 2000-06-22 | Alcon Laboratories, Inc. | Bis-amido polybiguanides and the use thereof to disinfect contact lenses and preserve pharmaceutical compositions |
| CN101857540A (en) * | 2009-04-09 | 2010-10-13 | 宁波大学 | Method for producing adipic acid, hexamethylenediamine hydrochloride and polyhexamethylene (di)guanidine chloride from nylon-66 through depolymerization |
| CN104650352A (en) * | 2013-11-20 | 2015-05-27 | 青岛水世界环保科技有限公司 | Poly-hexamethylene biguanide hydrochloride sterilizing and disinfecting agent |
| CN105217693A (en) * | 2015-08-26 | 2016-01-06 | 昆明理工大学 | A kind of method preparing iron oxide yellow and ammonium chloride |
Non-Patent Citations (1)
| Title |
|---|
| 刘永生: "从含盐酸废液中制取氯化铵的研究", 《有色金属（冶炼部分）》 * |
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