CN101177328A - Method for treating waste liquid of chitin and chitosan production - Google Patents
Method for treating waste liquid of chitin and chitosan production Download PDFInfo
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- CN101177328A CN101177328A CNA2007101577317A CN200710157731A CN101177328A CN 101177328 A CN101177328 A CN 101177328A CN A2007101577317 A CNA2007101577317 A CN A2007101577317A CN 200710157731 A CN200710157731 A CN 200710157731A CN 101177328 A CN101177328 A CN 101177328A
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- water
- chitosan
- washing water
- deproteinated
- chitin
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
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Abstract
The invention provides a novel technology to eliminate environmental pollution by resourceful treatment of the waste liquors of chitin and chitosan. First, the protein of shrimp and crab shells is removed by dilute alkali liquor and the dilute alkali liquor is used for two to four times; secondly, the waste alkali liquor after deporteinization is neutralized by acid with the fertilizers of N, P, K in proper quantity added to prepare protein peptide water flush fertilizer; thirdly, the deproteinized shell is de-calcified with 5 to 10% dilute nitric acid solution and the nitric acid solution is used for two to four times; fourthly, the waste acid liquor containing calcium nitrate is used to extract calcium nitrate tetrahydrate or directly used as fast-released calcium fertilizer; at the same time, the technology of continuous countercurrent washing is adopted to rinse the deproteinized, decalcified and de-acetylate materials so as to realize the ''zero-discharge'' of wastewater.
Description
Technical field
The invention belongs to chitin production technique field.Relate to simultaneously and produce the waste liquid comprehensive treating process, dispose waste liquid and produce the fertilising of dashing of nitrogenous, phosphorus, potassium and peptide, also relate to four water-calcium nitrate and extract or directly be used as quick-acting calcareous fertilisers.
Background technology
Chitin, chitosan be extensively be present in the crust of shrimp, crab, insect and cell wallss such as mushroom, fungi, bacterium in a kind of nitrogenous natural macromolecule amylose.Because this biomaterial has safety non-toxic, the physiological function of multiple excellence, excellent biological compatibility and biodegradability, thereby have been widely used at aspects such as medicine, food, daily use chemicals, weaving and environmental protection.
Existing chitin, chitosan production normally are raw material with the shrimp and crab shells, handle through " diluted acid decalcification ", " diluted alkaline deproteinated " and " concentrated base takes off acetyl ", make chitosan.This " three take off " technology produces a large amount of protein-contg alkaline waste waters, contains the acid waste water of calcium salt and the washes of each operation.1 ton of chitosan of every production can produce 350～500 tons of waste water.A large amount of animal proteinum and hydrolysate (peptide and amino acid) thereof, inorganic salt (CaCl in these waste water
2, NaCl), be the just discharging of simple neutralizing treatment usually, chemical oxygen demand (COD) and suspended solids (SS) severe overweight had both been wasted valuable natural resource, again serious environment pollution.
Existing many patents and document provide " treating waste water from production of chitin technology " (CN1321614A) in existing technology, " chitin and derivative produce in the closed cycle and the comprehensive utilization of waste liquid " (CN1467227) and " clean preparation process of chitin " (CN1526739) wait and provide the solution chitin to produce waste water utilization, the various technical schemes of minimizing contaminate environment.
Patent CN132164A carries out respectively utilizing behind the recyclable feed a part by-product of neutralizing treatment to acid and alkaline waste water again, but also produces a large amount of waste residues simultaneously; A large amount of washess are still needed to handle the back discharging with biochemical process, and step is loaded down with trivial details slightly.Patent CN1467227 adds discarded albumen respectively to be hydrolyzed in spent acid solution and waste lye, add trace elements such as Fe, Cu, Zn, Mn again, reconcentration, and spraying drying is made amino-acid trace element feed, fertilizer additive.Science and technology is combined acid, alkaline waste liquor fully and is utilized.But this end product contains a large amount of calcium sulfate and muriate, and practicality is probably restricted, and the pollution waste to washes does not add processing in addition.Patent CN1526739 provides and has used the proteolytic enzyme deproteinated, reclaims protein, reduces the technology of discharge of wastewater, but acid waste water and washes are still needed the special processing discharging.
Summary of the invention
The novel process that invention provides a kind of thorough improvement chitin, chitosan to produce waste liquid.Overall plan is that the acid waste water with deproteinated alkali lye waste water and decalcification all changes into the fertilizer that is used for agricultural, simultaneously each step material is adopted the continuous countercurrent washing process, can accomplish factory effluent " zero release ", to reach chitin, the utilization of chitosan production waste complete resource, thoroughly eliminate the purpose of environmental pollution.
Purpose of the present invention can realize by following technical measures.
1. decalcification behind the first deproteinated.Deproteinated after the existing decalcification of traditional technology, in diluted acid decalcification process, partial protein also can be dissolved by acid hydrolysis, is unfavorable for the recycling of protein and calcium salt.Change the decalcification again of first deproteinated into, then can avoid a small amount of protein hydrolyzate to infiltrate in the acid waste liquid of decalcification, and help the carrying out of decalcification reaction.
2. Deproteinated alkali lye reuse 2～4 times in order to improve the protein in the deproteinated alkaline waste liquor and the content of hydrolysate thereof, helps agricultural use, and has reduced the treatment capacity of waste water.The diluted alkaline concentration that deproteinated is used can be 3～10%, 80～100 ℃ of temperature, 3～5 hours time.After first shell material deproteinated operation is finished, will remain alkali lye and separate, give over to the Deproteinated alkali lye of next batch shell material.Every batch of Deproteinated diluted alkaline can be used for 2～4 batches of shell material deproteinated operations repeatedly for this reason, then isolates the deproteinated alkali lye that concentrates and dashes fertilising for being processed into protein peptide.
3. the rare nitric acid of decalcification.Traditional technology is that the dilute hydrochloric acid decalcification produces the spent acid solution that contains CaCl2, is difficult to find the reasonable use approach.And rare nitric acid decalcification, main component is a nitrocalcite in the spent acid solution, can be used as the readily avaiable fertilizer of acid soil and the nutritive medium of soilless culture on agricultural, has a extensive future.Although nitric acid is more higher than hydrochloric acid price, to handle properly, the economic benefit aspect is surplus to some extent still, importantly can fundamentally solve the calcium salt pollution problem.
4. rare nitric acid decalcification condition, concentration of nitric acid 4～10%, temperature: normal temperature, 6～12 hours time.Also have decolorization in the time of rare nitric acid decalcification, can obtain pure white chitin.
5. but the reuse of nitric acid decalcification acid solution is 2～4 times, in order to improve the content of nitrocalcite in the decalcification acid solution, reduces the treatment capacity of decalcification waste liquid, is convenient to reclaim Ca (NO
3)
24H
2O or directly use ca nitrate soln.After first shell material decalcification operation is finished, will remain acid solution and separate, give over to the acid solution of next batch shell material decalcification.So the diluted acid of every batch of decalcification can be used for the decalcification operation of 2～4 batches of shell material repeatedly, then isolates the decalcification acid solution that concentrates and supplies to reclaim four water-calcium nitrate or be directly used in agricultural.
6. the measure 2 described deproteinated alkali lye that concentrate contain protolysate, polypeptide, multiple amino acids and NaOH.Be neutralized to pH7～8 with sulfuric acid, add chemical fertilizer such as urea, monoammonium phosphate, saltpetre again, be deployed into and contain N, P
2O
5, K
2The protein peptide of O composition 5～15% is dashed fertilising.
7. the improvement of washing process, producing has in the middle of a large amount of waste water of chitin, chitosan discharging 3/4 in deproteinated, decalcification approximately, takes off acetyl after washing material process and produce.Traditional washing methods is each bath water, is disposable discharging entirely, not only contaminate environment but also waste water resource.
If washing process is adopted the continuous countercurrent washing process.Each time washing water that are material are established the storage tank storage, all do not discharge; The washing water first time of every batch materials are for the diluted acid of doing Deproteinated diluted alkaline of preparation or decalcification (take off first and second time of acetyl material washing water and all can be used as the diluted alkaline that the allotment deproteinated is used).The washing water second time of every batch materials are continued to employ, and do the washing water first time of next batch material.And the like, the N time washing water of every batch materials are continued to employ (N-1) the inferior washing water as the next batch material, and are washed with clear water for the last time.Adopt this continuous countercurrent washing process, the material washing behind the deproteinated promptly reaches neutral for 4～6 times.Whole washing process can be accomplished washing water " zero release ", has saved great amount of water resources again.
Outstanding advantage compared with prior art of the present invention is: 1. the technology that changes prior art, under the situation of quality that does not influence product chitin, chitosan and yield, can make full use of raw material-acid, alkali, can be made into available fertilizer at last, accomplish to make the best use of everything.2. the scientific utilization water resources with continuous countercurrent washing process rational allocation, is accomplished " zero release ".
Embodiment
Embodiment 1
Take by weighing 200g snow crab shell (I) and be immersed in the 1500mL 6%NaOH solution, heat 90～100 ℃ and kept 4 hours, separate deproteinated shell material (I) and deproteinated alkali lye (I).
Deproteinated shell material (I) is washed to neutrality, uses 1200mL water at every turn, wash altogether 5 times, it is stand-by to keep washing water respectively.With first washing water and than high alkali liquid, adjust deproteinated alkali lye (I) to 1500mL, NaOH6% as deproteinated alkali lye (II).
Take by weighing 200g snow crab shell (II), be immersed in the deproteinated alkali lye (II), heat 90～100 ℃ and kept 4 hours, separate deproteinated shell material (II) and deproteinated alkali lye (II).
With each time washing water of deproteinated shell material (I), deproteinated shell material (II) is carried out continuous countercurrent washing, promptly with the washing water second time of shell material (I), the washing water first time as shell material (II), the rest may be inferred, with the clear water washing, washes six times altogether and can reach neutrality at last.
Repeat aforesaid operations, 200g snow crab shell (III) is carried out deproteinated with the alkali lye (III) that alkali lye (II) is deployed into 1500mL 6%NaOH, then isolate deproteinated shell material (III) and deproteinated alkali lye (III).With each time washing water of shell material (II), shell material (III) is carried out the continuous countercurrent washing to neutral.
Alkali lye (III) is continued to employ, for further being processed into fertilizer.
Embodiment 2
Deproteinated shell material (I) is carried out decalcification with 1500mL 6% rare nitric acid intermittently stir, normal temperature kept 8 hours down, separated thick chitin (I) and decalcification acid solution (I).
Isolate chitin (I) and be washed to neutrality, each water 1200mL washes 4 times altogether.It is stand-by to keep washing water respectively.Adjust decalcification acid solution (I) to 1500mL with the 1st washing water and than concentrated nitric acid, nitric acid content 6% carries out decalcification with it to deproteinated shell material (II) as decalcification acid solution (II), normal temperature 8 hours.Separate thick chitin (II) and decalcification acid solution (II).
Each time washing water with thick chitin (I), thick chitin (II) is carried out the continuous countercurrent washing, and promptly the 2nd washing water of thick chitin (I) are as the 1st washing water of thick chitin (II), and the rest may be inferred, with the clear water washing, washing 5 times altogether can reach to neutrality at last.
Repeat the appeal operation, the acid solution (III) that is deployed into 1500mL 6% nitric acid with decalcification acid solution (II) is carried out decalcification to deproteinated shell material (III), then separate thick chitin (III) and decalcification acid solution (III), with each time washing water of thick chitin (II), thick chitin (III) is carried out the continuous countercurrent washing to neutral.
Embodiment 3
Take by weighing 50g exsiccant chitin, be immersed in and heat 95 ± 5 ℃ of maintenances in the 1000g 45%NaOH solution, carried out deacetylation 8 hours.Separate thick chitosan and high alkali liquid.High alkali liquid keeps reuse.
Wash thick chitosan to neutral, each water 800mL washes 7 times altogether, keeps each time respectively and washs water, uses with the continuous countercurrent washing of the thick chitosan of next batch.The 1st time and the 2nd washing water (NaOH＞5%) can be used for preparing the diluted alkaline that deproteinated is used.
Thick chitosan is through washing, dried chitosan 38.8g.
Embodiment 4
Get deproteinated alkali lye (III) (the containing NaOH 5.76%) 900g that example 1 makes, slowly add the vitriol oil and be neutralized to pH7.5, be cooled to room temperature, the a small amount of insolubles of elimination (additive capable of using as feed), and adding 57g saltpetre, 16g monoammonium phosphate and 27g urea are deployed into protein peptide and dash fertilising.Wherein N, P
2O
5, K
2O content＞5%, N: P
2O
5: K
2The ratio of O is about 3: 1: 3.5 and is suitable as fruit and vegetable towards fertilising.
Claims (5)
1. a chitin, chitosan are produced the treating waste liquid method, it is characterized in that getting in the processing step at preparation chitin, chitosan is that (1) uses earlier the diluted alkaline deproteinated, (2) use rare nitric acid decalcification again, (3) acetyl is taken off with high alkali liquid in the back, the method that the alkali in the three-step reaction, acid and generation waste water are administered;
(1) sig water behind the deproteinated is reused 2～4 times, make full use of alkali and improve protein content in the waste lye to reach, last waste lye is neutralized to pH7～8 with acid, adds urea, monoammonium phosphate, vitriolate of tartar, is deployed into the protein peptide that contains N, P, K 〉=5～15% and dashes fertilising; To neutral, washing water adopt the adverse current continuous washing method to shell material behind the deproteinated, do not discharge through washed several times with water;
(2) decalcification is reused 2～4 times with rare nitric acid, and to reach the purpose that makes full use of nitric acid and improve the content of nitrocalcite in the spent acid solution, last spent acid solution extracts four water-calcium nitrate or directly is used as quick-acting calcareous fertilisers; To neutral, washing water adopt the adverse current continuous washing method to thick chitin after the decalcification, do not discharge through washed several times with water;
(3) take off the alkali lye of high alkali liquid after isolating chitosan that acetyl is used, can be used for (1) deproteinated with the washing water preparation first time diluted alkaline of (1); Take off behind the acetyl thick chitosan through washed several times with water to neutral, washing water adopt the adverse current continuous washing method, do not discharge.
2. produce the treating waste liquid method according to the described chitin of claim 1, chitosan, it is characterized in that washing water described in step (1), (2), (3) adopt the adverse current continuous washing method, do not discharge: promptly each of material time washing water are established the storage tank storage, all do not discharge; The washing water first time of every batch materials, for the diluted acid of doing Deproteinated diluted alkaline of preparation or decalcification, the washing water second time of every batch materials are as the washing water first time of next batch material; And the like, the N time washing water of every batch materials are continued to employ the N-1 time washing water as the next batch material, and for the last time with the clear water washing, equally also continue to employ the N-1 time washing water as the next batch material.
3. produce the treating waste liquid method according to the described chitin of claim 1, chitosan, it is characterized in that in (1) deproteinated step: the diluted alkaline concentration of usefulness is 3～10%, 80～100 ℃ of temperature, 3～5 hours time.
4. produce the treating waste liquid method according to the described chitin of claim 1, chitosan, it is characterized in that in (2) decalcification step: concentration of nitric acid 4～10%, temperature are normal temperature, 6～12 hours time.
5. produce the treating waste liquid method according to the described chitin of claim 1, chitosan, it is characterized in that (3) take off in the acetyl step: use 40～50%NaOH solution, heating to keep 80～120 ℃, carried out deacetylation 8～20 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101577317A CN100567183C (en) | 2007-10-26 | 2007-10-26 | The method that chitin, chitosan are produced treating waste liquid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101577317A CN100567183C (en) | 2007-10-26 | 2007-10-26 | The method that chitin, chitosan are produced treating waste liquid |
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| Publication Number | Publication Date |
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| CN101177328A true CN101177328A (en) | 2008-05-14 |
| CN100567183C CN100567183C (en) | 2009-12-09 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557164A (en) * | 2010-12-15 | 2012-07-11 | 益海天成(连云港)化工有限公司 | Recycling method of high-salt industrial wastewater containing glycerin |
| US8318913B2 (en) | 2008-03-19 | 2012-11-27 | Agratech International, Inc. | Chitosan manufacturing process |
| CN101993257B (en) * | 2009-08-27 | 2013-05-15 | 林大昌 | Method for preparation of high-activity compound organic fertilizer by waste acid liquid of D-glucosamine hydrochloride |
| CN103332970A (en) * | 2013-06-06 | 2013-10-02 | 常大勇 | Method for producing functional fertilizers by comprehensive utilization of shrimp and crab shells |
| CN104448036A (en) * | 2014-12-02 | 2015-03-25 | 岭南师范学院 | Method for recycling waste hydrochloric acid in process of producing chitin |
| CN105622781A (en) * | 2016-03-22 | 2016-06-01 | 南京林业大学 | Method for extracting chitin from shrimp and crab shells by using eutectic ionic liquid |
| CN105753914A (en) * | 2016-04-27 | 2016-07-13 | 山东凯尔海洋生物科技有限公司 | Method for treating D-glucosamine hydrochloride acid pickle |
| CN110240520A (en) * | 2019-07-10 | 2019-09-17 | 张大庆 | A method of fertilizer is prepared using chitin production waste liquid |
| CN110724211A (en) * | 2019-10-31 | 2020-01-24 | 汕尾市海洋产业研究院 | High-value comprehensive utilization method of shrimp and crab shells based on reducing sugar catalytic oxidation and application thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2090515C1 (en) * | 1993-08-16 | 1997-09-20 | Банников Владимир Васильевич | Method of processing waste water from chitosan production |
| US6740752B2 (en) * | 2000-05-12 | 2004-05-25 | The Procter & Gamble Company | Process for preparing chitosan particles |
| CN1119298C (en) * | 2000-10-17 | 2003-08-27 | 陈启松 | Technique for treating waste water from production of chitin |
| CN1467227A (en) * | 2002-07-09 | 2004-01-14 | 邵建华 | Closed path circulation and comprehensive utilization for waste liquor of chitin and derivative production |
| CN1277845C (en) * | 2003-03-06 | 2006-10-04 | 国家海洋局第二海洋研究所 | Clean chitin producing process |
| RU2263079C1 (en) * | 2004-03-18 | 2005-10-27 | Федеральное государственное образовательное учреждение высшего профессионального образования Мурманский государственный технический университет | Method of purification of sewage at production of chitine from carapaces of crustacea |
| CN100402445C (en) * | 2005-06-08 | 2008-07-16 | 宁波大学 | Sewage treating method for chitin production process |
-
2007
- 2007-10-26 CN CNB2007101577317A patent/CN100567183C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8318913B2 (en) | 2008-03-19 | 2012-11-27 | Agratech International, Inc. | Chitosan manufacturing process |
| CN101993257B (en) * | 2009-08-27 | 2013-05-15 | 林大昌 | Method for preparation of high-activity compound organic fertilizer by waste acid liquid of D-glucosamine hydrochloride |
| CN102557164A (en) * | 2010-12-15 | 2012-07-11 | 益海天成(连云港)化工有限公司 | Recycling method of high-salt industrial wastewater containing glycerin |
| CN102557164B (en) * | 2010-12-15 | 2013-12-11 | 益海嘉里(连云港)化工有限公司 | Recycling method of high-salt industrial wastewater containing glycerin |
| CN103332970A (en) * | 2013-06-06 | 2013-10-02 | 常大勇 | Method for producing functional fertilizers by comprehensive utilization of shrimp and crab shells |
| CN104448036A (en) * | 2014-12-02 | 2015-03-25 | 岭南师范学院 | Method for recycling waste hydrochloric acid in process of producing chitin |
| CN104448036B (en) * | 2014-12-02 | 2016-11-30 | 岭南师范学院 | A kind of regeneration method of waste hydrochloric acid in chitin production process |
| CN105622781A (en) * | 2016-03-22 | 2016-06-01 | 南京林业大学 | Method for extracting chitin from shrimp and crab shells by using eutectic ionic liquid |
| CN105753914A (en) * | 2016-04-27 | 2016-07-13 | 山东凯尔海洋生物科技有限公司 | Method for treating D-glucosamine hydrochloride acid pickle |
| CN110240520A (en) * | 2019-07-10 | 2019-09-17 | 张大庆 | A method of fertilizer is prepared using chitin production waste liquid |
| CN110724211A (en) * | 2019-10-31 | 2020-01-24 | 汕尾市海洋产业研究院 | High-value comprehensive utilization method of shrimp and crab shells based on reducing sugar catalytic oxidation and application thereof |
| CN110724211B (en) * | 2019-10-31 | 2021-09-17 | 汕尾市海洋产业研究院 | High-value comprehensive utilization method of shrimp and crab shells based on reducing sugar catalytic oxidation and application thereof |
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