CN104892795A - Chitosan and seaweed fertilizer joint production method - Google Patents
Chitosan and seaweed fertilizer joint production method Download PDFInfo
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- CN104892795A CN104892795A CN201510333272.8A CN201510333272A CN104892795A CN 104892795 A CN104892795 A CN 104892795A CN 201510333272 A CN201510333272 A CN 201510333272A CN 104892795 A CN104892795 A CN 104892795A
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Abstract
The invention provides a chitosan and seaweed fertilizer joint production method and belongs to the technical field of aquatic product processing. In the chitosan production process, potassium hydroxide replaces sodium hydroxide and then potassium hydroxide waste liquor is used as a digestant for seaweed fertilizer production; hydrochloric acid is replaced by nitric acid and nitric acid waste liquor replaces part of phosphoric acid to be used as a neutralizer for a seaweed digestive liquid. The traditional thinking is changed, waste alkali liquor is utilized instead of being treated, the waste is turned into wealth, and treatment of the waste alkali liquor in chitosan production is avoided. Meanwhile, the potassium hydroxide waste liquor contains a large quantity of organic matters such as animal protein and the like, and the nitric acid waste liquor contains abundant calcium and microelements, so that produced seaweed fertilizer is rich in nutrition and better in fertilizer efficiency. Two production technologies are combined, the production cost of chitosan and the seaweed fertilizer is reduced, the quality of the seaweed fertilizer is improved, and the win-win effect is realized.
Description
Technical field
The invention belongs to technical field of aquatic product processing, relate to a kind of chitosan and seaweed fertilizer combine production method specifically.
Background technology
Chitosan is a kind of natural polymer biological polyoses, and being the key element of another maintenance human life after albumen, fat, VITAMIN, is the important source material of medicine, food, light industry, chemical industry, environmental protection etc.Containing abundant chitosan in the crust such as shrimp, crab, it is the main raw material producing chitosan.The main production utilizing shrimp shell or crab shell to produce chitosan is: remove the inorganic minerals such as the calcium in shrimp crab crust with hydrochloric acid soln; remove the organism such as the protein in shell and on shell with sodium hydroxide solution, finally obtain chitosan finished product by the operation such as sodium hydroxide solution deacetylate of about 40%.This producing and manufacturing technique is simple, and applicability is strong, but it is large to produce wastewater flow rate, and containing strong acid, highly basic and organism, serious environment pollution.This wastewater treatment difficulty is large, and costly, and the useful composition such as protein a large amount of in waste water, residual alkali also result in the very large wasting of resources while contaminate environment.
In recent years, report chitosan new process of production and method of wastewater treatment both at home and abroad, as enzymolysis process replaces highly basic deproteination, highly basic recycling etc., but there is the deficiencies such as production cost is high, facility investment is large.Therefore enterprise reduces sewage discharge in the urgent need to a kind of method that less investment, cost are low, simple.
Seaweed fertilizer take Seaweed Extract as the fertilizer of core substance, and its main production is with brown algas such as dry sea-tangles for raw material, adds potassium hydroxide solution and extracts in a heated condition as digestive pharmaceutical, after extracting liquid filtering with in phosphoric acid and etc. operation obtain seaweed fertilizer.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of chitosan and seaweed fertilizer combine production method, in the process of producing chitosan, replaces sodium hydroxide with potassium hydroxide, uses nitre acid instead of HCl; Then potassium hydroxide waste liquid is used as the digestive pharmaceutical that seaweed fertilizer is produced, is replaced by nitric acid waste part phosphoric acid to be used as the neutralizing agent of marine alga Digestive system; Turn waste into wealth, realize economizing on resources, the object of protection of the environment.
The present invention is achieved by the following technical solution:
A kind of chitosan and seaweed fertilizer combine production method, in the process of producing chitosan, replace sodium hydroxide with potassium hydroxide, then potassium hydroxide waste liquid is used as the digestive pharmaceutical that seaweed fertilizer is produced; Use nitre acid instead of HCl, replaced by nitric acid waste part phosphoric acid to be used as the neutralizing agent of marine alga Digestive system.
A kind of chitosan and seaweed fertilizer combine production method, concrete steps are as follows:
1, the potassium hydroxide solution of 4-6% (W/V) is added in a kettle., then add dry shrimp shell in the ratio of shrimp shell and potassium hydroxide solution 1:5 (W/V), be heated to 80-90 DEG C, insulation 30-90min, waste lye is collected, shrimp shell centrifuge dripping after insulation;
2, the shrimp shell after above-mentioned steps 1 being processed adds in the reactor containing 5-7% (W/V) potassium hydroxide solution, the potassium hydroxide solution volume added is with step 1, be heated to 80-90 DEG C, insulation 30-50min, waste lye is collected after insulation, centrifuge dripping after shrimp shell use water rinses, flushing waste water is incorporated in above-mentioned waste lye;
3, added by the shrimp shell after above-mentioned steps 2 alkaline purification in the reactor containing 5-6% (V/V) salpeter solution and soak 24-36h, the volume of salpeter solution is with the volume of step 1 potassium hydroxide solution; Soak complete collection waste nitric acid solution, shrimp shell centrifuge dripping;
4, the shrimp shell after above-mentioned steps 3 being processed adds in the reactor containing 5-7% (V/V) salpeter solution, and salpeter solution volume is with step 3, and immersion treatment 30-40h, collects waste nitric acid solution after immersion, shrimp shell centrifuge dripping;
5, shrimp shell step 4 obtained is washed to neutrality, centrifuge dripping, dries, obtains chitin;
6, the potassium hydroxide solution chitin that step 5 obtains being put into 50-55% soaks 8-12h, then be heated to 90-95 DEG C of insulation 20-24h, obtain chitosan, collect waste lye, centrifuge dripping after chitosan water is rinsed one time, flushing waste water is incorporated in above-mentioned waste lye;
7, the chitosan that step 6 obtains is washed with water to neutrality, then centrifuge dripping, dry, obtain chitosan finished product;
8, waste lye above-mentioned steps 1, step 2 and step 6 collected merges, concentration of potassium hydroxide in waste lye after merging is adjusted to 4-6% (W/V), add the potassium hydroxide waste lye after described adjustment concentration in a kettle., be heated to 65-75 DEG C, then dry sea-tangle is added, stir, insulation digestion 2-4h, filters postdigestive sea-tangle solution simultaneously;
9, the phosphoric acid solution being 85% by the filtrate step 3 of step 8, the waste nitric acid solution of step 4 and weight percent neutralizes, the volume adding waste nitric acid solution is the 6-10% of filtrate volume, the phosphoric acid solution volume added is the 2.8-3.4% of filtrate volume, obtain seaweed extracted liquor, fertile as liquid alga;
10, mixed by weight 1:1-1.5 ratio with furfural dregs by the sea-tangle filter residue of step 8, then granulation, dries, as soil solids fertilizer.
The present invention's beneficial effect compared with prior art:
(1) price of sodium hydroxide is far below potassium hydroxide, and therefore from cost consideration, in current chitosan production technique, carry out alkaline purification with sodium hydroxide prawn shell, the waste lye pH value of generation is high, containing large amount of organic, intractability is large.The present invention changes Traditional Thinking, and changed handling waste lye, for utilizing waste lye, adopts potassium hydroxide to replace sodium hydroxide, then potassium hydroxide waste liquid is used for the marine alga digestive pharmaceutical in seaweed fertilizer production process, turns waste into wealth, and eliminates the process that waste lye produced by chitosan.
(2) the present invention uses nitre acid instead of HCl in chitosan production technique, then nitric acid waste is used for the neutralizing agent of marine alga Digestive system, eliminates the process of spent acid solution in chitosan production.
(3) in chitosan production technique, containing organism such as a large amount of animal proteins in potassium hydroxide waste liquid, containing abundant calcium and trace element in nitric acid waste, make the seaweed fertilizer nutrition of production abundanter, fertilizer efficiency is better.
(4) production technique is simply effective, really achieves and economizes on resources and cleaner production, and two kinds of production technique associatings, reduce the production cost of chitosan and seaweed fertilizer, improve the quality of seaweed fertilizer, achieve doulbe-sides' victory effect simultaneously.
Embodiment
Below with dry shrimp shell for embodiment elaborates to the present invention, but protection scope of the present invention is not by any pro forma restriction of embodiment.
Embodiment 1:
A kind of chitosan and seaweed fertilizer combine production method, concrete steps are as follows:
1, at volume be 1000L stainless steel steam-jacked kettle in add the potassium hydroxide solution 500L of 5% (W/V), then dry shrimp shell 100Kg is added, be heated to 86 DEG C, insulation 50min, after insulation, waste liquid is drained into waste lye collecting tank, shrimp shell link-suspended basket centrifuge centrifuge dripping;
2, shrimp shell step 1 processed joins in the stainless steel steam-jacked kettle of 500L 6% (W/V) potassium hydroxide solution, be heated to 86 DEG C, insulation 30min, after insulation, potassium hydroxide waste liquid is drained into waste lye collecting tank, shrimp shell use water uses link-suspended basket centrifuge centrifuge dripping after rinsing.Wash water drains into waste lye collecting tank equally;
3, the shrimp shell after above-mentioned steps 2 alkaline purification is joined in the plastic tank containing 500L 6% (V/V) salpeter solution and soak 32h; After immersion, salpeter solution waste liquid is drained into spent acid solution collecting tank, shrimp shell link-suspended basket centrifuge centrifuge dripping;
4, the shrimp shell after above-mentioned steps 3 being processed joins immersion treatment 40h in the plastic tank containing 500L 6% (V/V) salpeter solution.After immersion, salpeter solution waste liquid is drained into spent acid solution collecting tank, shrimp shell link-suspended basket centrifuge centrifuge dripping;
5, the shrimp shell after above-mentioned steps 4 being processed uses link-suspended basket centrifuge centrifuge dripping after being washed to neutrality, then dries under daylight, obtains chitin;
The stainless steel steam-jacked kettle of the potassium hydroxide solution 6, put into the chitin that above-mentioned steps 5 obtains containing 55% (W/V) soaks 8h (being as the criterion with solution energy submergence chitin), then be heated to 95 DEG C of insulation 20h, obtain chitosan.Potassium hydroxide waste liquid enters waste lye collecting tank.Use link-suspended basket centrifuge centrifuge dripping after chitosan water is rinsed one time, flushing waste water drains into waste lye collecting tank equally;
7, the chitosan that step 6 obtains is washed with water to neutrality, use link-suspended basket centrifuge centrifuge dripping, dry, obtain chitosan finished product;
8, waste lye above-mentioned steps 1, step 2 and step 6 collected merges, concentration of potassium hydroxide in waste lye after merging is adjusted to 5%, the potassium hydroxide waste lye of 5 cube above-mentioned 5% is added in the reactor of 6 cubes, steam heating is used to be warming up to 68 DEG C, then 700 kilograms of dry sea-tangles are added, stir, insulation digestion 3h simultaneously.By postdigestive sea-tangle solution 150 order silk cover filterings;
9, the filtrate step 3 step 8 obtained, the nitric acid waste of step 4 and weight percent be 85% phosphoric acid solution neutralize, add that volume is filtrate volume 10% of nitric acid waste, add that volume is filtrate volume 3.0% of phosphoric acid solution.Seaweed extracted liquor is obtained after stirring, fertile as liquid alga, also compositely further can make compound seaweed fertilizer;
10, sea-tangle filter residue step 8 obtained mixes by weight 1:1.2 ratio with furfural dregs, and then granulation, dries, as soil solids fertilizer.
The present invention is by chitosan and seaweed fertilizer combination producing, potassium hydroxide waste liquid is directly used in the marine alga digestive pharmaceutical in seaweed fertilizer production process, turn waste into wealth, both eliminated chitosan and produced the process of waste lye, to turn increase in seaweed fertilizer the organic matters such as aquatic animal property albumen.Nitre acid instead of HCl is used in chitosan production technique, then part phosphoric acid is replaced by nitric acid waste to be used for the neutralizing agent of marine alga Digestive system, not only eliminate the process of spent acid solution in chitosan production, contain abundant calcium and trace element in nitric acid waste simultaneously, make the seaweed fertilizer nutrition of production abundanter, fertilizer efficiency is better.Technical solution of the present invention production technique is simply effective, really achieves and economizes on resources and cleaner production.
Claims (2)
1. chitosan and a seaweed fertilizer combine production method, is characterized in that described method is in the process of producing chitosan, replaces sodium hydroxide with potassium hydroxide, then potassium hydroxide waste liquid is used as the digestive pharmaceutical that seaweed fertilizer is produced; Use nitre acid instead of HCl, replaced by nitric acid waste part phosphoric acid to be used as the neutralizing agent of marine alga Digestive system.
2. a kind of chitosan according to claim 1 and seaweed fertilizer combine production method, is characterized in that concrete steps are as follows:
1) potassium hydroxide solution of 4-6% (W/V) is added in a kettle., then add dry shrimp shell in the ratio of shrimp shell and potassium hydroxide solution 1:5 (W/V), be heated to 80-90 DEG C, insulation 30-90min, waste lye is collected, shrimp shell centrifuge dripping after insulation;
2) by above-mentioned steps 1) process after shrimp shell add in the reactor containing 5-7% (W/V) potassium hydroxide solution, the same step 1) of potassium hydroxide solution volume added, be heated to 80-90 DEG C, insulation 30-50min, waste lye is collected after insulation, centrifuge dripping after shrimp shell use water rinses, flushing waste water is incorporated in above-mentioned waste lye;
3) by above-mentioned steps 2) shrimp shell after alkaline purification soaks 24-36h in adding containing 5-6% (V/V) salpeter solution reactor, and the volume of salpeter solution is with the volume of step 1) potassium hydroxide solution; Soak complete collection waste nitric acid solution, shrimp shell centrifuge dripping;
4) by above-mentioned steps 3) process after shrimp shell add in the reactor containing 5-7% (V/V) salpeter solution, the same step 3) of salpeter solution volume, immersion treatment 30-40h, collects waste nitric acid solution after immersion, shrimp shell centrifuge dripping;
5) by step 4) the shrimp shell that obtains is washed to neutrality, centrifuge dripping, and dry, obtain chitin;
6) by step 5) chitin that the obtains potassium hydroxide solution of putting into 50-55% soaks 8-12h, then be heated to 90-95 DEG C of insulation 20-24h, obtain chitosan, collect waste lye, centrifuge dripping after chitosan water is rinsed one time, flushing waste water is incorporated in above-mentioned waste lye;
7) by step 6) chitosan that obtains washes with water to neutrality, then centrifuge dripping, dry, obtains chitosan finished product;
8) by above-mentioned steps 1), step 2) and step 6) waste lye collected merges, concentration of potassium hydroxide in waste lye after merging is adjusted to 4-6% (W/V), add the potassium hydroxide waste lye after described adjustment concentration in a kettle., be heated to 65-75 DEG C, then dry sea-tangle is added, stir, insulation digestion 2-4h, filters postdigestive sea-tangle solution simultaneously;
9) by step 8) filtrate step 3), step 4) waste nitric acid solution and weight percent be 85% phosphoric acid solution neutralize, the volume adding waste nitric acid solution is the 6-10% of filtrate volume, the phosphoric acid solution volume added is the 2.8-3.4% of filtrate volume, obtain seaweed extracted liquor, fertile as liquid alga;
10) by step 8) sea-tangle filter residue mix with furfural dregs by weight 1:1-1.5 ratio, then granulation, dries, as soil solids fertilizer.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565853A (en) * | 2016-09-30 | 2017-04-19 | 中山市承铭农业技术开发有限公司 | Method for preparing raw materials of liquid fertilizer by using shrimp and crab shell-containing wastes |
| CN109180250A (en) * | 2018-11-19 | 2019-01-11 | 威海迪普森生物科技有限公司 | A kind of method that the phosphorus potassium method of the useless complete utilization of nothing prepares foliar fertilizer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020147318A1 (en) * | 2001-04-09 | 2002-10-10 | Cho Fu Chuan | Preparation method of water soluble carboxylmethyl chitosan having anti-lipid peroxidation ability |
| CN1911967A (en) * | 2006-06-20 | 2007-02-14 | 青岛科技大学 | Preparation method of chitin |
| CN101439995A (en) * | 2008-12-22 | 2009-05-27 | 中国水产科学研究院黄海水产研究所 | Clean production method of seaweed fertilizer |
| CN103332970A (en) * | 2013-06-06 | 2013-10-02 | 常大勇 | Method for producing functional fertilizers by comprehensive utilization of shrimp and crab shells |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020147318A1 (en) * | 2001-04-09 | 2002-10-10 | Cho Fu Chuan | Preparation method of water soluble carboxylmethyl chitosan having anti-lipid peroxidation ability |
| CN1911967A (en) * | 2006-06-20 | 2007-02-14 | 青岛科技大学 | Preparation method of chitin |
| CN101439995A (en) * | 2008-12-22 | 2009-05-27 | 中国水产科学研究院黄海水产研究所 | Clean production method of seaweed fertilizer |
| CN103332970A (en) * | 2013-06-06 | 2013-10-02 | 常大勇 | Method for producing functional fertilizers by comprehensive utilization of shrimp and crab shells |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565853A (en) * | 2016-09-30 | 2017-04-19 | 中山市承铭农业技术开发有限公司 | Method for preparing raw materials of liquid fertilizer by using shrimp and crab shell-containing wastes |
| CN109180250A (en) * | 2018-11-19 | 2019-01-11 | 威海迪普森生物科技有限公司 | A kind of method that the phosphorus potassium method of the useless complete utilization of nothing prepares foliar fertilizer |
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Effective date of registration: 20180126 Address after: Room 3012, No. 33, No. 33, four - flow north road, Licang District, Qingdao, Shandong Patentee after: Qingdao Haili Wo Biological Technology Co., Ltd. Address before: 266071 Shandong Province, Qingdao city Nanjing Road No. 106 Patentee before: Inst of Huanghai Sea Marine Products, Chinese Academy of Aquatic Product Science |
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Granted publication date: 20170804 Termination date: 20200616 |