CN101624230B - Method of processing waste water and recycling protein - Google Patents
Method of processing waste water and recycling protein Download PDFInfo
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- CN101624230B CN101624230B CN2008101383354A CN200810138335A CN101624230B CN 101624230 B CN101624230 B CN 101624230B CN 2008101383354 A CN2008101383354 A CN 2008101383354A CN 200810138335 A CN200810138335 A CN 200810138335A CN 101624230 B CN101624230 B CN 101624230B
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 102000004169 proteins and genes Human genes 0.000 title claims abstract description 24
- 108090000623 proteins and genes Proteins 0.000 title claims abstract description 24
- 239000002351 wastewater Substances 0.000 title abstract description 31
- 238000004064 recycling Methods 0.000 title abstract 2
- 229920001287 Chondroitin sulfate Polymers 0.000 claims abstract description 20
- SQDAZGGFXASXDW-UHFFFAOYSA-N 5-bromo-2-(trifluoromethoxy)pyridine Chemical compound FC(F)(F)OC1=CC=C(Br)C=N1 SQDAZGGFXASXDW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229940059329 chondroitin sulfate Drugs 0.000 claims abstract description 19
- 229920001661 Chitosan Polymers 0.000 claims abstract description 12
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000440 bentonite Substances 0.000 claims abstract description 6
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 14
- 238000011084 recovery Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- 238000004065 wastewater treatment Methods 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 6
- 239000002734 clay mineral Substances 0.000 claims description 6
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- 239000002594 sorbent Substances 0.000 claims description 6
- 241001465754 Metazoa Species 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 235000011837 pasties Nutrition 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 239000002250 absorbent Substances 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims description 2
- 235000013619 trace mineral Nutrition 0.000 claims description 2
- 239000011573 trace mineral Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000010802 sludge Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000003463 adsorbent Substances 0.000 abstract 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 210000000845 cartilage Anatomy 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
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- 235000013305 food Nutrition 0.000 description 2
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- 206010002383 Angina Pectoris Diseases 0.000 description 1
- 206010002660 Anoxia Diseases 0.000 description 1
- 241000976983 Anoxia Species 0.000 description 1
- 229920002567 Chondroitin Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
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- 241001494479 Pecora Species 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 241000282898 Sus scrofa Species 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
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- 210000000988 bone and bone Anatomy 0.000 description 1
- DLGJWSVWTWEWBJ-HGGSSLSASA-N chondroitin Chemical compound CC(O)=N[C@@H]1[C@H](O)O[C@H](CO)[C@H](O)[C@@H]1OC1[C@H](O)[C@H](O)C=C(C(O)=O)O1 DLGJWSVWTWEWBJ-HGGSSLSASA-N 0.000 description 1
- 229940107200 chondroitin sulfates Drugs 0.000 description 1
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- 230000003311 flocculating effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
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- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000036737 immune function Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 210000000867 larynx Anatomy 0.000 description 1
- 235000020997 lean meat Nutrition 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 206010027599 migraine Diseases 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 230000002107 myocardial effect Effects 0.000 description 1
- 208000010125 myocardial infarction Diseases 0.000 description 1
- 210000000537 nasal bone Anatomy 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 238000001694 spray drying Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
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Abstract
The invention relates to a method of processing waste water and recycling protein during the production of chondroitin sulfate, comprising the following steps: (1) adjusting the acidity; (2) adding powdery calcium-base bentonite; (3) adding chitosan: (4) adding polymeric aluminum; (5) filtering; and (6) drying and crushing. The invention has the advantages that bentonite of feedstuff is used as adsorbent to recycle the protein in the waste water from the production of the chondroitin sulfate, and the bentonite of feedstuff can be used as feedstuff additive; the chitosan which is polymeric flocculant can well process the protein in the waste water; after the protein in the waste water is recycled, the chemical oxygen demand (COD) of the waste water can be reduced by over 90 percent, and the subsequent low-concentration waste water can be easily processed by the conventional activated-sludge process; the waste water can be processed with simple process, the cost of investment is low, and the economic benefit and the environmental benefit are obvious.
Description
Technical field
The present invention relates to the water treatment field of environmental engineering, the wastewater treatment that specifically a kind of chondroitin sulfate is produced and the method for protein recovery.
Technical background
Chondroitin sulfate is the mixture of various chondroitin sulfates such as the chondroitin-4-suleate that extracts from the nasal bone of animals such as pig, ox, sheep, larynx bone and other all cartilages, 6-sulfuric acid ossein, Chondroitin A, B, its trade name is " Kang Deling ", its main application is to be used for the treatment of headache, migraine, moving sclerosis, coronary heart disease, stenocardia, the myocardial anoxia of reaching, in the medicine agent such as myocardial infarction, also be widely used in food, beverage and various healthcare products, in the product of taking a tonic or nourishing food to build up one's health, the domestic needs amount grows with each passing day, and is the hot-selling goods that the domestic market utmost point needs.In recent years, along with the continuous lifting of people to chondroitin sulfate understanding, the powerful medical health care function of chondroitin sulfate embodies day by day.Meanwhile,, make the impetus that the turnout presentation speed of chondroitin sulfate increases, and become China's export volume and be only second to proteinic biochemical products because the production technique of chondroitin sulfate is simple relatively.
The enzymolysis alcohol extracting method is generally adopted in the production of chondroitin sulfate, be about to animal cartilage under the katalysis of enzyme with salt (edible salt) hydrolysis, and then crystallization is extracted in ethanolic soln.This shows that the waste water that production process produces contains water-soluble proteins such as a large amount of enzymes and amino acid, according to the difference of production technique, Protein content is generally 2-25% in such waste water, and promptly Protein content is between milk and lean meat.If high-load protein waste water like this directly discharging causes the huge wasting of resources, it is extremely important therefore to develop effective protein proteins matter recovery technology.At present, the protein recovery treatment process in the waste water that produces in the chondroitin sulfate production process has biochemical process, ultrafiltration process, flocculent precipitation etc., and wherein biochemical process and ultrafiltration process have very big difficulty, and working cost is than higher.Flocculent precipitation is as a kind of comparatively effectively isolation technique, and, less investment simple to operate because of it is widely used.Protein recovery method commonly used at present is a spray drying technology, the advantage of this method is almost the protein in the waste water 100% can be reclaimed, shortcoming is to reclaim protein saltiness too high (surpassing 20%) just, restricted follow-up purposes as fodder additives etc., and in spray-dired process, produce large quantity of exhaust gas, cause odor pollution to a certain degree.Reverse osmosis membrane technology, as ultrafiltration etc., the protein that is used for reclaiming waste water also can be obtained good result, but higher because of its investment and running cost, generally seldom is used.And the production of chondroitin sulfate tends to a large amount of high densitys of association and produces waste water, because the special property of this waste water makes that the wastewater treatment difficulty is bigger.Because its chemical oxygen demand (COD) (COD) value generally is higher than 100000mg/L, and content of inorganic nitrogen in is very low, the trophic structure that is waste water composition is extremely unreasonable, and waste water is difficult to adopt the conventional activated sludge method to handle, and there is huge environmental risk in the direct discharging of high-concentration waste water.Therefore, it is imperative to develop a kind of effective chondroitin sulfate factory effluent comprehensive treatment technique and protein recovery method.
Summary of the invention
For solving the problems of the technologies described above, the present invention adopts the feed grade wilkinite as the protein in the sorbent material reclaim(ed) sulfuric acid chrondroitin factory effluent.Employing polymerize aluminum chloride etc. is strengthened the flocculating effect of wastewater treatment, and has obtained good effect.Method of the present invention is:
(1) with dilute hydrochloric acid chondroitin sulfate factory effluent pH value is transferred to 3.5-9.5, make solution I;
(2) with sorbent material water furnishing pasty state, add the above-mentioned solution I that modulates then, make solution II, wherein the mass concentration of sorbent material in solution II is 1-10%, continues to stir 10 minutes;
(3) solution II that obtains is under agitation slowly added the coagulant aids solution that mass concentration is 0.5-1.5%, continue to stir 3-5 minute, make solution III, wherein the concentration of coagulant aids in solution III is 200-1000mg/L;
(4) solution III that obtains is under agitation added the flocculant solution that mass concentration is 1-10%, continue to stir 1-3 minute, make solution IV, wherein the concentration of flocculation agent in solution IV such as polymerize aluminum chloride is 100-800mg/L;
(5) solution IV that obtains was left standstill 1-3 hour, abandoning supernatant is filtered the gained throw out and is recovery albumen just.
(6) will filter the gained throw out promptly reclaims albumen oven dry just, pulverizes.
The water treatment absorbent that adopts is Powdered calcium-base bentonite and diatomite isoreactivity clay mineral.
The water treatment coagulant aids that adopts is a chitosan.
The water treatment flocculant that adopts is polyaluminium sulfate, polymerize aluminum chloride, PAFS etc.
A kind of application of the inventive method is also disclosed in addition: reclaim the high protein throw out mainly as all kinds of fodder additivess that increase animal proteinum and trace element.
Advantage of the present invention is: 1. adopt the feed grade wilkinite as the protein in the sorbent material reclaim(ed) sulfuric acid chrondroitin factory effluent, therefore, the trophic structure that regenerant is formed is reasonable, is suitable for using as fodder additives; 2. adopt Nantural non-toxic polymeric flocculant chitosan that the protein recovery of waste water is had good treatment effect, and reclaim wilkinite in the first albumen, chitosan etc. and have the animal of promotion stomach and absorb and certain immune function; 3. the waste water behind the recovery protein can make chemical oxygen demand (COD) (COD) value descend more than 90%, very easily adopts the conventional activated sludge method that follow-up low concentration wastewater is handled.4. treatment process is simple, and cost of investment is cheap, and economic benefit and environmental benefit are obvious.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Embodiment 1
(1) gets a certain amount of chondroitin sulfate factory effluent, waste water ph is transferred to 3.5, make solution I with dilute hydrochloric acid;
(2) with a certain amount of Powdered calcium-base bentonite and diatomite isoreactivity clay mineral warm water furnishing pasty state, slowly add the above-mentioned solution I that modulates then, make solution II, wherein the mass concentration of active clay mineral in solution II is 1%, continues to stir about 10 minutes with certain speed;
(3) solution II that obtains under agitation slowly being added mass concentration is 0.5% chitosan solution, continues to stir 3-5 minute with certain speed, makes solution III, and wherein the concentration of chitosan in solution III is 200mg/L;
(4) solution III that obtains under agitation slowly being added mass concentration is 1% polymerize aluminum chloride, continues to stir 1-3 minute with certain speed, makes solution IV, and wherein the concentration of polymerize aluminum chloride in solution IV is 100mg/L;
(5) solution IV that obtains was left standstill 1-3 hour, abandoning supernatant is filtered the gained throw out and is recovery albumen just;
(6) will filter the gained throw out promptly reclaims albumen oven dry just, pulverizes.
Embodiment 2
The difference of present embodiment and embodiment 1 only is: pH value in the step (1) is transferred to 9.5; With the mass concentration of active clay mineral in solution in the step (2) is 10%; The adding mass concentration is 1.5% chitosan solution in step (3), and the concentration of chitosan in solution III is 1000mg/L; Adding mass concentration in step (4) is 10% polymerization alum liquor, and the concentration of polyaluminium sulfate in solution IV is 800mg/L.
Embodiment 3
The difference of present embodiment and embodiment 1 only is: pH value in the step (1) is transferred to 6; With the mass concentration of active clay mineral in solution in the step (2) is 5%; The adding mass concentration is 1% chitosan solution in step (3), and the concentration of chitosan in solution III is 600mg/L; Adding mass concentration in step (4) is 5% polyaluminium sulfate ferrous solution, and the concentration of PAFS in solution IV is 450mg/L.
With Yantai, Shandong chondroitin sulfate manufacturing enterprise is example: raw materials for production are the chicken cartilage, the turnout of its chondroitin sulfate is the 300-500 kg/day, the waste water generation is 3-8 ton/sky, the COD value 120000mg/L of waste water wherein, TOC value 84000mg/L, protein content 3-18% in the waste water, the wastewater treatment mode is discharged into local sewage work after adopting the water coolant dilution, after this enterprise adopts the inventive method, the COD value of waste water is reduced to 4000mg/L, TOC value 1100mg/L reclaims first albumen and accounts for 39% of dried kind of the total amount of throw out, has obtained satisfied effect.
With Weihai chondroitin sulfate manufacturing enterprise is example: raw materials for production are self-conceit pipe, the turnout of its chondroitin sulfate is the 80-120 kg/day, the waste water generation is 3-8 ton/sky, the COD value 100000mg/L of waste water wherein, TOC value 81000mg/L, protein content 2-10% in the waste water, the wastewater treatment mode is discharged into local sewage work after adopting the water coolant dilution, after this enterprise has adopted the present invention, the COD value of waste water is reduced to 300mg/L, TOC value 800mg/L reclaims first albumen and accounts for 27% of dried kind of the total amount of throw out, has obtained satisfied effect.
Claims (2)
1. the method for wastewater treatment and protein recovery is characterized in that comprising the steps:
(1) with dilute hydrochloric acid chondroitin sulfate factory effluent pH value is transferred to 3.5-9.5, make solution I; (2) with sorbent material water furnishing pasty state, add the above-mentioned solution I that modulates then, make solution II, wherein the mass concentration of sorbent material in solution II is 1-10%, continues to stir 10 minutes;
(3) solution II that obtains is under agitation added the coagulant aids solution that mass concentration is 0.5-1.5%, continue to stir 3-5 minute, make solution III, wherein the concentration of coagulant aids in solution III is 200-1000mg/L;
(4) solution III that obtains is under agitation slowly added the flocculant solution that mass concentration is 1-10%, continue to stir 1-3 minute, make solution IV, wherein the concentration of flocculant of polymeric aluminium chloride in solution IV is 100-800mg/L;
(5) solution IV that obtains was left standstill 1-3 hour, abandoning supernatant is filtered the gained throw out and is recovery albumen just;
(6) will filter the gained throw out promptly reclaims albumen oven dry just, pulverizes;
The water treatment absorbent that adopts is Powdered calcium-base bentonite and diatomite active clay mineral.
The water treatment coagulant aids that adopts is a chitosan.
The water treatment flocculant that adopts is polyaluminium sulfate, polymerize aluminum chloride, PAFS.
2. press the application of the method for described a kind of wastewater treatment of claim 1 and protein recovery, reclaim the high protein throw out as all kinds of fodder additivess that increase animal proteinum and trace element.
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| CN2008101383354A CN101624230B (en) | 2008-07-11 | 2008-07-11 | Method of processing waste water and recycling protein |
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| CN2008101383354A CN101624230B (en) | 2008-07-11 | 2008-07-11 | Method of processing waste water and recycling protein |
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| CN101624230B true CN101624230B (en) | 2011-06-15 |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101979634B (en) * | 2010-09-26 | 2012-10-03 | 许累峰 | Method for preparing fermentation nitrogen source from chondroitin sulfate production waste water |
| CN102382167B (en) * | 2011-11-01 | 2013-07-03 | 美泰科技(青岛)有限公司 | Method of recycling protein during production of chondroitin |
| CN102604837A (en) * | 2012-04-16 | 2012-07-25 | 盐城工学院 | Microalgae cell flocculating and harvesting technology |
| CN102774936B (en) * | 2012-05-10 | 2013-07-31 | 江南大学 | Sewage enzyme extraction facility |
| CN102690323A (en) * | 2012-06-14 | 2012-09-26 | 哈尔滨工业大学 | Method for recovering sludge through microwave |
| CN104903252B (en) * | 2013-04-18 | 2016-08-17 | 毛旭 | For processing the compositions of waste water |
| CN103627703B (en) * | 2013-12-19 | 2017-10-17 | 江西省科学院微生物研究所 | The synchronous Total DNA extraction method and kit for removing humic acid and mycoprotein |
| CN104799086A (en) * | 2015-04-24 | 2015-07-29 | 郭忠霖 | Marine product feed and processing technology thereof |
| CN106148242B (en) * | 2016-08-29 | 2019-04-05 | 香河县龙津生物工程有限责任公司 | A method of using chondroitin sulfate production Industry Waste bone mud as raw material solid fermenting and producing bacillus subtilis |
| CN106800584B (en) * | 2016-12-16 | 2019-10-25 | 浙江大学宁波理工学院 | The method of protein is recycled from Dai Yu Yu Porridge rinsing liquid |
| CN114956375A (en) * | 2022-05-12 | 2022-08-30 | 呼伦贝尔东北阜丰生物科技有限公司 | Secondary extraction process for protein in amino acid wastewater |
| CN115072942B (en) * | 2022-07-25 | 2023-01-17 | 威海蓝创环保设备有限公司 | Combined treatment process for aquatic product processing wastewater and domestic sewage |
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Denomination of invention: A method of wastewater treatment and protein recovery Effective date of registration: 20221230 Granted publication date: 20110615 Pledgee: Postal Savings Bank of China Limited Haiyang sub branch Pledgor: Yantai jinrunda animal nutrition Co.,Ltd. Registration number: Y2022980029775 |
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