CN107021580B - Method for recycling waste liquid generated after extracting tigogenin from sisal hemp - Google Patents
Method for recycling waste liquid generated after extracting tigogenin from sisal hemp Download PDFInfo
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- CN107021580B CN107021580B CN201710285154.3A CN201710285154A CN107021580B CN 107021580 B CN107021580 B CN 107021580B CN 201710285154 A CN201710285154 A CN 201710285154A CN 107021580 B CN107021580 B CN 107021580B
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- waste liquid
- tigogenin
- exchange resin
- anion exchange
- phosphate rock
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- 239000002699 waste material Substances 0.000 title claims abstract description 101
- 239000007788 liquid Substances 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 38
- GMBQZIIUCVWOCD-WWASVFFGSA-N Sarsapogenine Chemical compound O([C@@H]1[C@@H]([C@]2(CC[C@@H]3[C@@]4(C)CC[C@H](O)C[C@H]4CC[C@H]3[C@@H]2C1)C)[C@@H]1C)[C@]11CC[C@H](C)CO1 GMBQZIIUCVWOCD-WWASVFFGSA-N 0.000 title claims abstract description 33
- RTMWIZOXNKJHRE-UHFFFAOYSA-N Tigogenin Natural products CC1COC2CC(C)(OC12)C3CCC4C5CCC6CC(O)CCC6(C)C5CCC34C RTMWIZOXNKJHRE-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 244000198134 Agave sisalana Species 0.000 title claims abstract description 25
- 238000004064 recycling Methods 0.000 title claims abstract description 22
- 235000011624 Agave sisalana Nutrition 0.000 title claims description 17
- 238000001914 filtration Methods 0.000 claims abstract description 22
- 239000002244 precipitate Substances 0.000 claims abstract description 16
- 239000001397 quillaja saponaria molina bark Substances 0.000 claims abstract description 12
- 229930182490 saponin Natural products 0.000 claims abstract description 12
- 150000007949 saponins Chemical class 0.000 claims abstract description 12
- 239000002367 phosphate rock Substances 0.000 claims description 45
- 239000000843 powder Substances 0.000 claims description 37
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 239000003957 anion exchange resin Substances 0.000 claims description 28
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- -1 sulfate radical Chemical class 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 9
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 8
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 8
- 239000004571 lime Substances 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 7
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 6
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 5
- 230000008023 solidification Effects 0.000 claims description 5
- 239000003344 environmental pollutant Substances 0.000 claims description 4
- 239000008235 industrial water Substances 0.000 claims description 4
- 231100000719 pollutant Toxicity 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000010865 sewage Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 6
- 238000006386 neutralization reaction Methods 0.000 abstract description 5
- 239000002912 waste gas Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000013048 microbiological method Methods 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 description 13
- 239000002585 base Substances 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229940088597 hormone Drugs 0.000 description 3
- 239000005556 hormone Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 238000005842 biochemical reaction Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 241000108664 Nitrobacteria Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UREBDLICKHMUKA-DVTGEIKXSA-N betamethasone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@H](C)[C@@](C(=O)CO)(O)[C@@]1(C)C[C@@H]2O UREBDLICKHMUKA-DVTGEIKXSA-N 0.000 description 1
- 229960002537 betamethasone Drugs 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- WQLVFSAGQJTQCK-UHFFFAOYSA-N diosgenin Natural products CC1C(C2(CCC3C4(C)CCC(O)CC4=CCC3C2C2)C)C2OC11CCC(C)CO1 WQLVFSAGQJTQCK-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 239000003621 irrigation water Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- NWMIYTWHUDFRPL-UHFFFAOYSA-N sapogenin Natural products COC(=O)C1(CO)C(O)CCC2(C)C1CCC3(C)C2CC=C4C5C(C)(O)C(C)CCC5(CCC34C)C(=O)O NWMIYTWHUDFRPL-UHFFFAOYSA-N 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000003270 steroid hormone Substances 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002426 superphosphate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Removal Of Specific Substances (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a method for recycling waste liquid after extracting tigogenin from sisal, belonging to the technical field of sewage treatment in saponin industry. The method of the invention decomposes and filters harmful substances by combining chemical reaction and physical filtration, and realizes the purpose that precipitates, waste gas and waste liquid can be recycled. Compared with the traditional neutralization method and the microbiological method for treating the waste liquid generated in the production process of the tigogenin, the method has the characteristics of simple process, low cost, waste material recycling and no secondary pollution.
Description
Technical Field
The invention belongs to the technical field of saponin industrial sewage treatment, and particularly relates to a method for recycling waste liquid after extracting tigogenin from sisal.
Background
Tigogenin, english name: tigogenin, chinese alias: sisal sapogenin, also known as tikeginine, etc., is a basic raw material for synthesizing steroid hormone medicines, and the hormone is called 'medical gold' and 'mother of hormone'. Extracting tigogenin from sisal hemp, squeezing the sisal hemp residue after removing fiber, hydrolyzing sisal hemp juice with acid at a certain temperature and pressure, mixing the hydrolysate obtained after hydrolysis with lime, drying, extracting with ethanol under reflux, acidifying and decolorizing the extract, concentrating and crystallizing to obtain crude tigogenin, and recrystallizing the crude tigogenin to obtain the product. The downstream product monoene produced by utilizing the tigogenin can synthesize more than 120 hormone drugs such as betamethasone and the like. Tigogenin is also widely applied to industries such as food, cosmetics, animal husbandry and the like, is the most common and main basic raw material in the field of biological medicine and chemical industry, and belongs to a new medicine engineering technology which is supported and encouraged by the state.
However, during the extraction process of tigogenin, a large amount of waste water which is difficult to treat is generated, and the water resource protection is seriously threatened. The saponin production wastewater belongs to acid-containing high-concentration organic wastewater, and the following problems are generally existed: high COD concentration, high sugar content, high salt content, high acidity, high chloride ion content, high sulfate ion content, high chroma pollution and the like. If the wastewater in the sisal hemp saponin production process is not properly treated, the wastewater can bring serious pollution to the surrounding environment. Because tigogenin production enterprises are mostly distributed in remote areas close to raw material production places and water sources and far away from urban drainage pipe networks, if the tigogenin is directly discharged to water bodies without any treatment, the tigogenin can seriously pollute downstream rivers. A large amount of algae, sulfate reducing bacteria and the like are propagated, a large amount of stimulating gases such as SO2, H2S and the like are generated, dissolved oxygen in a water body is consumed, and the ecological environment of a river is changed; in addition, the discharge of a large amount of acidic substances in the wastewater can change the properties of surrounding water and soil, influence the growth of crops, destroy ecological balance and seriously influence the life of downstream residents.
At present, the waste liquid generated in the sisal hemp saponin industry in China is mainly treated in a harmless way by a neutralization method and a microbial decomposition method, and the effect is not satisfactory and is not enough. For example, Chinese patent "a method for treating industrial wastewater in the production process of tigogenin" (application No. CN201410260014.7, application date: 2014.06.12) discloses a method for treating industrial wastewater in the production process of tigogenin, which comprises the following steps: feeding the wastewater in the sisal hemp saponin production process into an alkali pretreatment tank, adjusting the pH value to an alkaline range, filtering, and separating into filter residue and filtrate sewage; mixing the filtrate and the sewage with domestic sewage, sending the mixture into a neutralization blending tank, measuring the COD content, adding N, P components according to the COD content, carrying out aeration stirring for more than 10 minutes, sending the mixture into a primary sedimentation tank for primary sedimentation, then sending the mixture into a biochemical tank for biochemical reaction, sending the sewage after the biochemical reaction into a secondary sedimentation tank for secondary sedimentation, separating supernatant liquid for discharge after the detection reaches the standard, and sending sludge at the bottom of the tank back to the biochemical tank for recycling. The strain added into the biochemical tank is a mixture of more than two of gram-negative bacillus-free, nitrobacteria, denitrifying bacteria, phosphorus-accumulating bacteria, filamentous bacteria and facultative heterotrophic bacteria, and the wastewater after the bacteria biochemical treatment enters a secondary sedimentation tank for sedimentation and is discharged after being detected to be qualified. Although the discharged wastewater meets the discharge standard of the emission standard of pollutants for water in saponin industry (GB 20425-2006), the residual amount of bacterial colonies in the water body is large, and the balance of a microbial ecosystem of the water body is easily destroyed after the discharged wastewater is discharged, so that the living environment of animals and plants is influenced.
Disclosure of Invention
The present invention aims to provide a method for recycling waste liquid after extracting tigogenin from sisal hemp, aiming at the defects of the prior art. According to the method for recycling the waste liquid after extracting the tigogenin from the sisal, the harmful substances are decomposed and filtered in a mode of combining chemical reaction and physical filtration, and the purpose that precipitates, waste gas and waste liquid can be recycled is achieved. Compared with the traditional neutralization method and the microbiological method for treating the waste liquid generated in the production process of the tigogenin, the method has the characteristics of simple process, low cost, waste material recycling and no secondary pollution.
In order to solve the technical problems, the invention adopts the technical scheme that:
a method for recycling waste liquid after extracting tigogenin from sisal hemp comprises the following steps:
a. measuring the ion content of sulfate radical, oxalate radical and chloride ion in the waste liquid;
b. adding phosphate rock powder into the waste liquid, wherein the equivalent ratio of the added phosphate rock powder to sulfate radical is 1 (1-3.5), uniformly stirring, wherein the phosphate rock powder and the sulfate radical react to generate calcium superphosphate crystals and calcium sulfate and release hydrogen fluoride gas, the hydrogen fluoride gas reacts with silicon dioxide and silicate in the phosphate rock powder to generate silicon tetrafluoride, collecting escaping gas and introducing the escaping gas into a water washing tower to obtain a fluosilicic acid solution, the calcium sulfate reacts with oxalic acid in the waste liquid to generate calcium oxalate precipitates and sulfuric acid, the sulfuric acid circularly reacts with the phosphate rock powder, standing for 2-5d for solidification, and passing through a 200-mesh and 300-mesh screen to obtain precipitates;
c. adding anion exchange resin into the waste liquid filtered in the step b, wherein the equivalent ratio of the added anion exchange resin to chloride ion is (1-3):1, stirring for 1-1.5h, passing through a 100-mesh 200-mesh screen, and filtering out the anion exchange resin;
d. c, introducing ozone into the waste liquid filtered in the step c, stirring, and standing for 3-5 hours;
e. and d, filtering the waste liquid after standing in the step d by using activated carbon, and obtaining the dischargeable waste liquid meeting the comprehensive sewage discharge standard after the detection is qualified. And if the detection is not qualified, returning to the step a to restart the processing.
Further, the granularity of the powdered rock phosphate in the step b is 100-200 meshes, and the grade of the powdered rock phosphate is more than 31 percent of P2O5。
Further, the mass fraction of the solute of the fluorosilicic acid solution obtained in the step b is 25-30%.
Preferably, for better removal of chloride ions from the waste liquid, the anion exchange resin in step c is a strongly basic anion exchange resin, and the anion exchange resin is pre-expanded by soaking in 15% saline before use.
Further, the ratio of the volume of the ozone introduced into the waste liquid in the step d to the volume of the waste liquid is (1-3): 1.
preferably, in order to make the pH value more alkaline, lime powder is added before the activated carbon is used for filtering in the step e, the mixture is stirred uniformly, the pH value is adjusted to 7.5-8.0, the mixture is kept still for 1-2d and is filtered by a 200-mesh and 300-mesh screen, and the filtered supernatant is filtered by the activated carbon.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. according to the method for recycling the waste liquid after extracting the tigogenin from the sisal, the concept of recycling the waste liquid is adopted, and the acid and the salt in the waste liquid are effectively separated through the reaction with the ground phosphate rock, the anion exchange resin, the ozone and the lime powder, so that the pH value and the chromaticity of water quality are improved, and the dissolved oxygen amount of a water body is increased. Finally, the contents of suspended substances, metal ions and chromaticity in the waste liquid are reduced again through the adsorption of the active carbon, and the dischargeable waste liquid meeting the discharge standard of the saponin industrial water pollutants is obtained. Wherein the ground phosphate rock reacts with sulfuric acid in the waste liquid to generate superphosphate and hydrogen fluoride gas which can be prepared into phosphate fertilizer, the hydrogen fluoride gas reacts with silicon dioxide and silicate in the ground phosphate rock to generate silicon tetrafluoride, and the silicon tetrafluoride is hydrolyzed by a water washing tower to obtain recyclable fluosilicic acid with solute mass fraction of 25-30%. Oxalic acid existing in the water body indirectly reacts with calcium sulfate, and recyclable calcium oxalate is separated out, so that the total recycling rate of sulfuric acid and oxalic acid in the waste liquid is up to 97%. The rest of the phosphate rock powder and the calcium sulfate can be filtered out by a screen, so that the added phosphate rock powder has no secondary pollution; the anion exchange resin can effectively remove residual sulfate ions, nitrate ions, chloride ions, carbonate ions and the like in the waste liquid, the contents of acid and salt in the water body are obviously reduced, and the anion exchange resin can be recycled without secondary pollution; ozone is introduced into the waste liquid and continuously stirred, so that not only can sterilization, decoloration and deodorization be realized, but also the oxygen content and the PH value of the water body can be improved; the lime powder is added, so that not only can organic matters in the water body be precipitated and bubbles on the water surface be reduced, but also the PH value of the waste liquid can be adjusted and controlled; finally, the invention uses the active carbon to filter the waste liquid, can further reduce the metal ions in the water body, and can also play roles of filtering, decoloring and the like. Although the waste liquid treated by the method meets the discharge standard of saponin industrial water pollutants (GB 20425-2006), the waste liquid retains higher sugar content and can realize higher value when being used as irrigation water of crops, so that the practically dischargeable waste water is relatively less, and the discharged waste liquid can play a role in increasing the weight of aquatic plants. After precipitation, waste gas recovery, acid-base regulation, filtration and purification by the method, the method realizes that precipitates, waste gas and waste liquid can be recycled, and has the effects of saving energy, reducing emission, changing waste into valuable and harmless purification.
2. According to the method for recycling the waste liquid after extracting the tigogenin from the sisal, the harmful substances are decomposed and filtered in a mode of combining chemical reaction and physical filtration, and the purpose that precipitates, waste gas and waste liquid can be recycled is achieved. Compared with the traditional neutralization method and the microbiological method for treating the waste liquid generated in the production process of the tigogenin, the method has the characteristics of simple process, low cost, waste material recycling and no secondary pollution.
Detailed Description
A method for recycling waste liquid after extracting tigogenin from sisal hemp is characterized by comprising the following steps:
a. measuring the ion content of sulfate radical, oxalate radical and chloride ion in the waste liquid;
b. adding phosphate rock powder into the waste liquid, wherein the equivalent ratio of the added phosphate rock powder to sulfate radical is 1 (1-3.5), uniformly stirring, wherein phosphate rock and sulfate radical react to generate calcium superphosphate crystals and calcium sulfate and release hydrogen fluoride gas, the hydrogen fluoride gas reacts with silicon dioxide and silicate in the phosphate rock powder to generate silicon tetrafluoride, collecting escaping gas and introducing the escaping gas into a water washing tower to obtain a fluosilicic acid solution, the calcium sulfate reacts with oxalic acid in the waste liquid to generate calcium oxalate precipitates and sulfuric acid, the sulfuric acid circularly reacts with the phosphate rock powder, standing for 2-5d for solidification, and passing through a 200-mesh and 300-mesh screen to obtain precipitates;
c. adding anion exchange resin into the waste liquid filtered in the step b, wherein the equivalent ratio of the added anion exchange resin to chloride ion is (1-3):1, stirring for 1-1.5h, passing through a 100-mesh 200-mesh screen, and filtering out the anion exchange resin;
d. c, introducing ozone into the waste liquid filtered in the step c, stirring, and standing for 3-5 hours;
e. and d, filtering the waste liquid after standing in the step d by using activated carbon, and obtaining the dischargeable waste liquid meeting the comprehensive sewage discharge standard after the detection is qualified. And if the detection is not qualified, returning to the step a to restart the processing.
In order to improve the utilization rate of the powdered rock phosphate and shorten the reaction time, the particle size of the powdered rock phosphate in the step b is 100-200 meshes, and the taste of the powdered rock phosphate is 31 percent P2O5。
In order to facilitate storage and transportation of the fluorosilicic acid solution, the mass fraction of the solute of the fluorosilicic acid solution obtained in the step b is 25-30%.
In order to increase the exchange efficiency of the anions, the anion exchange resin in step c is a strongly basic anion exchange resin.
In order to improve the decoloring, deodorizing and sterilizing capability, the ratio of the volume of the ozone introduced into the waste liquid in the step d to the volume of the waste liquid is (1-3): 1.
in order to increase the pH value of the wastewater, adding lime powder before filtering with active carbon in the step e, uniformly stirring, adjusting the pH value to 7.5-8.0, standing and precipitating for 1-2d, sieving with a 200-mesh and 300-mesh sieve, and filtering the filtered supernatant with active carbon.
Example 1
The method for recycling the waste liquid after extracting the tigogenin from the sisal hemp is characterized by comprising the following steps:
a. measuring the ion content of sulfate radical, oxalate radical and chloride ion in the waste liquid;
b. adding phosphate rock powder with the granularity of 200 meshes into the waste liquid, wherein the grade of the phosphate rock powder is 31 percent of P2O5The equivalent ratio of the added phosphate rock powder to the sulfate radical is 1:1, and the mixture is stirred uniformly, wherein the phosphate rock powder and the sulfate radicalReacting to generate calcium superphosphate crystals and calcium sulfate and releasing hydrogen fluoride gas, reacting the hydrogen fluoride gas with silicon dioxide and silicate in the powdered rock phosphate to generate silicon tetrafluoride, collecting the escaping gas and introducing the gas into a water washing tower to obtain a fluosilicic acid solution with the solute mass fraction of 25%, reacting the calcium sulfate with oxalic acid in waste liquid to generate calcium oxalate precipitates and sulfuric acid, circularly reacting the sulfuric acid with the powdered rock phosphate, standing for 5 days for solidification, and sieving with a 200-mesh sieve to obtain precipitates;
c. adding anion exchange resin into the waste liquid filtered in the step b, wherein the equivalent ratio of the added anion exchange resin to chloride ions is 3:1, stirring for 1h, sieving by a 200-mesh sieve, and filtering out the anion exchange resin;
d. and c, introducing ozone into the waste liquid filtered in the step c and stirring, wherein the ratio of the volume of the ozone introduced into the waste liquid to the volume of the waste liquid is 3:1, standing for 3 hours;
e. and d, filtering the waste liquid after standing in the step d by using activated carbon, and detecting to be qualified to obtain the dischargeable waste liquid meeting the comprehensive sewage discharge standard.
Example 2
The method for recycling the waste liquid after extracting the tigogenin from the sisal hemp is characterized by comprising the following steps:
a. measuring the ion content of sulfate radical, oxalate radical and chloride ion in the waste liquid;
b. adding phosphate rock powder with the granularity of 100 meshes into the waste liquid, wherein the grade of the phosphate rock powder is 33 percent of P2O5Adding phosphate rock powder and sulfate radical with the equivalent ratio of 1:3.5, uniformly stirring, wherein the phosphate rock powder and the sulfate radical react to generate calcium superphosphate crystals and calcium sulfate and release hydrogen fluoride gas, the hydrogen fluoride gas reacts with silicon dioxide and silicate in the phosphate rock powder to generate silicon tetrafluoride, collecting escaping gas and introducing the gas into a water washing tower to obtain a fluorosilicic acid solution with the solute mass fraction of 30%, the calcium sulfate reacts with oxalic acid in waste liquid to generate calcium oxalate precipitates and sulfuric acid, the sulfuric acid circularly reacts with the phosphate rock powder, standing for 2d for curing, and screening by a 300-mesh screen to obtain precipitates;
c. b, adding strong-base anion exchange resin into the waste liquid filtered in the step b, wherein the equivalent ratio of the added strong-base anion exchange resin to chloride ions is 1:1, stirring for 1.5h, sieving by using a 100-mesh sieve, and filtering out the strong-base anion exchange resin;
d. and c, introducing ozone into the waste liquid filtered in the step c and stirring, wherein the ratio of the volume of the ozone introduced into the waste liquid to the volume of the waste liquid is 1:1, standing for 5 hours;
e. and d, adding lime powder into the waste liquid after standing in the step d, uniformly stirring, adjusting the pH value to 8.0, standing and precipitating for 2d, sieving by using a 200-mesh sieve, filtering the filtered supernatant by using active carbon, and detecting to be qualified to obtain the dischargeable waste liquid meeting the comprehensive sewage discharge standard.
Example 3
The method for recycling the waste liquid after extracting the tigogenin from the sisal hemp is characterized by comprising the following steps:
a. measuring the ion content of sulfate radical, oxalate radical and chloride ion in the waste liquid;
b. adding powdered rock phosphate with the granularity of 150 meshes into the waste liquid, wherein the taste of the powdered rock phosphate is 35 percent of P2O5Adding phosphate rock powder and sulfate radical with the equivalent ratio of 1:2, uniformly stirring, wherein the phosphate rock powder and the sulfate radical react to generate calcium superphosphate crystals and calcium sulfate and release hydrogen fluoride gas, the hydrogen fluoride gas reacts with silicon dioxide and silicate in the phosphate rock powder to generate silicon tetrafluoride, collecting escaping gas and introducing the escaping gas into a water washing tower to obtain a fluosilicic acid solution with the solute mass fraction of 25%, the calcium sulfate reacts with oxalic acid in waste liquid to generate calcium oxalate precipitates and sulfuric acid, the sulfuric acid circularly reacts with the phosphate rock powder, standing for 4d for solidification, and screening through a 260-mesh screen to obtain precipitates;
c. b, adding strong-base anion exchange resin into the waste liquid filtered in the step b, wherein the equivalent ratio of the added strong-base anion exchange resin to chloride ions is 2:1, stirring for 1.5h, sieving by a 150-mesh sieve, and filtering out the strong-base anion exchange resin;
d. and c, introducing ozone into the waste liquid filtered in the step c and stirring, wherein the ratio of the volume of the ozone introduced into the waste liquid to the volume of the waste liquid is 2:1, standing for 4 hours;
e. and d, adding lime powder into the waste liquid after standing in the step d, uniformly stirring, adjusting the pH value to 7.5, standing and precipitating for 1d, sieving by using a 300-mesh sieve, filtering the filtered supernatant by using active carbon, and detecting to be qualified to obtain the dischargeable waste liquid meeting the comprehensive sewage discharge standard.
Test data
The waste liquid after extracting tigogenin from sisal is treated according to the methods of the 3 examples. The waste liquid used in the method is collected into 400L after being uniformly stirred in a collecting pool of the waste liquid generated in a sisal saponin production line of a certain company of Guangxi Nanning, and the collected waste liquid is divided into four parts (a control group, an example group 1, an example group 2 and an example group 3), wherein the example groups are purified by the methods of the example group 3. The test results were shown in the following table, using the test method required in the emission Standard of contaminants of Saponin Industrial Water (GB 20425-2006):
as can be seen from the above table, the waste liquid treated by the method of the embodiment of the invention completely meets the sewage discharge requirement of the industry, and the method for recycling the waste liquid after extracting the tigogenin from the sisal hemp has obvious effect. The wastewater of 3 example groups can be directly used for plant irrigation, and the actual water discharge amount is about 35% of the total sewage amount after the test of the company for several months, so the water discharge amount of the example groups is recorded as 35 in the table.
Claims (3)
1. A method for recycling waste liquid after extracting tigogenin from sisal hemp is characterized by comprising the following steps:
a. measuring the ion content of sulfate radical, oxalate radical and chloride ion in the waste liquid;
b. adding phosphate rock powder into the waste liquid, wherein the equivalent ratio of the added phosphate rock powder to sulfate radical is 1 (1-3.5), uniformly stirring, wherein the phosphate rock powder and the sulfate radical react to generate calcium superphosphate crystals and calcium sulfate and generate hydrogen fluoride gas, the hydrogen fluoride gas reacts with silicon dioxide and silicate in the phosphate rock powder to generate silicon tetrafluoride, collecting escaping gas and introducing the escaping gas into a water washing tower to obtain a fluosilicic acid solution, the calcium sulfate reacts with oxalic acid in the waste liquid to generate calcium oxalate precipitates and sulfuric acid, the sulfuric acid circularly reacts with the phosphate rock powder, standing for 2-5d for solidification, and passing through a 200-mesh and 300-mesh screen to obtain precipitates;
c. adding anion exchange resin into the waste liquid filtered in the step b, wherein the equivalent ratio of the added anion exchange resin to chloride ion is (1-3):1, stirring for 1-1.5h, passing through a 100-mesh 200-mesh screen, and filtering out the anion exchange resin;
d. c, introducing ozone into the waste liquid filtered in the step c, stirring, and standing for 3-5 hours;
e. d, filtering the waste liquid after standing in the step d by using activated carbon, and obtaining dischargeable waste liquid meeting the discharge standard of the saponin industrial water pollutants after the detection is qualified;
the granularity of the powdered rock phosphate in the step b is 100-200 meshes, and the grade of the powdered rock phosphate is more than 31 percent of P2O5；
The mass fraction of the solute of the fluorosilicic acid solution obtained in the step b is 25-30%;
the anion exchange resin in the above step c is a strongly basic anion exchange resin.
2. The method for recycling the waste liquid after extracting the tigogenin from the sisal hemp according to claim 1, wherein the ratio of the volume of the ozone introduced into the waste liquid in the step d to the volume of the waste liquid is (1-3): 1.
3. the method as claimed in claim 1, wherein the lime powder is added before the activated carbon is used for filtration in step e, the mixture is stirred uniformly, the pH value is adjusted to 7.5-8.0, the mixture is left for 1-2 days for precipitation, the obtained product is screened by a 200-mesh and 300-mesh screen, and the obtained supernatant is filtered by the activated carbon.
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| CN1461742A (en) * | 2002-05-27 | 2003-12-17 | 马最瑶 | Process for treating waste water and dregs of yam saponin industry |
| CN1488581A (en) * | 2003-08-14 | 2004-04-14 | 华中师范大学 | Yellow giner saponin industrial sewage treating method and comprehensive utilization |
| CN1792894A (en) * | 2005-11-17 | 2006-06-28 | 中国地质大学（武汉） | Process for treating yellow ginger saponin waste water by hydrochloric acid method |
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| CN101134625A (en) * | 2006-03-03 | 2008-03-05 | 倪文斌 | Method for wastewater comprehensive utilization of saponin production |
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| CN1461742A (en) * | 2002-05-27 | 2003-12-17 | 马最瑶 | Process for treating waste water and dregs of yam saponin industry |
| CN1488581A (en) * | 2003-08-14 | 2004-04-14 | 华中师范大学 | Yellow giner saponin industrial sewage treating method and comprehensive utilization |
| CN1792894A (en) * | 2005-11-17 | 2006-06-28 | 中国地质大学（武汉） | Process for treating yellow ginger saponin waste water by hydrochloric acid method |
| CN1814546A (en) * | 2006-03-03 | 2006-08-09 | 倪文斌 | Method for producing general superphosphate from waste water of yellow ginger processing by dry method |
| CN101134625A (en) * | 2006-03-03 | 2008-03-05 | 倪文斌 | Method for wastewater comprehensive utilization of saponin production |
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Denomination of invention: A method of reusing the waste liquid after extracting sisal saponin from sisal Effective date of registration: 20221117 Granted publication date: 20200825 Pledgee: Zhejiang Wenling Rural Commercial Bank Co.,Ltd. Pledgor: Wenling Qiliang Shoes Co.,Ltd. Registration number: Y2022980022273 |