CN107445414A - A kind of process for cleanly preparing of gallic acid - Google Patents
A kind of process for cleanly preparing of gallic acid Download PDFInfo
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- CN107445414A CN107445414A CN201710883573.7A CN201710883573A CN107445414A CN 107445414 A CN107445414 A CN 107445414A CN 201710883573 A CN201710883573 A CN 201710883573A CN 107445414 A CN107445414 A CN 107445414A
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- Prior art keywords
- gallic acid
- extracting agent
- agent
- production
- solid extracting
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- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 title claims abstract description 277
- 235000004515 gallic acid Nutrition 0.000 title claims abstract description 138
- 229940074391 gallic acid Drugs 0.000 title claims abstract description 137
- 238000000034 method Methods 0.000 title claims abstract description 74
- 230000008569 process Effects 0.000 title claims abstract description 55
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 70
- 239000007787 solid Substances 0.000 claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 claims abstract description 53
- 239000002351 wastewater Substances 0.000 claims abstract description 51
- 238000000605 extraction Methods 0.000 claims abstract description 43
- 238000012545 processing Methods 0.000 claims abstract description 32
- 230000007613 environmental effect Effects 0.000 claims abstract description 9
- 230000008929 regeneration Effects 0.000 claims abstract description 8
- 238000011069 regeneration method Methods 0.000 claims abstract description 8
- 239000010808 liquid waste Substances 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 62
- 239000007788 liquid Substances 0.000 claims description 49
- 239000002699 waste material Substances 0.000 claims description 42
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 36
- 239000001263 FEMA 3042 Substances 0.000 claims description 36
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 36
- 235000015523 tannic acid Nutrition 0.000 claims description 36
- 229940033123 tannic acid Drugs 0.000 claims description 36
- 229920002258 tannic acid Polymers 0.000 claims description 36
- LRBQNJMCXXYXIU-QWKBTXIPSA-N gallotannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@H]2[C@@H]([C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-QWKBTXIPSA-N 0.000 claims description 30
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 230000018044 dehydration Effects 0.000 claims description 10
- 238000006297 dehydration reaction Methods 0.000 claims description 10
- 238000005345 coagulation Methods 0.000 claims description 8
- 230000015271 coagulation Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000005516 engineering process Methods 0.000 claims description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims description 7
- 230000000813 microbial effect Effects 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 238000004062 sedimentation Methods 0.000 claims description 7
- 238000011001 backwashing Methods 0.000 claims description 6
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims description 6
- 230000020477 pH reduction Effects 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000003223 protective agent Substances 0.000 claims description 3
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 3
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 101100412856 Mus musculus Rhod gene Proteins 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 2
- 238000001816 cooling Methods 0.000 claims 1
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 4
- 238000012824 chemical production Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 235000011121 sodium hydroxide Nutrition 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 239000002253 acid Substances 0.000 description 16
- 239000012043 crude product Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- FZHLWVUAICIIPW-UHFFFAOYSA-M sodium gallate Chemical compound [Na+].OC1=CC(C([O-])=O)=CC(O)=C1O FZHLWVUAICIIPW-UHFFFAOYSA-M 0.000 description 13
- 235000014220 Rhus chinensis Nutrition 0.000 description 12
- 240000003152 Rhus chinensis Species 0.000 description 12
- 238000005189 flocculation Methods 0.000 description 12
- 230000016615 flocculation Effects 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 11
- 229940083542 sodium Drugs 0.000 description 10
- 235000015424 sodium Nutrition 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- 235000017399 Caesalpinia tinctoria Nutrition 0.000 description 8
- 241000388430 Tara Species 0.000 description 8
- 238000011049 filling Methods 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 230000006872 improvement Effects 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- -1 cleanser Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004061 bleaching Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 230000008676 import Effects 0.000 description 4
- 150000007530 organic bases Chemical class 0.000 description 4
- 238000003672 processing method Methods 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- 229920001864 tannin Polymers 0.000 description 4
- 239000001648 tannin Substances 0.000 description 4
- 235000018553 tannin Nutrition 0.000 description 4
- 238000009413 insulation Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 229940001482 sodium sulfite Drugs 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000002019 anti-mutation Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical class Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000004190 ion pair chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006198 methoxylation reaction Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical class OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- 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
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5281—Installations for water purification using chemical agents
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
Abstract
The invention belongs to chemical production field, discloses a kind of process for cleanly preparing of gallic acid.The technique includes alkaline process and produces and produce liquid waste processing step, the production liquid waste processing step includes SPE, back extraction regeneration, waste water subsequent processing steps, SPE step is to carry out extracting and enriching to the production waste water using solid extracting agent, and solid extracting agent is containing benzene ring structure monomer, with basic group high molecular polymer.Waste water can qualified discharge after subsequent processing steps, the process is overcome in prior art processing procedure using organic reagent as the defects of the secondary pollution that extractant is brought, on the one hand gallic acid is made to obtain high efficiente callback, on the other hand production discharged wastewater met the national standard is made, so as to realize the unification of environmental benefit, Social benefit and economic benefit.
Description
Technical field
The present invention relates to a kind of process for cleanly preparing of gallic acid, and in particular to one kind effectively removes and reclaims nutgall
Acid and tannic acid, realize the process for cleanly preparing of waste water reclaiming processing.
Background technology
Gallic acid also known as gallic acid, gallic acid, its chemical name are Gallic Acid, are white or micro- white
Color crystal, there are two kinds of needle-like and sheet.Gallic acid is a kind of widely used industrial chemicals, can be used as food oxydating resistance
Agent, colouring agent, cleanser, preservative etc., and with various biological effects such as antitumor, anti-inflammatory, anti-mutation.Gallic acid
Deep processed product has methoxylation derivative of pyrogallic acid, gallate ester compound, gallic acid etc., at present state
Interior product is used for exporting, and surcharge is high.
However, 4~5 tons of gallic acid waste liquids can typically be produced by often producing 1 ton of gallic acid.Typically contain 90 in waste liquid~
150g/L sodium chloride, 15~20g/L gallic acid, 2~8g/L tannic acid and a large amount of pigments, if these waste liquids are straight
Outer row is met, substantial amounts of gallic acid (often producing 1 ton of gallic acid product about 80 kilograms of gallic acids of outer row's loss) can be lost.Together
Although when due to gallic acid itself it is minimum to the toxicity of human body, halogenated hydrocarbons can be produced during drinking water disinfection by chlorine
Class material, human body is acted on " teratogenesis, carcinogenic, mutagenesis ", belongs to drinking water safety control object.And due to gallic acid
There is sterilization, suppress growth of microorganism, Biochemical method process can be produced serious influence, conventional bioanalysis can not
It is directly used in the processing of gallic acid production wastewater.Therefore, efficient gallic acid cleaning manufacturing technique method is developed, is advantageous to
The utilization rate of resource is improved, while realizes the qualified discharge processing of production waste water, there is good economy and environmental benefit.
Directly there are acid system, alkaline process and enzyme process by Chinese gall or the method for producing gallic acid by nutgall tannin at present, its
The technique of middle acid system and alkaline process production gallic acid is relatively simple, and investment is relatively low.But acid system and alkaline process can produce largely
Waste liquid, COD and BOD values are higher, and colourity is higher, less to the report of gallic acid process for cleanly preparing both at home and abroad at present.
The production of gallic acid alkaline process, by basic hydrolysis, acidifying, decolouring, filtering, obtains gallic acid mainly by raw materials for production
Crude product, then the process by crude product refining, through retrieval, prior art also discloses that the technical scheme of alkaline process clean manufacturing, such as China
Patent No. CN201210346668.2, this application case disclose a kind of gallic acid clean preparation method, and its processing step is as follows：
1) gallic acid produces.Chinese gall is crushed, puts into reaction cylinder, through alkaline hydrolysis, acidifying, decolouring, filtering, secondary decolourization is tied again
Brilliant, filtering, dry, obtain gallic acid finished product；2) processing of gallic acid production waste liquid.Waste liquid caused by gallic acid is imported
Waste liquid regulating reservoir, using N-503 espeletons solution as extractant, carry out the gallic acid in three-level counter-current extraction waste liquid, extraction
It is stripped after complete with excessive NaOH solution, gallic acid production stage, while regenerating extracting agent, extraction is returned after generating sodium gallate
Waste liquid after taking merge with other sanitary wastewaters after again by subsequent treatment, finally make waste liquid qualified discharge.This method is using multiple
Close organic solvent to reclaim the gallic acid in gallic acid production wastewater as extractant, achieve preferable effect.
But there is the defects of inevitable in this application case：1) methyl butyl ketone is easily lost in waste water and causes secondary pollution, so as to
Add the difficulty that waste water is subsequently administered；2) methyl butyl ketone is higher as extractant price, and its loss in waste water enters one
Step adds cost for wastewater treatment；3) row up to standard can be realized by producing water outlet of the waste liquid after biochemical treatment and needing to add hydrogen peroxide
Put；4) it is stripped in regenerated liquid due to containing a large amount of organic reagents, being not suitable for being directly used in production stage.
《Study on extracting gallic acid by butanol》Document in, it uses butanol as extractant, achieves preferably extraction effect
Fruit, the cost of butanol is more cheap, and the program reduces input cost to a certain extent, but the technical scheme does not have still
Solve the problems, such as that extractant is lost in and causes water environment secondary pollution.
Therefore, extracting way choice turns into the emphasis of research, and SPE is to utilize solid absorbent by fluid sample
In target compound absorption, then eluted with eluent, reach the purpose of separation and enrichment target compound, it is as sample
Product pretreatment technology, more and more extensive application has been obtained in the lab, if being substituted using suitable solid extracting agent is had
Machine reagent, it will the secondary pollution for avoiding organic reagent from being brought in processing procedure.
Through retrieval, prior art has issued for the technical scheme handled using solid phase extraction techniques organic acid,
Such as China Patent No. CN201510315751.7, this application case discloses a kind of highly polar organic acids and base mixture while extraction point
From analysis method, it carries the ODS solid-phase extraction columns of surfactant dynamic modification to the Organic Acid and Base in analyte simultaneously
Take, recycle ion pair chromatography to be analyzed, there is electrostatic and dredge using the ODS solid-phase extraction columns after surfactant-modified
The characteristics of water acts on, carries out suction-operated to Organic Acid and Base, however this method need by ODS post modification procedures, operate compared with
For trouble, and organic acids and base is adsorbed, it is necessary to which coupled ion reaches further to chromatographic technique simultaneously in SPE step
The purpose of separation, processing for gallic acid in gallic acid production wastewater do not apply to simultaneously.
Therefore, need a kind of new extraction mode of exploitation badly, gallic acid is obtained high efficiente callback, on the other hand make
Discharged wastewater met the national standard is produced, so as to realize the unification of environmental benefit, Social benefit and economic benefit.
The content of the invention
1. invention technical problems to be solved
In the clean manufacturing handling process of prior art gallic acid, the defects of generally presence：Produce liquid waste processing mistake
The extractant of gallic acid is usually organic solvent in journey, and price is higher, and organic solvent, which is lost in into waste water, causes secondary pollution,
Increase difficulty of governance.
This patent aims to provide a kind of new gallic acid clean manufacturing handling process, effectively removes and reclaims in waste water
Gallic acid and tannic acid, realize the recycling treatment of waste water.
2. technical scheme：
To reach above-mentioned purpose, technical scheme provided by the invention is：
The invention provides a kind of process for cleanly preparing of gallic acid, the technique includes alkaline process and produces and produce waste liquid
Processing step；The production liquid waste processing step includes SPE, back extraction regeneration, waste water subsequent processing steps；The solid phase
Extraction step is to carry out extracting and enriching to the production waste water using solid extracting agent；The solid extracting agent is containing phenyl ring knot
Structure monomer, with basic group high molecular polymer.
As further improvement of the present invention, the solid extracting agent is following product：The IRA- of Rhom and Hass
900、IRA-910、IRA-958、IRA-93、IRA-68；The NDA88, NDA99 of Jiangsu NJU Environmental Technology Co., Ltd.,
NDA900、NDA910；The MP62 of Beyer Co., Ltd, the solid extracting agent individually or can be used in series.
As further improvement of the present invention, described solid extracting agent average pore size is 3~50nm or specific surface area
＞ 600m2/g。
As further improvement of the present invention, the back extraction regeneration step is complete to SPE step using back washing agent
Solid extracting agent after is eluted, and restitutive protection's agent is contained in described back washing agent.
As further improvement of the present invention, the back washing agent is the sodium hydroxide solution containing restitutive protection's agent,
Restitutive protection's agent is in vulcanized sodium, NaHS, sodium hydrogensulfite, sodium sulfite, sodium pyrosulfite, sodium dithionite
One or more any combination.
As further improvement of the present invention, the sodium hydroxide solution mass concentration is 5%~15%, the reduction
Property protectant mass concentration be 1%~3%.
As further improvement of the present invention, the waste water subsequent processing steps include microbial hydrolytic acidification,
Anaerobic Treatment, Aerobic Process for Treatment, second coagulation sedimentation treatment step.
As further improvement of the present invention, the process for cleanly preparing of the gallic acid, carried out according to following steps：
Step (1), alkaline process production：Raw materials for production are put into reactor, is hydrolyzed, neutralizes, decolourizes, is acidified, cools down, ties
Brilliant, dehydration, washing, drying process step obtain gallic acid finished product；
Step (2), SPE：Caused production waste liquid passes through solid extracting agent after step (1) is produced, and produces waste liquid
In gallic acid, tannic acid is extracted, is enriched with into solid extracting agent；
Step (3), back extraction regeneration：Solid extracting agent after SPE is eluted, obtains back extraction regeneration
Liquid, the back extraction regenerated liquid are recyclable standby；
Step (4), waste water subsequent treatment：Waste liquid after step (2) processing is adjusted into pH to 7~9, into biochemical system,
Successively through microbial hydrolytic acidification, ECSB reactors Anaerobic Treatment, multi-stage aerobic biological treatment, second coagulation precipitation process
Step process.
3. beneficial effect
(1) process for cleanly preparing of a kind of gallic acid of the invention, its use solid extracting agent carry out gallic acid and
The extraction of tannic acid, the defects of causing secondary pollution when organic reagent extracts is avoided, reduces the difficulty of waste water subsequent treatment,
Realize waste water treatment and resource recycling is combined, reach the unification of environmental benefit, Social benefit and economic benefit.
(2) process for cleanly preparing of a kind of gallic acid of the invention, can be produced simultaneously using SPE mode
The trim process of Organic Pollutants in Wastewater, reduce into the organic pollutant category in biochemical treatment system waste water and total
Amount, the COD (COD) that waste water is produced after processing are cut down, and are provided convenience for the subsequent treatment of waste water；Follow-up place
Using hydrolysis acidification+granule sludge high efficiency anaerobic reactor processing during reason, biochemical system is enhanced to difficult biology in waste water
The removal effect of degradation material；Water outlet of the gallic acid production waste liquid after biochemical treatment in the prior art needs to add hydrogen peroxide
Qualified discharge can be realized after oxidation, qualified discharge, place can be achieved in the water outlet of method of the invention after coagulating kinetics
It is more excellent to manage effect.
(3) a kind of process for cleanly preparing of gallic acid of the invention, its solid extracting agent used contain benzene ring structure
Monomer and gallic acid, tannic acid benzene ring structure between produce nonpolar action power, so as to produce suction-operated, in addition, solid
Basic group in phase extractant can produce Hyarogen-bonding with the phenolic hydroxyl group in gallic acid, tannic acid, carboxyl, further add
Strong adsorption effect, simple to operate, the gallic acid of extracting and enriching, tannin acid recovering rate are higher.
(4) process for cleanly preparing of a kind of gallic acid of the invention, it adds going back for gallic acid in strippant
Originality protective agent, gallic acid, tannic acid and its salting liquid easily oxidized under alkaline environment is set favorably to be protected, the party
The gallic acid rate of recovery that method obtains is higher.
(5) process for cleanly preparing of a kind of gallic acid of the invention, solid extracting agent can obtain by back extraction in its step
To recycling utilization, cost is further saved.
(6) process for cleanly preparing of a kind of gallic acid of the invention, it is extracted back in gallic acid production liquid waste processing
The gallic acid regenerated liquid of receipts can direct plunge into be produced for gallic acid, and in the prior art in gallic acid production waste liquid
Used after can only further being handled containing a large amount of organic reagents, the present invention not only rationally make use of money using SPE mode
Source, and larger facility is provided for subsequent operation.
(7) process for cleanly preparing of a kind of gallic acid of the invention, the gallic acid that gained is produced using this method are obtained
Rate is higher, and content of beary metal is less than limit value, and the gallic acid of production has higher quality.
Brief description of the drawings
Fig. 1 is gallic acid production process for treating waste liquor flow chart
Specific implementation method
Below by way of embodiment, with reference to accompanying drawing, the invention will be further described.
Embodiment 1：
The production stage of the present embodiment gallic acid is as follows：
Step 1-1, prepared by raw materials for production：Chinese gall dry powder that is clean, drying is put into reactor, it is standby.
Step 1-2, hydrolyze：0.8 times of Chinese gall dry powder weight is added in reactor into step 1-1, mass fraction is
50% sodium hydrate aqueous solution, 90 DEG C are warming up to, are incubated 3.0 hours.
Step 1-3, crude product preparation process：The step 1-2 solution handled is put into acidifying kettle, uses mass fraction as 31%
Salt acid for adjusting pH value to 3.0, add the activated carbon of Chinese gall dry powder weight 8%, filtered at 85 DEG C with deckle board filter press, filter
Liquid temperature degree is cooled to less than 20 DEG C, and centrifugal dehydration obtains gallic acid crude product.
Step 1-4, finished product preparation process：By obtained gallic acid crude product input bleaching kettle in step 1-3,1.5 are added
Times deionized water of gallic acid crude product weight and the activated carbon of Chinese gall dry powder weight 3%, 85 DEG C are warming up to, are incubated 30 minutes
After filter, be cooled to room temperature, centrifugal dehydration, be drying to obtain gallic acid finished product.
Gallic acid content >=99.5% prepared by the production technology of the present embodiment, content of beary metal ＜ 0.1ppm.
With reference to Fig. 1, the processing step of the present embodiment gallic acid production waste liquid is as follows：
Step 2, SPE：Caused waste liquid imports gallic acid waste collection regulating reservoir and adjusted during gallic acid is produced
PH is saved, solid residue is removed through mechanical filter, filtrate enters SPE tower, flows through filling solid phase extraction with 0.5BV/h flow velocity
Take the fixed bed of agent, the model Shanghai (CompanyAddress of ROHM AND HAAS Chemical Co., Ltd. of described solid extracting agent：Shanghai City
Qingpu industrial park Song pools main road 8605；Contact method：IRA-910 (average pore size 35nm) 021-69211018), at this
Reason process one side is non-using being produced between the benzene ring structure monomer and gallic acid of solid extracting agent, the benzene ring structure of tannic acid
Polarity active force produces suction-operated, on the other hand using in the basic group in solid extracting agent and gallic acid, tannic acid
Phenolic hydroxyl group, carboxyl produce Hyarogen-bonding, further strengthen adsorption effect；Filtrate flows through the fixed bed of filling solid extracting agent
During, gallic acid, tannic acid from Wastewater by Solvent Extraction and are enriched with by solid extracting agent.
Step 3, back extraction：After extraction terminates, use quality fraction carries out back extraction recovery for 15% sodium hydroxide solution not to be had
Gallate-based, back extraction reagent is flowed through the fixed bed of solid extracting agent, be enriched in gallic acid in solid extracting agent, tannic acid with
Sodium hydroxide generation sodium gallate, tannic acid sodium are eluted, and sodium gallate, the tannic acid sodium back extraction regenerated liquid of generation can return
Receive standby, while solid extracting agent is regenerated.
Because gallic acid, tannic acid and its salt of formation are easily oxidized in the basic conditions, therefore the sodium hydroxide
With the addition of in solution mass concentration be 2% vulcanized sodium, NaHS and sodium pyrosulfite mixed solution as restitutive protection
Agent, so as to carry out favourable protection to gallic acid, tannic acid and sodium gallate, tannic acid sodium salt solution.
Step 4, production waste liquid subsequent treatment：Waste liquid after extraction enters comprehensive wastewater regulating reservoir, with other sanitary wastewaters
Merge, enter back into flocculation sedimentation tank flocculation sediment and handle and add milk of lime regulation pH value to 7, into biochemical system, through micro- life
Thing hydrolysis acidification, ECSB reactors Anaerobic Treatment, multi-stage aerobic biological treatment, biological oxidation water outlet add a small amount of PAC, PAM again
Flocculation removes SS through second coagulation precipitation process and qualified discharge is realized in colourity, water outlet.
By the gallic acid that above-mentioned handling process obtains compared with prior art processing method, the gallic acid rate of recovery carries
High by 8.5%, the waste water of discharge reaches《Integrated wastewater discharge standard (GB8978-1996)》First discharge standard.
Embodiment 2：
The production stage of the present embodiment gallic acid is as follows：
Step 1-1, prepared by raw materials for production：The Chinese gall hydrosol is put into reactor, it is standby.
Step 1-2, basic hydrolysis：1.0 times of Chinese gall hydrosol weight, quality point are added in reactor into step 1-1
Number is 45% sodium hydrate aqueous solution, is warming up to 110 DEG C and is incubated 2.5 hours.
Step 1-3, crude product preparation process：The solution of step 1-2 processing gained is put into acidifying kettle simultaneously, adds mass fraction
It is 2.5 for 31% salt acid for adjusting pH value, adds the activated carbon of Chinese gall hydrosol weight 8%, at 90 DEG C with deckle board press filtration
Machine filters, and filtrate temperature is cooled to less than 20 DEG C, and centrifugal dehydration obtains gallic acid crude product.
Step 1-4, finished product preparation process：By gallic acid crude product input bleaching kettle obtained by step 1-3, add 1.5 times and do not have
The deionized water of infanticide acid crude weight and the activated carbon of Chinese gall hydrosol weight 4%, be warming up to 90 DEG C insulation 30 minutes after
Filtering, is cooled to room temperature centrifugal dehydration, is drying to obtain gallic acid finished product.
Gained gallic acid content >=99.7%, content of beary metal ＜ 0.08ppm are prepared by the production technology of the present embodiment.
With reference to Fig. 1, the processing step of the production waste liquid of the present embodiment gallic acid is as follows：
Step 2, SPE：Caused waste liquid imports gallic acid waste collection regulating reservoir and adjusted during gallic acid is produced
PH is saved, removes solid residue through mechanical filter, filtrate enters SPE tower, flows through filling SPE with 1.0BV/h flow velocitys
The fixed bed of the agent, (CompanyAddress of model Jiangsu NJU Environmental Technology Co., Ltd. of the solid extracting agent：The economic skill in Nanjing
Art development zone Heng Jing roads 27；Contact method：NDA99 (average pore size 3nm) 025-68568042)；The step extracts principle
With embodiment 1, filtrate flow through filling solid extracting agent fixed bed process in, solid extracting agent by gallic acid, tannic acid from
Wastewater by Solvent Extraction is separated and is enriched with.
Step 3, back extraction：After extraction terminates, use quality fraction carries out back extraction recovery for 12% sodium hydroxide solution not to be had
Gallate-based, back extraction reagent is flowed through the fixed bed of solid extracting agent, be enriched in gallic acid in solid extracting agent, tannic acid with
Sodium hydroxide generation sodium gallate, tannic acid sodium are eluted, and sodium gallate, the tannic acid sodium back extraction regenerated liquid of generation can return
Receive standby, while solid extracting agent is regenerated.
Because gallic acid, tannic acid and its salt of formation are easily oxidized in the basic conditions, therefore the sodium hydroxide
Mass concentration is with the addition of in solution to be used as also for the mixed solution of 3% sodium hydrogensulfite, sodium sulfite and sodium dithionite
Originality protective agent, so as to carry out favourable protection to gallic acid, tannic acid and sodium gallate, tannic acid sodium salt solution.
Step 4, production waste liquid subsequent treatment：Waste liquid after extraction enters comprehensive wastewater regulating reservoir, with other sanitary wastewaters
Merge, enter back into flocculation sedimentation tank flocculation sediment and handle and add sodium hydroxide solution regulation pH value to 8, into biochemical system,
Be acidified through microbial hydrolytic, ECSB reactors Anaerobic Treatment, multi-stage aerobic biological treatment, biological oxidation water outlet adds on a small quantity again
PAC, PAM flocculation remove SS through second coagulation precipitation process and qualified discharge is realized in colourity, water outlet.
By the gallic acid that above-mentioned handling process obtains compared with prior art processing method, the gallic acid rate of recovery carries
High by 9.7%, the waste water of discharge reaches《Integrated wastewater discharge standard (GB8978-1996)》First discharge standard.
Embodiment 3：
The production stage of the present embodiment gallic acid is as follows：
Step 1-1, prepared by raw materials for production：Tara fine powder is put into reactor, it is standby.
Step 1-2, basic hydrolysis：The mass fraction of 0.9 times of addition Tara fine powder weight is in reactor into step 1-1
50% sodium hydrate aqueous solution, it is warming up to 110 DEG C and is incubated 3.5 hours.
Step 1-3, crude product preparation process：The solution of step 1-2 processing gained is put into acidifying kettle simultaneously, adds mass fraction
It is 2.5 for 31% salt acid for adjusting pH value, adds the activated carbon of Tara fine powder weight 10%, at 95 DEG C with deckle board filter press mistake
Filter, filtrate temperature are cooled to less than 20 DEG C, and centrifugal dehydration obtains gallic acid crude product.
Step 1-4, finished product preparation process：By gallic acid crude product input bleaching kettle obtained by step 1-3, add 2.0 times and do not have
The deionized water of infanticide acid crude weight and the activated carbon of Tara fine powder weight 2%, be warming up to 85 DEG C insulation 30 minutes after filter,
Room temperature centrifugal dehydration is cooled to, is drying to obtain gallic acid finished product.
Gained gallic acid content >=99.6%, content of beary metal ＜ 0.1ppm are prepared by the production technology of the present embodiment.
With reference to Fig. 1, the processing step of the production waste liquid of the present embodiment gallic acid is as follows：
Step 2, SPE：Caused waste liquid imports gallic acid waste collection regulating reservoir and adjusted during gallic acid is produced
PH is saved, removes solid residue through mechanical filter, filtrate enters SPE tower, flows through filling SPE with 1.5BV/h flow velocitys
The fixed bed of agent, the NDA88 of model Jiangsu NJU Environmental Technology Co., Ltd. of the solid extracting agent, its specific surface area are
650m2/g；Principle is extracted with embodiment 1, filtrate is flowed through in the fixed bed process of filling solid extracting agent, and solid extracting agent will not have
Gallate-based, tannic acid are separated and are enriched with from Wastewater by Solvent Extraction.
Step 3, back extraction：After extraction terminates, use quality fraction carries out back extraction recovery for 5% sodium hydroxide solution and not eaten
Sub- acid, makes back extraction reagent flow through the fixed bed of solid extracting agent, gallic acid, tannic acid and the hydrogen being enriched in solid extracting agent
Sodium oxide molybdena generation sodium gallate, tannic acid sodium are eluted, and sodium gallate, the tannic acid sodium back extraction regenerated liquid of generation are recyclable
It is standby, while solid extracting agent is regenerated.
Because gallic acid, tannic acid and its salt of formation are easily oxidized in the basic conditions, therefore the sodium hydroxide
The powerful reducing agents solution that mass concentration is 1% is with the addition of in solution and is used as restitutive protection's agent, so as to gallic acid, tannin
Acid and sodium gallate, tannic acid sodium salt solution carry out favourable protection.
Step 4, production waste liquid subsequent treatment：Waste liquid after extraction enters comprehensive wastewater after merging with other sanitary wastewaters and adjusted
Pond is saved, flocculation sedimentation tank flocculation sediment is entered back into and handle and add sodium hydroxide solution regulation pH value to 9, into biochemical system,
Be acidified through microbial hydrolytic, ECSB reactors Anaerobic Treatment, multi-stage aerobic biological treatment, biological oxidation water outlet adds on a small quantity again
PAC, PAM flocculation remove SS through second coagulation precipitation process and qualified discharge is realized in colourity, water outlet.
By the gallic acid that above-mentioned handling process obtains compared with prior art processing method, the gallic acid rate of recovery carries
High by 9.2%, the waste water of discharge reaches《Integrated wastewater discharge standard (GB8978-1996)》First discharge standard.
Embodiment 4：
The production stage of the present embodiment gallic acid is as follows：
Step 1-1, prepared by raw materials for production：Tara fine powder is put into reactor, it is standby.
Step 1-2, basic hydrolysis：The mass fraction of 0.9 times of addition Tara fine powder weight is in reactor into step 1-1
50% sodium hydrate aqueous solution, it is warming up to 110 DEG C and is incubated 3.5 hours.
Step 1-3, crude product preparation process：The solution of step 1-2 processing gained is put into acidifying kettle simultaneously, adds mass fraction
It is 2.5 for 31% salt acid for adjusting pH value, adds the activated carbon of Tara fine powder weight 10%, at 95 DEG C with deckle board filter press mistake
Filter, filtrate temperature are cooled to less than 20 DEG C, and centrifugal dehydration obtains gallic acid crude product.
Step 1-4, finished product preparation process：By gallic acid crude product input bleaching kettle obtained by step 1-3, add 2.0 times and do not have
The deionized water of infanticide acid crude weight and the activated carbon of Tara fine powder weight 2%, be warming up to 85 DEG C insulation 30 minutes after filter,
Room temperature centrifugal dehydration is cooled to, is drying to obtain gallic acid finished product.
Gained gallic acid content >=99.6%, content of beary metal ＜ 0.1ppm are prepared by the production technology of the present embodiment.
With reference to Fig. 1, the processing step of the production waste liquid of the present embodiment gallic acid is as follows：
Step 2, SPE：Caused waste liquid imports gallic acid waste collection regulating reservoir and adjusted during gallic acid is produced
PH is saved, removes solid residue through mechanical filter, filtrate enters SPE tower, flows through filling SPE with 1.5BV/h flow velocitys
The fixed bed of agent, the solid extracting agent be Jiangsu NJU Environmental Technology Co., Ltd. NDA900, (average pore size 50nm)；Extraction
Principle is taken with embodiment 1, filtrate is flowed through in the fixed bed process of filling solid extracting agent, and solid extracting agent is by gallic acid, list
Peaceful acid is separated and is enriched with from Wastewater by Solvent Extraction.
Step 3, back extraction：After extraction terminates, use quality fraction carries out back extraction recovery for 5% sodium hydroxide solution and not eaten
Sub- acid, makes back extraction reagent flow through the fixed bed of solid extracting agent, gallic acid, tannic acid and the hydrogen being enriched in solid extracting agent
Sodium oxide molybdena generation sodium gallate, tannic acid sodium are eluted, and sodium gallate, the tannic acid sodium back extraction regenerated liquid of generation are recyclable
It is standby, while solid extracting agent is regenerated.
Because gallic acid, tannic acid and its salt of formation are easily oxidized in the basic conditions, therefore the sodium hydroxide
The powerful reducing agents solution that mass concentration is 1% is with the addition of in solution and is used as restitutive protection's agent, so as to gallic acid, tannin
Acid and sodium gallate, tannic acid sodium salt solution carry out favourable protection.
Step 4, production waste liquid subsequent treatment：Waste liquid after extraction enters comprehensive wastewater after merging with other sanitary wastewaters and adjusted
Pond is saved, flocculation sedimentation tank flocculation sediment is entered back into and handle and add sodium hydroxide solution regulation pH value to 8, into biochemical system,
Be acidified through microbial hydrolytic, ECSB reactors Anaerobic Treatment, multi-stage aerobic biological treatment, biological oxidation water outlet adds on a small quantity again
PAC, PAM flocculation remove SS through second coagulation precipitation process and qualified discharge is realized in colourity, water outlet.
By the gallic acid that above-mentioned handling process obtains compared with prior art processing method, the gallic acid rate of recovery carries
High by 9.2%, the waste water of discharge reaches《Integrated wastewater discharge standard (GB8978-1996)》First discharge standard.
Schematically the present invention and embodiments thereof are described above, this describes no restricted, institute in accompanying drawing
What is shown is also one of embodiments of the present invention, and actual flow is not limited thereto.So if common skill of this area
Art personnel are enlightened by it, without departing from the spirit of the invention, without designing and the technical scheme for creativeness
Similar frame mode and embodiment, protection scope of the present invention all should be belonged to.
Claims (8)
- A kind of 1. process for cleanly preparing of gallic acid, it is characterised in that：The technique includes alkaline process and produces and produce at waste liquid Manage step；The production liquid waste processing step includes SPE, back extraction regeneration, waste water subsequent processing steps；The solid phase extraction It is to carry out extracting and enriching to the production waste water using solid extracting agent to take step；The solid extracting agent is containing benzene ring structure Monomer, with basic group high molecular polymer.
- 2. the process for cleanly preparing of gallic acid according to claim 1, it is characterised in that：The solid extracting agent is following Product：IRA-900, IRA-910, IRA-958, IRA-93, IRA-68 of Rhom and Hass；The big environmental protection science and technology in Jiangsu south is limited NDA88, NDA99, NDA900, NDA910 of company；The MP62 of Beyer Co., Ltd, the solid extracting agent can individually or series connection make With.
- 3. the process for cleanly preparing of gallic acid according to claim 1 or claim 2, it is characterised in that：Described solid extracting agent Average pore size is 3~50nm or specific surface area ＞ 600m2/g。
- 4. the process for cleanly preparing of gallic acid according to claim 1 or claim 2, it is characterised in that：The back extraction regeneration step It is that the solid extracting agent after the completion of SPE step is eluted using back washing agent, contains reproducibility in described back washing agent Protective agent.
- 5. the process for cleanly preparing of gallic acid according to claim 4, it is characterised in that：The back washing agent is to contain reduction Property protectant sodium hydroxide solution, restitutive protection's agent be vulcanized sodium, NaHS, sodium hydrogensulfite, sodium sulfite, Jiao Ya One or more of any combination in sodium sulphate, sodium dithionite.
- 6. the process for cleanly preparing of gallic acid according to claim 5, it is characterised in that：The sodium hydroxide solution quality Concentration is 5%~15%, and the mass concentration of restitutive protection's agent is 1%~3%.
- 7. the process for cleanly preparing of gallic acid according to claim 1 or claim 2, it is characterised in that：The waste water subsequent treatment Step includes microbial hydrolytic acidification, Anaerobic Treatment, Aerobic Process for Treatment, second coagulation sedimentation treatment step.
- 8. the process for cleanly preparing of gallic acid according to claim 1 or claim 2, it is characterised in that carried out according to following steps：Step (1), alkaline process production：Raw materials for production are put into reactor, be hydrolyzed, neutralize, decolourizing, being acidified, cooling down, crystallizing, Dehydration, washing, drying process step obtain gallic acid finished product；Step (2), SPE：Caused production waste liquid passes through solid extracting agent after step (1) is produced, and produces in waste liquid Gallic acid, tannic acid are extracted, are enriched with into solid extracting agent；Step (3), back extraction regeneration：Solid extracting agent after SPE is eluted, obtains being stripped regenerated liquid, institute It is recyclable standby to state back extraction regenerated liquid；Step (4), waste water subsequent treatment：Waste liquid after step (2) processing is adjusted into pH to 7~9, into biochemical system, successively Through microbial hydrolytic acidification, ECSB reactors Anaerobic Treatment, multi-stage aerobic biological treatment, second coagulation sedimentation treatment step Processing.
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Cited By (1)
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| CN110436707A (en) * | 2019-08-06 | 2019-11-12 | 南京大学 | A kind of gallic acid production wastewater biochemistry pre-treating method |
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Application publication date: 20171208 |
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