CN113371913A - Method for recycling wastewater from gallic acid enzyme production - Google Patents
Method for recycling wastewater from gallic acid enzyme production Download PDFInfo
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- CN113371913A CN113371913A CN202110696539.5A CN202110696539A CN113371913A CN 113371913 A CN113371913 A CN 113371913A CN 202110696539 A CN202110696539 A CN 202110696539A CN 113371913 A CN113371913 A CN 113371913A
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- gallic acid
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- composite resin
- wastewater
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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 112
- 238000000034 method Methods 0.000 title claims abstract description 65
- 229940074391 gallic acid Drugs 0.000 title claims abstract description 55
- 235000004515 gallic acid Nutrition 0.000 title claims abstract description 55
- 239000002351 wastewater Substances 0.000 title claims abstract description 32
- 102000004190 Enzymes Human genes 0.000 title claims abstract description 28
- 108090000790 Enzymes Proteins 0.000 title claims abstract description 28
- 238000004064 recycling Methods 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 133
- 229920005989 resin Polymers 0.000 claims abstract description 133
- 239000000805 composite resin Substances 0.000 claims abstract description 87
- 238000001914 filtration Methods 0.000 claims abstract description 40
- 239000000706 filtrate Substances 0.000 claims abstract description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 238000001179 sorption measurement Methods 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 238000003795 desorption Methods 0.000 claims abstract description 16
- 239000012452 mother liquor Substances 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 230000007062 hydrolysis Effects 0.000 claims abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 8
- 238000011084 recovery Methods 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 89
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 67
- 238000005406 washing Methods 0.000 claims description 52
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 50
- 239000011159 matrix material Substances 0.000 claims description 45
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 34
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000002360 preparation method Methods 0.000 claims description 26
- 238000002791 soaking Methods 0.000 claims description 25
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000004793 Polystyrene Substances 0.000 claims description 20
- 239000011324 bead Substances 0.000 claims description 20
- 239000004088 foaming agent Substances 0.000 claims description 20
- 229920002223 polystyrene Polymers 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 229910001566 austenite Inorganic materials 0.000 claims description 10
- 238000007334 copolymerization reaction Methods 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 claims description 5
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 5
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 229960002089 ferrous chloride Drugs 0.000 claims description 5
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 5
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- 230000002255 enzymatic effect Effects 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 11
- 230000008929 regeneration Effects 0.000 abstract description 4
- 238000011069 regeneration method Methods 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 238000011272 standard treatment Methods 0.000 abstract 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 4
- 238000007865 diluting Methods 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 2
- 238000003809 water extraction Methods 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000009283 thermal hydrolysis Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- 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
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/025—Thermal hydrolysis
-
- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
-
- 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
-
- 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
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for recycling wastewater from gallic acid enzyme method production, which comprises the following steps: heating and hydrolyzing mother liquor obtained after gallic acid crystallization and filtration, and then cooling to room temperature; performing centrifugal filtration treatment to obtain transparent purple black filtrate; performing resin column adsorption to make the final effluent gallic acid content less than 500 mg/L; and desorbing by using a sodium hydroxide solution to obtain a gallic acid desorption solution. Aiming at the industrial problem that the gallic acid enzyme method production wastewater contains a large amount of high-viscosity colloidal substances to block resin pore channels in the process of recycling the gallic acid by a resin method, the invention effectively degrades the colloidal substances into small molecular compounds by an acidic heating hydrolysis method, thereby effectively solving the problem. In addition, three types of composite resins are developed aiming at the characteristics of gallic acid and a recovery process, so that the adsorption capacity, the regeneration efficiency and the mechanical strength of the resins are effectively improved. In a word, the invention integrates standard treatment and resource utilization of the wastewater, and has good application prospect.
Description
Technical Field
The invention relates to the technical field of wastewater recycling treatment, in particular to a method for recycling wastewater produced by a gallic acid enzyme method.
Background
Gallic acid, chemical name 3,4, 5-trihydroxy benzoic acid, as an important fine chemical product, have wide application in fields such as food, biology, medicine, chemical industry, etc.
The existing gallic acid production process mainly comprises an acid hydrolysis method, an alkali hydrolysis method, a fermentation method and an enzyme method. Wherein, the enzyme method has the advantages of mild reaction conditions (normal pressure and 40-50 ℃), thorough raw material hydrolysis, few byproducts and the like. However, a large amount of high-concentration refractory organic wastewater is inevitably generated in the process of producing the gallic acid by the enzyme method. Therefore, how to effectively treat the wastewater is the key for green and efficient production of the gallic acid.
From the perspective of industrial application, the method has stronger market competitiveness for a method which can not only discharge the wastewater after reaching standards but also recover high value-added products. The resin adsorption method is an economic, efficient and feasible method for combining wastewater treatment and resource utilization, has the characteristics of good selectivity, high efficiency and thoroughness in separation, convenience in regeneration and the like, and has advantages in treatment of high-concentration refractory organic wastewater. However, the prior resin method for treating the gallic acid enzyme method production wastewater directly has the following problems: (1) the water extraction process of gallic acid produced by the enzyme method can generate a large amount of colloid substances which are difficult to degrade, so that the viscosity of the waste water produced by the gallic acid enzyme method is high, and the problems that a resin bed layer has large resistance, the colloid substances are easy to block the bed layer and the like are caused; (2) the prior commercial resin has the problems of low gallic acid adsorption capacity, serious resin loss, low regeneration efficiency and the like.
Disclosure of Invention
The invention aims to provide a method for recycling wastewater from gallic acid enzyme production aiming at the technical problems.
The technical scheme of the invention is as follows: a method for recycling wastewater from gallic acid enzyme production specifically comprises the following steps:
the method comprises the following steps: heating for hydrolysis
Adding mother liquor obtained after gallic acid crystallization and filtration into a high-pressure reaction kettle, heating to 120-150 ℃, carrying out heat preservation reaction for 1-5 h, and then cooling to room temperature;
step two: centrifugal filtration
Carrying out centrifugal filtration treatment on the mother liquor after reaction and temperature reduction to obtain transparent purple black filtrate;
step three: resin adsorption
Performing resin column adsorption on the purple black filtrate to ensure that the content of gallic acid in final effluent is less than 500 mg/L;
step four: desorption recovery
Desorbing by using 5-8% sodium hydroxide solution at 50-55 ℃, feeding alkali liquor from the upper end of the resin column according to 0.8-1.2 BV/h, and allowing desorption liquid to flow out from the lower end, wherein the effluent liquid is the desorption liquid of the gallic acid.
Further, the second step is specifically: carrying out centrifugal filtration treatment on the mother liquor after reaction and cooling by adopting a rotary drum centrifuge at the rotating speed of 1500-2000 rad/min to obtain primary filtrate; and standing the primary filtrate for 20-30 min, and performing secondary filtration to obtain secondary filtrate, wherein the secondary filtrate is transparent purple-black filtrate.
And further, the resin column adsorption in the third step specifically adopts a mode of connecting a plurality of resin columns in series for room temperature filtration.
Further, the resin column comprises a resin column body and a composite resin filled inside the resin column body.
Further, the composite resin is a first composite resin; the preparation method of the first composite resin comprises the following steps:
1) preparing a macroporous cross-linked resin matrix: mixing styrene and divinylbenzene according to the mass ratio of 4-17: 2-16, and then adding a mixture of styrene and divinylbenzene according to the mass ratio of 1: 1.2-1.7, uniformly mixing the pore-foaming agents, carrying out suspension copolymerization reaction, and extracting the pore-foaming agents after the reaction is finished to obtain macroporous crosslinked polystyrene beads; then extracting the macroporous crosslinked polystyrene beads with ethanol solvent for 8-12 h, drying at room temperature, and vacuum drying at 30-35 ℃ for 2-3 h to obtain a macroporous crosslinked resin matrix;
2) preparing a first composite resin: adding the macroporous cross-linked resin matrix into the acid body solution according to the proportion of 50-65 g/L, and carrying out ultrasonic treatment for 1-2 h at the stirring speed of 100-150 r/min; and then adding polyethylene glycol according to the proportion of 20-40 g/L, carrying out ultrasonic treatment for 3-5 h at the stirring speed of 200-350 r/min, carrying out suction filtration, and carrying out vacuum drying for 2-3 h at the temperature of 40-45 ℃ to obtain the first composite resin.
Furthermore, the acid body solution is obtained by mixing 1-2 mol/L ferric chloride solution, 0.3-0.5 mol/L ferrous chloride solution and 2-3 mol/L hydrochloric acid solution according to a volume ratio of 3-5: 1: 2-7.
Further, the composite resin adopts a second composite resin; the preparation method of the second composite resin comprises the following steps:
1) preparing a macroporous cross-linked resin matrix: mixing styrene and divinylbenzene according to the mass ratio of 4-17: 2-16, and then adding a mixture of styrene and divinylbenzene according to the mass ratio of 1: 1.2-1.7, uniformly mixing the pore-foaming agents, carrying out suspension copolymerization reaction, and extracting the pore-foaming agents after the reaction is finished to obtain macroporous crosslinked polystyrene beads; then extracting the macroporous crosslinked polystyrene beads with ethanol solvent for 8-12 h, drying at room temperature, and vacuum drying at 30-35 ℃ for 2-3 h to obtain a macroporous crosslinked resin matrix;
2) pretreatment of the macroporous cross-linked resin matrix: soaking the macroporous cross-linked resin matrix in 95% ethanol solution for 15-20 h, and washing with deionized water for 2-3 times; soaking the fabric in saturated salt solution for 15-20 h, and washing the fabric for 2-3 times by using deionized water; then soaking the mixture for 1-2 hours by using a hydrochloric acid solution with the concentration of 2-5%, and cleaning the mixture to be neutral by using deionized water; then soaking the mixture in a 1-3% sodium hydroxide solution for 3-5 h, washing the mixture with deionized water to be neutral, and discharging the liquid;
3) preparing a second composite resin: soaking the pretreated macroporous cross-linked resin matrix in a potassium permanganate solution according to the proportion of 500-800 mg/L, stirring and reacting for 1-1.5 hours at the temperature of 35-40 ℃, and washing for 2-3 times by using deionized water until the color of the potassium permanganate solution is not changed any more; adding a ferrous sulfate solution with the concentration of 5% into the washed macroporous cross-linked resin matrix according to the proportion of 30-50 g/L, and stirring and reacting for 2-3 h at the temperature of 35-40 ℃; and washing the resin with deionized water and acetone for 2-3 times in sequence, centrifugally dewatering, and drying the resin in vacuum at 40-45 ℃ for 6-8 hours to obtain second composite resin.
Further, the composite resin is a third composite resin; the preparation method of the third composite resin comprises the following steps:
1) modified gamma-Fe2O3The preparation of (1): mixing gamma-Fe2O3Ultrasonically dispersing the mixture in ethanol according to the proportion of 1 g/15-20 ml, then adding water and ammonia water with the volume ratio of 2: 15-20 to the ethanol being 1: 150-200, then starting stirring and heating to 30-35 ℃; then adding tetraethoxysilane with the volume ratio of 1: 15-20 to react for 1-2 hours, then adding tetraethoxysilane with the volume ratio of 1: 15-20 to ethanol and diethyldiethoxysilane with the volume ratio of 3: 75-100 to react for 4-5 hours, filtering, washing and drying to obtain the modified gamma-Fe2O3；
2) Preparation of a third composite resin:
taking oil phase raw materials: taking 1-2 parts of modified gamma-Fe by mass2O34-6 parts of methyl methacrylate, 0.8-1.2 parts of glycerol methacrylate, 0.8-1.2 parts of divinylbenzene and 0.08-0.12 part of benzoyl oxide; taking and modifying gamma-Fe2O3Toluene and gamma-Fe with the mass volume ratio of 3g/8ml2O3Cyclohexanol with mass volume ratio of 1g/2 ml;
taking water phase raw materials: taking 0.6-0.8 part of polyvinyl alcohol, 0.6-0.8 part of polyvinylpyrrolidone and 3-5 parts of sodium chloride according to the mass parts; taking and modifying gamma-Fe2O3Water with the mass volume ratio of 3g/200 ml;
fully dissolving the oil phase and the water phase, pouring the oil phase into the water phase, starting stirring to regulate oil drops to a proper size, heating to 70 ℃ at a speed of 1 ℃/min, keeping for 2-3 h, and then heating to 80 ℃ and keeping for 3-5 h to obtain precursor resin;
and then adding the precursor resin into a 35-65 wt% trimethyl ammonium chloride solution according to the mass volume ratio of 2g/7ml, reacting for 8-14 h at 65-75 ℃, and finally placing the product in a Soxhlet extractor to extract for 24h with a mixed solution of methanol and acetone to obtain a third composite resin.
Further, washing the adsorption column with distilled water after the step four is completed, specifically: and (3) after the alkali liquor is completely fed, using 0.8-1.2 BV of distilled water to wash the adsorption column for the second time according to 0.8-1.2 BV/h to obtain a washing solution, adding water to dilute the washing solution according to the proportion of 1:2, and mixing the diluted washing solution with the purple black filtrate obtained in the second step for subsequent treatment.
Compared with the prior art, the invention has the beneficial effects that:
(1) aiming at the problems that the gallic acid produced by an enzyme method generates a large amount of colloidal substances which are difficult to degrade in the water extraction process, so that the gallic acid enzyme method production wastewater is high in viscosity, the resin bed layer resistance is large, the colloidal substances are easy to block the bed layer and the like, the colloidal substances are converted into small molecular substances by a thermal hydrolysis method, and the industrial problem of recycling the gallic acid enzyme method wastewater by the resin method is effectively solved;
(2) the prior commercial resin has the problems of low adsorption capacity to gallic acid, serious resin loss, low regeneration efficiency and the like, and the resin is directionally modified by means of Friedel-crafts crosslinking, oxidation treatment, magnetic nanoparticles and the like, so that the recovery efficiency and the operation stability of the gallic acid are effectively improved.
Detailed Description
Example 1:
a method for recycling wastewater from gallic acid enzyme production specifically comprises the following steps:
the method comprises the following steps: heating for hydrolysis
Adding mother liquor obtained after gallic acid crystallization and filtration into a high-pressure reaction kettle, heating to 120 ℃, preserving heat, reacting for 1h, and then cooling to room temperature;
step two: centrifugal filtration
Carrying out centrifugal filtration treatment on the mother liquor after reaction and temperature reduction by adopting a rotary drum centrifuge at the rotating speed of 1500rad/min to obtain primary filtrate; standing the primary filtrate for 20min, and performing secondary filtration to obtain secondary filtrate, wherein the secondary filtrate is transparent purple black filtrate; wherein, the centrifugal filtration and the secondary filtration are both carried out by adopting 800-mesh filter cloth;
step three: resin adsorption
Performing resin column adsorption on the purple black filtrate to ensure that the content of gallic acid in final effluent is less than 500 mg/L; wherein, the adsorption of the resin column specifically adopts the mode of connecting a plurality of resin columns in series for room temperature filtration;
step four: desorption recovery
Desorbing with 5% sodium hydroxide solution at 50 deg.C, feeding alkali solution from the upper end of the resin column at a rate of 0.8BV/h, and allowing the desorption solution to flow out from the lower end, wherein the effluent is the desorption solution of gallic acid;
step five: washing adsorption column
And (5) after the alkali liquor is completely fed, washing the adsorption column for the second time by using 1BV of distilled water according to the ratio of 1BV/h to obtain a washing solution, diluting the washing solution by adding water according to the ratio of 1:2, and mixing the diluted washing solution with the purple black filtrate obtained in the second step for subsequent treatment.
The resin column comprises a resin column body and composite resin filled in the resin column body; the composite resin is a first composite resin; the preparation method of the first composite resin comprises the following steps:
1) preparing a macroporous cross-linked resin matrix: mixing styrene and divinylbenzene according to the mass ratio of 4:2, and then adding a mixture of styrene and divinylbenzene according to the mass ratio of 1: 1.2, uniformly mixing the pore-foaming agents, then carrying out suspension copolymerization reaction, and extracting the pore-foaming agents after the reaction is finished to obtain macroporous crosslinked polystyrene beads; then extracting the macroporous crosslinked polystyrene beads with ethanol solvent for 8h, airing at room temperature, and then drying in vacuum at 30 ℃ for 2h to obtain a macroporous crosslinked resin matrix;
2) preparing a first composite resin: adding the macroporous cross-linked resin matrix into the acid body solution according to the proportion of 50g/L, and carrying out ultrasonic treatment for 1h at the stirring speed of 100 r/min; then adding polyethylene glycol according to the proportion of 20g/L, carrying out ultrasonic treatment for 3h at the stirring speed of 200r/min, carrying out suction filtration, and carrying out vacuum drying for 2h at the temperature of 40 ℃ to obtain a first composite resin; wherein the acid body solution is obtained by mixing 1mol/L ferric chloride solution, 0.3mol/L ferrous chloride solution and 2mol/L hydrochloric acid solution according to the volume ratio of 3:1: 2.
Example 2:
a method for recycling wastewater from gallic acid enzyme production specifically comprises the following steps:
the method comprises the following steps: heating for hydrolysis
Adding mother liquor obtained after gallic acid crystallization and filtration into a high-pressure reaction kettle, heating to 130 ℃, keeping the temperature, reacting for 5 hours, and then cooling to room temperature;
step two: centrifugal filtration
Carrying out centrifugal filtration treatment on the reacted and cooled mother liquor by adopting a rotary drum centrifuge at the rotating speed of 2000rad/min to obtain primary filtrate; standing the primary filtrate for 25min, and performing secondary filtration to obtain secondary filtrate, wherein the secondary filtrate is transparent purple black filtrate; wherein, the centrifugal filtration and the secondary filtration are both carried out by adopting 1000-mesh filter cloth;
step three: resin adsorption
Performing resin column adsorption on the purple black filtrate to ensure that the content of gallic acid in final effluent is less than 500 mg/L; wherein, the adsorption of the resin column specifically adopts the mode of connecting a plurality of resin columns in series for room temperature filtration;
step four: desorption recovery
Desorbing with 5% sodium hydroxide solution at 50 deg.C, feeding alkali solution from the upper end of the resin column at a rate of 1BV/h, and allowing the desorption solution to flow out from the lower end, wherein the effluent is the desorption solution of gallic acid;
step five: washing adsorption column
And (5) after the alkali liquor is completely fed, washing the adsorption column for the second time by using 1BV of distilled water according to the ratio of 1BV/h to obtain a washing solution, diluting the washing solution by adding water according to the ratio of 1:2, and mixing the diluted washing solution with the purple black filtrate obtained in the second step for subsequent treatment.
The resin column comprises a resin column body and composite resin filled in the resin column body; the composite resin is a first composite resin; the preparation method of the first composite resin comprises the following steps:
1) preparing a macroporous cross-linked resin matrix: mixing styrene and divinylbenzene according to the mass ratio of 10:3, and then adding a mixture of styrene and divinylbenzene according to the mass ratio of 1: 1.5, uniformly mixing the pore-foaming agents, then carrying out suspension copolymerization reaction, and extracting the pore-foaming agents after the reaction is finished to obtain macroporous crosslinked polystyrene beads; then extracting the macroporous crosslinked polystyrene beads with an ethanol solvent for 10h, airing at room temperature, and then drying in vacuum at 32 ℃ for 2h to obtain a macroporous crosslinked resin matrix;
2) preparing a first composite resin: adding the macroporous cross-linked resin matrix into the acid body solution according to the proportion of 60g/L, and carrying out ultrasonic treatment for 2 hours at the stirring speed of 120 r/min; adding polyethylene glycol according to the proportion of 30g/L, carrying out ultrasonic treatment for 4 hours at the stirring speed of 300r/min, carrying out suction filtration, and carrying out vacuum drying for 2-3 hours at the temperature of 42 ℃ to obtain a first composite resin; wherein the acid body solution is obtained by mixing 1mol/L ferric chloride solution, 0.4mol/L ferrous chloride solution and 2mol/L hydrochloric acid solution according to the volume ratio of 4:1: 6.
Example 3:
a method for recycling wastewater from gallic acid enzyme production specifically comprises the following steps:
the method comprises the following steps: heating for hydrolysis
Adding mother liquor obtained after gallic acid crystallization and filtration into a high-pressure reaction kettle, heating to 150 ℃, keeping the temperature, reacting for 5 hours, and then cooling to room temperature;
step two: centrifugal filtration
Carrying out centrifugal filtration treatment on the reacted and cooled mother liquor by adopting a rotary drum centrifuge at the rotating speed of 2000rad/min to obtain primary filtrate; standing the primary filtrate for 30min, and performing secondary filtration to obtain secondary filtrate, wherein the secondary filtrate is transparent purple black filtrate; wherein, the centrifugal filtration and the secondary filtration are both carried out by 1500-mesh filter cloth;
step three: resin adsorption
Performing resin column adsorption on the purple black filtrate to ensure that the content of gallic acid in final effluent is less than 500 mg/L; wherein, the adsorption of the resin column specifically adopts the mode of connecting a plurality of resin columns in series for room temperature filtration;
step four: desorption recovery
Desorbing with 8% sodium hydroxide solution at 55 deg.C, feeding alkali solution from the upper end of the resin column at a rate of 1.2BV/h, and allowing the desorption solution to flow out from the lower end, wherein the effluent is the desorption solution of gallic acid;
step five: washing adsorption column
And (5) after the alkali liquor is completely fed, washing the adsorption column for the second time by using 1BV of distilled water according to the ratio of 1BV/h to obtain a washing solution, diluting the washing solution by adding water according to the ratio of 1:2, and mixing the diluted washing solution with the purple black filtrate obtained in the second step for subsequent treatment.
The resin column comprises a resin column body and composite resin filled in the resin column body; the composite resin is a first composite resin; the preparation method of the first composite resin comprises the following steps:
1) preparing a macroporous cross-linked resin matrix: mixing styrene and divinylbenzene according to the mass ratio of 1:4, and then adding a mixture of styrene and divinylbenzene according to the mass ratio of 1: 1.7, uniformly mixing the pore-foaming agents, then carrying out suspension copolymerization reaction, and extracting the pore-foaming agents after the reaction is finished to obtain macroporous crosslinked polystyrene beads; then extracting the macroporous crosslinked polystyrene beads with an ethanol solvent for 12h, airing at room temperature, and then drying in vacuum at 35 ℃ for 3h to obtain a macroporous crosslinked resin matrix;
2) preparing a first composite resin: adding the macroporous cross-linked resin matrix into the acid body solution according to the proportion of 65g/L, and carrying out ultrasonic treatment for 2 hours at the stirring speed of 150 r/min; adding polyethylene glycol according to the proportion of 40g/L, carrying out ultrasonic treatment for 5 hours at the stirring speed of 200-350 r/min, carrying out suction filtration, and carrying out vacuum drying for 3 hours at the temperature of 45 ℃ to obtain a first composite resin; wherein the acid body solution is obtained by mixing 2mol/L ferric chloride solution, 0.5mol/L ferrous chloride solution and 3mol/L hydrochloric acid solution according to the volume ratio of 5:1: 7.
Example 4:
the difference from example 1 is: the resin column comprises a resin column body and composite resin filled in the resin column body; the composite resin adopts a second composite resin; the preparation method of the second composite resin comprises the following steps:
1) preparing a macroporous cross-linked resin matrix: mixing styrene and divinylbenzene according to the mass ratio of 2:1, and then adding a mixture of styrene and divinylbenzene according to the mass ratio of 1: 1.2, uniformly mixing the pore-foaming agents, then carrying out suspension copolymerization reaction, and extracting the pore-foaming agents after the reaction is finished to obtain macroporous crosslinked polystyrene beads; then extracting the macroporous crosslinked polystyrene beads with ethanol solvent for 8h, airing at room temperature, and then drying in vacuum at 30 ℃ for 2h to obtain a macroporous crosslinked resin matrix;
2) pretreatment of the macroporous cross-linked resin matrix: soaking the macroporous cross-linked resin matrix in 95% ethanol solution for 15h, and washing with deionized water for 2 times; soaking in saturated saline solution for 15h, and washing with deionized water for 2 times; then soaking the mixture for 1 hour by using a hydrochloric acid solution with the concentration of 2%, and cleaning the mixture to be neutral by using deionized water; then soaking the mixture for 3 hours by using a sodium hydroxide solution with the concentration of 1%, washing the mixture to be neutral by using deionized water, and discharging the liquid;
3) preparing a second composite resin: soaking the pretreated macroporous cross-linked resin matrix in a potassium permanganate solution according to the proportion of 500mg/L, stirring and reacting for 1h at the temperature of 35 ℃, and washing for 2 times by using deionized water when the color of the potassium permanganate solution is not changed any more; adding a ferrous sulfate solution with the concentration of 5% into the washed macroporous cross-linked resin matrix according to the proportion of 30g/L, and stirring and reacting for 2 hours at the temperature of 35 ℃; washing with deionized water and acetone for 2 times in sequence, centrifugally dewatering, and vacuum drying at 40 deg.C for 6h to obtain second composite resin.
Example 5:
the difference from example 1 is: the resin column comprises a resin column body and composite resin filled in the resin column body; the composite resin adopts a second composite resin; the preparation method of the second composite resin comprises the following steps:
1) preparing a macroporous cross-linked resin matrix: mixing styrene and divinylbenzene according to the mass ratio of 8:5, and then adding a mixture of styrene and divinylbenzene according to the mass ratio of 1: 1.5, uniformly mixing the pore-foaming agents, then carrying out suspension copolymerization reaction, and extracting the pore-foaming agents after the reaction is finished to obtain macroporous crosslinked polystyrene beads; then extracting the macroporous crosslinked polystyrene beads with an ethanol solvent for 10h, airing at room temperature, and then drying in vacuum at 32 ℃ for 3h to obtain a macroporous crosslinked resin matrix;
2) pretreatment of the macroporous cross-linked resin matrix: soaking the macroporous cross-linked resin matrix in 95% ethanol solution for 15h, and washing with deionized water for 3 times; soaking in saturated saline solution for 15h, and washing with deionized water for 3 times; then soaking the mixture for 1 hour by using a hydrochloric acid solution with the concentration of 3%, and cleaning the mixture to be neutral by using deionized water; then soaking the mixture for 4 hours by using a sodium hydroxide solution with the concentration of 2%, washing the mixture to be neutral by using deionized water, and discharging the liquid;
3) preparing a second composite resin: soaking the pretreated macroporous cross-linked resin matrix in a potassium permanganate solution according to the proportion of 600mg/L, stirring and reacting for 1h at the temperature of 38 ℃, and washing for 3 times by using deionized water until the color of the potassium permanganate solution is not changed any more; adding a ferrous sulfate solution with the concentration of 5% into the washed macroporous cross-linked resin matrix according to the proportion of 40g/L, and stirring and reacting for 3 hours at the temperature of 38 ℃; washing with deionized water and acetone for 3 times, centrifuging, and vacuum drying at 42 deg.C for 7 hr to obtain second composite resin.
Example 6:
the difference from example 3 is: the resin column comprises a resin column body and composite resin filled in the resin column body; the composite resin adopts a second composite resin; the preparation method of the second composite resin comprises the following steps:
1) preparing a macroporous cross-linked resin matrix: mixing styrene and divinylbenzene according to the mass ratio of 17:16, and then adding a mixture of styrene and divinylbenzene according to the mass ratio of 1: 1.7, uniformly mixing the pore-foaming agents, then carrying out suspension copolymerization reaction, and extracting the pore-foaming agents after the reaction is finished to obtain macroporous crosslinked polystyrene beads; then extracting the macroporous crosslinked polystyrene beads with an ethanol solvent for 12h, airing at room temperature, and then drying in vacuum at 35 ℃ for 3h to obtain a macroporous crosslinked resin matrix;
2) pretreatment of the macroporous cross-linked resin matrix: soaking the macroporous cross-linked resin matrix in 95% ethanol solution for 20h, and washing with deionized water for 3 times; then soaking the mixture in saturated salt solution for 20 hours, and washing the mixture for 3 times by using deionized water; then soaking the mixture for 2 hours by using a hydrochloric acid solution with the concentration of 5%, and cleaning the mixture to be neutral by using deionized water; then soaking the mixture for 5 hours by using a sodium hydroxide solution with the concentration of 3%, washing the mixture to be neutral by using deionized water, and discharging the liquid;
3) preparing a second composite resin: soaking the pretreated macroporous cross-linked resin matrix in a potassium permanganate solution according to the proportion of 800mg/L, stirring and reacting for 1.5 hours at the temperature of 40 ℃, and washing for 3 times by using deionized water until the color of the potassium permanganate solution is not changed any more; adding a ferrous sulfate solution with the concentration of 5% into the washed macroporous cross-linked resin matrix according to the proportion of 50g/L, and stirring and reacting for 2-3 h at the temperature of 40 ℃; and washing the resin with deionized water and acetone for 3 times in sequence, centrifugally dewatering, and drying the resin in vacuum at the temperature of 45 ℃ for 6-8 hours to obtain second composite resin.
Example 7:
the difference from example 1 is: the resin column comprises a resin column body and composite resin filled in the resin column body; the composite resin adopts a third composite resin; the preparation method of the third composite resin comprises the following steps:
1) modified gamma-Fe2O3The preparation of (1): mixing gamma-Fe2O3Ultrasonically dispersing in ethanol according to the proportion of 1g/15ml, then adding water and ammonia water with the volume ratio of 2:15 to the ethanol being 1:150, then starting stirring and heating to 30 ℃; then adding tetraethoxysilane with the volume ratio of 1:15 to ethanol for reaction for 1 hour, then adding tetraethoxysilane with the volume ratio of 1:15 to ethanol and diethyldiethoxysilane with the volume ratio of 3:75 to ethanol for reaction for 4 hours, filtering, washing and drying to obtain the modified gamma-Fe2O3；
2) Preparation of a third composite resin:
taking oil phase raw materials: taking 1 part of modified gamma-Fe according to the mass part2O34 parts of methyl methacrylate, 0.8 part of glycerol methacrylate, 0.8 part of divinylbenzene and 0.08-part of benzoyl oxide; taking and modifying gamma-Fe2O3Toluene and gamma-Fe with the mass volume ratio of 3g/8ml2O3Cyclohexanol with mass volume ratio of 1g/2 ml;
taking water phase raw materialMaterial preparation: taking 0.6 part of polyvinyl alcohol, 0.6 part of polyvinylpyrrolidone and 3 parts of sodium chloride according to the mass parts; taking and modifying gamma-Fe2O3Water with the mass volume ratio of 3g/200 ml;
then fully dissolving the oil phase and the water phase, pouring the oil phase into the water phase, starting stirring to regulate oil drops to a proper size, heating to 70 ℃ at a speed of 1 ℃/min, keeping for 2h, and then heating to 80 ℃ and keeping for 3h to obtain precursor resin;
and then adding the precursor resin into a 35 wt% trimethyl ammonium chloride solution according to the mass volume ratio of 2g/7ml, reacting for 8 hours at 65 ℃, and finally placing the product in a Soxhlet extractor to extract for 24 hours by using a methanol and acetone mixed solution to obtain a third composite resin.
Example 8:
the difference from example 1 is: the resin column comprises a resin column body and composite resin filled in the resin column body; the composite resin adopts a third composite resin; the preparation method of the third composite resin comprises the following steps:
1) modified gamma-Fe2O3The preparation of (1): mixing gamma-Fe2O3Ultrasonically dispersing in ethanol according to the proportion of 1g/18ml, then adding water and ammonia water with the volume ratio of 2:18 to the ethanol being 1:180, then starting stirring and heating to 32 ℃; then adding tetraethoxysilane with the volume ratio of 1:180 of ethanol for reaction for 1.5h, then adding tetraethoxysilane with the volume ratio of 1:18 of ethanol and diethyl diethoxysilane with the volume ratio of 3:81 of ethanol for reaction for 4.5h, filtering, washing and drying to obtain the modified gamma-Fe2O3；
2) Preparation of a third composite resin:
taking oil phase raw materials: taking 1.5 parts of modified gamma-Fe by mass2O35 parts of methyl methacrylate, 1.0 part of glycerol methacrylate, 1.0 part of divinylbenzene and 0.1 part of benzoyl oxide; taking and modifying gamma-Fe2O3Toluene and gamma-Fe with the mass volume ratio of 3g/8ml2O3Cyclohexanol with mass volume ratio of 1g/2 ml;
taking water phase raw materials: taking according to parts by mass0.8 part of polyvinyl alcohol, 0.8 part of polyvinylpyrrolidone and 4 parts of sodium chloride; taking and modifying gamma-Fe2O3Water with the mass volume ratio of 3g/200 ml;
then fully dissolving the oil phase and the water phase, pouring the oil phase into the water phase, starting stirring to regulate oil drops to a proper size, heating to 70 ℃ at a speed of 1 ℃/min, keeping for 2.5h, and then heating to 80 ℃ and keeping for 4h to obtain precursor resin;
and then adding the precursor resin into a 50 wt% trimethyl ammonium chloride solution according to the mass volume ratio of 2g/7ml, reacting for 12h at 70 ℃, and finally placing the product in a Soxhlet extractor to extract for 24h with a methanol and acetone mixed solution to obtain a third composite resin.
Example 9:
the difference from example 1 is: the resin column comprises a resin column body and composite resin filled in the resin column body; the composite resin adopts a third composite resin; the preparation method of the third composite resin comprises the following steps:
1) modified gamma-Fe2O3The preparation of (1): mixing gamma-Fe2O3Ultrasonically dispersing in ethanol according to the proportion of 1g/20ml, then adding water and ammonia water with the volume ratio of 2:20 to ethanol and 1:200 to ethanol, then starting stirring and heating to 35 ℃; then adding tetraethoxysilane with the volume ratio of 1:20 to ethanol for reaction for 2 hours, then adding tetraethoxysilane with the volume ratio of 1:20 to ethanol and diethyldiethoxysilane with the volume ratio of 3:100 to ethanol for reaction for 5 hours, filtering, washing and drying to obtain the modified gamma-Fe2O3；
2) Preparation of a third composite resin:
taking oil phase raw materials: taking 2 parts of modified gamma-Fe according to the mass part2O34-6 parts of methyl methacrylate, 1.2 parts of glycerol methacrylate, 1.2 parts of divinylbenzene and 0.12 part of benzoyl oxide; taking and modifying gamma-Fe2O3Toluene and gamma-Fe with the mass volume ratio of 3g/8ml2O3Cyclohexanol with mass volume ratio of 1g/2 ml;
taking water phase raw materials: 0.8 part of polyvinyl alcohol and 0 part of polyvinyl alcohol are taken according to the mass parts.8 parts of polyvinylpyrrolidone and 5 parts of sodium chloride; taking and modifying gamma-Fe2O3Water with the mass volume ratio of 3g/200 ml;
then fully dissolving the oil phase and the water phase, pouring the oil phase into the water phase, starting stirring to regulate oil drops to a proper size, heating to 70 ℃ at a speed of 1 ℃/min, keeping for 3 hours, and then heating to 80 ℃ and keeping for 5 hours to obtain precursor resin;
and then adding the precursor resin into a 65 wt% trimethyl ammonium chloride solution according to the mass volume ratio of 2g/7ml, reacting for 14h at 75 ℃, and finally placing the product in a Soxhlet extractor to extract for 24h with a methanol and acetone mixed solution to obtain a third composite resin.
Experimental example:
respectively treating the process wastewater mother liquor generated in the process of producing gallic acid by the enzyme method in a certain chemical plant by using the processes of the embodiments 1 to 9, wherein the specific treatment results are shown in table 1;
table 1: results of the Processes described in examples 1-9 for treating wastewater mother liquor of gallic acid Process
As a result: the wastewater mother liquor treated by the processes of the embodiments 1 to 9 can reach the first-level standard A, and the recovery rate of the gallic acid is higher than 95%.
Claims (9)
1. A method for recycling wastewater from gallic acid enzyme production is characterized by comprising the following steps:
the method comprises the following steps: heating for hydrolysis
Adding mother liquor obtained after gallic acid crystallization and filtration into a high-pressure reaction kettle, heating to 120-150 ℃, carrying out heat preservation reaction for 1-5 h, and then cooling to room temperature;
step two: centrifugal filtration
Carrying out centrifugal filtration treatment on the mother liquor after reaction and temperature reduction to obtain transparent purple black filtrate;
step three: resin adsorption
Performing resin column adsorption on the purple black filtrate to ensure that the content of gallic acid in final effluent is less than 500 mg/L;
step four: desorption recovery
Desorbing by using 5-8% sodium hydroxide solution at 50-55 ℃, feeding alkali liquor from the upper end of the resin column according to 0.8-1.2 BV/h, and allowing desorption liquid to flow out from the lower end, wherein the effluent liquid is the desorption liquid of the gallic acid.
2. The method for recycling the wastewater from the gallic acid enzyme process according to claim 1, wherein the second step is specifically: carrying out centrifugal filtration treatment on the mother liquor after reaction and cooling by adopting a rotary drum centrifuge at the rotating speed of 1500-2000 rad/min to obtain primary filtrate; and standing the primary filtrate for 20-30 min, and performing secondary filtration to obtain secondary filtrate, wherein the secondary filtrate is transparent purple-black filtrate.
3. The method for recycling the wastewater from the gallic acid enzyme process according to claim 1, wherein the adsorption of the resin column in step three is performed by room temperature filtration with a series connection of a plurality of resin columns.
4. The method for recycling wastewater from gallic acid enzymatic production according to claim 3, wherein the resin column comprises a resin column body and a composite resin filled in the resin column body.
5. The method for recycling the wastewater from the gallic acid enzyme process according to claim 4, wherein the composite resin is a first composite resin; the preparation method of the first composite resin comprises the following steps:
1) preparing a macroporous cross-linked resin matrix: mixing styrene and divinylbenzene according to the mass ratio of 4-17: 2-16, and then adding a mixture of styrene and divinylbenzene according to the mass ratio of 1: 1.2-1.7, uniformly mixing the pore-foaming agents, carrying out suspension copolymerization reaction, and extracting the pore-foaming agents after the reaction is finished to obtain macroporous crosslinked polystyrene beads; then extracting the macroporous crosslinked polystyrene beads with ethanol solvent for 8-12 h, drying at room temperature, and vacuum drying at 30-35 ℃ for 2-3 h to obtain a macroporous crosslinked resin matrix;
2) preparing a first composite resin: adding the macroporous cross-linked resin matrix into the acid body solution according to the proportion of 50-65 g/L, and carrying out ultrasonic treatment for 1-2 h at the stirring speed of 100-150 r/min; and then adding polyethylene glycol according to the proportion of 20-40 g/L, carrying out ultrasonic treatment for 3-5 h at the stirring speed of 200-350 r/min, carrying out suction filtration, and carrying out vacuum drying for 2-3 h at the temperature of 40-45 ℃ to obtain the first composite resin.
6. The method for recycling the wastewater from the gallic acid enzyme process according to claim 5, wherein the acid body solution is obtained by mixing 1-2 mol/L ferric chloride solution, 0.3-0.5 mol/L ferrous chloride solution, and 2-3 mol/L hydrochloric acid solution according to a volume ratio of 3-5: 1: 2-7.
7. The method for recycling wastewater from gallic acid enzyme process according to claim 4, wherein the composite resin is a second composite resin; the preparation method of the second composite resin comprises the following steps:
1) preparing a macroporous cross-linked resin matrix: mixing styrene and divinylbenzene according to the mass ratio of 4-17: 2-16, and then adding a mixture of styrene and divinylbenzene according to the mass ratio of 1: 1.2-1.7, uniformly mixing the pore-foaming agents, carrying out suspension copolymerization reaction, and extracting the pore-foaming agents after the reaction is finished to obtain macroporous crosslinked polystyrene beads; then extracting the macroporous crosslinked polystyrene beads with ethanol solvent for 8-12 h, drying at room temperature, and vacuum drying at 30-35 ℃ for 2-3 h to obtain a macroporous crosslinked resin matrix;
2) pretreatment of the macroporous cross-linked resin matrix: soaking the macroporous cross-linked resin matrix in 95% ethanol solution for 15-20 h, and washing with deionized water for 2-3 times; soaking the fabric in saturated salt solution for 15-20 h, and washing the fabric for 2-3 times by using deionized water; then soaking the mixture for 1-2 hours by using a hydrochloric acid solution with the concentration of 2-5%, and cleaning the mixture to be neutral by using deionized water; then soaking the mixture in a 1-3% sodium hydroxide solution for 3-5 h, washing the mixture with deionized water to be neutral, and discharging the liquid;
3) preparing a second composite resin: soaking the pretreated macroporous cross-linked resin matrix in a potassium permanganate solution according to the proportion of 500-800 mg/L, stirring and reacting for 1-1.5 hours at the temperature of 35-40 ℃, and washing for 2-3 times by using deionized water until the color of the potassium permanganate solution is not changed any more; adding a ferrous sulfate solution with the concentration of 5% into the washed macroporous cross-linked resin matrix according to the proportion of 30-50 g/L, and stirring and reacting for 2-3 h at the temperature of 35-40 ℃; and washing the resin with deionized water and acetone for 2-3 times in sequence, centrifugally dewatering, and drying the resin in vacuum at 40-45 ℃ for 6-8 hours to obtain second composite resin.
8. The method for recycling wastewater from gallic acid enzyme process according to claim 4, wherein the composite resin is a third composite resin; the preparation method of the third composite resin comprises the following steps:
1) modified gamma-Fe2O3The preparation of (1): mixing gamma-Fe2O3Ultrasonically dispersing the mixture in ethanol according to the proportion of 1 g/15-20 ml, then adding water and ammonia water with the volume ratio of 2: 15-20 to the ethanol being 1: 150-200, then starting stirring and heating to 30-35 ℃; then adding tetraethoxysilane with the volume ratio of 1: 15-20 to react for 1-2 hours, then adding tetraethoxysilane with the volume ratio of 1: 15-20 to ethanol and diethyldiethoxysilane with the volume ratio of 3: 75-100 to react for 4-5 hours, filtering, washing and drying to obtain the modified gamma-Fe2O3；
2) Preparation of a third composite resin:
taking oil phase raw materials: taking 1-2 parts of modified gamma-Fe by mass2O34 to 6 parts of methyl methacrylate, 0.8 to 1.2 parts of glycerol methacrylate, 0.8 to 1.2 parts of divinylbenzene and 0.08 to 0.12 part of benzyl oxideAcyl; taking and modifying gamma-Fe2O3Toluene and gamma-Fe with the mass volume ratio of 3g/8ml2O3Cyclohexanol with mass volume ratio of 1g/2 ml;
taking water phase raw materials: taking 0.6-0.8 part of polyvinyl alcohol, 0.6-0.8 part of polyvinylpyrrolidone and 3-5 parts of sodium chloride according to the mass parts; taking and modifying gamma-Fe2O3Water with the mass volume ratio of 3g/200 ml;
fully dissolving the oil phase and the water phase, pouring the oil phase into the water phase, starting stirring to regulate oil drops to a proper size, heating to 70 ℃ at a speed of 1 ℃/min, keeping for 2-3 h, and then heating to 80 ℃ and keeping for 3-5 h to obtain precursor resin;
and then adding the precursor resin into a 35-65 wt% trimethyl ammonium chloride solution according to the mass volume ratio of 2g/7ml, reacting for 8-14 h at 65-75 ℃, and finally placing the product in a Soxhlet extractor to extract for 24h with a mixed solution of methanol and acetone to obtain a third composite resin.
9. The method for recycling the wastewater from the gallic acid enzyme process according to claim 1, wherein the adsorption column is washed with distilled water after step four, specifically: and (3) after the alkali liquor is completely fed, using 0.8-1.2 BV of distilled water to wash the adsorption column for the second time according to 0.8-1.2 BV/h to obtain a washing solution, adding water to dilute the washing solution according to the proportion of 1:2, and mixing the diluted washing solution with the purple black filtrate obtained in the second step for subsequent treatment.
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| CN102008942A (en) * | 2010-10-18 | 2011-04-13 | 陕西科技大学 | Method for removing tannic acid pollutant from aminated magnetic nano composite particles |
| CN107445349A (en) * | 2017-09-26 | 2017-12-08 | 南京大学 | A kind of recycling processing method of gallic acid production wastewater |
| 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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