CN115010588B - Vanillin preparation method for reducing COD of wastewater - Google Patents
Vanillin preparation method for reducing COD of wastewater Download PDFInfo
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- CN115010588B CN115010588B CN202210712312.XA CN202210712312A CN115010588B CN 115010588 B CN115010588 B CN 115010588B CN 202210712312 A CN202210712312 A CN 202210712312A CN 115010588 B CN115010588 B CN 115010588B
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- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 title claims abstract description 56
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 235000012141 vanillin Nutrition 0.000 title claims abstract description 55
- 239000002351 wastewater Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- CGQCWMIAEPEHNQ-UHFFFAOYSA-N Vanillylmandelic acid Chemical compound COC1=CC(C(O)C(O)=O)=CC=C1O CGQCWMIAEPEHNQ-UHFFFAOYSA-N 0.000 claims abstract description 90
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 67
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 65
- 239000012535 impurity Substances 0.000 claims abstract description 56
- 239000000706 filtrate Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 150000007524 organic acids Chemical class 0.000 claims abstract description 42
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 37
- 238000006114 decarboxylation reaction Methods 0.000 claims abstract description 31
- 238000001914 filtration Methods 0.000 claims abstract description 27
- 239000005750 Copper hydroxide Substances 0.000 claims abstract description 12
- 229910001956 copper hydroxide Inorganic materials 0.000 claims abstract description 12
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 53
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 52
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- 239000007864 aqueous solution Substances 0.000 claims description 39
- 239000002253 acid Substances 0.000 claims description 27
- 125000005842 heteroatom Chemical group 0.000 claims description 19
- 230000001105 regulatory effect Effects 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 11
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 11
- 229940112669 cuprous oxide Drugs 0.000 claims description 11
- 238000012360 testing method Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000919 ceramic Substances 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims 2
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 15
- 230000001172 regenerating effect Effects 0.000 abstract description 10
- 230000001590 oxidative effect Effects 0.000 abstract description 7
- 239000007800 oxidant agent Substances 0.000 abstract description 6
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000001376 precipitating effect Effects 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 description 43
- 238000011069 regeneration method Methods 0.000 description 43
- 238000005070 sampling Methods 0.000 description 20
- 239000002994 raw material Substances 0.000 description 14
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 13
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 13
- 229960002510 mandelic acid Drugs 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000005485 electric heating Methods 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 229960001867 guaiacol Drugs 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000009499 Vanilla fragrans Nutrition 0.000 description 1
- 244000263375 Vanilla tahitensis Species 0.000 description 1
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/295—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with inorganic bases, e.g. by alkali fusion
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a vanillin preparation method for reducing COD of wastewater, which comprises pretreatment, oxidation and decarboxylation steps, wherein copper sulfate and 3-methoxy-4-hydroxy-mandelic acid are mixed in an acidic system in the pretreatment steps, organic acid impurities are removed through reaction, the content of the organic acid is controlled to be less than 100ppm, and the copper sulfate is excessive in the pretreatment steps. The excessive copper sulfate is converted into nano-scale copper hydroxide in an alkaline system and is used as an oxidant to carry out oxidation reaction with the pretreated 3-methoxy-4-hydroxy-mandelic acid. And after the oxidation reaction is finished, filtering and precipitating, removing decarboxylation reaction of the filtrate to obtain vanillin, and regenerating filter residues by copper sulfate. The COD content in the wastewater obtained by the method is as low as 1000mg/L, the copper sulfate is renewable, the process is simple, and the production cost is low.
Description
Technical Field
The invention relates to a preparation method of vanillin for reducing COD of wastewater, belonging to the technical field of chemical synthesis of perfume.
Background
Vanillin, commonly known as vanillin, has a chemical name of 3-methoxy-4-hydroxybenzaldehyde, has a special fragrance of vanilla, is usually white or pale yellow crystalline powder, is a synthetic spice with the largest yield in the world, and is widely applied to the food and spice processing industry. From the wide application and importance of vanillin in various industries, the synthesis process of vanillin has been a long-standing research hotspot.
At present, two main processes for preparing vanillin are available, one is to adopt copper oxide (or other transition metal oxides) as an oxidant, and prepare vanillin after oxidizing mandelic acid for decarboxylation. For example, CN1016190188 discloses a method for preparing vanillin by chemical oxidation, which has high yield but complex process flow.
The second main process is to use a catalyst to catalyze oxygen to oxidize mandelic acid and decarboxylate to obtain vanillin, and the process is simple, but can generate a large amount of exhaust emission.
The prior art comprises three steps of condensation, oxidation and decarboxylation of vanillin prepared from guaiacol. Since the condensation and oxidation steps are performed under alkaline conditions and the decarboxylation steps are performed under acidic conditions, a large amount of wastewater and waste sodium sulfate are generated in the process of adjusting the pH, wherein a large amount of organic matters and inorganic matters are dissolved in the generated wastewater, and degradation treatment is difficult to perform.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a vanillin preparation method for reducing COD of wastewater.
In the process of researching the traditional vanillin preparation process, the invention discovers that COD of the vanillin wastewater obtained after the phase separation in the decarboxylation step is up to 10000mg/L, and the main organic matter composition is organic hetero acid and a small amount of tar through analysis.
Because the 3-methoxy-4-hydroxy mandelic acid is obtained by condensing guaiacol and glyoxylic acid, the glyoxylic acid can generate side reaction in the reaction process to generate various water-soluble organic hybrid acid compounds mainly comprising oxalic acid, glycollic acid and the like, and the organic substances can finally enter the wastewater to cause the COD of the wastewater to be too high. Aiming at the organic mixed acid impurities, the invention further researches that part of organic mixed acid compounds can be subjected to complex reaction with transition metal ions to generate salts which are difficult to dissolve in water, and the organic mixed acid in the 3-methoxy-4-hydroxy mandelic acid solution obtained by condensation reaction of guaiacol and glyoxylate can be removed if the organic mixed acid is subjected to a certain pretreatment process.
The invention discovers that in the oxidation process, copper sulfate is converted into nano-scale copper hydroxide by adopting proper process conditions, so that the oxidation active site can be increased, the oxidation reaction efficiency is effectively improved, and the tar production amount is reduced.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a vanillin preparation method for reducing COD of wastewater, which comprises the following steps:
1) Mixing 3-methoxy-4-hydroxy-mandelic acid solution containing organic acid impurities with excessive copper sulfate aqueous solution to react the organic acid impurities with copper sulfate to reduce the content of the organic acid impurities in the reaction solution to 0-100ppm, preferably 10-50ppm, and filtering to remove the precipitate to obtain filtrate A;
2) Heating the filtrate A, adding NaOH aqueous solution into the filtrate A under stirring to adjust the pH to 12.0-14.0, preferably 13.0-13.5, converting copper sulfate into nano-copper hydroxide, carrying out oxidation reaction with 3-methoxy-4-hydroxy-mandelic acid, and filtering to obtain filtrate B;
3) And regulating the pH value of the filtrate B to 2-3 by using a sulfuric acid aqueous solution for decarboxylation reaction, then adding toluene for extraction, standing and separating to remove wastewater, and obtaining an oil phase containing vanillin.
In the present invention, step 1) the 3-methoxy-4-hydroxy-mandelic acid solution, wherein the 3-methoxy-4-hydroxy-mandelic acid content is 5 to 6wt%, preferably 5.5 to 5.8wt%;
the 3-methoxy-4-hydroxy-mandelic acid solution has an organic acid impurity content of 500-2000ppm, preferably 1000-1500ppm, and mainly comprises oxalic acid, glycolic acid and the like;
the 3-methoxy-4-hydroxy mandelic acid is obtained by condensing guaiacol and glyoxylic acid, and is a compound disclosed in the prior art. The 3-methoxy-4-hydroxy-mandelic acid solution refers to a condensation reaction solution (the composition of which is mainly a mixed solution of a 3-methoxy-4-hydroxy-mandelic acid product and water) after the reaction of guaiacol and glyoxylic acid, and can be prepared by any realizable method disclosed in the prior art, for example, in some specific examples of the present invention, the method disclosed in patent CN109956858A is preferred.
In the present invention, the copper sulfate aqueous solution of step 1) has a concentration of 5.0 to 20.0wt%, preferably 10.0 to 15.0wt%;
the copper sulfate is used in an amount of 95-165%, preferably 105-145% of the mass of 3-methoxy-4-hydroxy-mandelic acid. This step requires a substantial excess of added copper sulfate over the organic miscellaneous acid impurities, with one portion being reacted as a pretreatment agent to remove the organic miscellaneous acid impurities and the other portion being used for the subsequent oxidation step.
In the present invention, the reaction in step 1) is carried out at a temperature of 15 to 30℃and preferably 20 to 25℃for a period of 0.15 to 1h and preferably 0.25 to 0.3h.
In the present invention, the filtrate A in step 2) is heated to a temperature of 60.0 to 130.0 ℃, preferably 80.0 to 120.0 ℃.
In the present invention, the stirring speed in step 2) is 400.0 to 2000.0rpm, preferably 1000.0 to 1500.0rpm.
In the present invention, the concentration of the aqueous NaOH solution in the step 2) is 5.0 to 50.0wt%, preferably 20.0 to 30.0wt%;
the NaOH aqueous solution is preferably added dropwise in a continuous feeding manner, and the feeding time is preferably 0.5-2.0h, preferably 1.0-1.5h. Heating to proper temperature, and dripping alkali solution under stirring to generate nano Cu (OH) 2 And (3) precipitating to be used as an oxidant in the mandelic acid oxidation reaction step.
In the invention, the oxidation reaction in the step 2) is carried out at a temperature of 60.0-130.0 ℃, preferably 80.0-120.0 ℃ for 5.0-10.0 hours, preferably 6.0-8.0 hours, and the time of the oxidation reaction is counted from the completion of the dropwise addition of the NaOH aqueous solution.
In the invention, the filtration in the step 2) is preferably performed by adopting a nano ceramic membrane;
the filter residue obtained by filtering and separating can be washed by water (such as deionized), filtered again, and the filtrate is combined for the decarboxylation reaction in the step 3); the washing and filtering operation can be repeated for a plurality of times until the filtrate does not contain vanillin;
the filter residue (cuprous oxide) obtained by filtering and separating can be used for recycling the copper sulfate through regeneration treatment.
In the present invention, the aqueous sulfuric acid concentration in step 3) is 30 to 70wt%, preferably 40 to 50wt%.
In the present invention, the decarboxylation reaction in step 3) is carried out at a temperature of 25 to 40 ℃, preferably 25 to 30 ℃, for a time of 0.5 to 2 hours, preferably 1 to 1.5 hours.
In the invention, the toluene extraction in the step 3) is carried out, and the toluene consumption is 1-2 times, preferably 1.2-1.5 times, of the mass of the filtrate B; the extraction temperature is 25-40deg.C, preferably 25-30deg.C.
In the invention, the oil phase containing vanillin in the step 3) can reach a conversion rate of more than 100 percent, the vanillin selectivity is more than 98.5 percent, the organic acid impurity is lower than 20ppm, and the tar content is lower than 60ppm based on the initial raw material 3-methoxy-4-hydroxy mandelic acid.
In the invention, the waste water in the step 3) has the COD lower than 1000mg/L, the organic acid impurity content lower than 60ppm and the tar content lower than 30ppm.
The invention also provides a method for recycling the copper sulfate by regenerating the filter residue obtained by filtering and separating in the step 2), which comprises the steps of mixing the filter residue (cuprous oxide) with a sulfuric acid aqueous solution, and then introducing air to react with the cuprous oxide to obtain the copper sulfate.
In the method of the invention, the dosage of the sulfuric acid aqueous solution is 8.5-42.5 times, preferably 15-30 times, of the mass of the filter residue;
the aqueous sulfuric acid concentration is 7.5-30wt%, preferably 12.5-25wt%.
In the process of the present invention, the flow rate of the air in the reactor per unit volume is 20 to 400 mL/(min.L) Reactor for producing a catalyst ) Preferably 120-300 mL/(min.L) Reactor for producing a catalyst )。
In the process of the invention, the reaction is carried out at a temperature of 15.0 to 35.0 ℃, preferably 20.0 to 25.0 ℃, for a time of 2.0 to 6.0 hours, preferably 3.0 to 4.0 hours.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
the invention provides a vanillin preparation method for reducing COD of wastewater, which comprises pretreatment, oxidation and decarboxylation steps, wherein in the pretreatment step, copper sulfate and 3-methoxy-4-hydroxy-mandelic acid are mixed in an acidic system, organic acid impurities are removed through reaction, the content of organic acid is controlled to be less than 100ppm, and the copper sulfate is excessive in the step. The excessive copper sulfate is converted into nano-scale copper hydroxide in an alkaline system and is used as an oxidant to carry out oxidation reaction with the pretreated 3-methoxy-4-hydroxy-mandelic acid. And after the oxidation reaction is finished, filtering and precipitating, removing decarboxylation reaction of the filtrate to obtain vanillin, and regenerating filter residues by copper sulfate. The COD content in the wastewater obtained by the method is as low as 1000mg/L, the copper sulfate is renewable, the process is simple, and the production cost is low.
Drawings
FIG. 1 is an HPLC chart of a sample analysis of an oil phase containing vanillin prepared in example 1.
Detailed Description
The following further describes the technical scheme of the present invention, but is not limited thereto, and all modifications and equivalents of the technical scheme of the present invention are included in the scope of the present invention without departing from the scope of the technical scheme of the present invention.
HPLC analysis conditions: chromatographic model: shimadzu LC-20A; the sample injection amount is 5 mu L; the UV detection wavelength is 248nm; column incubator: 40 ℃; flow rate: 0.4ml/min; and (5) quantifying by an external standard method.
The 3-methoxy-4-hydroxy-mandelic acid solution used in the following examples was prepared according to the method of example 1 of patent CN109956858A, specifically the condensation reaction solution obtained after the completion of the reaction and aging.
The other raw materials in the examples were common commercial raw materials unless otherwise specified.
Example 1
A preparation method of vanillin for reducing COD of wastewater comprises the following steps:
1) Pretreatment:
1500g of a 3-methoxy-4-hydroxy-mandelic acid solution (organic hetero acid impurity content 2000 ppm) having a concentration of 6wt% was mixed with 1551g of a copper sulfate aqueous solution having a concentration of 7.5wt%, and the organic hetero acid impurity and copper sulfate were allowed to react at 15℃for 0.15 hours, filtered with a Buchner funnel to remove the precipitate, to give a filtrate A, and the organic hetero acid content was measured to be 50ppm.
2) An oxidation step:
transferring the filtrate A into a 5L stainless steel kettle, controlling the stirring rotation speed to 1000rpm, heating to 80 ℃ by adopting electric heating, regulating the pH value of the solution to 12.5 by slowly dripping NaOH aqueous solution with the concentration of 12.5wt%, keeping the dripping time for 1h to convert copper sulfate into nano-scale copper hydroxide, continuing the thermal insulation oxidation reaction for 10h, filtering with a 50nm ceramic membrane after the reaction is finished, adding 1L deionized water into filter residues for washing, filtering again, regenerating the secondary filter residues in a regeneration kettle, merging the primary filter residues and the secondary filter residues to obtain a filtrate B, and sampling to obtain 100% of mandelic acid conversion rate and 98.8% of main product selectivity.
3) Decarboxylation:
the pH of the filtrate B is regulated to 2-3 by a sulfuric acid aqueous solution with the concentration of 70wt%, decarboxylation reaction is carried out for 0.5h at the temperature of 25 ℃, toluene with the mass of 1 time of that of the filtrate B is used for extraction, and standing and liquid separation are carried out at the temperature of 25 ℃ to remove wastewater, so that an oil phase containing vanillin is obtained.
The oil phase sampling test raw material 3-methoxy-4-hydroxy mandelic acid conversion rate is 100%, vanillin selectivity is 98.8%, organic acid impurity is 0ppm, and tar content is 30ppm.
The COD of the wastewater is 566mg/L, the content of organic acid impurities is 10ppm, and the content of tar is 20ppm.
4) And a copper sulfate regeneration step:
48g of filter residue (cuprous oxide) is transferred into a 5L regeneration kettle; 1315g of 8.2wt% sulfuric acid aqueous solution was prepared, and added to a regeneration tank, and air was introduced into the regeneration tank at a rate of 350mL/min (flow rate per unit volume of reactor: 70 mL/(min. L) Reactor for producing a catalyst ) After controlling the temperature to be about 17.5 ℃ and reacting for 2 hours, a copper sulfate solution with the concentration of 7.5 weight percent is obtained, and the regeneration is completed.
Example 2
A preparation method of vanillin for reducing COD of wastewater comprises the following steps:
1) Pretreatment:
1500g of a 3-methoxy-4-hydroxy-mandelic acid solution (organic acid impurity content: 1800 ppm) having a concentration of 5.8% by weight was mixed with 562g of a copper sulfate aqueous solution having a concentration of 15% by weight, and the organic acid impurity and copper sulfate were allowed to react at 30℃for 1 hour, filtered with a Buchner funnel to remove the precipitate, to obtain a filtrate A having an organic acid content of 60ppm.
2) An oxidation step:
transferring the filtrate A into a 5L stainless steel kettle, controlling the stirring rotation speed to 1000rpm, heating to 125 ℃ by adopting electric heating, regulating the pH value of the solution to 14 by slowly dripping NaOH aqueous solution with the concentration of 20wt%, keeping the dripping time for 0.75h to convert copper sulfate into nano-grade copper hydroxide, continuing the thermal insulation oxidation reaction for 6h, filtering by a 50nm ceramic membrane after the reaction is finished, adding 1L deionized water into filter residues, washing the filter residues, filtering again, regenerating the secondary filter residues in a regeneration kettle, merging the primary filter residues and the secondary filter residues to obtain a filtrate B, and sampling to obtain 100% of mandelic acid conversion rate and 98.9% of main product selectivity.
3) Decarboxylation:
the pH of the filtrate B is regulated to 2-3 by a sulfuric acid aqueous solution with the concentration of 60wt%, decarboxylation reaction is carried out for 0.8h at the temperature of 40 ℃, toluene with the mass being 2 times that of the filtrate B is used for extraction, and standing and liquid separation are carried out at the temperature of 40 ℃ to remove waste water, thus obtaining an oil phase containing vanillin.
The oil phase sampling test raw material 3-methoxy-4-hydroxy mandelic acid conversion rate is 100%, vanillin selectivity is 98.9%, organic acid impurity is 0ppm, and tar content is 50ppm.
The COD of the wastewater is 1000mg/L, the content of organic acid impurities is 55ppm, and the content of tar is 20ppm.
4) And a copper sulfate regeneration step:
38g of filter residue (cuprous oxide) was transferred to a 5L regeneration kettle; 478g of an aqueous sulfuric acid solution having a concentration of 20.5wt% was prepared, and the mixture was fed into a regeneration tank, and air was introduced into the regeneration tank at a rate of 100mL/min (flow rate per unit volume of the reactor: 20 mL/(min. L) Reactor for producing a catalyst ) After 2.5 hours of reaction at about 25 ℃, a copper sulfate solution with a concentration of 15wt% is obtained, and the regeneration is completed.
Example 3
A preparation method of vanillin for reducing COD of wastewater comprises the following steps:
1) Pretreatment:
1500g of a 3-methoxy-4-hydroxy-mandelic acid solution having a concentration of 6wt% (organic hetero acid impurity content: 1500 ppm) was mixed with 2036g of a copper sulfate aqueous solution having a concentration of 5wt%, and the organic hetero acid impurity was allowed to react with copper sulfate at 20℃for 0.3 hours by standing, filtered with a Buchner funnel to remove the precipitate, to obtain a filtrate A, the organic hetero acid content of which was found to be 25ppm.
2) An oxidation step:
transferring the filtrate A into a 5L stainless steel kettle, controlling the stirring rotation speed to 2000rpm, heating to 120 ℃ by adopting electric heating, regulating the pH value of the solution to 12 by slowly dripping NaOH aqueous solution with the concentration of 30wt%, keeping the dripping time for 1.75 hours to convert copper sulfate into nano-grade copper hydroxide, continuing the thermal insulation oxidation reaction for 5.5 hours, filtering by using a 50nm ceramic membrane after the reaction is finished, adding 1L deionized water into filter residues for washing, filtering again, regenerating the secondary filter residues in a regeneration kettle, merging the primary filter residues and the secondary filter residues to obtain a filtrate B, and sampling to obtain 100% of mandelic acid conversion rate and 99.0% of main product selectivity.
3) Decarboxylation:
the pH of the filtrate B is regulated to 2-3 by a sulfuric acid aqueous solution with the concentration of 50wt%, decarboxylation reaction is carried out for 1h at 35 ℃, toluene with the mass 1.5 times that of the filtrate B is used for extraction, and standing and liquid separation are carried out at 35 ℃ to remove wastewater, thus obtaining an oil phase containing vanillin.
The oil phase sampling test raw material 3-methoxy-4-hydroxy mandelic acid conversion rate is 100%, vanillin selectivity is 99.1%, organic acid impurity is 5ppm, and tar content is 40ppm.
The COD of the wastewater is 200mg/L, the content of organic acid impurities is 25ppm, and the content of tar is 16ppm.
4) And a copper sulfate regeneration step:
46g of filter residue (cuprous oxide) was transferred to a 5L regeneration kettle; 1935g of 7.6wt% sulfuric acid aqueous solution was prepared, and added to a regeneration tank, and air was introduced into the regeneration tank at 1750mL/min (flow rate per unit volume of reactor: 350 mL/(min. L) Reactor for producing a catalyst ) After 5 hours of reaction at about 35 ℃, a copper sulfate solution with the concentration of 5wt% is obtained, and the regeneration is completed.
Example 4
A preparation method of vanillin for reducing COD of wastewater comprises the following steps:
1) Pretreatment:
1500g of a 3-methoxy-4-hydroxy-mandelic acid solution having a concentration of 5.2% by weight (organic hetero acid impurity content: 1200 ppm) was mixed with 684g of a copper sulfate aqueous solution having a concentration of 17.5% by weight, and the organic hetero acid impurity and copper sulfate were allowed to react at 25℃for 0.25 hours, and the mixture was filtered with a Buchner funnel to remove the precipitate, to obtain a filtrate A, the organic hetero acid content of which was 45ppm was measured.
2) An oxidation step:
transferring the filtrate A into a 5L stainless steel kettle, controlling the stirring rotation speed to be 400rpm, heating to 70 ℃ by adopting electric heating, regulating the pH value of the solution to 13 by slowly dripping NaOH aqueous solution with the concentration of 40wt%, keeping the dripping time for 2 hours to convert copper sulfate into nano-scale copper hydroxide, continuing the thermal insulation oxidation reaction for 7 hours, filtering by using a 50nm ceramic membrane after the reaction is finished, adding 1L deionized water into filter residues, washing the filter residues, filtering again, regenerating the secondary filter residues in a regeneration kettle, merging the primary filter residues and the secondary filter residues to obtain a filtrate B, and sampling to obtain 100% of mandelic acid conversion rate and 98.9% of main product selectivity.
3) Decarboxylation:
the pH of the filtrate B is regulated to 2-3 by using a sulfuric acid aqueous solution with the concentration of 40wt%, decarboxylation reaction is carried out for 1.5 hours at the temperature of 28 ℃, toluene with the mass being 2 times that of the filtrate B is used for extraction, standing and liquid separation are carried out at the temperature of 28 ℃ to remove wastewater, and thus an oil phase containing vanillin is obtained.
The oil phase sampling test raw material 3-methoxy-4-hydroxy mandelic acid conversion rate is 100%, vanillin selectivity is 98.9%, organic acid impurity is 10ppm, and tar content is 30ppm.
The COD of the wastewater is measured to be 350mg/L, the content of organic acid impurities is 45ppm, and the content of tar is 10ppm.
4) And a copper sulfate regeneration step:
54g of filter residue (cuprous oxide) is transferred to a 5L regeneration kettle; 565g of 25wt% sulfuric acid aqueous solution was prepared, and added to a regeneration tank, and air was introduced into the regeneration tank at a rate of 600mL/min (flow rate per unit volume of the reactor: 120 mL/(min. L) Reactor for producing a catalyst ) After the reaction is carried out for 6 hours at the temperature of about 30 ℃, a copper sulfate solution with the concentration of 17.5 weight percent is obtained, and the regeneration is completed.
Example 5
A preparation method of vanillin for reducing COD of wastewater comprises the following steps:
1) Pretreatment:
1500g of a 3-methoxy-4-hydroxy-mandelic acid solution having a concentration of 5.4wt% (organic hetero acid impurity content 1400 ppm) was mixed with 589g of a copper sulfate aqueous solution having a concentration of 17.5wt%, and the organic hetero acid impurity and copper sulfate were allowed to react at 25℃for 0.65h, and the mixture was filtered with a Buchner funnel to remove the precipitate, whereby filtrate A was obtained, and the organic hetero acid content was found to be 30ppm.
2) An oxidation step:
transferring the filtrate A into a 5L stainless steel kettle, controlling the stirring rotation speed to 1500rpm, heating to 60 ℃ by adopting electric heating, regulating the pH value of the solution to 13.5 by slowly dripping 50wt% NaOH aqueous solution, keeping the dripping time for 0.5h to convert copper sulfate into nano-grade copper hydroxide, continuing the thermal insulation oxidation reaction for 5h, filtering with a 50nm ceramic membrane after the reaction is finished, adding 1L deionized water into filter residues for washing, filtering again, regenerating the secondary filter residues in a regeneration kettle, merging the primary filter residues and the secondary filter residues to obtain a filtrate B, and sampling to obtain 100% of mandelic acid conversion rate and 99.25% of main product selectivity.
3) Decarboxylation:
the pH of the filtrate B is regulated to 2-3 by a sulfuric acid aqueous solution with the concentration of 30wt%, decarboxylation reaction is carried out for 2 hours at the temperature of 32 ℃, toluene with the mass 1.6 times that of the filtrate B is used for extraction, and standing and liquid separation are carried out at the temperature of 32 ℃ to remove wastewater, so that an oil phase containing vanillin is obtained.
The oil phase sampling test raw material 3-methoxy-4-hydroxy mandelic acid conversion rate is 100%, vanillin selectivity is 99.25%, organic acid impurity is 0ppm, and tar content is 50ppm.
The COD of the wastewater is 400mg/L, the content of organic acid impurities is 30ppm, and the content of tar is 20ppm.
4) And a copper sulfate regeneration step:
53g of filter residue (cuprous oxide) is transferred to a 5L regeneration kettle; matching with471g of 29wt% strength aqueous sulfuric acid solution was introduced into the regeneration tank, and air was introduced into the regeneration tank at 1050mL/min (flow rate per unit volume of the reactor: 210 mL/(min. L) Reactor for producing a catalyst ) After 3.5 hours of reaction at 15 ℃, a copper sulfate solution with the concentration of 20 weight percent is obtained, and the regeneration is completed.
Example 6
A preparation method of vanillin for reducing COD of wastewater comprises the following steps:
1) Pretreatment:
1500g of a 3-methoxy-4-hydroxy-mandelic acid solution having a concentration of 5wt% (content of organic hetero acid impurity 1900 ppm) was mixed with 787g of a copper sulfate aqueous solution having a concentration of 10wt%, and the organic hetero acid impurity and copper sulfate were allowed to react at 20℃for 0.75 hours, filtered with a Buchner funnel to remove the precipitate, to obtain a filtrate A, the content of the organic hetero acid was 45ppm.
2) An oxidation step:
transferring the filtrate A into a 5L stainless steel kettle, controlling the stirring rotation speed to 1250rpm, heating to 100 ℃ by adopting electric heating, regulating the pH value of the solution to 13.25 by slowly dripping NaOH aqueous solution with the concentration of 5wt%, keeping the dripping time for 1.5h to convert the copper sulfate into nano-scale copper hydroxide, continuing the thermal insulation oxidation reaction for 9h, filtering with a 50nm ceramic membrane after the reaction is finished, adding 1L deionized water into the filter residue for washing, filtering again, regenerating the secondary filter residue in a regeneration kettle, merging the primary filter residue and the secondary filter residue to obtain filtrate B, and sampling to obtain 100% of mandelic acid conversion rate and 98.5% of main product selectivity.
3) Decarboxylation:
the pH of the filtrate B is regulated to 2-3 by using 35wt% sulfuric acid aqueous solution, decarboxylation reaction is carried out for 1.25h at 40 ℃, toluene extraction with 1.8 times of the mass of the filtrate B is carried out, standing and liquid separation are carried out at 40 ℃ to remove waste water, and thus an oil phase containing vanillin is obtained.
The oil phase sampling test raw material 3-methoxy-4-hydroxy mandelic acid conversion rate is 100%, vanillin selectivity is 98.5%, organic acid impurity is 0ppm, and tar content is 20ppm.
The COD of the wastewater is measured to be 250mg/L, the content of organic acid impurities is 45ppm, and the content of tar is 8ppm.
4) And a copper sulfate regeneration step:
35g of filter residue (cuprous oxide) was transferred to a 5L regeneration kettle; 709g of 16.6wt% sulfuric acid aqueous solution was prepared, and added to a regeneration tank, and air was introduced into the regeneration tank at a rate of 1500mL/min (flow rate per unit volume of the reactor: 300 mL/(min. L) Reactor for producing a catalyst ) After 4 hours of reaction at about 20 ℃, a copper sulfate solution with the concentration of 10wt percent is obtained, and the regeneration is completed.
Example 7
A preparation method of vanillin for reducing COD of wastewater comprises the following steps:
1) Pretreatment:
1500g of a 3-methoxy-4-hydroxy-mandelic acid solution (organic acid impurity content 1000 ppm) with a concentration of 6wt% and 1164g of a copper sulfate aqueous solution with a concentration of 12.5wt% are mixed, the organic acid impurity and copper sulfate are allowed to react at 20 ℃ for 0.2h, and the mixture is filtered by a Buchner funnel to remove precipitate; the filtrate A was obtained, and the organic hetero acid content was found to be 30ppm.
2) An oxidation step:
transferring the filtrate A into a 5L stainless steel kettle, controlling the stirring rotation speed to 1750rpm, heating to 130 ℃ by adopting electric heating, regulating the pH value of the solution to 13.75 by slowly dripping NaOH aqueous solution with the concentration of 25wt%, keeping the dripping time for 1.25h to convert copper sulfate into nano-grade copper hydroxide, continuing the thermal insulation oxidation reaction for 8h, filtering with a 50nm ceramic membrane after the reaction is finished, adding 1L deionized water into filter residues for washing, filtering again, regenerating the secondary filter residues in a regeneration kettle, merging the primary filter residues and the secondary filter residues to obtain a filtrate B, and sampling to obtain 100% of mandelic acid conversion rate and 99.5% of main product selectivity.
3) Decarboxylation:
the pH of the filtrate B is regulated to 2-3 by using a sulfuric acid aqueous solution with the concentration of 55wt%, decarboxylation reaction is carried out for 1.75 hours at the temperature of 25 ℃, toluene with the mass 1.2 times that of the filtrate B is used for extraction, and standing and liquid separation are carried out at the temperature of 25 ℃ to remove wastewater, so that an oil phase containing vanillin is obtained.
The oil phase sampling test raw material 3-methoxy-4-hydroxy mandelic acid conversion rate is 100%, vanillin selectivity is 99.5%, organic acid impurity is 0ppm, and tar content is 15ppm.
The COD of the wastewater is 180mg/L, the content of organic acid impurities is 30ppm, and the content of tar is 5ppm.
4) And a copper sulfate regeneration step:
65g of filter residue (cuprous oxide) is transferred into a 5L regeneration kettle; 1018g of a 12.5wt% sulfuric acid aqueous solution was prepared, and added to a regeneration tank, and air was introduced into the regeneration tank at a rate of 2000mL/min (flow rate per unit volume of the reactor: 400 mL/(min. L) Reactor for producing a catalyst ) After the reaction is carried out for 3 hours at the temperature of about 22.5 ℃, a copper sulfate solution with the concentration of 12.5 weight percent is obtained, and the regeneration is completed.
Comparative example 1
The preparation method of reference example 1 only differs in that: omitting the pretreatment step of the step 1), and adjusting the addition sequence of the copper sulfate to the step 2), wherein other operations are unchanged after the addition of the alkali solution is finished.
The oil phase sampling test raw material 3-methoxy-4-hydroxy mandelic acid conversion rate is 100%, vanillin selectivity is 98%, organic acid impurity is 500ppm, and tar content is 60ppm.
The COD of the wastewater is 10200mg/L, the content of organic acid impurities is 4500ppm, and the content of tar is 20ppm.
Comparative example 2
The preparation method of reference example 1 only differs in that: in the step (1), copper sulfate is replaced by ferric sulfate with the same mass as an oxidant, and other operations are unchanged.
Step 2) oxidation reaction: the mandelic acid conversion was measured by sampling and the main product selectivity was 92%.
Step 3) decarboxylation reaction: the oil phase is sampled and tested, the conversion rate of the raw material 3-methoxy-4-hydroxy mandelic acid is 50%, the selectivity of vanillin is 92%, the organic acid impurity is 700ppm, and the tar content is 12200ppm.
The COD of the wastewater is 22000mg/L, the organic acid impurity content is 4400ppm, and the tar content is 300ppm.
Comparative example 3
The preparation method of reference example 1 only differs in that: in the step 1), copper sulfate is replaced by copper chloride with the same quality as an oxidant, and other operations are unchanged.
Step 2) oxidation reaction: the mandelic acid conversion was 99% and the main product selectivity was 96% as measured by sampling.
Step 3) decarboxylation reaction: the oil phase sampling test raw material 3-methoxy-4-hydroxy mandelic acid has a conversion rate of 99%, vanillin selectivity of 96%, organic acid impurity of 700ppm and tar content of 1200ppm.
The COD of the wastewater is 2500mg/L, the content of organic acid impurities is 440ppm, and the content of tar is 115ppm.
Comparative example 4
Vanillin was prepared according to the method of example 1, except that: naOH is not added in the step (2), and other operations are unchanged.
Step 2) oxidation reaction: the mandelic acid conversion was 100% and the main product selectivity was 30% as measured by sampling.
Step 3) decarboxylation reaction: the oil phase sampling test raw material 3-methoxy-4-hydroxy mandelic acid conversion rate is 100%, vanillin selectivity is 30%, organic acid impurity is 0ppm, and tar content is 55%.
The COD of the wastewater is 21771mg/L, the content of organic acid impurities is 20ppm, and the tar content is 6600ppm.
Claims (32)
1. The preparation method of vanillin for reducing COD in wastewater is characterized by comprising the following steps:
1) Mixing 3-methoxy-4-hydroxy-mandelic acid solution containing organic acid impurities with excessive copper sulfate aqueous solution to react the organic acid impurities with copper sulfate to reduce the content of the organic acid impurities in the reaction solution to 0-100ppm, and filtering to remove precipitate to obtain filtrate A;
2) Heating the filtrate A, adding NaOH aqueous solution into the filtrate A under stirring to adjust the pH to 12.0-14.0, converting copper sulfate into nanoscale copper hydroxide, carrying out oxidation reaction with 3-methoxy-4-hydroxy-mandelic acid, and filtering to obtain filtrate B;
3) And regulating the pH value of the filtrate B to 2-3 by using a sulfuric acid aqueous solution for decarboxylation reaction, then adding toluene for extraction, standing and separating to remove wastewater, and obtaining an oil phase containing vanillin.
2. The method according to claim 1, wherein in step 1), the content of the organic hetero acid-type impurity in the reaction liquid is reduced to 10 to 50ppm.
3. The method according to claim 1, wherein the 3-methoxy-4-hydroxy-mandelic acid solution of step 1) has a 3-methoxy-4-hydroxy-mandelic acid content of 5 to 6wt%;
the 3-methoxy-4-hydroxy-mandelic acid solution has an organic mixed acid impurity content of 500-2000ppm, wherein the organic mixed acid impurity is oxalic acid or glycollic acid; and/or
The concentration of the copper sulfate aqueous solution in the step 1) is 5.0-20.0wt%;
the dosage of the copper sulfate is 95-165% of the mass of the 3-methoxy-4-hydroxy-mandelic acid.
4. The method according to claim 3, wherein the 3-methoxy-4-hydroxy-mandelic acid solution has a 3-methoxy-4-hydroxy-mandelic acid content of 5.5 to 5.8wt%.
5. The method according to claim 3, wherein the 3-methoxy-4-hydroxy-mandelic acid solution has an organic hetero acid impurity content of 1000 to 1500ppm.
6. A method of preparing according to claim 3, wherein the aqueous copper sulphate solution has a concentration of 10.0-15.0wt%.
7. A method of preparation according to claim 3, wherein the copper sulphate is used in an amount of 105-145% by mass of 3-methoxy-4-hydroxy-mandelic acid.
8. The process according to claim 1, wherein the reaction in step 1) is carried out at a temperature of 15 to 30℃for a period of 0.15 to 1h.
9. The method according to claim 8, wherein the reaction is carried out at a temperature of 20 to 25 ℃ for a time of 0.25 to 0.3h.
10. The preparation method according to claim 1, wherein the filtrate a in step 2) is heated to a temperature of 60.0-130.0 ℃; and/or
The stirring speed in the step 2) is 400.0-2000.0rpm.
11. The preparation method according to claim 10, wherein the filtrate a is heated to a temperature of 80.0-120.0 ℃.
12. The method of claim 10, wherein the stirring speed is 1000.0-1500.0rpm.
13. The method according to claim 1, wherein the aqueous NaOH solution in step 2) has a concentration of 5.0-50.0wt%;
the NaOH aqueous solution adopts a continuous feeding mode, and the feeding time is 0.5-2.0h.
14. The method of claim 13, wherein the aqueous NaOH solution has a concentration of 20.0-30.0wt%.
15. The method of claim 13, wherein the addition time is 1.0 to 1.5 hours.
16. The method of claim 13, wherein the aqueous NaOH solution is added dropwise.
17. The method according to claim 1, wherein the oxidation reaction in step 2) is carried out at a reaction temperature of 60.0 to 130.0 ℃ for a reaction time of 5.0 to 10.0 hours, and the reaction time is counted from the completion of the dropwise addition of the aqueous NaOH solution; and/or
And step 2), the filtration adopts a nano ceramic membrane.
18. The method according to claim 17, wherein the oxidation reaction is carried out at a temperature of 80.0 to 120.0 ℃ for a time of 6.0 to 8.0 hours.
19. The method according to claim 1, wherein the aqueous sulfuric acid solution in step 3) has a concentration of 30 to 70wt%; and/or
Step 3) decarboxylation reaction, wherein the temperature is 25-40 ℃ and the time is 0.5-2h; and/or
Step 3) extracting toluene, wherein the dosage of toluene is 1-2 times of the mass of the filtrate B; the extraction temperature is 25-40 ℃.
20. The method of claim 19, wherein the aqueous sulfuric acid solution has a concentration of 40-50wt%.
21. The process of claim 19, wherein the decarboxylation reaction is carried out at a temperature of 25-30 ℃ for a time of 1-1.5 hours.
22. The process according to claim 19, wherein the toluene is extracted in an amount of 1.2 to 1.5 times the mass of the filtrate B.
23. The process of claim 19, wherein the toluene extraction is carried out at a temperature of 25-30 ℃.
24. The method according to claim 1, wherein the oil phase containing vanillin in step 3) has a conversion rate of 100%, a vanillin selectivity of 98.5% or more, an organic acid impurity content of less than 20ppm and a tar content of less than 60ppm;
and 3) testing the waste water with COD lower than 1000mg/L, organic acid impurity content lower than 60ppm and tar content lower than 30ppm.
25. The method of claim 1, wherein the method for recovering copper sulfate from the filter residue regenerated by the filtering separation in step 2) comprises mixing the filter residue with an aqueous sulfuric acid solution, and then introducing air to react with cuprous oxide to obtain copper sulfate.
26. The method according to claim 25, wherein the amount of the aqueous sulfuric acid solution is 8.5 to 42.5 times the mass of the residue.
27. The method according to claim 26, wherein the amount of the aqueous sulfuric acid solution is 15 to 30 times the mass of the residue.
28. The method of claim 25, wherein the aqueous sulfuric acid solution has a concentration of 7.5 to 30wt%.
29. The method of claim 28, wherein the aqueous sulfuric acid solution has a concentration of 12.5-25wt%.
30. The method according to claim 25, wherein the flow rate of the air in the reactor per unit volume is 20 to 400 mL/(min.l) Reactor for producing a catalyst ) The method comprises the steps of carrying out a first treatment on the surface of the And/or
The reaction is carried out at 15.0-35.0 ℃ for 2.0-6.0h.
31. The method according to claim 30, wherein the flow rate of the air in the reactor per unit volume is 120-300 mL/(min.L) Reactor for producing a catalyst )。
32. The process of claim 30 wherein the reaction is carried out at a temperature of 20.0 to 25.0 ℃ for a period of 3.0 to 4.0 hours.
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