CN102134131A - Method for treating wastewater generated in process of synthesizing vanillin by glyoxylic acid method - Google Patents
Method for treating wastewater generated in process of synthesizing vanillin by glyoxylic acid method Download PDFInfo
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- CN102134131A CN102134131A CN 201110022510 CN201110022510A CN102134131A CN 102134131 A CN102134131 A CN 102134131A CN 201110022510 CN201110022510 CN 201110022510 CN 201110022510 A CN201110022510 A CN 201110022510A CN 102134131 A CN102134131 A CN 102134131A
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Abstract
The invention discloses a method for treating wastewater generated in a process of synthesizing vanillin by a glyoxylic acid method. The method comprises the following steps of: concentrating the wastewater to remove about 50 percent of water, simultaneously improving the concentration of sodium sulfate in the wastewater to about 20 percent from about 9 percent, and removing the sodium sulfate by cooling crystallization and filter separation; selectively adsorbing aromatic compounds in the vanillin production wastewater through macroporous resin to effectively reduce the concentration of organic wastes in the wastewater, wherein the chemical oxygen demand (CODCr) is reduced to about 4,000mg/L; and adding ferrous sulfate-hydrogen peroxide into the resin adsorbed wastewater to perform oxidation treatment to degrade aliphatic organic substances, or reducing the CODCr of the wastewater to about 100mg/L by biochemical treatment so as to reach national level one discharge standard.
Description
Technical field
The present invention relates to a kind of organic wastewater treatment process, relate in particular to a kind of method that the waste water that produces in the acetaldehyde acid system synthesis of vanillin process is handled.
Background technology
Vanillin food grade,1000.000000ine mesh is a kind of important spices and foodstuff additive, is widely used in the perfuming of various food and cosmetics of everyday use, and the year usage quantity in the whole world has reached about 1.7 ten thousand tons at present.Yuan Hong has discussed the technology (Food Additives Used in China, z1,2003) of the synthetic vanirone of acetaldehyde acid system comprehensively in " progress and the development trend of the synthetic vanirone novel process of domestic acetaldehyde acid system " literary composition.The acetaldehyde acid system also is the most frequently used in the world vanillin food grade,1000.000000ine mesh synthetic method of present method, it is compared with traditional nitrosylation method has the low comparatively speaking characteristics of administering easily with the three wastes of cost, and the vanillin food grade,1000.000000ine mesh that obtains with this production accounts for more than 80% of global vanillin food grade,1000.000000ine mesh market.
Owing in the process of acetaldehyde acid system synthesis of vanillin, can produce the waste water that is equivalent to 40 times of vanillin food grade,1000.000000ine meshs, and the COD of waste water
CrAbout 6000mg/L, contains sodium sulfate about 9% is high salt and high COD
CrWaste water is difficult to reach emission standard by conventional processing.Have the investigator adopt pre-treatment-pressurized aeration bio-oxidation technology handle the vanillin food grade,1000.000000ine mesh factory effluent (water resources protection [J], 2007,23,67-9).Its method is: reactor is under the 200kPa pressure condition, and COD volumetric loading rate reaches 5.5-8.0kg/m
3D, water inlet COD mass concentration is 2000-2500mg/L, and the reaction times is 8-10 hour, and the water outlet COD mass concentration after the processing has reached sewage comprehensive discharge primary standard less than 100mg/L.By analyzing (see figure 1) as can be known, in the waste water that produces at acetaldehyde acid system synthesis of vanillin, its organism can be divided into aromatics and fatty compounds two classes.
Aromatics in the waste water as: be not extracted completely vanillin food grade,1000.000000ine mesh, methyl catechol, and by products such as ortho vanillin and dialdehyde, various aromatics (see figure 1)s.Fatty compounds in the waste water is as the methyl alcohol that reclaims fully not, unreacted raw material oxoethanoic acid completely in the reaction, and the oxalic dialdehyde of bringing in oxoethanoic acid is with oxalic acid etc.The aromatics that higher proportion is arranged in the waste water is even this waste water is administered the still difficult requirement that reaches discharging by biological process.In addition, contained aromatics is raw material, intermediate and the by product of vanillin food grade,1000.000000ine mesh production process in the vanillin food grade,1000.000000ine mesh factory effluent, the structure of ingredient is clear and definite, can utilize the polarity of these aromatics to be significantly less than the polarity of fatty compounds in the waste water, can be used after by the macroporous resin adsorption method aromatics being collected.
Contained sodium sulfate is the one of the main reasons of vanillin food grade,1000.000000ine mesh waste water incompatibility biochemical treatment in the waste water, waste water can reclaim a large amount of sodium sulfate by concentrating with crystallization, make simultaneously waste water biodegradability be improved significantly, simultaneously as long as the recovery of the proper sodium sulfate of method also has certain economic benefits.
Summary of the invention
The purpose of this invention is to provide a kind of method that the waste water that produces in the acetaldehyde acid system synthesis of vanillin process is handled, waste water makes wastewater flow rate reduce about 50% by concentrating earlier, concentrate back waste water and tell sodium sulfate about 80% through crystallisation by cooling and solid-liquid separation, removing aromatics by absorption with macroporous adsorbent resin again is used, pass through technical finesse of molysite catalyzed oxidation or biochemical treatment again, effectively reduce and realize water outlet COD
CrMass concentration reaches wastewater discharge standard.
The method that the waste water that produces in the acetaldehyde acid system synthesis of vanillin process is handled of the present invention, the technical scheme that it adopted is specific as follows:
1) the pH value of the former water of adjusting waste water gets the waste water of pH value to 6～8.
2) the control wastewater temperature concentrates the waste water of step 1) more than 20 ℃, makes waste water proportion at room temperature reach 1.10～1.15.
3) waste water crystallisation by cooling makes sodium sulfate contained in the waste water with the crystallization of sal glauberi form.
4) after the crystallization fully, tell sal glauberi, and with the less water washing crystal, washings and waste water merge by filtration.
5) step 4) waste water is removed aromatics in the waste water through nonpolar or low-pole macroporous resin adsorption, the COD of waste water after adsorbing
CrDrop to 3000～6000mg/L.
6) waste water after adsorption treatment again by ferrous salt-hydrogen peroxide oxidation or biochemical treatment to reaching emission standard.
Regulate the former water pH of waste water value and use solid sodium hydroxide or aqueous sodium hydroxide solution.
Concentrated mode is conventional distillation, thin film evaporation, multiple-effect evaporation or membrane filtration mode.Wastewater temperature need be controlled at more than 20 ℃ in the concentration process, separates out after the sodium sulfate supersaturation preventing.By spissated waste water COD
CrReach 10000～20000mg/L, contain 16～26w/v% sodium sulfate.
For making sulfate crystal more complete, during crystallization, wastewater temperature need be controlled at-5～6 ℃, and after the Crystallization Separation, sodium sulfate concentration is 2～6w/v% in the waste water, COD
CrReach 12000～25000mg/L, this moment, the waste water total amount reduced to 25～40v/v% of the former water of waste water.
Ferrous salt-hydrogen peroxide oxidation method, ferrous salt is selected ferrous sulfate or iron protochloride, and add-on is the 0.02w/v ‰-0.1w/v ‰ of the waste water of step 5) processing, and the hydrogen peroxide add-on is the 0.5-8w/v% of the waste water of step 5) processing.
Biochemical processing method is handled, and can be diluted to back below the sodium sulfate 3w/v% with low-solids water or membrane filtration gained clear water according to the content of sodium sulfate in the waste water and adopt the routine biochemistry treatment process.
Emission standard is a national grade one discharge standard.
The beneficial effect that technical solution of the present invention realizes:
The present invention reduces about 50% by concentrating the waste water total amount that need can be handled, and the sodium sulfate concentration in the waste water is brought up to about 20%, sodium sulfate in the waste water can be separated out with the sal glauberi form by crystallization, the sal glauberi of separating out can change into anhydrous sodium sulphate or directly utilize; The waste water total amount further drops to about 30% after separating out sodium sulfate, sodium sulfate concentration drops to 2～6%, and the also corresponding raising of organic concentration is about 3 times in the waste water, help macroporous resin and optionally adsorb aromatics in the vanillin food grade,1000.000000ine mesh factory effluent, with the organic waste concentration in effective reduction waste water, the aromatics that absorption obtains can be converted into recyclings such as vanillin food grade,1000.000000ine mesh by certain processing; Through only remaining 20% left and right sides fatty compounds in the waste water after the resin absorption, and sodium sulfate concentration only needs suitably to handle the back reaches waste water treatment by biochemical treatment purpose 2～6%.
Adopt the waste water total amount that present method not only can reduce greatly needs discharging, the sodium sulfate that can reclaim in the waste water simultaneously utilizes, also recyclable utilize the aromatics in the waste water and convert it into useful compound utilize the COD in the waste water simultaneously
CrWith sodium sulfate concentration obviously descended improved waste water can biochemical degree, be a kind of highly effective method.
Description of drawings
Fig. 1 is the process that aromatics produces in the acetaldehyde acid system synthesis of vanillin process.
Embodiment
Describe technical scheme of the present invention in detail below in conjunction with accompanying drawing.
With 3.80M
3Vanillin food grade,1000.000000ine mesh factory effluent (COD
Cr6245mg/L, sodium sulphate content are 8.95%), keep wastewater temperature earlier and under 30～40 ℃ of conditions, use 10M
2Permeable membrane handle and to concentrate, being concentrated into volume is 1.8M
3To concentrate back waste water again and transfer in the 2000L enamel still, logical chilled brine is cooled to Nei Wen-4～0 ℃, separates out sal glauberi.Wash solid by centrifugation and with less water, obtain 658 kilograms of solid sal glauberis.It is 1.23M that filtrate and washings merge the back cumulative volume
3, this moment density wastewater during COD
Cr18978mg/L, sodium sulphate content are 3.2%.Above-mentioned density wastewater during added the 25L resin absorption 5 hours, told resin, the COD of waste water through simple filtration
CrDrop to 4245mg/L.Add infiltration gained clear water 400L again through the waste water after the absorption, make sodium sulfate concentration be reduced to 2.5% after, with carrying out biochemical treatment, make COD through the bacterial classification of taming
CrDrop to 95mg/L.
With 3.80M
3Vanillin food grade,1000.000000ine mesh factory effluent (COD
Cr6645mg/L, sodium sulphate content are 9.13%), concentrate with conventional vacuum distillation method, being concentrated into volume is 1.90M
3To concentrate back waste water again and transfer in the 2000L enamel still, logical chilled brine is cooled to Nei Wen-5～-2 ℃, separates out sal glauberi.Wash solid by centrifugation and with less water, obtain 652 kilograms of solid sal glauberis.It is 1.38M that filtrate and washings merge the back cumulative volume
3, this moment density wastewater during COD
Cr19678mg/L, sodium sulphate content are 2.8%.Above-mentioned density wastewater during added the 25L resin absorption 5 hours, told resin, the COD of waste water through simple filtration
CrDrop to 4510mg/L.Waste water 0.2 kilogram in ferrous sulfate of adding after resin absorption is handled and 70 kilograms of oxidations of 30% hydrogen peroxide 4 hours, its COD after testing
CrBe 125mg/L.
Claims (7)
1. method that the waste water that produces in the acetaldehyde acid system synthesis of vanillin process is handled, the technical scheme that it adopted is specific as follows:
1) the pH value of the former water of adjusting waste water gets the waste water of pH value to 6～8;
2) the control wastewater temperature concentrates the waste water of step 1) more than 20 ℃, makes waste water proportion at room temperature reach 1.10～1.15;
3) waste water crystallisation by cooling makes sodium sulfate contained in the waste water with the crystallization of sal glauberi form;
4) after the crystallization fully, tell sal glauberi, and with the less water washing crystal, washings and waste water merge by filtration;
5) step 4) waste water is removed aromatics in the waste water through nonpolar or low-pole macroporous resin adsorption, the COD of waste water after adsorbing
CrDrop to 3000～6000mg/L;
6) waste water after adsorption treatment passes through ferrous salt-hydrogen peroxide oxidation or biochemical treatment again to emission standard.
2. the method that the waste water that produces in the acetaldehyde acid system synthesis of vanillin process is handled according to claim 1 is characterized in that regulating the former water pH of waste water value and uses solid sodium hydroxide or aqueous sodium hydroxide solution.
3. the method that the waste water that produces in the acetaldehyde acid system synthesis of vanillin process is handled according to claim 1 is characterized in that described step 2) spissated waste water COD
CrReach 10000～20000mg/L, contain 16～26w/v% sodium sulfate.
4. the method that the waste water that produces in the acetaldehyde acid system synthesis of vanillin process is handled according to claim 1, when it is characterized in that the step 3) crystallization, described wastewater temperature need be controlled at-5～6 ℃.
5. the method that the waste water that produces in the acetaldehyde acid system synthesis of vanillin process is handled according to claim 1, it is characterized in that the step 3) Crystallization Separation after, sodium sulfate concentration is 2～6w/v% in the waste water, COD
CrReach 12000～25000mg/L, this moment, the waste water total amount reduced to 25～40v/v% of the former water of described waste water.
6. the method that the waste water that produces in the acetaldehyde acid system synthesis of vanillin process is handled according to claim 1, it is characterized in that described ferrous salt-hydrogen peroxide oxidation method, ferrous salt is ferrous sulfate or iron protochloride, add-on is the 0.02w/v ‰-0.1w/v ‰ of the waste water of step 5) processing, and the hydrogen peroxide add-on is the 0.5-8w/v% of the waste water of step 5) processing.
7. the method that the waste water that produces in the acetaldehyde acid system synthesis of vanillin process is handled according to claim 1, it is characterized in that described biochemical processing method processing, after being diluted to sodium sulfate 3w/v% according to the content of sodium sulfate in the waste water with low-solids water or membrane filtration gained clear water, adopt the routine biochemistry treatment process.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102644091A (en) * | 2012-04-13 | 2012-08-22 | 沈阳化工大学 | Method for preparing o-vanillin |
| EP2768778A1 (en) * | 2012-03-16 | 2014-08-27 | Rhodia Operations | Method for treating production effluents of an aromatic compound derived from dihydroxybenzene |
| CN108911415A (en) * | 2018-08-08 | 2018-11-30 | 彤程化学（中国）有限公司 | Recycling processing method containing Vulkacit M wastewater |
| CN110902919A (en) * | 2019-11-27 | 2020-03-24 | 怀化旺达生物科技有限公司 | Method for treating wastewater generated in production of thiosemicarbazide |
| CN111392933A (en) * | 2020-03-09 | 2020-07-10 | 中国恩菲工程技术有限公司 | Method for reducing COD in wastewater and wastewater treatment method |
| CN112624462A (en) * | 2019-09-24 | 2021-04-09 | 万华化学集团股份有限公司 | Vanillin production wastewater treatment process |
| CN115010588A (en) * | 2022-06-22 | 2022-09-06 | 万华化学集团股份有限公司 | Vanillin preparation method for reducing COD (chemical oxygen demand) of wastewater |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2768778A1 (en) * | 2012-03-16 | 2014-08-27 | Rhodia Operations | Method for treating production effluents of an aromatic compound derived from dihydroxybenzene |
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| CN108911415A (en) * | 2018-08-08 | 2018-11-30 | 彤程化学（中国）有限公司 | Recycling processing method containing Vulkacit M wastewater |
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| CN110902919A (en) * | 2019-11-27 | 2020-03-24 | 怀化旺达生物科技有限公司 | Method for treating wastewater generated in production of thiosemicarbazide |
| CN111392933A (en) * | 2020-03-09 | 2020-07-10 | 中国恩菲工程技术有限公司 | Method for reducing COD in wastewater and wastewater treatment method |
| CN115010588A (en) * | 2022-06-22 | 2022-09-06 | 万华化学集团股份有限公司 | Vanillin preparation method for reducing COD (chemical oxygen demand) of wastewater |
| CN115010588B (en) * | 2022-06-22 | 2024-02-02 | 万华化学集团股份有限公司 | Vanillin preparation method for reducing COD of wastewater |
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Application publication date: 20110727 |