CN110040894A - A kind of processing method of the low-concentration acetic acid wastewater containing mineral acid and organic impurities - Google Patents
A kind of processing method of the low-concentration acetic acid wastewater containing mineral acid and organic impurities Download PDFInfo
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- CN110040894A CN110040894A CN201910305220.8A CN201910305220A CN110040894A CN 110040894 A CN110040894 A CN 110040894A CN 201910305220 A CN201910305220 A CN 201910305220A CN 110040894 A CN110040894 A CN 110040894A
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- calcium
- calcium acetate
- acetic acid
- acetate
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 282
- 239000002351 wastewater Substances 0.000 title claims abstract description 68
- 239000002253 acid Substances 0.000 title claims abstract description 32
- 239000012535 impurity Substances 0.000 title claims abstract description 20
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 15
- 239000011707 mineral Substances 0.000 title claims abstract description 15
- 238000003672 processing method Methods 0.000 title claims abstract description 10
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims abstract description 103
- 239000001639 calcium acetate Substances 0.000 claims abstract description 103
- 235000011092 calcium acetate Nutrition 0.000 claims abstract description 103
- 229960005147 calcium acetate Drugs 0.000 claims abstract description 103
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 100
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000007787 solid Substances 0.000 claims abstract description 41
- 239000012065 filter cake Substances 0.000 claims abstract description 40
- 239000000725 suspension Substances 0.000 claims abstract description 37
- 238000003795 desorption Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 31
- 239000001301 oxygen Substances 0.000 claims abstract description 31
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 28
- 239000000706 filtrate Substances 0.000 claims abstract description 28
- 238000001914 filtration Methods 0.000 claims abstract description 28
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011575 calcium Substances 0.000 claims abstract description 20
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 14
- 239000005416 organic matter Substances 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- 230000002308 calcification Effects 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- 235000011132 calcium sulphate Nutrition 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 28
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 24
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 20
- 239000001175 calcium sulphate Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 12
- 229940090181 propyl acetate Drugs 0.000 claims description 12
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 claims description 12
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 11
- 235000021419 vinegar Nutrition 0.000 claims description 10
- 239000000052 vinegar Substances 0.000 claims description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 8
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 3
- 238000005336 cracking Methods 0.000 claims description 3
- 238000002309 gasification Methods 0.000 claims description 3
- 239000011973 solid acid Substances 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- HFNUUHLSQPLBQI-UHFFFAOYSA-N acetic acid;calcium Chemical compound [Ca].CC(O)=O HFNUUHLSQPLBQI-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 11
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 230000032050 esterification Effects 0.000 description 8
- 238000005886 esterification reaction Methods 0.000 description 8
- 238000000926 separation method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 235000011056 potassium acetate Nutrition 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 239000002920 hazardous waste Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- CBXUNMSHTDLQEU-UHFFFAOYSA-N acetic acid;furan-2-carbaldehyde Chemical compound CC(O)=O.O=CC1=CC=CO1 CBXUNMSHTDLQEU-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- COVXERDUDZWKQL-UHFFFAOYSA-L [Ca++].[Ca++].CC([O-])=O.CC([O-])=O Chemical compound [Ca++].[Ca++].CC([O-])=O.CC([O-])=O COVXERDUDZWKQL-UHFFFAOYSA-L 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 238000003359 percent control normalization Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- 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
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/041—Treatment of water, waste water, or sewage by heating by distillation or evaporation by means of vapour compression
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- 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
Abstract
The invention discloses a kind of processing methods of low-concentration acetic acid wastewater containing mineral acid and organic impurities, it carries out that the acetic acid in waste water is changed into calcium acetate by calcification processing, sulfuric acid is changed into calcium sulfate to waste water using calcium carbonate, the filter cake of sulfur acid calcium and the filtrate containing calcium acetate is obtained by filtration；Filtrate containing calcium acetate carries out MVR and handles to obtain calcium acetate suspension, calcium acetate suspension is through being obtained by filtration filter cake and calcium acetate aqueous solution containing calcium acetate, calcium acetate aqueous solution is crystallized to be dried to obtain calcium acetate, merge to obtain calcium acetate solid with the filter cake containing calcium acetate, calcium acetate solid acidolysis generates acetic acid and calcium sulfate；The filter cake of calcium sulfate and/or sulfur acid calcium carries out Thermal desorption, and the vapor of the vapor containing organic matter and crystallizing and drying generation that the gas of Thermal desorption processing formation, MVR processing generate, which enters, faces the progress deep purifying processing of oxygen cracker.The method of the present invention realizes the recycling and purified treatment of the low-concentration acetic acid wastewater of sulfur acid and organic impurities.
Description
Technical field
The invention belongs to industrial acetic acid waste water treatment fields, are related to a kind of low concentration vinegar containing mineral acid and organic impurities
The processing method of sour waste water realizes the purification and recycling treatment of low-concentration acetic acid wastewater.
Background technique
Acetic acid is a kind of critically important industrial chemicals, also can be used as solvent and is widely used in the industries such as pharmacy, chemical industry, dyestuff
In.The low-concentration acetic acid industrial wastewater of a large amount of sulfur acids can be generated in the production process of acetate, the COD value of waste water is up to several
Ten thousand even hundreds of thousands mgO2/ L, these waste water belong to hazardous waste, and purified treatment difficulty is very big.
Strong acid waste water is generally industrially handled using direct incineration method or neutralisation, but can largely waste acetic acid resource.
Therefore the resource utilization of low-concentration acetic acid wastewater, which utilizes, seems of crucial importance.Currently, separating and recovering the side of acetic acid from waste water
Method mainly includes membrane separation process, absorption method, extraction, esterification process, rectification method etc..That there are film preparations is at high cost, easy for membrane separation process
The shortcomings that pollution；That there are adsorbent reactivations in absorption method is at high cost, vulnerable to heavy metal ion pollution the disadvantages of；Extraction is due to extraction
Agent is taken to need to recycle, the loss of extractant is larger；Esterification process is limited, ester since there are a large amount of water by reaction balance
It is too low to change reaction rate；Rectification method since acetic acid is close with the boiling point of water, and the boiling point of water be lower than acetic acid, the two it is relatively volatile
Degree is also close, therefore can not obtain acetic acid by conventional rectification, needs to use special extract rectification method, big so as to cause equipment investment,
Rectifying is at high cost.
Patent CN103588336A provides a kind of method using low-concentration acetic acid wastewater, comprising the following steps: (1) mistake
Filter processing: first acetic acid wastewater is filtered, is cleaned；(2) potassium hydroxide neutralisation treatment: is added into filtered acetic acid wastewater
Neutralization reaction occurs, is sufficiently mixed acetic acid wastewater with potassium hydroxide using blender stirring, acetic acid reacts life with potassium hydroxide
At potassium acetate, the PH to 7~9 of acetic acid wastewater is adjusted；(3) gained acetic acid wastewater after neutralization concentration: is led into cooling tower pair
Cooling tower carries out moisturizing, and with the operation of cold water Tower System, the concentration of potassium acetate is increased in the cooling water of cooling tower；(4) it evaporates
Crystallization: after potassium acetate reaches 20g/L~2700g/L in the cooling water of cooling tower, gained cooling water is evaporated and is crystallized
To potassium acetate.The invention can handle the acetic acid in acetic acid wastewater to obtain potassium acetate recycling, and this method is practical, operation
Safety and stability.This method is only applicable to the acetic acid wastewater without other inorganic acids and other organic impurities.
Patent CN 1626494A disclose it is a kind of using n-octyl alcohol be extractant furfural acetic acid is handled in pulsed extraction tower
Then the method for waste water is handled using n-hexane as entrainer using the furfural acetic acid wastewater of intermittent azeotropic rectifying purification & isolation acetic acid
The acetic acid that quality purity is greater than 98.0% or more can be obtained in method, and acetate concentration is less than 0.5% in waste water, but the extraction of process
Agent loss is larger, and processed waste water must not direct emission.
Patent CN104926010A is related to a kind for the treatment of process of acetic acid wastewater, includes the following steps: (1) pre-treatment: will
The waste water that the acetate concentration that production process generates is 10~15wt% control temperature at 40 DEG C hereinafter, successively through cloth envelop collector and
After hollow fiber ultrafiltration membrane filtering, suspended matter and precipitate therein are removed；(2) UF membrane: by acetic acid obtained in step (1)
Waste water, by the acetic acid in concentration repeatedly further recycling waste water, makes the vinegar in the concentrate being finally discharged with antipollution nanofiltration membrane
The concentration of acid reaches 40wt%, is recycled in gained dilution return step (1)；(3) it post-processes: by gained in step (2)
Concentrate through rectification and purification, gained acetic acid recovery uses.
The low concentration vinegar containing mineral acid (sulfuric acid) and organic impurities is all not directed in the processing method of above-mentioned waste water
The processing method of acid.
Summary of the invention
The purpose of the present invention is being directed to the low-concentration acetic acid wastewater containing mineral acid and organic impurities, it is not easy to wave using calcium acetate
Hair and calcium sulfate principle not soluble in water, are changed into calcium acetate for the acetic acid in waste water, sulfuric acid is changed into calcium sulfate, pass through filtering
Calcium sulfate is isolated, then carries out the separation of calcium acetate and organic impurities in filtrate, calcium acetate obtains acetic acid and sulphur through a step acidolysis
Sour calcium realizes the purification and recycling treatment of low-concentration acetic acid wastewater.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of processing method of the low-concentration acetic acid wastewater containing mineral acid and organic impurities, comprising: using calcium carbonate to useless
Water carries out calcification processing, the acetic acid in waste water is changed into calcium acetate, sulfuric acid is changed into calcium sulfate, and sulfur acid calcium is obtained by filtration
Filter cake and filtrate containing calcium acetate；Filtrate containing calcium acetate carries out MVR and handles to obtain calcium acetate suspension, calcium acetate suspension warp
Filter cake and calcium acetate aqueous solution containing calcium acetate is obtained by filtration, calcium acetate aqueous solution is crystallized to be dried to obtain calcium acetate, and contains vinegar
The filter cake of sour calcium merges to obtain calcium acetate solid, and calcium acetate solid carries out acidolysis processing and generates acetic acid and calcium sulfate；Calcium sulfate and/
Or the filter cake of sulfur acid calcium carries out Thermal desorption processing, the gas containing organic steam of Thermal desorption processing formation, MVR processing generate
Vapor containing organic matter and the vapor that generates of crystallizing and drying enter and face oxygen cracker and carry out deep purifying processing.
Preferably, the processing method of the low-concentration acetic acid wastewater containing mineral acid and organic impurities, including following step
It is rapid:
Step (1), calcification processing: calcium carbonate is added in the low acetic acid wastewater containing mineral acid and organic impurities, makes waste water
PH value is increased to 6~7, the acetic acid in waste water is changed into calcium acetate, sulfuric acid is changed into calcium sulfate, is formed and contains calcium sulfate and vinegar
The suspension of sour calcium；
The suspension that step (2), calcification processing obtain is filtered, and removes solid suspended impurity and sulfuric acid in waste water
Calcium, obtains the filter cake of sulfur acid calcium and the filtrate containing calcium acetate, and filtrate goes MVR device progress MVR to handle to obtain calcium acetate suspension
Liquid, the vapor containing organic matter that MVR processing generates, which enters, faces oxygen cracker；Calcium acetate suspension is filtered, and is contained
The filter cake and calcium acetate aqueous solution of calcium acetate, calcium acetate aqueous solution is crystallized to be dried to obtain calcium acetate, and the filter cake containing calcium acetate
Calcium acetate solid is obtained after merging, the vapor generated during crystallizing and drying, which enters, faces oxygen cracker；
Step (3), calcium acetate solid carry out acidolysis and handle to obtain acetic acid and calcium sulphate solid, and acetic acid returns to esterification work
The filter cake of sequence, calcium sulphate solid and/or sulfur acid calcium carries out Thermal desorption processing, obtains the sulfuric acid that content of organics is lower than 0.1%
Calcium solid, the gas containing organic steam that Thermal desorption processing is formed, which enters, faces the processing of oxygen cracker deep purifying.
The mineral acid is sulfuric acid.Acetic acid content is in the low-concentration acetic acid wastewater containing mineral acid and organic impurities
0.5~10wt%, the content of organics other than acetic acid are 0.01~0.5wt%, and sulfuric acid content is 1~5wt%.
Organic matter other than the acetic acid be methyl acetate, ethyl acetate, propyl acetate, tert-butyl acetate, acetic acid just
At least one of butyl ester, methanol, ethyl alcohol, propyl alcohol, the tert-butyl alcohol, n-butanol organic matter.
The additional amount of the calcium carbonate is determined by the stoichiometric ratio of sulfuric acid and acetic acid and calcium carbonate.Waste water through calcification at
The suspension that the pH value obtained after reason is 6~7.
The calcium acetate aqueous solution handles to obtain calcium acetate concentration to be that 30~40wt% obtains calcium acetate suspension through MVR
Liquid.The MVR processing time is 1~2 hour, and the generation rate of vapor is 850~1450m in MVR treatment process3/h。
The generation rate of vapor is 200~400m during crystallizing and drying3/h。
The temperature of the Thermal desorption is 200~400 DEG C.The generation rate of vapor is 2~11m during Thermal desorption3/
h。
The acidolysis processing are as follows: calcium carbonate solid and sulfuric acid occur acidolysis reaction and generates acetic acid and calcium sulfate.Described
Sulfuric acid is the concentrated sulfuric acid that mass fraction is not less than 98%.The dosage of sulfuric acid is determined by the stoichiometric ratio of sulfuric acid and calcium carbonate.
It is organic that containing for generation is handled into gas, the MVR that the gas for facing oxygen cracker includes the generation of calcium sulfate Thermal desorption
The vapor that the vapor and crystallizing and drying of object generate carries out deep purifying processing, deep purifying processing under air conditions
Purification reaction temperature be 250~450 DEG C, reaction pressure is normal pressure, and the residence time is 0.1~10kgh/m3, air is passed through
Amount is 1~5:1 with the volume ratio for facing the vapor of oxygen cracker is entered.The heat that deep purifying processing is released is filled for MVR
Set the gasification of liquid；Face oxygen cracker and realize autothermal equilibrium, is not necessarily to external energy；Face in the water in oxygen cracker exit
COD value is 0~40mgO2/ L reaches the requirement of integrated wastewater discharge standard GB8979-1996, and VOC is total in the exhaust gas given off
Amount is 5~50mg/m3, reach the requirement of chemical industry Volatile organic emissions standard DB32/3151-2016.
Beneficial effects of the present invention:
The present invention faces oxygen cracking-acidolysis new technology route using waste water calcification-MVR-, by calcification processing by waste water
In acetic acid be changed into calcium acetate, sulfuric acid is changed into calcium sulfate, be isolated by filtration out calcium sulfate, then pass through MVR, crystallizing and drying
The separation of calcium acetate and organic impurities in filtrate is realized in equal operations, and calcium acetate obtains acetic acid and calcium sulfate through a step acidolysis, calcification
Thermal desorption is carried out with the calcium sulfate that acidolysis is handled, the method for the present invention not only realizes the separation of organic impurities and vinegar in waste water
Acid separation, by hazardous waste be changed into harmless solid material calcium sulfate and can reuse acetic acid, realize recycling treatment, pole
The earth reduces the cost of business processes hazardous waste；Gas, MVR processing and the crystallization that calcium sulfate Thermal desorption generates simultaneously are dry
The dry vapor containing organic matter generated handles the purified water being changed into without further biochemical treatment by deep purifying,
Realize the deep purifying processing of the low-concentration acetic acid wastewater of sulfur acid.
Detailed description of the invention
Fig. 1 is the process flow chart of the processing method of the low-concentration acetic acid wastewater of the invention containing mineral acid and organic impurities.
Specific embodiment
Embodiment 1
Acetic acid wastewater composition: acetic acid quality score 4.8%, methanol quality score 0.11%, propyl alcohol mass fraction 0.03%,
Tert-butyl alcohol mass fraction 0.09%, methyl acetate mass fraction 0.09%, propyl acetate mass fraction 0.05%, tert-butyl acetate
Mass fraction 0.03%, sulfuric acid mass fraction are 1.4%, remaining is moisture.
2000kg acetic acid wastewater is added in a kettle, is slowly added to 110.2kg calcium carbonate under stirring, at room temperature
After stirring 1 hour, the pH value of waste water is increased to 6.7, forms the suspension containing calcium sulfate.
Above-mentioned suspension filtering, obtains filter cake (weight in wet base 42.5kg), filter cake Thermal desorption 3 hours at 200 DEG C obtain organic
Object content is the calcium sulphate solid 36.8kg of 0.09wt%, and the generation rate of vapor is 2.36m during Thermal desorption3/h。
The filtrate being obtained by filtration removes MVR device, is handled 1.5 hours by MVR device, and the generation rate of vapor is
1416.35m3/ h obtains calcium acetate suspension (content of calcium acetate is 40wt%).Calcium acetate suspension is obtained by filtration containing vinegar
The filter cake of sour calcium, the filtrate containing calcium acetate, filtrate is crystallized to be dried to obtain calcium acetate, and 124.8kg vinegar is obtained after merging with filter cake
Sour calcium solid, the generation rate of vapor is 232.96m during crystallizing and drying3/h.Addition 98% is dense in calcium acetate solid
Sulfuric acid 80kg carries out acidolysis reaction, and reaction solution filtering obtains calcium sulphate solid 91.8kg, acetic acid 92.7kg, obtained calcium sulfate
Solid carries out Thermal desorption, and acetic acid returns to esterification system.
It is steamed by the water containing methanol, propyl alcohol, the tert-butyl alcohol, methyl acetate, propyl acetate, tert-butyl acetate that MVR device steams
The steam of the vapor containing organic matter and crystallizing and drying generation that air and heat parsing generates, which enters, faces oxygen cracker, in air
Under the conditions of carry out deep purifying processing, deep purifying processing purification reaction temperature be 250 DEG C, reaction pressure is normal pressure, stop
Time is 5kgh/m3, air intake and the volume ratio into the vapor for facing oxygen cracker are 1:1, by facing oxygen cracking
COD value is 6mgO in the water that device comes out2/ L, VOC concentration is 5mg/m in gas phase3.The heat that deep purifying processing is released is used for
The gasification of MVR device liquid；Face oxygen cracker and realize autothermal equilibrium, is not necessarily to external energy.
Embodiment 2
Acetic acid wastewater composition: acetic acid quality score 6.7%, ethyl alcohol mass fraction 0.08%, propyl alcohol mass fraction 0.04%,
Tert-butyl alcohol mass fraction 0.12%, ethyl acetate mass fraction 0.07%, propyl acetate mass fraction 0.04%, tert-butyl acetate
Mass fraction 0.05%, sulfuric acid mass fraction are 2.2%, remaining is moisture.
2000kg acetic acid wastewater is added in a kettle, is slowly added to 156.7kg calcium carbonate under stirring, at room temperature
After stirring 1 hour, the pH value of waste water is increased to 6.8, forms the suspension containing calcium sulfate.
Above-mentioned suspension filtering, obtains filter cake (weight in wet base 74.2kg), filter cake Thermal desorption 3 hours at 200 DEG C obtain organic
Object content is the calcium sulphate solid 60.5kg of 0.09wt%, and the generation rate of vapor is 5.68m during Thermal desorption3/h。
Filtrate removes MVR device, and after being handled 1.5 hours by MVR device, the generation rate of vapor is 1298.26m3/ h, obtains
To calcium acetate suspension (content of calcium acetate is 38wt%).Calcium acetate suspension is obtained by filtration filter cake containing calcium acetate, is contained
The filtrate of calcium acetate, filtrate is crystallized to obtain calcium acetate, is dried after merging with filter cake, obtains 170.5kg calcium acetate
Solid, the generation rate of vapor is 346.18m during crystallizing and drying3/h.98% concentrated sulfuric acid is added in calcium acetate solid
106.6kg carries out acidolysis reaction, and reaction solution filtering obtains calcium sulphate solid 140.8kg, acetic acid 128.5kg, obtained calcium sulfate
Solid carries out Thermal desorption, and acetic acid returns to esterification system.
It is steamed by the water containing ethyl alcohol, propyl alcohol, the tert-butyl alcohol, ethyl acetate, propyl acetate, tert-butyl acetate that MVR device steams
The steam of the vapor containing organic matter and crystallizing and drying generation that air and heat parsing generates, which enters, faces oxygen cracker, in air
Under the conditions of carry out deep purifying processing, deep purifying processing purification reaction temperature be 300 DEG C, reaction pressure is normal pressure, stop
Time is 10kgh/m3, air intake and the volume ratio into the vapor for facing oxygen cracker are 5:1, by facing oxygen cracking
COD value is 9mgO in the water that device comes out2/ L, VOC concentration is 11mg/m in gas phase3。
Embodiment 3
Acetic acid wastewater composition: acetic acid quality score 5.9%, ethyl alcohol mass fraction 0.11%, propyl alcohol mass fraction 0.03%,
N-butanol mass fraction 0.07%, methyl acetate mass fraction 0.09%, propyl acetate mass fraction 0.05%, tert-butyl acetate
Mass fraction 0.03%, sulfuric acid mass fraction are 2.3%, remaining is moisture.
1800kg acetic acid wastewater is added in a kettle, is slowly added to 130.8kg calcium carbonate under stirring, at room temperature
After stirring 1 hour, the pH value of waste water is increased to 6.4, forms the suspension containing calcium sulfate.
It is obtained filter cake (weight in wet base 70.6kg) after above-mentioned suspension filtering, filter cake Thermal desorption 3 hours, Thermal desorption at 200 DEG C
The content of organics obtained afterwards is the calcium sulphate solid 55.6kg of 0.09wt%, and the generation rate of vapor is during Thermal desorption
6.22m3/h。
The filtrate being obtained by filtration removes MVR device, is handled 1.5 hours by MVR device, and the generation rate of vapor is
1166.52m3/ h, the content for obtaining calcium acetate in acetic acid and suspension is 35wt%.Calcium acetate suspension is obtained by filtration containing vinegar
The filter cake of sour calcium, the filtrate containing calcium acetate, filtrate is crystallized to obtain calcium acetate, is dried, obtains after merging with filter cake
138.8kg calcium acetate solid, the generation rate of vapor is 320.78m during crystallizing and drying3/h.It is added in calcium acetate solid
98% concentrated sulfuric acid 87kg carries out acidolysis reaction, and reaction solution filtering obtains calcium sulphate solid 101.4kg, acetic acid 103.2kg is obtained
The calcium sulphate solid arrived carries out Thermal desorption, and acetic acid returns to esterification system.
It is steamed by the water containing ethyl alcohol, propyl alcohol, n-butanol, methyl acetate, propyl acetate, tert-butyl acetate that MVR device steams
The steam of the gas containing organic steam and crystallizing and drying generation that air and heat parsing generates, which enters, faces oxygen cracker, in sky
Deep purifying processing is carried out under the conditions of gas, the purification reaction temperature of deep purifying processing is 450 DEG C, and reaction pressure is normal pressure, is stopped
Staying the time is 7kgh/m3, air intake and the volume ratio into the vapor for facing oxygen cracker are 2:1, are split by facing oxygen
Solving COD value in the water that device comes out is 14mgO2/ L, VOC concentration is 8mg/m in gas phase3。
Embodiment 4
Acetic acid wastewater composition: acetic acid quality score 7.3%, ethyl alcohol mass fraction 0.13%, tert-butyl alcohol mass fraction
0.05%, propyl acetate mass fraction 0.08%, tert-butyl acetate mass fraction 0.03%, sulfuric acid mass fraction is 4.2%,
Remaining is moisture.
1500kg acetic acid wastewater is added in a kettle, is slowly added to 155.6kg calcium carbonate under stirring, at room temperature
After stirring 1 hour, the pH value of waste water is increased to 6.6, forms the suspension containing calcium sulfate.
It is obtained filter cake (weight in wet base 112.7kg) after above-mentioned suspension filtering, filter cake Thermal desorption 3 hours, Thermal desorption at 200 DEG C
The content of organics obtained afterwards is the calcium sulphate solid 87.5kg of 0.09wt%, and the generation rate of vapor is during Thermal desorption
10.45m3/h。
The filtrate being obtained by filtration removes MVR device, is handled 1.5 hours by MVR device, and the generation rate of vapor is
884.04m3/ h, the content of calcium acetate is 35wt% in the calcium acetate suspension of generation.Calcium acetate suspension contains through being obtained by filtration
The filter cake of calcium acetate, the filtrate containing calcium acetate, filtrate is crystallized to obtain calcium acetate, is dried, obtains after merging with filter cake
To 143.1kg calcium acetate solid, the generation rate of vapor is 330.72m during crystallizing and drying3/h.Add in calcium acetate solid
The concentrated sulfuric acid 90kg for entering 98% carries out acidolysis reaction, and reaction solution filtering obtains calcium sulphate solid 103.7kg, acetic acid 99.5kg, sulphur
Sour calcium solid, which produces, carries out Thermal desorption, and acetic acid returns to esterification system.
By MVR device steam containing ethyl alcohol, the tert-butyl alcohol, propyl acetate, the vapor of tert-butyl acetate organic matter, Thermal desorption
The vapor containing organic matter generated and the steam of crystallizing and drying generation, which enter, faces oxygen cracker, carries out under air conditions
Deep purifying processing, the purification reaction temperature of deep purifying processing are 350 DEG C, and reaction pressure is normal pressure, residence time 2kg
h/m3, air intake and the volume ratio into the vapor for facing oxygen cracker are 3:1, the water come out by facing oxygen cracker
Middle COD value is 11mgO2/ L, VOC concentration is 9mg/m in gas phase3。
Embodiment 5
Acetic acid wastewater composition: acetic acid quality score 8.2%, propyl alcohol mass fraction 0.02%, n-butanol mass fraction
0.07%, methyl acetate mass fraction 0.05%, ethyl acetate mass fraction 0.09%, propyl acetate mass fraction 0.07%,
Tert-butyl acetate mass fraction 0.04%, sulfuric acid mass fraction are 4.7%, remaining is moisture.
1700kg acetic acid wastewater is added in a kettle, is slowly added to 197.8kg calcium carbonate under stirring, at room temperature
After stirring 1 hour, the pH value of waste water is increased to 6.5, forms the suspension containing calcium sulfate.
It is obtained filter cake (weight in wet base 136.6kg) after above-mentioned suspension filtering, filter cake Thermal desorption 3 hours, Thermal desorption at 200 DEG C
The calcium sulphate solid 120.3kg that content of organics is 0.09wt% is obtained afterwards, and the generation rate of vapor is during Thermal desorption
6.76m3/h。
The filtrate being obtained by filtration removes MVR device, is handled 1.5 hours by MVR device, and the generation rate of vapor is
980.40m3/ h, the content of calcium acetate is 37wt% in the calcium acetate suspension of generation.Calcium acetate suspension contains through being obtained by filtration
The filter cake of calcium acetate, the filtrate containing calcium acetate, filtrate is crystallized to obtain calcium acetate, is dried, obtains after merging with filter cake
To 182.2kg calcium acetate solid, the generation rate of vapor is 386.07m during crystallizing and drying3/h.Add in calcium acetate solid
The concentrated sulfuric acid 115kg for entering 98% carries out acidolysis reaction, and reaction solution filtering obtains calcium sulphate solid 133.6kg, acetic acid 139.4kg,
Calcium sulphate solid carries out Thermal desorption, and acetic acid returns to esterification system.
By MVR device steam containing propyl alcohol, n-butanol, methyl acetate, ethyl acetate, propyl acetate, tert-butyl acetate
The steam of the vapor containing organic matter and crystallizing and drying generation that vapor, Thermal desorption generate, which enters, faces oxygen cracker,
Deep purifying processing is carried out under air conditions, the purification reaction temperature of deep purifying processing is 280 DEG C, and reaction pressure is normal pressure,
Residence time is 6kgh/m3, air intake and the volume ratio into the vapor for facing oxygen cracker are 1:1, by facing oxygen
COD value is 12mgO in the water that cracker comes out2/ L, VOC concentration is 14mg/m in gas phase3。
Claims (10)
1. a kind of processing method of the low-concentration acetic acid wastewater containing mineral acid and organic impurities, characterized by comprising: use carbon
Sour calcium carries out calcification processing to waste water, the acetic acid in waste water is changed into calcium acetate, sulfuric acid is changed into calcium sulfate, is obtained by filtration and contains
The filter cake of calcium sulfate and filtrate containing calcium acetate；Filtrate containing calcium acetate carries out MVR and handles to obtain calcium acetate suspension, calcium acetate
For suspension through filter cake and calcium acetate aqueous solution containing calcium acetate is obtained by filtration, calcium acetate aqueous solution is crystallized to be dried to obtain acetic acid
Calcium, and the filter cake containing calcium acetate merge to obtain calcium acetate solid, and calcium acetate solid carries out acidolysis processing and generates acetic acid and calcium sulfate；
The filter cake of calcium sulfate and/or sulfur acid calcium carries out Thermal desorption processing, and what the gas of Thermal desorption processing formation, MVR processing generated contains
The vapor that the vapor and crystallizing and drying of organic matter generate, which enters, faces the progress deep purifying processing of oxygen cracker.
2. according to the method described in claim 1, characterized by the following steps:
Step (1), calcification processing: being added calcium carbonate in the low acetic acid wastewater containing mineral acid and organic impurities, by the vinegar in waste water
Acid is changed into calcium acetate, sulfuric acid is changed into calcium sulfate, forms the suspension containing calcium sulfate and calcium acetate；
The suspension that step (2), calcification processing obtain is filtered, and obtains the filter cake of sulfur acid calcium and the filtrate containing calcium acetate,
Filtrate carries out MVR and handles to obtain calcium acetate suspension, and the vapor containing organic matter that MVR processing generates, which enters, faces oxygen cracking dress
It sets；Calcium acetate suspension is filtered, and obtains the filter cake and calcium acetate aqueous solution containing calcium acetate, and calcium acetate aqueous solution is crystallized dry
It is dry to obtain calcium acetate, and calcium acetate solid is obtained after the merging of the filter cake containing calcium acetate, the vapor generated during crystallizing and drying
Into facing oxygen cracker；
Step (3), calcium acetate solid carry out acidolysis and handle to obtain acetic acid and calcium sulphate solid, calcium sulphate solid and/or sulfur acid
The filter cake of calcium carries out Thermal desorption processing, obtains the calcium sulphate solid that content of organics is lower than 0.1%, and generation contains organic steam
Gas enter face oxygen cracker deep purifying processing.
3. according to the method described in claim 1, it is characterized in that the low-concentration acetic acid containing mineral acid and organic impurities is useless
Acetic acid content is 0.5~10wt% in water, and the content of organics other than acetic acid is 0.01~0.5wt%, sulfuric acid content is 1~
5wt%.
4. according to the method described in claim 3, it is characterized in that the organic matter other than the acetic acid is methyl acetate, acetic acid
At least one of ethyl ester, propyl acetate, tert-butyl acetate, n-butyl acetate, methanol, ethyl alcohol, propyl alcohol, the tert-butyl alcohol, n-butanol.
5. according to the method described in claim 1, it is characterized in that the filtrate containing calcium acetate handles to obtain acetic acid through MVR
Calcium concentration is the calcium acetate suspension of 30~40wt%.
6. according to the method described in claim 1, it is characterized in that the temperature of the Thermal desorption is 200~400 DEG C.
7. according to the method described in claim 1, it is characterized in that the acidolysis is handled are as follows: calcium carbonate solid and sulfuric acid occur
Acidolysis reaction generates acetic acid and calcium sulfate.
8. according to the method described in claim 1, it is characterized in that the sulfuric acid is the dense sulphur that mass fraction is not less than 98%
Acid.
9. according to the method described in claim 1, it is characterized in that carrying out deep purifying processing, deep purifying under air conditions
The purification reaction temperature of processing is 250~450 DEG C, and reaction pressure is normal pressure, and the residence time is 0.1~10kgh/m3, air
Intake is 1~5:1 with the volume ratio for facing the vapor of oxygen cracker is entered.
10. according to the method described in claim 1, it is characterized in that the heat that deep purifying processing is released is used for MVR device liquid
The gasification of body.
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