CN110040896A - A kind of processing method of the low-concentration acetic acid wastewater of sulfur acid - Google Patents
A kind of processing method of the low-concentration acetic acid wastewater of sulfur acid Download PDFInfo
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- CN110040896A CN110040896A CN201910305873.6A CN201910305873A CN110040896A CN 110040896 A CN110040896 A CN 110040896A CN 201910305873 A CN201910305873 A CN 201910305873A CN 110040896 A CN110040896 A CN 110040896A
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- calcium acetate
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- acetate
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 234
- 239000002351 wastewater Substances 0.000 title claims abstract description 61
- 239000002253 acid Substances 0.000 title claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 22
- 239000011593 sulfur Substances 0.000 title claims abstract description 22
- 238000003672 processing method Methods 0.000 title claims abstract description 9
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims abstract description 97
- 235000011092 calcium acetate Nutrition 0.000 claims abstract description 97
- 239000001639 calcium acetate Substances 0.000 claims abstract description 97
- 229960005147 calcium acetate Drugs 0.000 claims abstract description 97
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 68
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 65
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000012065 filter cake Substances 0.000 claims abstract description 38
- 239000000725 suspension Substances 0.000 claims abstract description 36
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 34
- 238000003795 desorption Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 28
- 239000001301 oxygen Substances 0.000 claims abstract description 28
- 239000000706 filtrate Substances 0.000 claims abstract description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001914 filtration Methods 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 22
- 239000005416 organic matter Substances 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 19
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 18
- 239000011575 calcium Substances 0.000 claims abstract description 18
- 230000002308 calcification Effects 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000000746 purification Methods 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 4
- 235000011132 calcium sulphate Nutrition 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
- 238000004227 thermal cracking Methods 0.000 claims description 13
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 239000001175 calcium sulphate Substances 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 4
- 229940090181 propyl acetate Drugs 0.000 claims description 4
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002309 gasification Methods 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims 1
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- 239000006228 supernatant Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- 239000000052 vinegar Substances 0.000 description 8
- 235000021419 vinegar Nutrition 0.000 description 8
- 238000000197 pyrolysis Methods 0.000 description 7
- 238000000605 extraction Methods 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000000284 extract Substances 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000002920 hazardous waste Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CPGKMLVTFNUAHL-UHFFFAOYSA-N [Ca].[Ca] Chemical compound [Ca].[Ca] CPGKMLVTFNUAHL-UHFFFAOYSA-N 0.000 description 1
- HFNUUHLSQPLBQI-UHFFFAOYSA-N acetic acid;calcium Chemical compound [Ca].CC(O)=O HFNUUHLSQPLBQI-UHFFFAOYSA-N 0.000 description 1
- ZCHPKWUIAASXPV-UHFFFAOYSA-N acetic acid;methanol Chemical compound OC.CC(O)=O ZCHPKWUIAASXPV-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
The invention discloses a kind of processing methods of the low-concentration acetic acid wastewater of sulfur acid, it include: that calcification processing is carried out to waste water using calcium carbonate, acetic acid in waste water is changed into calcium acetate, sulfuric acid is changed into calcium sulfate, filtering, obtain the filter cake and calcium acetate aqueous solution of sulfur acid calcium；Calcium acetate aqueous solution carries out MVR and handles to obtain calcium acetate suspension, calcium acetate suspension is through being obtained by filtration filter cake and filtrate containing calcium acetate, filtrate crystallisation is dried to obtain calcium acetate, merge to obtain calcium acetate solid with the filter cake containing calcium acetate, calcium acetate solid is used for the calcification processing of waste water by being thermally cracked to produce acetone and calcium carbonate, Calcium Carbonate Cyclic；Filter cake containing calcium sulfate carries out Thermal desorption processing, and the vapor that the vapor containing organic matter, the crystallizing and drying that the vapor containing organic matter of Thermal desorption processing formation, MVR processing generate generate, which enters, faces the progress deep purifying processing of oxygen cracker.The method of the present invention realizes the resource utilization and purification of acetic acid wastewater.
Description
Technical field
The invention belongs to industrial acetic acid waste water treatment fields, are related to a kind of processing of the low-concentration acetic acid wastewater of sulfur acid
Method.
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.
Chinese patent CN1354139A discloses a kind of processing method of waste water containing acetic acid, using active carbon and equipped with urging
The reactor for changing layer, is separated and recovered from out acetic acid from waste water, is gone with the acetic acid for being adsorbed on reactor activity layer of charcoal mixed with methanol
It closes, it is allowed to be reacted in ion-exchange resin catalyzed layer, generate acetic acid methanol and water；And methyl acetate therein is then because holding
It is easily separated and flutter and catch, and regeneration can be gone.
United States Patent (USP) US5306398 handles acetic acid wastewater by the way that one or more of metal Coupling agent are added, and makes the vinegar of waste water
Acid and water association property weaken significantly, increase the relative volatility of its acetic acid and water, then easily by the method for rectifying
Acetic acid wastewater is separated, the purity of recovery of acetic acid is up to 98.0% or more, and processed waste water acetate concentration is 0.2% or so.
Chinese patent CN101898952A discloses a kind of recovery method of low-concentration acetic acid wastewater processing that pharmaceutical factory generates,
It mainly include two-stage extraction tower, stripper and acetic acid refining tower and its corresponding ancillary equipment, acetic acid waste liquid extracts from second level first
Top of tower is taken to be added, extractant is added through two-stage extraction tower, after two-stage extracts with certain flow velocity from level-one extraction tower bottom
Raffinate grade rich in acetic acid enters acetic acid refining tower and is separated, and tower bottom obtains high-purity acetic acid, and the extractant of recovered overhead can
Rejoin the use of extractant system circulation；Aqueous solution after two-stage extracts containing a small amount of extractant enters stripper, bottom
Discharge treated waste water can be directly entered discharge, the oil of tower top phase-splitter is mutually the recyclable recycling of extractant.More than
In 100ppm hereinafter, the acetic acid purity of recycling is greater than 99.0wt%, the rate of recovery is all larger than the waste water acetic acid content of process
98.0%.
The processing method of above-mentioned waste water is all not directed to the processing side of the low-concentration acetic acid of sulfur acid and organic impurities
Method.
Summary of the invention
The purpose of the present invention is being directed to the low-concentration acetic acid wastewater of sulfur acid, according to calcium acetate is not volatile and calcium sulfate not
It is dissolved in the principle of water, acetic acid in waste water is changed into calcium acetate, sulfuric acid is changed into calcium sulfate, it is solid that calcium sulfate is isolated by filtration out
Body, then the separation of calcium acetate and organic impurities in filtrate is carried out, calcium acetate thermal cracking obtains acetone and calcium carbonate, to realize vinegar
The resource utilization and purification of sour waste water.
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 of sulfur acid, comprising: waste water is carried out at calcification using calcium carbonate
Reason, is changed into calcium acetate for the acetic acid in waste water, sulfuric acid is changed into calcium sulfate, and filtering obtains the filter cake and acetic acid of sulfur acid calcium
Calcium aqueous solution；Calcium acetate aqueous solution carries out MVR and handles to obtain calcium acetate suspension, and calcium acetate suspension is obtained by filtration containing acetic acid
The filter cake of calcium and filtrate, filtrate crystallisation are dried to obtain calcium acetate, and the filter cake containing calcium acetate merges to obtain calcium acetate solid, acetic acid
Calcium solid is used for the calcification processing of waste water by being thermally cracked to produce acetone and calcium carbonate, Calcium Carbonate Cyclic；Filter containing calcium sulfate
Cake carries out Thermal desorption processing, and the water containing organic matter of the vapor containing organic matter, MVR processing generation that Thermal desorption processing is formed steams
The vapor that gas, crystallizing and drying generate, which enters, faces the progress deep purifying processing of oxygen cracker.
The processing method of the low-concentration acetic acid wastewater of sulfur acid of the present invention, comprising the following steps:
Step (1), calcification processing: calcium carbonate is added in the low acetic acid wastewater of sulfur acid and is formed and contains calcium sulfate and calcium acetate
Suspension；
The suspension that step (2), calcification processing obtain is filtered, and removes solid suspension and calcium sulfate in waste water,
Obtain the filter cake and calcium acetate aqueous solution of sulfur acid calcium；The filter cake of sulfur acid calcium carries out Thermal desorption, obtains content of organics and is lower than
0.1% calcium sulphate solid, the vapor containing organic matter that Thermal desorption processing is formed are net into oxygen cracker progress depth is faced
Change processing；Calcium acetate aqueous solution goes MVR device to carry out MVR processing, obtains calcium acetate suspension, and what MVR processing generated contains organic
The vapor of object enters and faces oxygen cracker；Filter cake and filtrate containing calcium acetate, filtrate knot is obtained by filtration in calcium acetate suspension
Crystalline substance is dried to obtain calcium acetate, and the filter cake containing calcium acetate merges to obtain calcium acetate solid, and the vapor that crystallizing and drying generates enters
Face oxygen cracker；
Calcium acetate solid obtained in step (3), step (2) carries out being thermally cracked to produce acetone and calcium carbonate, and calcium carbonate returns
It returns in step (1) and is recycled, acetone recycling and reusing.
Acetic acid content is no more than 10wt%, preferably 0.5~10wt% in the low-concentration acetic acid wastewater of the sulfur acid,
Content of organics other than acetic acid is no more than 0.5wt%, preferably 0.01~0.5wt%, and sulfuric acid content is no more than 5wt%, excellent
It is selected as 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.
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 pyrolysis eutectoid temperature is 200~400 DEG C.During Thermal desorption the generation rate of vapor be 2.5~
5.0m3/h。
It is 30~40wt% that the calcium acetate aqueous solution, which handles through MVR and is concentrated into calcium acetate concentration,.MVR handles calcium acetate
The time of aqueous solution is 1~2 hour, and the generation rate of vapor is 900~1200m in MVR treatment process3/h。
The generation rate of vapor is 280~520m during crystallizing and drying3/h。
The processing of calcium acetate thermal cracking generates acetone gas, it is contemplated that safety problem, the thermal cracking is in heat scission reaction
It is carried out in device, the condition of thermal cracking is nitrogen atmosphere, 160~200 DEG C of temperature；The acetone condensing recovery that thermal cracking generates, in temperature
It is stored at 35 DEG C of degree or less, dry and ventilated.
It include the vapor containing organic matter, the calcium sulfate pyrolysis that MVR processing generates into the gas for facing oxygen cracker
It analyses the vapor containing organic matter formed, the vapor that calcium acetate crystallizing and drying generates, deep purifying is carried out under air conditions
Processing, deep purifying treatment conditions are as follows: purification reaction temperature is 250~450 DEG C, and reaction pressure is normal pressure, residence time 0.1
~10kgh/m3, it is preferably 1~2 that air intake, which is 1~5:1 with the volume ratio into the vapor for facing oxygen cracker:
1, the heat that deep purifying processing is released is used for the gasification of MVR device liquid；Face oxygen cracker and realize autothermal equilibrium, without outer
Add energy；Facing COD value in the water in oxygen cracker exit is 0~40mgO2/ L reaches integrated wastewater discharge standard GB8979-
1996 requirement, VOC total amount is 5~50mg/m in the tail gas given off3, reach chemical industry Volatile organic emissions standard
The requirement of DB32/3151-2016.
Beneficial effects of the present invention:
The present invention faces oxygen cracking-thermal cracking new technology route using waste water calcification-MVR-, will be given up by calcification processing
Acetic acid in water is changed into calcium acetate, sulfuric acid is changed into calcium sulfate, and calcium sulfate is isolated by filtration out, and calcium sulfate is pyrolyzed
Analysis, then by the separation of calcium acetate and organic impurities in the operations such as MVR, crystallizing and drying realization filtrate, calcium acetate thermal cracking is obtained
Acetone and calcium carbonate.The method of the present invention not only realizes the recycling of the separation of organic impurities and acetone in waste water, by hazardous waste
It is changed into harmless solid material calcium sulfate, realizes recycling treatment, significantly reduces the cost of business processes hazardous waste；
The vapor containing organic matter that gas, MVR processing and the crystallizing and drying that calcium sulfate Thermal desorption generates simultaneously generate passes through
Deep purifying processing is changed into the purified water without further biochemical treatment, realizes the depth of the low-concentration acetic acid wastewater of sulfur acid
Spend purified treatment.
Detailed description of the invention
Fig. 1 is the process flow chart of the processing method of the low-concentration acetic acid wastewater of sulfur acid of the present invention.
Specific embodiment
Embodiment 1
Acetic acid wastewater composition: acetic acid quality score 8.8%, ethyl alcohol mass fraction 0.14%, butanol mass fraction 0.09%,
Ethyl acetate mass fraction 0.09%, butyl acetate mass fraction 0.06%, sulfuric acid mass fraction are 2.4%, remaining is moisture.
2000kg acetic acid wastewater is added in a kettle, is slowly added to 194.5kg 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 and calcium acetate.
It is obtained filter cake (weight in wet base 74.8kg) after above-mentioned suspension filtering, filter cake Thermal desorption 3 hours at 380 DEG C are had
The calcium sulphate solid 68.5kg of machine object content 0.03wt%, the generation rate of vapor is 2.61m during Thermal desorption3/h.It crosses
It filters obtained filtrate and removes MVR device, handled 1.5 hours by MVR device, the generation rate of vapor is 1176.78m3/ h, obtains
Calcium acetate suspension (content of calcium acetate is 37wt%).Filter cake containing calcium acetate is obtained by filtration, containing vinegar in calcium acetate suspension
The filtrate of sour calcium, filtrate is crystallized to be dried to obtain calcium acetate, and 227.8kg calcium acetate, crystallizing and drying mistake are obtained after merging with filter cake
The generation rate of vapor is 482.69m in journey3/h.Calcium acetate is transferred in pyrolysis reactor, in nitrogen atmosphere, temperature
Carry out thermal cracking at 160 DEG C, obtain 82.1kg acetone and 136.7kg calcium carbonate, acetone condensing recovery, 35 DEG C of temperature or less,
It is stored at dry and ventilated, calcium carbonate returns to calcification process.
The vapor containing organic matter of calcium sulfate Thermal desorption formation contains ethyl alcohol, butanol, acetic acid second by what MVR device steamed
The steam of the gas containing organic steam and crystallizing and drying generation that the vapor of ester and butyl acetate, Thermal desorption generate enters
Face oxygen cracker and carry out deep purifying, deep purifying processing, the purification reaction of deep purifying processing are carried out under air conditions
Temperature is 250 DEG C, and reaction pressure is normal pressure, residence time 0.1kgh/m3, oxygen cracker is faced in air intake and entrance
Vapor volume ratio be 2:1, by face oxygen cracker come out water in COD value be 19mgO2/ L, VOC concentration is in gas phase
22mg/m3。
Embodiment 2
Acetic acid wastewater composition: acetic acid quality score 8.5%, ethyl alcohol mass fraction 0.17%, butanol mass fraction 0.09%,
Ethyl acetate mass fraction 0.06%, butyl acetate mass fraction 0.07%, sulfuric acid mass fraction are 3.3%, remaining is moisture.
2000kg acetic acid wastewater is added in a kettle, is slowly added to 205.8kg calcium carbonate under stirring, at room temperature
After stirring 1 hour, the pH value of waste water is increased to 6.9, forms the suspension containing calcium sulfate and calcium acetate.
It is obtained filter cake (weight in wet base 105.9kg) after above-mentioned suspension filtering, filter cake Thermal desorption 3 hours at 350 DEG C are had
The calcium sulphate solid 96kg of machine object content 0.03wt%, the generation rate of vapor is 4.11m during Thermal desorption3/h.Filtering
Obtained filtrate removes MVR device, is handled 1.5 hours by MVR device, and the generation rate of vapor is 1148.98m3/ h, obtains vinegar
Sour calcium suspension (content of calcium acetate is 34wt%).Filter cake containing calcium acetate is obtained by filtration, containing acetic acid in calcium acetate suspension
The filtrate of calcium, filtrate is crystallized to be dried to obtain calcium acetate, and 212.3kg calcium acetate, crystallizing and drying process are obtained after merging with filter cake
The generation rate of middle vapor is 512.85m3/h.Calcium acetate is transferred in pyrolysis reactor, in nitrogen atmosphere, temperature 160
Thermal cracking is carried out at DEG C, obtains 77.7kg acetone and 139.5kg calcium carbonate, acetone condensing recovery, in 35 DEG C of temperature or less, drying
Ventilation storage, calcium carbonate return to calcification neutralization step.
The vapor containing organic matter of calcium sulfate Thermal desorption formation contains ethyl alcohol, butanol, acetic acid second by what MVR device steamed
The steam of the gas containing organic steam and crystallizing and drying generation that the vapor of ester and butyl acetate, Thermal desorption generate enters
Face oxygen cracker and carry out deep purifying, deep purifying processing, the purification reaction of deep purifying processing are carried out under air conditions
Temperature is 450 DEG C, and reaction pressure is normal pressure, residence time 10kgh/m3, oxygen cracker is faced in air intake and entrance
Vapor volume ratio be 1:1, by face oxygen cracker come out water in COD value be 13mgO2/ L, VOC concentration is in gas phase
20mg/m3。
Embodiment 3
Acetic acid wastewater composition: acetic acid quality score 5.4%, methanol quality score 0.21%, butanol mass fraction 0.06%,
Methyl acetate mass fraction 0.07%, propyl acetate mass fraction 0.09%, sulfuric acid mass fraction are 3.7%, remaining is moisture.
1800kg acetic acid wastewater is added in a kettle, is slowly added to 148.4kg 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 and calcium acetate.
Filter cake weight in wet base 106.7kg is obtained after above-mentioned suspension filtering, filter cake Thermal desorption 3 hours at 350 DEG C obtain organic
The calcium sulphate solid 98.6kg of object content 0.03wt%, the generation rate of vapor is 3.36m during Thermal desorption3/h.Filtering
Obtained filtrate removes MVR device, is handled 1.5 hours by MVR device, and the generation rate of vapor is 1172.48m3/ h, obtains vinegar
Sour calcium suspension (content of calcium acetate is 35wt%).Filter cake containing calcium acetate is obtained by filtration, containing acetic acid in calcium acetate suspension
The filtrate of calcium, filtrate is crystallized to be dried to obtain calcium acetate, and 127.1kg calcium acetate, crystallizing and drying process are obtained after merging with filter cake
The generation rate of middle vapor is 293.74m3/h.Calcium acetate is transferred in pyrolysis reactor, in nitrogen atmosphere, temperature 160
Thermal cracking is carried out at DEG C, obtains 43.3kg acetone and 80.5kg calcium carbonate, acetone condensing recovery, in 35 DEG C of temperature or less, drying
Ventilation storage, calcium carbonate return to calcification neutralization step.
The vapor containing organic matter of calcium sulfate Thermal desorption formation contains methanol, butanol, tumer by what MVR device steamed
The steam of the gas containing organic steam and crystallizing and drying generation that the vapor of ester and propyl acetate, Thermal desorption generate enters
Face oxygen cracker and carry out deep purifying, deep purifying processing, the purification reaction of deep purifying processing are carried out under air conditions
Temperature is 300 DEG C, and reaction pressure is normal pressure, residence time 5kgh/m3, oxygen cracker is faced in air intake and entrance
The volume ratio of vapor is 5:1, is 12mgO by facing COD value in the water that oxygen cracker comes out2/ L, VOC concentration is in gas phase
9mg/m3。
Embodiment 4
Acetic acid wastewater composition: acetic acid quality score 7.7%, methanol quality score 0.21%, propyl alcohol mass fraction 0.06%,
Tert-butyl acetate mass fraction 0.09%, sulfuric acid mass fraction are 2.5%, remaining is moisture.
1800kg acetic acid wastewater is added in a kettle, is slowly added to 160.6kg calcium carbonate under stirring, at room temperature
After stirring 1 hour, the pH value of waste water is increased to 6.1, forms the suspension containing calcium sulfate and calcium acetate.
Filter cake weight in wet base 68.9kg is obtained after above-mentioned suspension filtering, filter cake is carried out Thermal desorption 3 hours at 300 DEG C, heat
The calcium sulphate solid of content of organics 0.03wt% obtained after parsing, total 61kg, the generation speed of vapor during Thermal desorption
Rate is 3.28m3/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
1081.27m3/ h obtains calcium acetate suspension (content of calcium acetate is 37wt%).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 181.2kg vinegar is obtained after merging with filter cake
Sour calcium, the generation rate of vapor is 383.95m during crystallizing and drying3/h.Calcium acetate is transferred in pyrolysis reactor,
Nitrogen atmosphere carries out thermal cracking at 160 DEG C of temperature, obtains 63.4kg acetone and 112.2kg calcium carbonate, acetone condensing recovery,
35 DEG C of temperature or less, store at dry and ventilated, calcium carbonate returns to calcification neutralization step.
The vapor containing organic matter of calcium sulfate Thermal desorption formation contains methanol, propyl alcohol and acetic acid fourth by what MVR device steamed
The steam of the gas containing organic steam and crystallizing and drying generation that vapor, the Thermal desorption of ester generate, which enters, faces oxygen cracking dress
Carry out deep purifying is set, deep purifying processing is carried out under air conditions, the purification reaction temperature of deep purifying processing is 280
DEG C, reaction pressure is normal pressure, residence time 2kgh/m3, air intake and enter the vapor for facing oxygen cracker
Volume ratio is 1:1, is 11mgO by facing COD value in the water that oxygen cracker comes out2/ L, VOC concentration is 16mg/m in gas phase3。
Embodiment 5
Acetic acid wastewater composition: acetic acid quality score 9.2%, methanol quality score 0.21%, ethyl alcohol mass fraction 0.06%,
Tert-butyl acetate mass fraction 0.09%, tert-butyl alcohol mass fraction are 0.05%, and sulfuric acid mass fraction is 4.1%, remaining is water
Point.
1600kg acetic acid wastewater is added in a kettle, 188.7kg calcium carbonate is slowly added under stirring, then in room
After lower stirring 1 hour of temperature, the pH value of waste water is increased to 6.6, forms the suspension containing calcium sulfate and calcium acetate.
It is obtained filter cake (weight in wet base 104.2kg) after above-mentioned suspension filtering, filter cake Thermal desorption 3 hours at 360 DEG C are had
The calcium sulphate solid 97.2kg of machine object content 0.03wt%, the generation rate of vapor is 2.90m during Thermal desorption3/h.It crosses
Filtrate after filter removes MVR device, is handled 1.5 hours by MVR device, and the generation rate of vapor is 929.58m3/ h, obtains vinegar
Sour calcium suspension (content of calcium acetate is 40wt%).Filter cake containing calcium acetate is obtained by filtration, containing acetic acid in calcium acetate suspension
The filtrate of calcium, filtrate is crystallized to be dried to obtain calcium acetate, and 192.4kg calcium acetate, crystallizing and drying process are obtained after merging with filter cake
The generation rate of middle vapor is 359.15m3/h.Calcium acetate is transferred in pyrolysis reactor, in nitrogen atmosphere, temperature 160
Thermal cracking is carried out at DEG C, obtains 68.6kg acetone and 121.4kg calcium carbonate, acetone condensing recovery, in 35 DEG C of temperature or less, drying
Ventilation storage, calcium carbonate return to calcification neutralization step.
The vapor containing organic matter of calcium sulfate Thermal desorption formation contains methanol, ethyl alcohol, acetic acid uncle by what MVR device steamed
The water of the gas containing organic steam and crystallizing and drying generation that the vapor of butyl ester and tert-butyl alcohol organic matter, Thermal desorption generate
Vapour, which enters, faces oxygen cracker progress deep purifying, deep purifying processing is carried out under air conditions, deep purifying is handled net
Changing reaction temperature is 400 DEG C, and reaction pressure is normal pressure, residence time 8kgh/m3, oxygen cracking is faced in air intake and entrance
The volume ratio of the vapor of device is 4:1, is 18mgO by facing COD value in the water that oxygen cracker comes out2/ L, VOC is dense in gas phase
Degree is 13mg/m3。
Claims (9)
1. a kind of processing method of the low-concentration acetic acid wastewater of sulfur acid, characterized by comprising: using calcium carbonate to waste water into
Row calcification processing, is changed into calcium acetate for the acetic acid in waste water, sulfuric acid is changed into calcium sulfate, and filtering obtains the filter of sulfur acid calcium
Cake and calcium acetate aqueous solution；Calcium acetate aqueous solution carries out MVR and handles to obtain calcium acetate suspension, and calcium acetate suspension is through filtering
To containing calcium acetate filter cake and filtrate, filtrate crystallisation be dried to obtain calcium acetate, and the filter cake containing calcium acetate merges to obtain calcium acetate
Solid, calcium acetate solid are used for the calcification processing of waste water by being thermally cracked to produce acetone and calcium carbonate, Calcium Carbonate Cyclic；Contain sulphur
The filter cake of sour calcium carries out Thermal desorption processing, and what the vapor containing organic matter of Thermal desorption processing formation, MVR processing generated contains organic
The vapor that vapor, the crystallizing and drying of object 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: be added in the low acetic acid wastewater of sulfur acid calcium carbonate formed it is outstanding containing calcium sulfate and calcium acetate
Supernatant liquid；
The filter cake and calcium acetate aqueous solution of sulfur acid calcium is obtained by filtration in the suspension that step (2), calcification processing obtain；Sulfur acid calcium
Filter cake carry out Thermal desorption, obtain content of organics be lower than 0.1% calcium sulphate solid；Calcium acetate aqueous solution carries out MVR processing
Calcium acetate suspension is obtained, calcium acetate suspension is dried to obtain through filter cake and filtrate containing calcium acetate, filtrate crystallisation is obtained by filtration
Calcium acetate, and the filter cake containing calcium acetate merge to obtain calcium acetate solid；The vapor containing organic matter of Thermal desorption processing formation,
The vapor of the vapor containing organic matter, crystallizing and drying generation that MVR processing generates, which enters, faces oxygen cracker；
Calcium acetate solid obtained in step (3), step (2) carries out being thermally cracked to produce acetone and calcium carbonate, and calcium carbonate returns to
It is recycled in step (1), acetone recycling and reusing.
3. according to the method described in claim 1, it is characterized in that acetic acid contains in the low-concentration acetic acid wastewater of the sulfur acid
Amount is 0.5~10wt%, and the content of organics other than acetic acid is 0.01~0.5wt%, 1~5wt% of sulfuric acid content.
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 calcium acetate aqueous solution obtains acetic acid after MVR is handled
The calcium acetate suspension of 30~40wt% of calcium concentration.
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 condition of the thermal cracking is nitrogen atmosphere, temperature 160
~200 DEG C.
8. according to the method described in claim 1, it is characterized in that carrying out deep purifying processing, deep purifying under air conditions
Treatment conditions are as follows: purification reaction temperature 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.
9. 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
Gasification.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111689851A (en) * | 2020-04-30 | 2020-09-22 | 南京工业大学 | Method for preparing acetate and calcium chloride from glucosamine waste acid solution |
| CN111847480A (en) * | 2020-05-26 | 2020-10-30 | 南京工业大学 | Purification treatment and resource recycling method for industrial sodium chloride waste salt |
| CN114262108A (en) * | 2020-09-16 | 2022-04-01 | 上海医药工业研究院 | Method for treating wastewater containing hydrochloric acid and acetic acid |
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| CN101481189A (en) * | 2009-01-20 | 2009-07-15 | 大连理工大学 | Integrated process of furfural production as well as wastewater, waste slag and waste gas treatment |
| CN105198716A (en) * | 2014-06-23 | 2015-12-30 | 高嵩 | Acetone-generating method for treating furfural wastewater |
| CN107098415A (en) * | 2017-05-31 | 2017-08-29 | 南京工业大学 | The processing method and system of a kind of salt-containing organic wastewater |
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| CN101481189A (en) * | 2009-01-20 | 2009-07-15 | 大连理工大学 | Integrated process of furfural production as well as wastewater, waste slag and waste gas treatment |
| CN105198716A (en) * | 2014-06-23 | 2015-12-30 | 高嵩 | Acetone-generating method for treating furfural wastewater |
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| CN111689851A (en) * | 2020-04-30 | 2020-09-22 | 南京工业大学 | Method for preparing acetate and calcium chloride from glucosamine waste acid solution |
| CN111689851B (en) * | 2020-04-30 | 2022-04-12 | 南京工业大学 | Method for preparing acetate and calcium chloride from glucosamine waste acid solution |
| CN111847480A (en) * | 2020-05-26 | 2020-10-30 | 南京工业大学 | Purification treatment and resource recycling method for industrial sodium chloride waste salt |
| CN114262108A (en) * | 2020-09-16 | 2022-04-01 | 上海医药工业研究院 | Method for treating wastewater containing hydrochloric acid and acetic acid |
| CN114262108B (en) * | 2020-09-16 | 2024-03-19 | 上海医药工业研究院 | Treatment method of wastewater containing hydrochloric acid and acetic acid |
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