CN110040895A - A kind of processing method of the low-concentration acetic acid wastewater of metal ion and organic impurities - Google Patents
A kind of processing method of the low-concentration acetic acid wastewater of metal ion and organic impurities Download PDFInfo
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- CN110040895A CN110040895A CN201910305395.9A CN201910305395A CN110040895A CN 110040895 A CN110040895 A CN 110040895A CN 201910305395 A CN201910305395 A CN 201910305395A CN 110040895 A CN110040895 A CN 110040895A
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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 248
- 239000002351 wastewater Substances 0.000 title claims abstract description 81
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 22
- 239000012535 impurity Substances 0.000 title claims abstract description 17
- 238000003672 processing method Methods 0.000 title claims abstract description 15
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims abstract description 98
- 239000001639 calcium acetate Substances 0.000 claims abstract description 98
- 235000011092 calcium acetate Nutrition 0.000 claims abstract description 98
- 229960005147 calcium acetate Drugs 0.000 claims abstract description 98
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 51
- 239000012065 filter cake Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 35
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 34
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000003795 desorption Methods 0.000 claims abstract description 28
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 26
- 239000000706 filtrate Substances 0.000 claims abstract description 24
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011575 calcium Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 21
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 20
- 239000005416 organic matter Substances 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 19
- 230000002308 calcification Effects 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 10
- 238000004064 recycling Methods 0.000 claims abstract description 9
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims abstract description 6
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 32
- 239000001301 oxygen Substances 0.000 claims description 32
- 229910052760 oxygen Inorganic materials 0.000 claims description 32
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000725 suspension Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 16
- 238000004227 thermal cracking Methods 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 10
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 claims description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 7
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 7
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- -1 Dichlorodiphenyl Acetate Chemical compound 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000005336 cracking Methods 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
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- HFNUUHLSQPLBQI-UHFFFAOYSA-N acetic acid;calcium Chemical compound [Ca].CC(O)=O HFNUUHLSQPLBQI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 238000002309 gasification Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000005649 metathesis reaction Methods 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 238000000197 pyrolysis Methods 0.000 description 8
- 235000011056 potassium acetate Nutrition 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000008247 solid mixture Substances 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000002920 hazardous waste Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- 239000000052 vinegar Substances 0.000 description 3
- 235000021419 vinegar Nutrition 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002699 waste material Substances 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
Landscapes
- 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)
Abstract
The invention discloses the processing methods of a kind of metal ion and the low-concentration acetic acid wastewater of organic impurities, it include: that waste water carries out calcification processing, make in waste water that acetic acid is changed into calcium acetate, sulfate radical is changed into calcium sulfate precipitation, while metal ion in waste water is changed into hydroxide precipitating；Waste water filtering obtains the filter cake of sulfur acid calcium and hydroxide, calcium acetate aqueous solution；Calcium acetate aqueous solution is handled to obtain calcium acetate supersaturated solution by MVR, the filter cake containing calcium acetate and filtrate is obtained by filtration, filtrate crystallisation is dried to obtain calcium acetate, and the filter cake containing calcium acetate merges to obtain calcium acetate solid, and calcium acetate solid carries out being thermally cracked to produce acetone and calcium carbonate；The filter cake of sulfur acid calcium and hydroxide carries out Thermal desorption processing, and the gas containing organic steam, the MVR of Thermal desorption processing generation handle the vapor that the vapor generated containing organic matter and crystallizing and drying generate and carry out deep purifying processing.The method of the present invention realizes the purification and recycling treatment of acetic acid wastewater.
Description
Technical field
The invention belongs to industrial acetic acid waste water treatment field, it is related to a kind of low dense containing metal ion and organic impurities
Spend purification and the recycling processing method of acetic acid wastewater.
Background technique
In acetic acid ester production process, the reaction of sulfuric acid catalysis esterification is carried out due to using acetic acid and alcohol, unavoidably
The acetic acid wastewater of low concentration can be generated, the COD value of waste water is up to tens of thousands of to hundreds of thousands mgO2/L.Simultaneously as acetic acid wastewater contains
There is sulfuric acid, to storage container there are certain corrosivity, causes in acetic acid wastewater dissolved with a small amount of metal sulfate.Such is useless
Water belongs to hazardous waste, increases difficulty to the purified treatment of acetic acid wastewater.
Strong acid waste water is generally industrially handled using direct incineration method or neutralisation, but these processing methods will cause vinegar
Sour resource largely wastes, therefore the resource utilization utilization of low-concentration acetic acid wastewater seems of crucial importance.Currently, dividing from waste water
Method from recovery of acetic acid mainly includes membrane separation process, absorption method, extraction, esterification process, rectification method etc..There are films for membrane separation process
Preparation cost height, disadvantage easy to pollute；Absorption method there are adsorbent reactivations it is at high cost, vulnerable to metal ion pollution the disadvantages of；Extraction
It follows the example of since extractant needs to recycle, the loss of extractant is larger；Esterification process by reaction due to being balanced there are a large amount of water
Limitation, esterification reaction rate is too low；Rectification method is since acetic acid is close with the boiling point of water, and the boiling point of water is lower than acetic acid, the two
Relative volatility it is also close, therefore acetic acid can not be obtained by conventional rectification, needed using special extract rectification method, so as to cause setting
Standby investment is big, and rectifying is at high cost.
In recent years, there is no realize being effectively treated for Dichlorodiphenyl Acetate heavy metal ions in wastewater for acetic acid wastewater process field.
CN204310859U discloses a kind of concentration and separation device of low-concentration acetic acid wastewater, and the device is by giving up the acetic acid of low concentration
Water is handled under pressurised conditions by reverse osmosis membrane processing unit, the acetic acid wastewater being concentrated.Similarly,
CN204702602U provides similar waste water high-pressure treatment apparatus, is carried out at concentration using reverse osmosis membrane to waste water
Reason.But membrane separation process cannot the waste water relative complex to ingredient be effectively separated, thus the money for the waste water that limits that treated
Sourceization utilizes, and film is easily contaminated when handling the waste water containing heavy metal ion.
CN101898952A discloses a kind of recovery method of low-concentration acetic acid wastewater processing that pharmaceutical factory generates, and mainly includes
Two-stage extraction tower, stripper and acetic acid refining tower and its corresponding ancillary equipment are rich in the raffinate of acetic acid after two-stage extracts
Grade enters acetic acid refining tower and is separated, and tower bottom obtains high-purity acetic acid, and the extractant of recovered overhead can rejoin extractant system
System is recycled；Aqueous solution after two-stage extracts containing a small amount of extractant enters stripper, bottom discharge treated waste water
Discharge can be directly entered.It is handled using acetic acid wastewater of this method to metal ion, although higher quality can be obtained
Acetate products, but the waste water of stripper bottom discharge contains the heavy metal ion of higher concentration, needs to be further processed.Another party
Face, extractant have certain solubility in water, often bring the pollution of the third substance, and that there are solvent reclamations is easily newborn
The problem of change.
CN106380393A discloses a kind of method of heat pump-multi-effect distillation recovery of acetic acid from low-concentration acetic acid wastewater,
Using heat pump-multi-effect distillation combined system recovery of acetic acid, heat pump column overhead steam after compression, can be used not only as heat pump tower tower bottom
Heat, moreover it is possible to waste water be preheated, and the heat source as next rectifying tower reboiler, relative to individually multi-effect distillation
System energy consumption is lower.The heavy metal ion in waste water cannot be effectively treated in this method, and treated, and waste water cannot still reach state
Family's discharge standard.
CN103588336A discloses a kind of method using low-concentration acetic acid wastewater, and the acetic acid in acetic acid wastewater is handled
Obtain potassium acetate recycling, comprising the following steps: (1) waste water filtering, removal of impurities；(2) it is added into filtered acetic acid wastewater
Neutralization reaction occurs for potassium hydroxide, generates potassium acetate；(3) concentration, so that the concentration of potassium acetate increases；(4) to cooling tower
In liquor kalii acetici reach a certain concentration after, gained cooling water is evaporated crystallization and obtains potassium acetate.This method practicability
By force, acetic acid neutralization, condensing crystallizing are obtained potassium acetate to recycle, provides new approaches for the resource utilization of acetic acid wastewater.
But this method can consume huge energy using common evaporative crystallization, and be directly concentrated and evaporated knot after being neutralized
The waste water containing metal ion cannot be effectively treated in the method for brilliant potassium acetate, and obtained potassium acetate product cannot reach the need in market
It asks.
Summary of the invention
Inventor's discovery must first remove metal in the low-concentration acetic acid wastewater containing metal ion and organic impurities from
Son and organic impurities, are just able to achieve recycling and purified treatment.In order to solve deficiency in the prior art, the present invention uses waste water
Calcification-double decomposition-MVR- faces oxygen cracking-thermal cracking process route, first carries out calcification processing to waste water, and acetic acid is made to form vinegar
Sour calcium, and metal ion is formed and is precipitated, recycle MVR technology to isolate organic impurities, while being concentrated to get calcium acetate, then will
Calcium acetate carries out thermal cracking and obtains product acetone, and it is dense finally face oxygen cracking to the issuable secondary pollution of each process
Purified treatment is spent, realizes the purification and recycling treatment of the low-concentration acetic acid wastewater of metal ion and organic impurities, effectively
Acetic acid resource is utilized, while hazardous waste is changed into harmless solid material.
To achieve the goals above, the invention adopts the following technical scheme:
The processing method of the low-concentration acetic acid wastewater of a kind of metal ion and organic impurities, comprising: calcium is carried out to waste water
Change processing, makes that the acetic acid in waste water is changed into calcium acetate, sulfate ion is changed into calcium sulfate precipitation, metal ion is changed into hydrogen
Oxide precipitation；It is filtered by the waste water of calcification processing, filter cake, the calcium acetate for obtaining sulfur acid calcium and hydroxide are water-soluble
Liquid；The calcium acetate aqueous solution is handled by MVR (mechanical vapor recompression technology) and obtains calcium acetate supersaturated solution, calcium acetate
Supersaturated solution filtering, obtains the filter cake and filtrate containing calcium acetate, filtrate crystallisation is dried to obtain calcium acetate, and the filter containing calcium acetate
Cake merges to obtain calcium acetate solid, and calcium acetate solid carries out being thermally cracked to produce acetone and calcium carbonate, and Calcium Carbonate Cyclic is used for waste water
Calcification processing；Contain a small amount of organic matter in the filter cake of sulfur acid calcium and hydroxide, Thermal desorption processing, Thermal desorption are carried out to it
Handle what the gas containing organic steam generated, the vapor containing organic matter that MVR processing generates and crystallizing and drying generated
Vapor enters and faces oxygen cracker, and deep purifying processing is carried out under air conditions.
Specifically, the processing method of the low-concentration acetic acid wastewater of the metal ion and organic impurities includes following step
It is rapid:
Step (1), using calcium carbonate as calcification agent, Dichlorodiphenyl Acetate waste water carry out calcification processing, the acetic acid in waste water is changed into
Calcium acetate, sulfate ion are changed into calcium sulfate precipitation, and the pH value of waste water is increased to 6~7 at this time；Oxidation is added into waste water again
Metathesis reaction occurs for calcium and metal ion, so that metal ion is changed into hydroxide precipitating, is formed and contain hydroxide, sulfuric acid
The suspension of calcium and calcium acetate；
The material that step (2), step (1) obtain is filtered, and obtains filter cake, the calcium acetate of sulfur acid calcium and hydroxide
Aqueous solution；The filter cake for obtaining sulfur acid calcium and hydroxide carries out Thermal desorption processing, Thermal desorption processing generate containing organic matter
Vapor, which enters, faces the progress deep purifying processing of oxygen cracker；Calcium acetate aqueous solution enters MVR device, handles to obtain through MVR
Calcium acetate supersaturated solution, the vapor containing organic matter that MVR processing generates, which enters, faces oxygen cracker；Calcium acetate supersaturation is molten
Filter cake and filtrate containing calcium acetate is obtained by filtration in liquid, and filtrate crystallisation is dried to obtain calcium acetate, and the filter cake containing calcium acetate merges
Calcium acetate solid is obtained, the vapor that crystallizing and drying generates enters and faces oxygen cracker；
Step (3), calcium acetate solid carry out being thermally cracked to produce acetone and calcium carbonate, and calcium carbonate is used for back to step (1)
Calcification processing, acetone recycling and reusing.
The acetic acid wastewater contains organic matter such as lower aliphatic alcohols or its acetate, metal sulphur other than acetic acid, acetic acid
Hydrochlorate, sulfuric acid.
The content of acetic acid is 0.5wt%~10wt% in the acetic acid wastewater, and the content of the organic matter other than acetic acid is
0.01wt%~0.5wt%, the content of metal sulfate are 0.05wt%~5wt%, 1~5wt% of content of sulfuric acid.
Organic matter other than the acetic acid is lower aliphatic alcohols or its acetate, specially methanol, ethyl alcohol, propyl alcohol, uncle
At least one of butanol, n-butanol, methyl acetate, ethyl acetate, propyl acetate, tert-butyl acetate, n-butyl acetate.
The metal sulfate is ferric sulfate, in nickel sulfate, chromium sulfate, magnesium sulfate, manganese sulfate, copper sulphate, zinc sulfate
At least one.
In step (1), the additional amount of calcium carbonate is determined by the stoichiometric ratio of sulfuric acid and acetic acid and calcium oxide.Calcium oxide
Additional amount is determined by the stoichiometric ratio of metal ion and calcium oxide.
In step (2), the temperature of the Thermal desorption is 200~400 DEG C.The production of vapor during the Thermal desorption
Raw rate is 10~100m3/h.The filter cake of sulfur acid calcium and hydroxide through Thermal desorption handle content of organics is less than
The metal oxide of 0.1wt% and the solid mixture of calcium sulfate are harmless solid material.
The calcium acetate aqueous solution handles 1~2h by MVR, is concentrated to get the acetic acid that acetic acid calcium content is 30~40wt%
Calcium supersaturated solution, the generation rate of vapor is 1000~4000m in MVR treatment process3/ h, the portion in calcium acetate aqueous solution
Divide organic impurities to enter in MVR gas phase, realizes that the organic impurities in aqueous solution is separated with calcium acetate.
It include the vapor containing organic matter, the MVR processing production that Thermal desorption processing generates into the gas for facing oxygen cracker
The vapor of the raw vapor containing organic matter, crystallizing and drying generation, carries out deep purifying processing, depth is net under air conditions
Change 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 and the volume ratio into the vapor for facing oxygen cracker are 1~5:1.The heat that deep purifying processing is released
Amount is used for the gasification of MVR device liquid；Face oxygen cracker and realize autothermal equilibrium, is not necessarily to external energy；Face oxygen cracker to go out
COD value is 0~40mgO in water at mouthful2/ L reaches the requirement of integrated wastewater discharge standard GB8979-1996, the tail given off
VOC total amount is 5~50mg/m in gas3, reach the requirement of chemical industry Volatile organic emissions standard DB32/3151-2016,
By facing water, the equal qualified discharge of vapour that oxygen cracker comes out.
In step (3), the condition of the thermal cracking is nitrogen atmosphere, 160~200 DEG C of temperature.Thermal cracking is in thermal cracking
It is carried out in reactor.The thermal cracking carries out in pyrolysis reactor, acetone condensing recovery, 35 DEG C of temperature or less, it is dry
Dry, ventilation storage.
Beneficial effects of the present invention:
The present invention is directed to the acetic acid wastewater containing metal sulfate, sulfuric acid, lower aliphatic alcohols or its acetate, using waste water
Calcification-double decomposition-MVR- faces oxygen cracking-thermal cracking new technology route, realizes that organic impurities are obtained with recycling in waste water
Acetone separation, recycle acetone resource, while hazardous waste be changed into harmless solid material, significantly reduce at enterprise
The cost of hazardous waste is managed, and waste water is changed into the purified water without further biochemical treatment, realizes metal ion
With the purification and recycling treatment of the low-concentration acetic acid wastewater of organic impurities.
Detailed description of the invention
Fig. 1 is the processing technological flow figure of the low-concentration acetic acid wastewater of metal ion of the present invention and organic impurities.
Specific embodiment
Below with reference to embodiment, the present invention is further described, but the present invention is not limited to listed embodiment.
Embodiment 1
Acetic acid wastewater composition: acetic acid quality score 9.5%, ferric sulfate mass fraction 4.4%, chromium sulfate mass fraction
0.05%, nickel sulfate mass fraction 0.42%, ethyl alcohol mass fraction 0.2%, tert-butyl alcohol mass fraction 0.15%, ethyl acetate matter
Score 0.1%, tert-butyl acetate mass fraction 0.05% are measured, sulfuric acid mass fraction is 3.1%, remaining is moisture.
The above-mentioned acetic acid wastewater of 2000kg is added in a kettle, 222.9kg calcium carbonate is slowly added under stirring, in room
Temperature is lower to stir 1 hour progress calcification processing, then 40.4kg calcium oxide is added in a kettle, continues stirring 1 hour, formation contains
The suspension of hydroxide, calcium sulfate and calcium acetate.
Above-mentioned suspension is filtered, is obtained filter cake (weight in wet base 262.5kg), filter cake carries out Thermal desorption 3 hours at 400 DEG C,
The metal oxide of content of organics 0.06wt% and the solid mixture of calcium sulfate, total 235.6kg, pyrolysis are obtained after Thermal desorption
The generation rate of vapor is 11.2m during analysis3/h。
The calcium acetate aqueous solution being obtained by filtration enters MVR device processing 1.2h, the calcium acetate supersaturation generated by MVR device
The content of calcium acetate is 36wt% in suspension, and the generation rate of vapor is 1215.56m in MVR treatment process3/h.Acetic acid
Filter cake and filtrate containing calcium acetate is obtained by filtration in calcium supersaturation suspension, and filtrate crystallisation is dried to obtain calcium acetate, and contains acetic acid
The filter cake of calcium merges to obtain 247kg calcium acetate solid, and the generation rate of vapor is 182.1m during crystallizing and drying3/h.Vinegar
Sour calcium solid is placed in pyrolysis reactor, in a nitrogen atmosphere, 170 DEG C of thermal crackings of temperature, obtain 91.6kg acetone and
158.2kg calcium carbonate, calcium carbonate return to calcification process, and acetone condensing recovery is store 35 DEG C of temperature or less, dry, ventilation
It deposits.
The vapor containing ethyl alcohol, the tert-butyl alcohol, ethyl acetate and tert-butyl acetate organic matter that is steamed by MVR device, pyrolysis
The raw gas containing organic steam of division and the aqueous vapor of crystallizing and drying generation, which enter, faces oxygen cracker, in 300 DEG C, air
Deep purifying processing is carried out under atmosphere, air intake and the volume ratio into the water vapour for facing oxygen cracker are 3:1, reaction
Pressure is normal pressure, residence time 5kgh/m3；It is 27mgO by facing COD value in the water that oxygen cracker comes out2/ L, in gas phase
VOC concentration is 33mg/m3。
Embodiment 2
The composition of acetic acid wastewater: acetic acid quality score 8.5%, ferric sulfate mass fraction 3.9%, chromium sulfate mass fraction
0.08%, nickel sulfate mass fraction 0.37%, magnesium sulfate mass fraction 0.07%, ethyl alcohol mass fraction 0.2%, n-butanol quality
Score 0.07%, ethyl acetate mass fraction 0.1%, n-butyl acetate mass fraction 0.05%, sulfuric acid mass fraction are
4.5%, remaining is moisture.
The above-mentioned acetic acid wastewater of 10000kg is added in a kettle, is slowly added to 1081.3kg calcium carbonate under stirring,
It stirs 2 hours at room temperature, then 178.4kg calcium oxide is added in a kettle, continue stirring 1.5 hours, formation contains hydroxide
The suspension of object, calcium sulfate and calcium acetate.
Above-mentioned suspension is filtered, is obtained filter cake (weight in wet base 1485.5kg), filter cake carries out Thermal desorption 3 hours at 400 DEG C,
Obtain the metal oxide of content of organics 0.05wt% and the solid mixture of calcium sulfate, total 1276.7kg, Thermal desorption process
The generation rate of middle vapor is 84.5m3/h。
Filtered filtrate enters MVR device processing 2h, acetic acid in the calcium acetate supersaturation suspension generated by MVR device
The content of calcium is 40wt%, and the generation rate of vapor is 3937.11m in MVR treatment process3/h.Calcium acetate supersaturation suspends
Filter cake and filtrate containing calcium acetate is obtained by filtration in liquid, and filtrate crystallisation is dried to obtain calcium acetate, and the filter cake containing calcium acetate merges
1163.2kg calcium acetate solid is obtained, the generation rate of vapor is 1085.3m during crystallizing and drying3/h.Calcium acetate solid
It is placed in pyrolysis reactor, thermal cracking is carried out at nitrogen atmosphere, 170 DEG C, obtains 427.0kg acetone and 736.2kg calcium carbonate,
Calcium carbonate returns to calcification process.
The vapor containing ethyl alcohol, n-butanol, ethyl acetate and n-butyl acetate organic matter that is steamed by MVR device, pyrolysis
The raw gas containing organic steam of division and the steam of crystallizing and drying generation, which enter, faces oxygen cracker, in 300 DEG C, air
Deep purifying processing is carried out under atmosphere, air intake and the volume ratio into the water vapour for facing oxygen cracker are 2:1, reaction
Pressure is normal pressure, residence time 6kgh/m3, it is 27mgO by facing COD value in the water that oxygen cracker comes out2/ L, in gas phase
VOC concentration is 39mg/m3。
Embodiment 3
The composition of acetic acid wastewater: acetic acid quality score 5.5%, ferric sulfate mass fraction 2.7%, chromium sulfate mass fraction
0.01%, nickel sulfate mass fraction 0.57%, manganese sulfate mass fraction 0.04%, ethyl alcohol mass fraction 0.1%, tert-butyl alcohol quality
Score 0.18%, ethyl acetate mass fraction 0.1%, tert-butyl acetate mass fraction 0.09%, sulfuric acid mass fraction are
3.6%, remaining is moisture.
The above-mentioned acetic acid wastewater of 8000kg is added in a kettle, is slowly added to 642.5kg calcium carbonate under stirring, then
After being stirred at room temperature 1.5 hours, then 105.4kg calcium oxide is added in a kettle, continues stirring 1 hour, formation contains hydrogen
The suspension of oxide, calcium sulfate and calcium acetate.
Filter cake (weight in wet base 875.2kg) will be obtained after the filtering of above-mentioned mixed liquor, it is small that filter cake is carried out to Thermal desorption 3 at 400 DEG C
When, the metal oxide of the content of organics 0.05wt% obtained after Thermal desorption and the solid mixture of calcium sulfate, altogether
752.6kg, the generation rate of vapor is 50.9m during Thermal desorption3/h。
Filtered filtrate goes MVR device to handle 2h, calcium acetate in the calcium acetate saturation suspension generated by MVR device
Content is 38wt%, and the generation rate of vapor is 3710.08m in MVR treatment process3/h.Calcium acetate supersaturation suspension warp
The filter cake containing calcium acetate and filtrate is obtained by filtration, filtrate crystallisation is dried to obtain calcium acetate, and the filter cake containing calcium acetate merges to obtain
584.5kg calcium acetate, the generation rate of vapor is 593.4m during crystallizing and drying3/h.Calcium acetate solid is placed in thermal cracking
Reactor carries out thermal cracking under 170 DEG C, nitrogen atmosphere, obtains 214.5kg acetone and 369.9kg calcium carbonate, and calcium carbonate returns
To calcification neutralization step.
The vapor containing ethyl alcohol, the tert-butyl alcohol, ethyl acetate and tert-butyl acetate organic matter that is steamed by MVR device, pyrolysis
The raw gas containing organic steam of division and the steam of crystallizing and drying generation, which enter, faces oxygen cracker, in 300 DEG C, air
Deep purifying processing is carried out under atmosphere, air intake and the volume ratio into the water vapour for facing oxygen cracker are 3.5:1, instead
Answering pressure is normal pressure, residence time 7kgh/m3, it is 26mgO by facing COD value in the water that oxygen cracker comes out2/ L, gas phase
Middle VOC concentration is 39mg/m3。
Embodiment 4
The composition of acetic acid wastewater: acetic acid quality score 7.6%, ferric sulfate mass fraction 3.8%, chromium sulfate mass fraction
0.02%, nickel sulfate mass fraction 0.35%, zinc sulfate mass fraction 0.06%, propyl alcohol mass fraction 0.15%, tert-butyl alcohol matter
Amount score 0.16%, propyl acetate mass fraction 0.09%, tert-butyl acetate mass fraction 0.09%, sulfuric acid mass fraction are
4.6%, remaining is moisture.
The above-mentioned acetic acid wastewater of 4500kg is added in a kettle, is slowly added to 486.3kg calcium carbonate under stirring, then
After being stirred at room temperature 1 hour, then 81.1kg calcium oxide is added in a kettle, continues stirring 1 hour, formation contains hydroxide
The suspension of object, calcium sulfate and calcium acetate.
Filter cake (weight in wet base 646.7kg) will be obtained after the filtering of above-mentioned mixed liquor, it is small that filter cake is carried out to Thermal desorption 3 at 400 DEG C
When, the metal oxide of the content of organics 0.05wt% obtained after Thermal desorption and the solid mixture of calcium sulfate, altogether
556.1kg, the generation rate of vapor is 37.6m during Thermal desorption3/h。
Filtered filtrate goes MVR device to handle 2h, calcium acetate in the calcium acetate saturation suspension generated by MVR device
Content is 37wt%, and the generation rate of vapor is 1811.84m in MVR treatment process3/h.Calcium acetate supersaturation suspension warp
The filter cake containing calcium acetate and filtrate is obtained by filtration, filtrate crystallisation is dried to obtain calcium acetate, and the filter cake containing calcium acetate merges to obtain
454.5kg calcium acetate solid, the generation rate of vapor is 481.5m during crystallizing and drying3/h.Calcium acetate solid is placed in heat
Cracking reactor carries out thermal cracking under 170 DEG C, nitrogen atmosphere, obtains 166.8kg acetone and 287.6kg calcium carbonate, calcium carbonate
Back to calcification process.
The vapor containing propyl alcohol, the tert-butyl alcohol, propyl acetate and tert-butyl acetate organic matter that is steamed by MVR device, pyrolysis
The raw gas containing organic steam of division and the aqueous vapor of crystallizing and drying generation, which enter, faces oxygen cracker, in 300 DEG C, air
Deep purifying processing is carried out under atmosphere, air intake and the volume ratio into the water vapour for facing oxygen cracker are 2.5:1, instead
Answering pressure is normal pressure, residence time 8kgh/m3, it is 27mgO by facing COD value in the water that oxygen cracker comes out2/ L, gas phase
Middle VOC concentration is 38mg/m3。
Embodiment 5
The composition of acetic acid wastewater: acetic acid quality score 3.2%, ferric sulfate mass fraction 3.3%, chromium sulfate mass fraction
0.02%, nickel sulfate mass fraction 0.28%, sulfuric acid Copper mass fraction 0.02%, methanol quality score 0.01%, ethyl alcohol quality
Score 0.03%, tert-butyl alcohol mass fraction 0.12%, methyl acetate mass fraction 0.05%, ethyl acetate mass fraction
0.06%, tert-butyl acetate mass fraction 0.17%, sulfuric acid mass fraction is 4.1%, remaining is moisture.
The above-mentioned acetic acid wastewater of 6500kg is added in a kettle, is slowly added to 421.95kg calcium carbonate under stirring, so
After be stirred at room temperature 1.5 hours after, then in a kettle be added 100.5kg calcium oxide, continue stirring 1 hour, formation contains
The suspension of hydroxide, calcium sulfate and calcium acetate.
Filter cake (weight in wet base 822.7kg) will be obtained after the filtering of above-mentioned mixed liquor, it is small that filter cake is carried out to Thermal desorption 3 at 400 DEG C
When, the metal oxide of the content of organics 0.05wt% obtained after Thermal desorption and the solid mixture of calcium sulfate, altogether
707.39kg, the generation rate of vapor is 47.8m during Thermal desorption3/h。
After filtered filtrate removes MVR device 2h, calcium acetate contains in the calcium acetate that is generated by MVR device saturation suspension
Amount is 35wt%, and the generation rate of vapor is 3213.22m in MVR treatment process3/h.Calcium acetate supersaturation suspension passes through
The filter cake containing calcium acetate and filtrate are filtered, filtrate crystallisation is dried to obtain calcium acetate, and the filter cake containing calcium acetate merges to obtain
292.3kg calcium acetate solid, the generation rate of vapor is 337.8m during crystallizing and drying3/h.Calcium acetate solid is placed in heat
Cracking reactor carries out thermal cracking at nitrogen atmosphere, 170 DEG C, obtains 107.3kg acetone and 184.9kg calcium carbonate, calcium carbonate
Back to calcification process.
The vapor containing methanol, ethyl alcohol, the tert-butyl alcohol, ethyl acetate and tert-butyl acetate organic matter that is steamed by MVR device,
The aqueous vapor that the gas containing organic steam and crystallizing and drying that Thermal desorption generates generate, which enters, faces oxygen cracker, 300 DEG C,
Deep purifying processing is carried out under air atmosphere, air intake and the volume ratio into the water vapour for facing oxygen cracker are 4:1,
Reaction pressure is normal pressure, residence time 7kgh/m3.It is 22mgO by facing COD value in the water that oxygen cracker comes out2/ L, gas
VOC concentration is 31mg/m in phase3。
Claims (10)
1. a kind of processing method of the low-concentration acetic acid wastewater of metal ion and organic impurities, characterized by comprising: acetic acid
Waste water carries out calcification processing, makes that the acetic acid in waste water is changed into calcium acetate, sulfate ion is changed into calcium sulfate precipitation, metal from
Son is changed into hydroxide precipitating；Be filtered by the waste water of calcification processing, obtain sulfur acid calcium and hydroxide filter cake,
Calcium acetate aqueous solution；Calcium acetate aqueous solution is handled to obtain calcium acetate supersaturated solution by MVR, and calcium acetate supersaturated solution filters,
The filter cake and filtrate containing calcium acetate are obtained, filtrate crystallisation is dried to obtain calcium acetate, and the filter cake containing calcium acetate merges to obtain acetic acid
Calcium solid, calcium acetate solid carry out being thermally cracked to produce acetone and calcium carbonate；The filter cake of sulfur acid calcium and hydroxide is pyrolyzed
Analysis processing, the vapor and knot containing organic matter of the gas containing organic steam, MVR processing generation that Thermal desorption processing generates
The dry vapor generated of crystalline substance, which enters, faces oxygen cracker, and deep purifying processing is carried out under air conditions.
2. processing method according to claim 1, it is characterised in that the following steps are included:
Step (1), using calcium carbonate as calcification agent, Dichlorodiphenyl Acetate waste water carry out calcification processing, the acetic acid in waste water is changed into acetic acid
Calcium, sulfate ion are changed into calcium sulfate precipitation；Calcium oxide is added into waste water again and metathesis reaction occurs for metal ion, makes
Metal ion is changed into hydroxide precipitating, forms the suspension containing hydroxide, calcium sulfate and calcium acetate；
The material that step (2), step (1) obtain is filtered, and filter cake, the calcium acetate for obtaining sulfur acid calcium and hydroxide are water-soluble
Liquid；The filter cake for obtaining sulfur acid calcium and hydroxide carries out Thermal desorption processing, and the water containing organic matter that Thermal desorption processing generates steams
Gas, which enters, faces the progress deep purifying processing of oxygen cracker；Calcium acetate aqueous solution handles to obtain calcium acetate supersaturated solution through MVR,
The vapor containing organic matter that MVR processing generates, which enters, faces oxygen cracker MVR device generation calcium acetate saturation suspension；Acetic acid
Filter cake and filtrate containing calcium acetate is obtained by filtration in calcium supersaturated solution, and filtrate crystallisation is dried to obtain calcium acetate, and contains calcium acetate
Filter cake merge to obtain calcium acetate solid, the vapor that crystallizing and drying generates enters and faces oxygen cracker；
Step (3), calcium acetate solid carry out being thermally cracked to produce acetone and calcium carbonate, and calcium carbonate is used for calcification back to step (1)
Processing, acetone recycling and reusing.
3. processing method according to claim 1 or 2, it is characterised in that the content of acetic acid is in the acetic acid wastewater
The content of 0.5wt%~10wt%, the organic matter other than acetic acid are 0.01wt%~0.5wt%, and the content of metal sulfate is
0.05wt%~5wt%, 1~5wt% of content of sulfuric acid.
4. processing method according to claim 3, it is characterised in that the organic matter other than the acetic acid is methanol, second
Alcohol, propyl alcohol, the tert-butyl alcohol, n-butanol, methyl acetate, ethyl acetate, propyl acetate, tert-butyl acetate, in n-butyl acetate extremely
Few one kind.
5. processing method according to claim 3, it is characterised in that the metal sulfate be ferric sulfate, nickel sulfate,
At least one of chromium sulfate, magnesium sulfate, manganese sulfate, copper sulphate, zinc sulfate.
6. processing method according to claim 1 or 2, it is characterised in that calcium acetate aqueous solution is handled to obtain acetic acid by MVR
Calcium content is the calcium acetate supersaturated solution of 30~40wt%.
7. processing method according to claim 1 or 2, it is characterised in that the temperature of the Thermal desorption is 200~400
℃。
8. processing method according to claim 1 or 2, it is characterised in that the condition of the thermal cracking be nitrogen atmosphere,
Temperature is 160~200 DEG C.
9. method according to claim 1 or 2, it is characterised in that deep purifying treatment conditions are as follows: purification reaction temperature is
250~450 DEG C, reaction pressure is normal pressure, and the residence time is 0.1~10kgh/m3, oxygen cracking is faced in air intake and entrance
The volume ratio of the water vapour of device is 1~5:1.
10. method according to claim 1 or 2, it is characterised in that the heat that deep purifying processing is released is used for MVR device
The gasification of liquid.
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| Publication number | Priority date | Publication date | Assignee | Title |
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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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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