CN111689857A - Resource utilization method of ethyl acetate production wastewater - Google Patents
Resource utilization method of ethyl acetate production wastewater Download PDFInfo
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- CN111689857A CN111689857A CN202010421097.9A CN202010421097A CN111689857A CN 111689857 A CN111689857 A CN 111689857A CN 202010421097 A CN202010421097 A CN 202010421097A CN 111689857 A CN111689857 A CN 111689857A
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- ethyl acetate
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- ethanol
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 title claims abstract description 318
- 239000002351 wastewater Substances 0.000 title claims abstract description 93
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 164
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 129
- 239000007788 liquid Substances 0.000 claims abstract description 73
- 238000001179 sorption measurement Methods 0.000 claims abstract description 63
- 238000003795 desorption Methods 0.000 claims abstract description 57
- 238000005185 salting out Methods 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003463 adsorbent Substances 0.000 claims abstract description 33
- 238000005886 esterification reaction Methods 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 238000005336 cracking Methods 0.000 claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 31
- 239000001301 oxygen Substances 0.000 claims abstract description 31
- 238000001704 evaporation Methods 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000013078 crystal Substances 0.000 claims abstract description 25
- 230000008020 evaporation Effects 0.000 claims abstract description 25
- 239000002535 acidifier Substances 0.000 claims abstract description 24
- 230000032050 esterification Effects 0.000 claims abstract description 24
- 230000020477 pH reduction Effects 0.000 claims abstract description 20
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000007664 blowing Methods 0.000 claims abstract description 8
- 239000012071 phase Substances 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 14
- 239000002808 molecular sieve Substances 0.000 claims description 14
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 14
- 230000008929 regeneration Effects 0.000 claims description 13
- 238000011069 regeneration method Methods 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 239000008213 purified water Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 238000004364 calculation method Methods 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical group 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical group [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- -1 and Al is used2O3 Substances 0.000 claims 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 235000002639 sodium chloride Nutrition 0.000 description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 8
- 238000004064 recycling Methods 0.000 description 7
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 6
- 229910052939 potassium sulfate Inorganic materials 0.000 description 6
- 235000011151 potassium sulphates Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002957 persistent organic pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 235000011056 potassium acetate Nutrition 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 239000001632 sodium acetate Substances 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention discloses a resource utilization method of ethyl acetate production wastewater, which comprises the following steps: conveying the ethyl acetate production wastewater to a rectifying tower for rectification, extracting ethyl acetate and ethanol from the top of the tower, conveying the liquid extracted from the bottom of the tower to an adsorption system, and adsorbing acetic acid by an adsorbent; blowing off residual wastewater when the adsorbent is saturated, then converting acetic acid adsorbed by the adsorbent into acetate by using a desorption agent, conveying desorption liquid containing the acetate to an acidification esterification system, carrying out acidification treatment on the desorption liquid by using an acidifying agent, and then adding ethanol for esterification reaction; adding the acidified esterified product liquid into a salting-out system, adding a salting-out agent for salting-out, recovering an oil phase generated by salting-out, and sending a water phase generated by salting-out to an evaporation system; and (4) rectifying the evaporated condensate in a rectifying tower, and carrying out dry-process oxygen cracking on crystals generated by evaporation in the air or oxygen atmosphere under the action of a catalyst. The method provided by the invention can be used for efficiently recovering valuable components in the ethyl acetate production wastewater and realizing the purification treatment of the wastewater.
Description
Technical Field
The invention belongs to the field of chemical wastewater treatment, relates to a recycling method of ethyl acetate production wastewater, and particularly relates to a resource utilization method of ethyl acetate production wastewater.
Background
Ethyl acetate is an important chemical basic raw material, a certain amount of high-concentration organic wastewater can be discharged in the production process of an ethyl acetate product, part of the wastewater comes from the wastewater generated in the product separation process, and the other part of the wastewater is the flushing wastewater generated after the reaction kettle operates for one period. Most of the wastewater is mixed wastewater, the main components of the wastewater are acetic acid, ethanol and ethyl acetate, the content of organic matters is extremely high, the average content is about 20000mg/L under normal conditions, and when the process steady state is destroyed, the COD of the discharged wastewater can reach hundreds of thousands. The ethyl acetate waste water belongs to dangerous waste, and the direct discharge can cause very serious environmental pollution. If the method can effectively purify and treat the ethyl acetate wastewater, and recover and utilize acetic acid, ethanol and ethyl acetate in the wastewater, the method has important significance in the aspects of resource sustainable utilization, environmental protection and the like.
Aiming at the esterification wastewater, the Chinese patent application CN104803542A designs a wastewater purification technology comprising the steps of pretreatment, biochemical treatment, advanced oxidation and membrane treatment, can effectively solve the problem that the esterification wastewater cannot reach the discharge standard, realizes the comprehensive treatment and water recycling of the esterification wastewater, but does not recycle valuable components such as esters in the wastewater. The Chinese invention patent CN101575288A discloses a method for treating waste water containing ethyl acetate, wherein the waste water is aerated, ethyl acetate is carried to an adsorber by hot air, and the ethyl acetate in the adsorber is recovered by using activated carbon. The Chinese patent application CN105776376A utilizes gas stripping, absorption and desorption technologies to recover ester-containing wastewater, wherein a gas stripping unit is combined with an absorption unit to enrich and recover esters in the wastewater, a desorption unit is combined with an absorption unit to realize the recycling of an absorbent, the system can transfer esters in a water phase to a gas phase and then recover the esters in the gas phase, and the problem of equipment scaling caused by biomass during the rectification and recovery of the ester-containing wastewater can be prevented. Aiming at ethyl acetate wastewater and ethyl acetate esterification brought water, Chinese patent application CN106693429A designs an ethanol and ethyl acetate recovery system, wherein ethanol and ethyl acetate in esterification brought water and water in a water washing system are effectively recovered from the top of a rectifying tower, treated wastewater is extracted from the bottom of the rectifying tower, and the treated wastewater is directly sent to a sewage treatment process. Chinese invention patent CN101100329A discloses a method for recycling waste water in ethyl acetate production, wherein a waste water mixture containing ester and alcohol generated in the ethyl acetate production process is rectified and recycled by a rectifying and recycling tower to recycle ester and alcohol components, and the waste water in the recycling tower kettle is sent to a phase separator of a dehydrating tower to wash alcohol after recycling heat, so that ethanol and ethyl acetate in the waste water can be effectively recycled, and the heat in the rectifying tower kettle can be effectively utilized.
Disclosure of Invention
The main components of the waste water produced in the ethyl acetate production are acetic acid, ethanol and ethyl acetate, according to the physical and chemical properties of the acetic acid, the ethanol, the ethyl acetate and water, the inventor considers that the ethyl acetate and the ethanol are separated from the waste water firstly, and then the waste water containing the acetic acid is recycled. Therefore, the inventor adopts a coupling system of various separation technologies to purify and recycle the wastewater in the production of the ethyl acetate with high pollution and high COD value, firstly uses rectification to separate the ethanol and the ethyl acetate, and then adopts the adsorption and desorption, acidification esterification and salting-out with low energy consumption and low investment to recycle the acetic acid in the wastewater.
The purpose of the invention is realized by the following technical scheme:
a resource utilization method of ethyl acetate production wastewater comprises the following steps: conveying the ethyl acetate production wastewater to a rectifying tower for rectification, collecting most of ethyl acetate and ethanol from the top of the rectifying tower and returning the ethyl acetate and ethanol to an ethyl acetate production system, conveying the liquid collected from the bottom of the rectifying tower to an adsorption system, adsorbing acetic acid by an adsorbent, and discharging purified water discharged by the adsorption system after reaching the standard; when the adsorption of an adsorbent in an adsorption system is saturated, blowing off residual wastewater by using compressed air, then converting acetic acid adsorbed by the adsorbent into acetate by using a desorption agent to realize the desorption of the acetic acid, conveying desorption liquid containing the acetate to an acidification esterification system, carrying out acidification treatment on the desorption liquid by using an acidifying agent, and then adding ethanol for esterification reaction to generate ethyl acetate; the acidified esterified product liquid enters a salting-out system, a salting-out agent is added for salting-out, an oil phase generated by salting-out returns to an ethyl acetate production system, and a water phase generated by salting-out is sent to an evaporation system; the condensate generated by evaporation is sent to rectification for continuous recovery of valuable components, and crystals generated by evaporation are subjected to dry-process oxygen cracking under the atmosphere of air or oxygen and under the action of a catalyst.
The resource utilization method of the ethyl acetate production wastewater specifically comprises the following steps:
rectifying in step (1): conveying the ethyl acetate production wastewater into a rectifying tower for rectification, collecting most of ethyl acetate and ethanol in the wastewater from the top of the rectifying tower as reflux liquid, and returning the reflux liquid to an ethyl acetate production system; the liquid extracted from the tower bottom of the rectifying tower is waste water containing acetic acid;
step (2), adsorption and desorption: the produced liquid in the tower kettle of the rectifying tower is conveyed to an adsorption system, acetic acid is adsorbed by using an adsorbent, and COD in the purified water discharged by the adsorption system is reduced to 50mgO2below/L; when the adsorption of the adsorbent in the adsorption system is saturated, the liquid produced in the tower bottom of the rectifying tower is input and switched to a new or completely regenerated adsorption system; the adsorption system with saturated adsorption is switched to a regeneration system, the compressed air is used for blowing off the residual wastewater in the regeneration system, and then the desorption agent is used for converting the acetic acid adsorbed by the adsorbent into acetate to obtain desorption liquid containing the acetate, so that the desorption of the acetic acid is realized;
step (3), acidification and esterification: the desorption liquid enters an acidification esterification system, acidification treatment is carried out on the desorption liquid by using an acidifying agent, and then excessive ethanol is added for carrying out esterification reaction to produce ethyl acetate;
step (4), salting out: sending the acidified esterified product liquid into a salting-out system, adding a salting-out agent, after salting-out is finished, carrying out phase splitting to obtain an oil phase and a water phase, wherein the oil phase can be directly used as a reflux liquid to return to an ethyl acetate production system, so that the oil phase is recycled;
and (5) evaporating and crystallizing: the water phase generated by salting out is sent to an evaporation crystallization system for evaporation treatment, the evaporated condensate is sent to a rectifying tower for re-purification, and the crystal product generated by evaporation is sent to a dry-process temporary oxygen cracking system;
step (6), dry-process oxygen-critical cracking: in the air or oxygen atmosphere, the crystal is subjected to dry-process temporary oxygen cracking under the action of a catalyst, residual pollutants in the crystal are purified, a crystal product with the organic matter residue of less than 1 per thousand is obtained, the crystal product is used as a salting-out agent to be circulated back to a salting-out system or sold to the outside, and the concentration of non-methane total hydrocarbons in tail gas generated by the dry-process temporary oxygen cracking is less than 50mg/Nm3And the waste water can reach the discharge standard and can be directly discharged.
The ethyl acetate production wastewater refers to wastewater generated in ethyl acetate production, and mainly comprises ethyl acetate, ethanol and acetic acid. The COD value of the ethyl acetate production wastewater is 10000-100000 mg/L, the total content of ethanol and ethyl acetate is 5-50 g/L, and the content of acetic acid is 5-50 g/L.
The rectification conditions are as follows: the temperature of the top of the rectifying tower is 73-80 ℃, the temperature of the tower bottom is 110-135 ℃, the number of tower plates is 10-15, and 450 type ceramic corrugated plate efficient packing is adopted.
The adsorbent is a solid adsorbent with high-efficiency adsorption performance on acetic acid, and is selected from resin, activated carbon, molecular sieves and the like, and the particle size of the adsorbent is 8-50 meshes. The resin is weak alkaline resin, and can be selected from D331 resin; the molecular sieve is a carbon molecular sieve, and can be specifically selected from an SLCMS-260 type carbon molecular sieve.
The filling amount of the adsorbent in the adsorption system is 0.5-50L/(kg) according to the liquid-phase airspeed of the wastewater in the adsorption systemadsH) calculation.
The desorption agent is sodium hydroxide or potassium hydroxide solution, preferably sodium hydroxide solution with the mass fraction of 25-30%.
The volume ratio of the total amount of the desorbent to the total amount of the liquid extracted from the tower bottom of the rectifying tower entering the adsorption system is 1/50-1/10.
The content of acetate in the desorption solution is 10 to 30 percent.
The acidifier is concentrated sulfuric acid with the mass fraction of 98% or concentrated hydrochloric acid with the mass fraction of 30%; the mass ratio of the acidifying agent to the desorption liquid is 1: 2-10, and preferably 1: 10.
And acidifying the desorption solution to form an acetic acid aqueous solution, wherein the water content is high, and in order to ensure that the acetic acid is close to complete reaction and improve the recovery rate of acid, the dosage of the ethanol is controlled to be 5-15 times of the theoretical dosage of the ethanol.
The salting-out agent is sulfate or chloride corresponding to the acidifying agent, and is potassium salt or sodium salt identical to the anion of the acidifying agent, and the cation of the salt after acidification is identical to that of the desorption agent, and is selected from potassium sulfate, potassium chloride, sodium sulfate and sodium chloride. The salting-out agent may be selected from nitrate, specifically potassium nitrate or sodium nitrate.
Adding a salting-out agent into the acidified esterification product liquid until the concentration of the salting-out agent in water reaches 0.5-5.5 mol/L.
The catalyst is metal oxide catalyst and is made of Al2O3、SiO2、TiO2One of the ZSM-5 molecular sieve, the rare earth Y molecular sieve, the MCM-41 molecular sieve and the H-MOR molecular sieve is taken as a carrier, a transition metal oxide is taken as an active component, and the load capacity of the active component is 1-15%; the particle size of the catalyst is 0.01-0.2 mm, and the granular catalyst can be well and uniformly mixed with salt, so that the oxygen cracking can be smoothly carried out.
The transition metal oxide is one or two oxides of titanium oxide, copper oxide, cerium oxide, nickel oxide, vanadium oxide, chromium oxide, iron oxide, manganese oxide, cobalt oxide, zinc oxide, lanthanum oxide and molybdenum oxide.
The amount of the catalyst is 20-100 wt% of the mass of the crystal (i.e. salt). The material after dry-process oxygen-critical cracking can be washed by water to recover the catalyst.
The temperature of the dry-process oxygen cracking is 300-800 ℃.
The invention has the following technical effects:
the invention adopts a coupling system of various separation technologies to purify and recycle the wastewater in the production of the ethyl acetate with high pollution and high COD value. The ethanol and the ethyl acetate in the ethyl acetate production wastewater are recovered by rectification, and the total recovery rate of the ethanol and the ethyl acetate reaches over 99.5 percent. And the produced liquid of the rectifying tower kettle is purified by an adsorption system, the adsorbed acetic acid is completely recovered by a regeneration system, the concentration of the acetic acid in desorption liquid is realized, the desorption liquid amount is greatly reduced compared with the feeding amount of the original wastewater and is only 1/50-1/10 of the total amount of the original wastewater. The acidification esterification system and the salting-out system carry out high-efficiency recovery and conversion on the acetic acid in the desorption solution, the recovery rate of the acetic acid reaches more than 80 percent, and the recovery of valuable substances is realized. The salting-out agent used in the salting-out process is purified and recovered by an evaporative crystallization system and a dry-process temporary oxygen cracking system, the generated salt crystal product can be recycled as the salting-out agent in the salting-out process, and new pollutants are not generated in the two systems.
The concentration of various organic matters in the purified water treated by the method meets the requirements of national standards GB21904-2008 'discharge standard of pollutants for pharmaceutical industry of chemical synthesis' and GB31571-2015 'discharge standard of pollutants for petrochemical industry', and the purified water can be directly discharged without further treatment; meanwhile, the concentration of various organic matters in the tail gas discharged by the system meets the requirements of GB16297-1996 integrated emission Standard of atmospheric pollutants and Jiangsu province local Standard DB32/3151-2016 emission Standard of volatile organic matters in chemical industry, and the tail gas can be directly discharged without further treatment.
Drawings
FIG. 1 is a schematic diagram of the resource utilization method of the ethyl acetate production wastewater.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to the following examples.
The concentration of organic pollutants in the gas and the content of organic matters in the liquid are analyzed by an SP-6890 type gas chromatograph, and the COD value (chemical oxygen demand) in the liquid is tested and analyzed by an intelligent digestion instrument and a COD rapid detector.
Example 1
The rectification adopts a packed tower: the temperature of the top of the rectifying tower is 73-80 ℃, the temperature of the bottom of the rectifying tower is 110-135 ℃, the number of tower plates is 10, and 450 type ceramic corrugated plate efficient packing is adopted. The adsorption system adopts a fixed bed, the adsorbent adopts weak alkaline resin D331, the granularity is 8-50 meshes, and the loading capacity is 100 kg; the acidifying agent is concentrated hydrochloric acid with concentration of 30%; the salting-out agent adopts sodium chloride; the catalyst used in the dry-process oxygen cracking is CeO2/SiO2，CeO2The loading amount of the catalyst is 15%, the particle size of the catalyst is 0.022-0.18 mm, the dosage of the catalyst is 40 wt% of the crystal mass, and the dry-method oxygen cracking temperature is 400 ℃.
The COD value of the waste water produced in the ethyl acetate production is 50000mgO2The content of acetic acid in the solution was 0.8 wt%, and the total content of ethyl acetate and ethanol was 3.05 wt%.
As shown in fig. 1, the ethyl acetate production wastewater is conveyed to a rectifying tower for rectification, the total recovery rate of ethanol and ethyl acetate in the extraction liquid at the top of the rectifying tower is 99.5% (the total recovery rate of ethanol and ethyl acetate is the ratio of the total amount of ethanol and ethyl acetate in the extraction liquid at the top of the rectifying tower to the total amount of ethanol and ethyl acetate in the wastewater in the ethyl acetate production), the extraction liquid at the bottom of the rectifying tower contains acetic acid, and the COD value is 12000mgO2And L. The produced liquid in the tower kettle of the rectifying tower is conveyed to an adsorption system at a feeding flow rate of 1t/h, is adsorbed at normal temperature and normal pressure, and is continuously operated for 24h through the adsorption system, and the COD concentration of the purified water is stabilized at 23-35 mgO2And L. When the adsorption of the adsorbent in the adsorption system is saturated, inputting and switching the wastewater into a new adsorption system, switching the adsorption system with saturated adsorption into a regeneration system, blowing off the residual wastewater in the regeneration system by utilizing compressed air, then using 30 wt% of sodium hydroxide solution as a desorption agent to convert the acetic acid adsorbed by the adsorbent into sodium acetate, wherein the content of the sodium acetate in the desorption solution is 20 wt%, and the desorption solution enters the acidification esterification system at the average flow rate of 48.5 kg/h. Removing according to the mass ratio of the acidifying agent to the desorption liquid of 1:10Adding an acidifying agent into the auxiliary liquid, acidifying the desorption liquid, and adding ethanol with the amount 5 times of the theoretical amount of ethanol for esterification reaction to generate ethyl acetate. Adding sodium chloride into the acidified esterification product liquid until the concentration of the sodium chloride in water reaches 5.2mol/L, after salting out is finished, carrying out phase separation, wherein an oil phase generated by salting out is a mixture of ethyl acetate, ethanol and water, the total content of the ethanol and the ethyl acetate is 85 wt%, and the recovery rate of the acetic acid reaches 82.5 wt%. The water phase generated by salting out is sent to an evaporation crystallization system for evaporation treatment, the evaporated condensate is sent to a rectifying tower for re-purification, the crystals generated by evaporation crystallization are sent to a dry-process near-oxygen cracking system for dry-process near-oxygen cracking under the air atmosphere and under the action of a catalyst, sodium chloride crystals with the organic residue of 0.5mg/g are generated, and the concentration of organic pollutants in the generated tail gas is detected to be 1.8mg/Nm3。
Example 2
On the basis of example 1, the following adjustments were made: the adsorbent filled in the adsorption system is activated carbon, the granularity is 8-50 meshes, and the filling amount is 100 kg; the acidifier adopts 98% concentrated sulfuric acid by mass; the salting-out agent adopts potassium sulfate; the catalyst used in the dry-process oxygen cracking is MnO2/Al2O3，MnO2The loading amount is 15%, the particle size of the catalyst is 0.012-0.2 mm, the dosage of the catalyst is 50 wt% of the crystal mass, and the temperature of the temporary oxygen cracking is 500 ℃.
The COD value of the waste water produced in the ethyl acetate production is 49000mgO2The content of acetic acid in the solution was 0.76% by weight, and the total content of ethyl acetate and ethanol was 3.12% by weight.
Conveying the ethyl acetate production wastewater into a rectifying tower (the tower top temperature of the rectifying tower is 73-80 ℃, the tower bottom temperature of the rectifying tower is 110-135 ℃, the number of tower plates is 10, and a 450 type ceramic corrugated plate efficient filler is adopted) for rectification, wherein the total recovery rate of ethanol and ethyl acetate in the tower top produced liquid of the rectifying tower is 99.6 percent, and the COD value of the tower bottom produced liquid of the rectifying tower is 11500mgO2And L. The produced liquid at the tower bottom of the rectifying tower is conveyed to an adsorption system at a feeding flow rate of 1t/h, is adsorbed at normal temperature and normal pressure, and is continuously operated for 24h through the adsorption system, and the COD concentration of the purified water is stabilized at 20-37 mgO2And L. To-be-adsorbed system adsorbent adsorption saturationThe waste water is input and switched to a new adsorption system, the adsorption system with saturated adsorption is switched to a regeneration system, the compressed air is used for blowing off the residual waste water in the regeneration system, then 30 wt% of potassium hydroxide solution is used as a desorption agent, the acetic acid adsorbed by the adsorption agent is converted into potassium acetate, the content of the potassium acetate in desorption liquid is 23 wt%, and the desorption liquid enters an acidification esterification system with the average flow rate of 47 kg/h. Adding an acidifying agent into the desorption liquid according to the mass ratio of the acidifying agent to the desorption liquid of 1:10, acidifying the desorption liquid, and adding ethanol with the amount 10 times of the theoretical amount of ethanol for esterification reaction to generate ethyl acetate. And (2) supplementing potassium sulfate into the acidified esterification product liquid until the concentration of the potassium sulfate in water reaches 0.65mol/L, after salting out is finished, carrying out phase separation, wherein an oil phase generated by salting out is a mixture of ethyl acetate, ethanol and water, wherein the total content of the ethanol and the ethyl acetate reaches 84.2 wt%, and the recovery rate of the acetic acid reaches 84.1 wt%. The water phase generated by salting out is sent to an evaporation crystallization system for evaporation treatment, the evaporated condensate is sent to a rectifying tower for re-purification, the crystals generated by evaporation crystallization are sent to a dry-process near-oxygen cracking system for dry-process near-oxygen cracking under the air atmosphere and under the action of a catalyst, potassium sulfate crystals with the organic residue of 0.4mg/g are generated, and the concentration of organic pollutants in the generated tail gas is detected to be 1.2mg/Nm3。
Example 3
On the basis of example 1, the following adjustments were made: the adsorbent filled in the adsorption system is an SLCMS-260 type carbon molecular sieve, the granularity is 8-50 meshes, and the filling amount is 100 kg; the acidifier adopts 98% concentrated sulfuric acid by mass fraction; the salting-out agent adopts sodium sulfate; the catalyst used in the dry-process oxygen cracking is V2O5-MOO3/TiO2，V2O5The loading is 1%, MOO3The loading amount is 9%, the particle size of the catalyst is 0.011-0.2 mm, the dosage of the catalyst is 100 wt% of the crystal mass, and the temperature of the temporary oxygen cracking is 600 ℃.
The COD value of the waste water from the ethyl acetate production is 50550mgO2The content of acetic acid was 0.82% by weight, and the total content of ethyl acetate and ethanol was 3.11% by weight.
Waste ethyl acetate productionWater is conveyed to a packing rectifying tower (the temperature of the top of the rectifying tower is 73-80 ℃, the temperature of a tower bottom is 110-135 ℃, the number of tower plates is 10, and high-efficiency packing of 450 type ceramic corrugated plates is adopted) for rectification, the total recovery rate of ethanol and ethyl acetate in the extraction liquid at the top of the rectifying tower is 99.8 percent, and the COD value of the extraction liquid at the tower bottom of the rectifying tower is 12500mgO2And L. The produced liquid at the tower bottom of the rectifying tower is conveyed to an adsorption system at a feeding flow rate of 1t/h, is adsorbed at normal temperature and normal pressure, and is continuously operated for 24h through the adsorption system, and the COD concentration of the purified water is stabilized at 19-41 mgO2And L. When the adsorption of the adsorbent in the adsorption system is saturated, inputting and switching the wastewater into a new adsorption system, switching the adsorption system with saturated adsorption into a regeneration system, blowing off the residual wastewater in the regeneration system by utilizing compressed air, then using 30 wt% of sodium hydroxide solution as a desorption agent to convert acetic acid adsorbed by the adsorbent into sodium acetate, wherein the content of the sodium acetate in desorption liquid is 18 wt%, and the desorption liquid enters an acidification esterification system at the average flow rate of 49 kg/h. Adding an acidifying agent into the desorption liquid according to the mass ratio of the acidifying agent to the desorption liquid of 1:10, acidifying the desorption liquid, and adding ethanol with 15 times of the theoretical amount of ethanol for esterification reaction to generate ethyl acetate. And (3) supplementing sodium sulfate into the acidified esterification product liquid until the concentration of the sodium sulfate in the reaction liquid reaches 2.5mol/L, after salting-out is finished, carrying out phase separation, wherein an oil phase generated by salting-out is a mixture of ethyl acetate, ethanol and water, wherein the total content of the ethanol and the ethyl acetate is 86 wt%, and the recovery rate of the acetic acid reaches 86.8 wt%. The water phase generated by salting out is sent to an evaporation crystallization system for evaporation treatment, the evaporated condensate is sent to a rectifying tower for re-purification, the crystals generated by evaporation crystallization are sent to a dry-process near-oxygen cracking system for dry-process near-oxygen cracking under the air atmosphere and under the action of a catalyst, potassium sulfate crystals with the organic residue of 0.4mg/g are generated, and the concentration of organic pollutants in the generated tail gas is detected to be 1.1mg/Nm3。
Example 4
On the basis of example 1, the following adjustments were made: the adsorbent filled in the fixed bed is weakly alkaline resin D311, the granularity is 8-50 meshes, and the filling amount is 100 kg; the acidifying agent is hydrochloric acid with the concentration of 30 percent; the salting-out agent adopts potassium chloride; the catalyst used in the dry-process oxygen cracking is as follows: cr (chromium) component2O3/Al2O3，Cr2O3The loading amount is 9.3%, the particle size of the catalyst is 0.01-0.2 mm, the dosage of the catalyst is 20 wt% of the salt mass, and the temperature of the temporary oxygen cracking is 550 ℃.
The COD value of the waste water generated in the production of the ethyl acetate is 50250mgO2The content of acetic acid was 0.79% by weight, and the total content of ethyl acetate and ethanol was 3.3% by weight.
Conveying the ethyl acetate production wastewater to a filler rectifying tower (the tower top temperature of the rectifying tower is 73-80 ℃, the tower bottom temperature is 110-135 ℃, the number of tower plates is 15, and 450 type ceramic corrugated plate high-efficiency filler is adopted) for rectifying, wherein the total recovery rate of ethanol and ethyl acetate in the tower top extract of the rectifying tower is 99.5%, and the COD value of the tower bottom extract of the rectifying tower is 12000mgO2And L. The produced liquid at the tower bottom of the rectifying tower is conveyed to an adsorption system at a feeding flow rate of 1t/h, is adsorbed at normal temperature and normal pressure, and is continuously operated for 24h through the adsorption system, and the COD concentration of the purified water is stabilized at 15-39 mgO2And L. When the adsorbent in the adsorption system is saturated, inputting and switching the liquid extracted from the tower bottom of the rectifying tower to the completely regenerated adsorption system, switching the adsorption system with saturated adsorption to a regeneration system, blowing off the residual wastewater in the regeneration system by utilizing compressed air, then using 30 wt% potassium hydroxide solution as a desorption agent to convert the acetic acid adsorbed by the adsorbent into potassium acetate, wherein the potassium acetate content in the desorption liquid is 21 wt%, and the desorption liquid enters the acidification esterification system at the average flow rate of 46.8 kg/h. Adding an acidifying agent into the desorption liquid according to the mass ratio of the acidifying agent to the desorption liquid of 1:10, acidifying the desorption liquid, and adding ethanol with 15 times of the theoretical amount of ethanol for esterification reaction to generate ethyl acetate. And (3) supplementing potassium chloride into the acidified esterification product liquid until the concentration of the potassium chloride in water reaches 4.0mol/L, after salting-out is finished, carrying out phase separation, wherein an oil phase generated by salting-out is a mixture of ethyl acetate, ethanol and water, the total content of the ethanol and the ethyl acetate is 90 wt%, and the recovery rate of the acetic acid reaches 88.1 wt%. The water phase generated by salting out is sent to an evaporation crystallization system for evaporation treatment, the evaporated condensate is sent to a rectifying tower for re-purification, the crystal product generated by evaporation crystallization is sent to a dry-process oxygen-adjacent cracking system, and the dry-process oxygen-adjacent cracking is carried out under the air atmosphere and under the action of a catalystPotassium chloride crystal with organic residue of 0.8mg/g is produced, and the concentration of organic pollutant in the produced tail gas is detected to be 0.9mg/Nm3。
Claims (10)
1. A resource utilization method of ethyl acetate production wastewater is characterized by comprising the following steps: conveying the ethyl acetate production wastewater to a rectifying tower for rectification, extracting ethyl acetate and ethanol from the top of the tower, conveying the liquid extracted from the tower bottom of the rectifying tower to an adsorption system, and adsorbing acetic acid by an adsorbent; when the adsorption of an adsorbent in an adsorption system is saturated, blowing off residual wastewater by using compressed air, then converting acetic acid adsorbed by the adsorbent into acetate by using a desorption agent, conveying desorption liquid containing the acetate to an acidification esterification system, carrying out acidification treatment on the desorption liquid by using an acidifier, and then adding ethanol for esterification reaction to generate ethyl acetate; adding the acidified esterified product liquid into a salting-out system, adding a salting-out agent for salting-out, recovering an oil phase generated by salting-out, and sending a water phase generated by salting-out to an evaporation system; and (4) rectifying the evaporated condensate in a rectifying tower, and carrying out dry-process oxygen cracking on crystals generated by evaporation in the air or oxygen atmosphere under the action of a catalyst.
2. The resource utilization method of the ethyl acetate production wastewater according to claim 1, characterized by comprising the following steps:
rectifying in step (1): conveying the ethyl acetate production wastewater into a rectifying tower for rectification, collecting ethyl acetate and ethanol from the top of the rectifying tower, and returning the ethyl acetate and ethanol to an ethyl acetate production system; the liquid extracted from the tower bottom of the rectifying tower is waste water containing acetic acid;
step (2), adsorption and desorption: the produced liquid in the tower kettle of the rectifying tower is conveyed to an adsorption system, acetic acid is adsorbed by using an adsorbent, and the purified water discharged by the adsorption system is reduced to 50mgO2below/L; when the adsorption of the adsorbent in the adsorption system is saturated, the liquid produced in the tower bottom of the rectifying tower is input and switched to a new or completely regenerated adsorption system; the adsorption system with saturated adsorption is switched into a regeneration system, the residual wastewater in the regeneration system is blown away by compressed air, and then acetic acid adsorbed by the adsorbent is converted into acetate by a desorption agent to obtain the acetic acidAcetate desorption solution;
step (3), acidification and esterification: the desorption liquid enters an acidification esterification system, acidification treatment is carried out on the desorption liquid by using an acidifying agent, and then excessive ethanol is added for carrying out esterification reaction to produce ethyl acetate;
step (4), salting out: sending the acidified esterified product liquid into a salting-out system, adding a salting-out agent, after salting-out is completed, carrying out phase splitting to obtain an oil phase and a water phase, and returning the oil phase to an ethyl acetate production system;
and (5) evaporating and crystallizing: the water phase generated by salting out is sent to an evaporation crystallization system for evaporation treatment, the evaporated condensate is sent to a rectifying tower for rectification, and the crystals generated by evaporation are sent to a dry-process oxygen-adjacent cracking system;
step (6), dry-process oxygen-critical cracking: carrying out dry-process temporary oxygen cracking on the crystals under the action of a catalyst in the air or oxygen atmosphere to obtain a crystal product with the organic matter residue of less than 1 per mill, wherein the concentration of non-methane total hydrocarbons in the generated tail gas is less than 50mg/Nm3。
3. The resource utilization method of the ethyl acetate production wastewater according to claim 1 or 2, characterized in that the total content of ethanol and ethyl acetate in the ethyl acetate production wastewater is 5-50 g/L, and the content of acetic acid is 5-50 g/L.
4. The resource utilization method of the ethyl acetate production wastewater according to claim 1 or 2, characterized in that the rectification conditions are as follows: the temperature of the top of the rectifying tower is 73-80 ℃, the temperature of the bottom of the rectifying tower is 110-135 ℃, and the number of tower plates is 10-15.
5. The resource utilization method of ethyl acetate production wastewater according to claim 1 or 2, characterized in that the adsorbent is any one of weakly alkaline resin, activated carbon and carbon molecular sieve, and the particle size of the adsorbent is 8-50 meshes; the filling amount of the adsorbent in the adsorption system is 0.5-50L/(kg) of liquid-phase airspeed of the wastewater in the adsorption systemadsH) calculation.
6. The resource utilization method of the ethyl acetate production wastewater according to claim 1 or 2, characterized in that the desorbent is a sodium hydroxide or potassium hydroxide solution, preferably a sodium hydroxide solution with a mass fraction of 25-30%;
the volume ratio of the total amount of the desorbent to the total amount of the liquid extracted from the tower bottom of the rectifying tower entering the adsorption system is 1/50-1/10.
7. The resource utilization method of ethyl acetate production wastewater according to claim 1 or 2, characterized in that the acidifying agent is concentrated sulfuric acid or concentrated hydrochloric acid; the mass ratio of the acidifying agent to the desorption liquid is 1: 2-10, and preferably 1: 10;
the salting-out agent is potassium salt or sodium salt which is the same as the anion of the acidifying agent, and the cation of the salt formed after the acidification is the same as the cation in the desorption agent; adding a salting-out agent into the acidified esterification product liquid until the concentration of the salting-out agent in water reaches 0.5-5.5 mol/L.
8. The resource utilization method of the ethyl acetate production wastewater according to claim 1 or 2, characterized in that the amount of the ethanol is 5-15 times of the theoretical amount of the ethanol.
9. The resource utilization method of ethyl acetate production wastewater according to claim 1 or 2, characterized in that the catalyst is a metal oxide catalyst, and Al is used2O3、SiO2、TiO2One of the ZSM-5 molecular sieve, the rare earth Y molecular sieve, the MCM-41 molecular sieve and the H-MOR molecular sieve is taken as a carrier, a transition metal oxide is taken as an active component, the loading capacity is 1-15%, and the particle size of the catalyst is 0.01-0.2 mm; the dosage of the catalyst is 20-100 wt% of the mass of the crystal; the temperature of the dry-process oxygen cracking is 300-800 ℃.
10. The resource utilization method of ethyl acetate production wastewater according to claim 9, characterized in that the transition metal oxide is one or two oxides of titanium oxide, copper oxide, cerium oxide, nickel oxide, vanadium oxide, chromium oxide, iron oxide, manganese oxide, cobalt oxide, zinc oxide, lanthanum oxide, and molybdenum oxide.
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| CN114380352A (en) * | 2022-01-26 | 2022-04-22 | 山东微研生物科技有限公司 | Recovery device and recovery method for ethyl acetate in beta-carotene extraction wastewater |
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| CN113480070A (en) * | 2021-05-31 | 2021-10-08 | 浙江奇彩环境科技股份有限公司 | Recycling treatment method for desorption liquid of phenol wastewater adsorbed by macroporous resin |
| CN114380352A (en) * | 2022-01-26 | 2022-04-22 | 山东微研生物科技有限公司 | Recovery device and recovery method for ethyl acetate in beta-carotene extraction wastewater |
| CN114380352B (en) * | 2022-01-26 | 2023-10-13 | 山东微研生物科技有限公司 | Recovery device and recovery method for ethyl acetate in beta-carotene extraction wastewater |
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