CN109516623B - Comprehensive utilization method of tributoxyethyl phosphate wastewater - Google Patents
Comprehensive utilization method of tributoxyethyl phosphate wastewater Download PDFInfo
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- CN109516623B CN109516623B CN201811367616.7A CN201811367616A CN109516623B CN 109516623 B CN109516623 B CN 109516623B CN 201811367616 A CN201811367616 A CN 201811367616A CN 109516623 B CN109516623 B CN 109516623B
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- monobutyl ether
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- 239000002351 wastewater Substances 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 65
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 75
- -1 phosphate ester Chemical class 0.000 claims abstract description 61
- 229910001868 water Inorganic materials 0.000 claims abstract description 54
- 238000004821 distillation Methods 0.000 claims abstract description 51
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 35
- 239000010452 phosphate Substances 0.000 claims abstract description 35
- 239000012153 distilled water Substances 0.000 claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 21
- 230000002378 acidificating effect Effects 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 239000002808 molecular sieve Substances 0.000 claims abstract description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 15
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000007127 saponification reaction Methods 0.000 claims abstract description 11
- 239000012670 alkaline solution Substances 0.000 claims abstract description 9
- 239000003929 acidic solution Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 25
- 229910052698 phosphorus Inorganic materials 0.000 claims description 25
- 239000011574 phosphorus Substances 0.000 claims description 25
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 24
- 230000018044 dehydration Effects 0.000 claims description 24
- 238000006297 dehydration reaction Methods 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 238000001514 detection method Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- TVAJJUOMNRUGQA-UHFFFAOYSA-N 2-butoxyethyl dihydrogen phosphate Chemical compound CCCCOCCOP(O)(O)=O TVAJJUOMNRUGQA-UHFFFAOYSA-N 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- 238000001228 spectrum Methods 0.000 claims description 3
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims 1
- 238000004065 wastewater treatment Methods 0.000 abstract description 6
- 239000002910 solid waste Substances 0.000 abstract description 5
- 239000012043 crude product Substances 0.000 abstract 2
- 230000003472 neutralizing effect Effects 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000001502 supplementing effect Effects 0.000 abstract 1
- 239000003513 alkali Substances 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 15
- 239000003063 flame retardant Substances 0.000 description 14
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 13
- 239000012071 phase Substances 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 235000011121 sodium hydroxide Nutrition 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 11
- 230000000149 penetrating effect Effects 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- 230000020477 pH reduction Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- MPFVDKFRCLZQKV-UHFFFAOYSA-L disodium;2-butoxyethyl phosphate Chemical compound [Na+].[Na+].CCCCOCCOP([O-])([O-])=O MPFVDKFRCLZQKV-UHFFFAOYSA-L 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001944 continuous distillation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 238000004042 decolorization Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000005517 mercerization Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
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- 238000004806 packaging method and process Methods 0.000 description 1
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- 229920001277 pectin Polymers 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 150000005691 triesters Chemical class 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
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- 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
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/1411—Esters of phosphorous acids with hydroxyalkyl compounds with further substituents on alkyl
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- 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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/046—Treatment of water, waste water, or sewage by heating by distillation or evaporation under vacuum produced by a barometric column
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- C02F1/26—Treatment of water, waste water, or sewage by extraction
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- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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Abstract
The invention discloses a treatment method of tributyloxyethyl phosphate ester wastewater, which comprises the following steps: carrying out saponification reaction on TBEP alkaline washing wastewater and alkaline solution to ensure that residual phosphate in the wastewater completely reacts to generate phosphate sodium salt to obtain saponified wastewater, supplementing an acidic solution into the saponified wastewater for reaction, standing for layering, and separating a lower-layer acidic water phase and an upper-layer oil phase; neutralizing the lower acidic water phase and distilling to obtain industrial salt and distilled water; distilling and dehydrating the upper oil phase, continuously distilling to obtain a crude product of the ethylene glycol monobutyl ether and a distillation base solution, circularly dehydrating the crude product of the ethylene glycol monobutyl ether by a molecular sieve packed tower, and collecting; and neutralizing, distilling and dehydrating the distillation base solution to obtain TBEP sodium salt. The invention solves the problems of generation and treatment of dangerous solid wastes in the wastewater treatment method in the prior art, and thoroughly solves the problem that the scale formation and blockage of the sodium phosphate salt in the MVR pipeline of the high-efficiency distillation system can not be normally used.
Description
Technical Field
The invention relates to a comprehensive utilization method of tributoxyethyl phosphate wastewater.
Background
Tributoxyethyl pHospHate flame retardant, British name Tris (2-butoxyethyl) pHospate, abbreviated as TBEP, and ethylene glycol monobutyl ether phosphotriester, the molecular formula of which is C18H39O7P, molecular weight 398. The flame retardant plasticizer is a flame retardant plasticizer, is mainly used for flame retardance and plasticization of polyurethane rubber, cellulose, polyvinyl alcohol and the like, and has good low-temperature characteristics. The product has wide application, continuously increased market demand, low smoke, no halogen, no toxicity and other characteristics, and accords with the development direction of halogen-free and environment-friendly flame retardant, so the product has good development prospect. About 0.5 ton of alkaline wastewater can be generated when 1 ton of TBEP finished products are produced in the generation process of the flame retardant TBEP, and the amount of the generated wastewater is huge. The waste water of TBEP mainly contains TBEP, TBEP sodium salt, sodium chloride, sodium hydroxide and ethylene glycol monobutyl ether. In general, COD in waste water produced in TBEP exceeds 10000mg/l, total phosphorus exceeds 30000ppm, the content of emission is limited to be seriously out of standard, and the waste water is discharged after reaching the standard by a complex waste water treatment process.
At present, the research on the phosphate flame retardant wastewater treatment technology in China is less, and the treatment technology aiming at TBEP alkaline wastewater is not available. At present, the TBEP alkali washing wastewater in China generally adopts a general phosphorus-containing wastewater treatment technology: namely oxidation, flocculation precipitation dephosphorization, efficient distillation, dehydration and desalination, and the distilled water is discharged after reaching the biochemical treatment standard, industrial salt is separated, and the distillation residual liquid is treated as hazardous waste. The method can ensure that the effluent is qualified, but has the following problems:
pretreatment measures before distillation such as oxidation, flocculation, precipitation and dephosphorization of TBEP wastewater cannot remove phosphorus in water, the phosphorus is still dissolved in the wastewater in the form of TBEP sodium salt, and the pretreatment causes increase of dangerous solid waste due to addition of agents such as flocculant and the like.
2, when the TBEP wastewater is continuously distilled and dehydrated to separate chlorine elements and phosphorus elements in water, TBEP sodium salt in the wastewater is separated out along with the reduction of water, the form of the TBEP sodium salt is similar to high-viscosity sludge, and the TBEP sodium salt cannot be centrifugally separated according to a common crystallization sodium chloride mode, so that the problems of extremely poor steam heating effect, low distillation efficiency, high equipment failure and stopping rate and the like are easily caused.
And 3, the content of sodium chloride in the TBEP wastewater is extremely low, and when the TBEP wastewater is pretreated by an environmental protection station and then is combined with other phosphate ester wastewater for MVR dehydration, the appearance and the content of sodium chloride of the industrial salt separated by the salt do not meet the quality standard of the industrial salt due to the large amount of TBEP sodium salt.
4. The recyclable ethylene glycol monobutyl ether in the wastewater has no effective recycling process, and wastes are caused.
Since there are no patents and literature on alkaline washing wastewater of tributoxyethyl phosphate flame retardant, representative patents and literature commonly used for phosphoric acid triester wastewater are now exemplified: patent No. CN104692571A provides a method for treating weak alkaline wastewater: rectifying and dehydrating to separate out industrial salt, continuously cooling the residual liquid, filtering the separated industrial salt, adding phosphoric acid, liquid caustic soda and the like into the filtered residual liquid, and then pyrophosphoryzing at the high temperature of 250 ℃ and 850 ℃ to obtain pyrophosphate for sale. The innovation point of the patent is that sodium phosphate and residual phosphate are made into marketable products through high-temperature pyrophosphorylation, but the recycling of available raw materials in waste water, such as phenol and the like, which can be reused in phosphate production is not considered. Patent No. CN101979347A provides a method for treating phosphoric acid triester flame retardant wastewater: firstly adding acid to adjust the pH value of the phosphate ester wastewater to 4-6, then adding hydrogen peroxide, carrying out oxidation reaction in the presence of a surface catalyst, carrying out operations such as biochemistry, flocculating settling dephosphorization and the like, and finally discharging after reaching the standard. In this method, the decomposition of phosphate ester as inorganic phosphorus is attempted by a typical lower oxidation method, but the purpose of completely decomposing phosphate ester and its sodium salt is practically impossible. Patent No. CN101704606A discloses a method for treating organophosphorus wastewater, which comprises the following steps: firstly, adding acid into the organic phosphorus wastewater to adjust the pH value to 3-4, adding hydrogen peroxide to perform catalytic oxidation, then entering a micro-electrolysis device to perform further oxidation, removing water, performing multi-stage hydrogen peroxide oxidation, and finally performing flocculation sedimentation to remove phosphorus. The method adopts an electrolysis device to decompose organic phosphorus into inorganic phosphorus, and if the method aims at high-concentration organic phosphorus wastewater of phosphate esters, an electrolytic oxidation method needs to dilute a water sample first, so that more wastewater is generated, and the power consumption is huge.
In the 'research on pretreatment process of organic phosphate ester generation wastewater' in '2012, environmental protection', a 'liquid film extraction-acidification sedimentation-complexation extraction' combined process is proposed to treat organic phosphate flame retardant wastewater, the removal rates of COD and phosphorus in the wastewater reach 93% and 97% respectively, however, the process flow of the technology is complex, a large amount of solvent and acid are needed to be used, more wastewater and solid waste are additionally generated, the treatment cost is high in a comprehensive view, and the technology is not suitable for large-scale treatment of phosphate ester wastewater by enterprises.
As researches on phosphate substances at home and abroad show, the structure of the phosphate is very stable, and the common oxidation method cannot thoroughly destroy the structure of the phosphate and decompose the phosphate into inorganic phosphorus, so that the production wastewater of the flame retardant TBEP cannot remove the phosphorus-containing substances in the wastewater and decompose organic matters by adopting conventional oxidation, flocculation, precipitation and other modes. The high-end oxidation methods such as high-temperature high-pressure oxidation, electrolysis, catalytic electrolysis and the like are adopted, so that the effect of decomposing phosphate into inorganic phosphorus can be achieved, but the problems of incapability of adapting to high-phosphate-content wastewater, low treatment efficiency, high power consumption cost and the like exist, and the practical application of the phosphate in factories is limited.
The use of mercerizing penetrant and ethylene glycol monobutyl ether phosphate sodium salt (TBEP sodium salt) is introduced:
when the mercerizing cycle is carried out on the textile, the viscosity of the caustic soda solution is higher, the permeability of the alkali liquor is poorer, and after the mercerizing penetrating agent is added, the surface tension of the concentrated alkali liquor is reduced, the penetration of the alkali liquor is facilitated, the uniformity of mercerizing is improved, and the surface mercerizing is reduced. When the cotton yarn blank is directly mercerized, due to the fact that the cotton yarn blank contains hydrophobic natural impurities such as wax and pectin, fibers on the surface of the cotton yarn are swelled violently in a concentrated alkali solution, the length of the cotton yarn is shortened sharply, and alkali liquor cannot permeate into the fibers. The mercerizing agent with strong penetrability must be added to make mercerizing action quick and uniform, and can greatly shorten mercerizing time. Generally, the carbon atom number of the fatty alcohol suitable for the mercerizing penetrating agent is less than 8, preferably 4-6, the carbon chain of the fatty alcohol is short, the alkali resistance is relatively high, the surface activity is very low and the permeability is very poor in a neutral aqueous solution, but under the condition of 180-280g/l alkali liquor, the mercerizing penetrating agent is enriched on the surface of the fiber due to the action of electrolyte, the carbon chain of the fatty alcohol is short, a regular monomolecular layer adsorption film is easily formed, the surface tension is reduced, and the alkali liquor is enabled to quickly penetrate into the fiber.
The ethylene glycol monobutyl ether phosphate, namely TBEP, has excellent permeability in alkali liquor of more than 180g/l, can be prepared into a mercerizing penetrating agent, generally takes TBEP diester sodium salt as a main component, has diester permeability stronger than monoester, has small bubble surface, and does not influence the recovery process of light alkali. Some mercerizing penetrants with alkali resistance requirements are selected to be mainly TBEP monoester sodium salt. Common mercerizing penetrating agents in the market usually take phosphate sodium salt as a main material, and are compounded with other auxiliary agents to improve the permeability or alkali resistance of the mercerizing penetrating agents.
The usual production process for sodium salt of TBEP is as follows: ethylene glycol monobutyl ether with P2O5Or polyphosphoric acid reaction, and then adjusting the pH value (1% aqueous solution) to 7.0-9.0 by using NaOH aqueous solution. Finally, adding a small amount of hydrogen peroxide for decolorization, and filtering to obtain a finished product. By adjusting ethylene glycol monobutyl ether and P2O5The content ratio of the monoester to the diester can be adjusted.
The patent with the application publication number CN 102503973A, namely a preparation method of a strong alkali resistant mercerizing penetrating agent ethylene glycol butyl ether phosphate, adopts a method similar to the above formulaThe method for synthesizing the sodium salt of ethylene glycol monobutyl ether phosphate adopts polyphosphoric acid as a phosphating agent to replace P2O5The mercerizing penetrating agent with the phosphoric monoester mass content of more than 90 percent and extremely high content can be prepared, and the alkali resistance performance is excellent. It can be known that different production processes are designed to obtain different contents of diester and monoester according to the compounding requirements of mercerizing penetrant manufacturers.
The wastewater generated in the TBEP production process contains a large amount of ethylene glycol monobutyl ether phosphate sodium salt, and no relevant literature about the purification of the ethylene glycol monobutyl ether phosphate sodium salt in the wastewater is found through the search of patent literature. The mass content of the ethylene glycol monobutyl ether phosphate diester sodium salt in the TBEP production wastewater is more than 75 percent, and as the original process of a company does not have a link of separating inorganic salt from organic salt, the final phosphate ester sodium salt solid obtained by distilling and dehydrating the wastewater contains sodium chloride with the mass of nearly 1/3, the mass content of the effective component of the ethylene glycol monobutyl ether phosphate diester sodium salt is less than 50 percent, the sodium chloride is difficult to be sold as a main compound component of a mercerization penetrating agent, and the sodium chloride can only be treated as dangerous solid waste. The flame retardant TBEP belongs to one of environment-friendly flame retardants, and is widely applied, so that the market demand is vigorous, the production capacity in China is increased year by year, the main bottleneck for limiting enterprises to increase the production scale by efficiently and inexpensively treating the production wastewater of the TBEP is the main development direction of the new technology, namely recovering raw materials, preparing byproducts, reducing treatment links and comprehensively treating components in the wastewater, and finally the effects of reducing the treatment cost of the TBEP wastewater and ensuring that the wastewater treatment equipment keeps higher running rate are achieved.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a comprehensive utilization method of tributoxyethyl phosphate wastewater, and by adopting the method, the wastewater is used as a usable resource to produce various products, the qualified discharge of the wastewater is ensured, and the problem of treatment of alkaline washing wastewater of the tributoxyethyl phosphate flame retardant is radically solved.
A treatment method of tributyloxyethyl phosphate wastewater is characterized by comprising the following steps:
1) saponification reaction: heating TBEP alkaline washing wastewater to 60-85 ℃, adding an alkaline solution while stirring, controlling the pH value of the wastewater to be 8-9, stirring, carrying out heat preservation reaction, and reacting residual TBEP in the wastewater to generate phosphate sodium salt to obtain saponified wastewater; the saponification reaction process is as follows:
2) acidifying and extracting: step 1), keeping the temperature of the saponified wastewater at 60-85 ℃, slowly dripping an acidic solution while stirring, controlling the pH value of the saponified wastewater to be stable at 1-2, stirring, carrying out heat preservation reaction, reacting phosphate sodium salt in the saponified wastewater to generate water-insoluble ethylene glycol monobutyl ether phosphate, then standing and layering, and separating a lower-layer acidic water phase and an upper-layer oil phase; the acidification extraction reaction process is as follows:
3) recovering ethylene glycol monobutyl ether: carrying out reduced pressure distillation on the upper oil phase obtained in the step 2) to remove and recover water and ethylene glycol monobutyl ether in the upper oil phase, and distilling to obtain acidic distilled water, crude ethylene glycol monobutyl ether and kettle bottom liquid, wherein the water content of the crude ethylene glycol monobutyl ether is 0.15-0.2%;
4) acid water neutralization distillation: combining the lower-layer acidic water phase obtained in the step 2) with the acidic distilled water obtained in the step 3), adjusting the pH of the mixed solution obtained by combining to be neutral through an alkaline solution, carrying out reduced pressure distillation, evaporating to recover moisture, and obtaining industrial salt and distilled water, wherein the obtained distilled water meets the standard of alkaline washing water for TBEP production;
5) molecular sieve dehydration: at normal temperature, circularly dehydrating the crude ethylene glycol monobutyl ether obtained in the step 3) through a molecular sieve packed tower to obtain an ethylene glycol monobutyl ether finished product with the water content lower than 0.1 percent, wherein the obtained ethylene glycol monobutyl ether finished product meets the use standard of TBEP esterification reaction;
6) preparation of TBEP sodium salt: adding an alkaline solution into the kettle bottom solution obtained in the step 3) to adjust the pH value to be neutral, then putting the kettle bottom solution into a distillation kettle to carry out reduced pressure distillation and dehydration until no water is evaporated, discharging the material in the distillation kettle while the material is hot, and cooling the discharged hot material in a drying oven to 40 ℃ for complete solidification to obtain a solidified TBEP sodium salt; step 6) the reaction process for preparing TBEP sodium salt is as follows:
the treatment method of the tributyloxyethyl phosphate ester wastewater is characterized in that in the step 2), the acidic solution is a hydrochloric acid aqueous solution, and the mass fraction of the hydrochloric acid aqueous solution is 15-30%; the stirring and heat preservation reaction time is 0.5-1.5 h, preferably 1 h.
The treatment method of the tributyloxyethyl phosphate ester wastewater is characterized in that in the step 4), the temperature for carrying out reduced pressure distillation dehydration is 70-80 ℃, and the vacuum degree is within 10 kPa.
The treatment method of the tributyloxyethyl phosphate ester wastewater is characterized in that in the step 3), the reduced pressure distillation of the upper oil phase is divided into two stages, wherein the first stage is distillation dehydration, the distillation temperature is 70-75 ℃, and the vacuum degree is within 200 Pa; the second stage is to distill and remove ethylene glycol monobutyl ether, the distillation temperature is 145-150 ℃, and the vacuum degree is within 200 Pa.
The treatment method of the tributyloxyethyl phosphate ester wastewater is characterized in that in the step 5), the type of the molecular sieve used in the molecular sieve packed tower is a 3A molecular sieve.
The treatment method of the tributyloxyethyl phosphate ester wastewater is characterized in that in the step 6), the temperature for reduced pressure distillation and dehydration is 145-150 ℃, and the vacuum degree is within 6 kPa.
The treatment method of the tributyloxyethyl phosphate wastewater is characterized in that in the step 6), nuclear magnetic phosphorus spectrum PMNR detection is carried out on the obtained TBEP sodium salt, and the detection results include that the TBEP diester sodium salt content is 75-85%, the TBEP monoester disodium salt content is 10-25%, the water content is 2-5%, the mass content of sodium chloride is less than or equal to 0.1%, and the content of organic phosphorus effective components is more than or equal to 94.9%.
The treatment method of the tributyloxyethyl phosphate ester wastewater is characterized in that in the steps 1), 4) and 6), the alkaline solution is a sodium hydroxide aqueous solution, and the mass fraction of the sodium hydroxide aqueous solution is 20-30%.
The treatment method of the tributoxyethyl phosphate wastewater is characterized in that in the step 2), the dropping speed of the acidic solution is dropwise added.
Compared with the prior art, the invention has the following beneficial effects:
(1) reacting the tributyloxyethyl phosphate in the tributyloxyethyl phosphate wastewater to generate a phosphate sodium salt and generate more recyclable ethylene glycol monobutyl ether through saponification reaction; the temperature of the alkali washing process for preparing the tributoxyethyl phosphate generally does not exceed 70 ℃, the time is short, and the tributoxyethyl phosphate dissolved in a water layer is difficult to generate the sodium phosphate through saponification reaction.
(2) Aiming at the separation and recovery of the ethylene glycol monobutyl ether in the saponification wastewater, if the conventional rectification method is adopted for separation and recovery, the water is completely distilled, and then the ethylene glycol monobutyl ether is distilled out. The conventional recovery method has two problems, namely firstly, the dehydration by the rectification method cannot adopt reduced pressure distillation, otherwise, ethylene glycol monobutyl ether is carried out, and the water distillation under normal pressure consumes long time and consumes large energy; secondly, after dehydration to a certain degree, the sodium phosphate in the bottom material is liquid at high temperature but has higher requirement on the evaporation temperature of the ethylene glycol monobutyl ether, and the total amount of the ethylene glycol monobutyl ether is less relative to the bottom material, thereby increasing the distillation temperature and improving the distillation difficulty and energy consumption. The invention adopts acidification extraction reaction to react phosphate sodium salt in the saponification wastewater to generate a water-insoluble ethylene glycol monobutyl ether phosphate hydroxyl compound, the ethylene glycol monobutyl ether phosphate hydroxyl compound has strong extraction effect on ethylene glycol monobutyl ether, and can extract the ethylene glycol monobutyl ether in a water layer, and after layering, an upper oil phase mainly containing the ethylene glycol monobutyl ether phosphate hydroxyl compound and the ethylene glycol monobutyl ether and a lower acidic water phase mainly containing sodium chloride, hydrogen chloride and water are respectively obtained.
(3) Acid water layer neutralization distillation: after the lower acidic aqueous phase is neutralized to neutrality, the wastewater can be desalted through distillation operation, and distilled water meeting the washing requirements of TBEP production is distilled out. Most of the industrial salt obtained in the stage is generated by the reaction of added hydrochloric acid and TBEP sodium salt in the acidification and extraction stage, and a small part of the industrial salt is generated by the neutralization reaction of alkaline washing wastewater stock solution and acid water. According to the invention, the acidic water layer neutralizes distilled water obtained by distillation, and the water requirement of the TBEP production process is as follows: the appearance is colorless transparent liquid, the PH is 6-8, the chemical oxygen demand COD is less than or equal to 1000mg/L, the ammonia nitrogen is less than or equal to 5mg/L, the total phosphorus is less than or equal to 10mg/L, and the iron is less than or equal to 0.3mg/L, wherein the COD is mainly derived from residual ethylene glycol monobutyl ether.
(4) Although the water content of the upper oil phase is reduced by controlling the temperature through acidification and extraction, most water in the upper oil phase is removed through continuous distillation and dehydration, trace water can not be brought into the distilled ethylene glycol monobutyl ether, and the ethylene glycol monobutyl ether with the water content of more than 0.1 percent can not be directly used for the esterification reaction for preparing the tributoxyethyl phosphate, which can cause the problems of catalyst inactivation and the like, the recovered ethylene glycol monobutyl ether needs to be further dehydrated, but the acidification, extraction and continuous distillation and dehydration processes of the invention reduce the water content of the recovered ethylene glycol monobutyl ether to an extremely low degree (the water content is lower than 0.2 percent), so that a molecular sieve packed tower can be used for further removing water, the molecular sieve has good effect of absorbing water molecules, can be dried and dehydrated for repeated use, and has lower relative operation cost, through molecular sieve adsorption and dehydration, the recovered ethylene glycol monobutyl ether meets the quality standard of recovery and reutilization.
(5) Preparation of TBEP sodium salt: because pure TBEP sodium salt has extremely high viscosity and is easy to solidify under the condition of low temperature, and has low viscosity flow state above 140 ℃, the reaction control temperature is kept above 140 ℃ without causing scaling and bottom valve blockage in reaction equipment, and simultaneously dehydration can enable the TBEP sodium salt to be easier to solidify and be convenient for packaging and storage.
(6) The method of the invention realizes the preparation of the phosphorus-containing organic matter in the wastewater into the sodium salt of ethylene glycol monobutyl ether phosphate with higher effective component, the recovery of the ethylene glycol monobutyl ether in the wastewater and the return of the ethylene glycol monobutyl ether to the esterification reaction of the tributoxy ethyl phosphate for use, the solidification of sodium ions and chloride ions in the wastewater into usable industrial salt, and the reuse of the separated distilled water in each process of the return of the sodium ions and the chloride ions to the tributoxy ethyl phosphate, thereby finally realizing the purpose of maximally generating new economic value for useful substances in the wastewater. Meanwhile, the process solves the problems of generation and treatment of dangerous solid wastes in the wastewater treatment method in the prior art, thoroughly solves the problem that the sodium phosphate salt in the MVR pipeline of the high-efficiency distillation system cannot be normally used due to scaling blockage, and has great significance for promoting the recyclable generation of the tributyloxyethyl phosphate flame retardant.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
The content units% in the following examples refer to the content units in mass percent.
Example 1:
waste water: TBEP production alkali washing wastewater is analyzed: 14058.7ppm of total phosphorus, 112965.3mg/L of COD, 9 of pH, 0.0347% of sodium chloride, 4.85% of ethylene glycol monobutyl ether, 6.04% of TBEP, 9.2% of TBEP diester sodium salt, and colorless transparent liquid after precipitation and filtration.
A treatment method of tributyloxyethyl phosphate wastewater comprises the following steps:
1) saponification reaction: stirring and heating 330kg of TBEP alkaline washing wastewater in a reaction kettle to 85 ℃, adding 30% sodium hydroxide aqueous solution while stirring, controlling the pH value of the wastewater in the reaction kettle to be 8-9 (10.47 kg of the sodium hydroxide aqueous solution is added in total), keeping the temperature for reaction for 3 hours, and ending the saponification reaction to obtain saponification wastewater;
2) acidifying and extracting: step 1) keeping the temperature of the saponified wastewater at 85 ℃, dropwise adding a 30% hydrochloric acid aqueous solution while stirring, controlling the pH value of the saponified wastewater to be stable at 1-2 (adding 31.46kg of the hydrochloric acid aqueous solution in total), stirring, keeping the temperature, reacting for 1h to enable phosphate sodium salt in the saponified wastewater to react to generate water-insoluble ethylene glycol monobutyl ether phosphate, then standing and layering to separate 304.6kg of a lower-layer acidic aqueous phase and 65.2kg of an upper-layer oil phase; measuring COD of the obtained lower acidic aqueous phase to be 351.7mg/L, wherein the COD detection standard is GB 11914-89;
3) recovering ethylene glycol monobutyl ether: distilling 65.2kg of the upper oil phase obtained in the step 2) under reduced pressure, controlling the distillation temperature to be 70-72 ℃ and the vacuum degree to be within 200Pa, distilling and dehydrating until no water is evaporated, and then controlling the distillation temperature to be 145-147 ℃ and the vacuum degree to be within 200Pa, and distilling and removing the ethylene glycol monobutyl ether; finally, 0.91kg of acid distilled water and 24.59kg of crude ethylene glycol monobutyl ether are recovered in total, and the total amount of residual kettle bottom liquid in the kettle is about 38.75 kg; detecting the moisture content of the obtained crude ethylene glycol monobutyl ether, wherein the moisture content is 0.15%;
4) acid water neutralization distillation: 305.51kg of mixed liquid obtained by combining the lower-layer acidic water phase obtained in the step 2) and the acidic distilled water obtained in the step 3), adjusting the pH of the mixed liquid to be neutral by 30% of sodium hydroxide aqueous solution (10.67 kg of sodium hydroxide aqueous solution is added in total), then carrying out reduced pressure distillation and dehydration, wherein the distillation temperature is 80 ℃, the distillation vacuum degree is 10kPa, and 15.7kg of industrial salt without impurities and 298.4kg of colorless distilled condensed water with white crystals are obtained by distillation; the obtained industrial salt is detected according to the detection standard GB/T5462-2003, and the detection result is as follows: 96% of sodium chloride, 4% of water, no water-insoluble substances, no calcium and magnesium ions and no sulfate ions, and the quality meets the first-grade quality standard of sun-cured industrial salt;
5) molecular sieve dehydration: at normal temperature, circularly dehydrating the crude ethylene glycol monobutyl ether obtained in the step 3) through a molecular sieve packed tower, wherein the molecular sieve packed tower is filled with a 3A molecular sieve, the circularly dehydrating time is 24 hours, and finally, 24.09kg of colorless and transparent ethylene glycol monobutyl ether product is obtained, the water content of the product is detected to be 0.05%, and the purity of the ethylene glycol monobutyl ether product is detected to be 99.6% by using gas chromatography;
6) preparation of TBEP sodium salt: adding 30% of sodium hydroxide aqueous solution into the kettle bottom liquid obtained in the step 3) while stirring to adjust the pH of the solution to 7 (23.64 kg of the sodium hydroxide aqueous solution is added in total), then heating to 145-147 ℃, keeping the temperature and stirring for reaction for 1 hour, then putting the mixture into a distillation kettle together for vacuum distillation and dehydration, wherein the distillation temperature is 145-147 ℃, the distillation vacuum degree is within 6kPa until no water is evaporated, totally distilling and recovering to obtain 17.6kg of distilled water, detecting that the pH value of the feed liquid in the distillation kettle is still 7, keeping the temperature of the feed liquid in the kettle at 145-147 ℃, discharging the material in the kettle while the material is hot, cooling the discharged material to 40 ℃ in a drying box to completely solidify to obtain 43.77kg of TBEP sodium salt solid, carrying out nuclear magnetic phosphorus spectrum PMNR detection on the obtained TBEP sodium salt solid, and converting the mass content in the phosphorus-containing component to: 1.71 percent of TBEP, 83.50 percent of TBEP diester sodium salt and 14.79 percent of TBEP monoester disodium salt, wherein the content of TBEP diester sodium salt in the components meets the compounding requirement of the mercerizing penetrating agent with high permeability. The water content of the obtained TBEP sodium salt solid is detected to be 3 percent, and the content of chloride ions in the TBEP sodium salt solid is detected to be 0.096 percent according to the GB/T13025.3 method.
In the embodiment 1, the distilled water obtained in the step 4) and the distilled water obtained in the step 6) are combined, the process is combined to obtain 315.99kg of distilled water, the combined distilled water is detected, the ammonia nitrogen detection standard is GB7479-87, the total phosphorus detection standard is GB11893-89, the iron detection standard is GB11911-89, and the final detection result is as follows: colorless transparent liquid in appearance, pH 7, COD 338.89mg/L, no ammonia nitrogen, no total phosphorus and no iron; the obtained distilled water product meets the quality requirement and can be recycled in TBEP production.
Example 2: a method for treating wastewater containing tributoxyethyl phosphate is carried out under the same conditions as in example 1, but different from example 1 in that the pH value of acidification in step 2) is controlled to 3 to 4, and it is considered that the saponified wastewater is in an emulsified state in which it cannot be separated into layers, and TBEP sodium salt is not reacted into a TBEP hydroxyl compound.
Example 3: the method for treating wastewater containing tributoxyethyl phosphate is the same as that in example 1, but different from example 1, the acidification pH value in step 2) is controlled to be below 1, and the COD of the lower acidic aqueous phase measured by sampling is 359.1mg/L, and the result is considered to be the same as that in example 1 in consideration of detection errors.
Example 4: a method for treating wastewater of tributyloxyethyl phosphate is provided, the method conditions are the same as example 1, but different from example 1, the temperature of reduced pressure distillation dehydration in step 6) is changed to 155-158 ℃, until no water is distilled out, the moisture content in the obtained final TBEP sodium salt solid is 1.1%, and the cooled TBEP sodium salt is discharged to solidify smoothly.
Example 5: a method for treating wastewater of tributyloxyethyl phosphate is provided, the method conditions are the same as example 1, but different from example 1, the temperature of reduced pressure distillation dehydration in step 6) is changed to 135-138 ℃, until no water is distilled out, the moisture content in the obtained final TBEP sodium salt solid is 5.5%, and the cooled TBEP sodium salt is discharged to solidify smoothly.
Example 6: a method for treating wastewater of tributoxyethyl phosphate is provided, the method conditions are the same as example 1, but different from example 1, the temperature of reduced pressure distillation dehydration in step 6) is changed to 118-120 ℃, until no water is distilled out, the moisture content in the obtained final TBEP sodium salt solid is 13.3%, and the cooled TBEP sodium salt is still in a soft mud state and can not be solidified after being discharged and cooled to 40 ℃ for more than 12 hours.
The description is given for the sole purpose of illustrating embodiments of the inventive concept and should not be taken as limiting the scope of the invention to the particular forms set forth in the embodiments, but rather as being limited only to the equivalents thereof as may be contemplated by those skilled in the art based on the teachings herein.
Claims (10)
1. A treatment method of tributyloxyethyl phosphate wastewater is characterized by comprising the following steps:
1) saponification reaction: heating TBEP alkaline washing wastewater to 60-85 ℃, adding an alkaline solution while stirring, controlling the pH value of the wastewater to be 8-9, stirring, carrying out heat preservation reaction, and reacting residual TBEP in the wastewater to generate phosphate sodium salt to obtain saponified wastewater;
2) acidifying and extracting: step 1), keeping the temperature of the saponified wastewater at 60-85 ℃, slowly dripping an acidic solution while stirring, controlling the pH value of the saponified wastewater to be stable at 1-2, stirring, carrying out heat preservation reaction, reacting phosphate sodium salt in the saponified wastewater to generate water-insoluble ethylene glycol monobutyl ether phosphate, then standing and layering, and separating a lower-layer acidic water phase and an upper-layer oil phase;
3) recovering ethylene glycol monobutyl ether: carrying out reduced pressure distillation on the upper oil phase obtained in the step 2) to remove and recover water and ethylene glycol monobutyl ether in the upper oil phase, and distilling to obtain acidic distilled water, crude ethylene glycol monobutyl ether and kettle bottom liquid, wherein the water content of the crude ethylene glycol monobutyl ether is 0.15-0.2%;
4) acid water neutralization distillation: combining the lower-layer acidic water phase obtained in the step 2) with the acidic distilled water obtained in the step 3), adjusting the pH of the mixed solution obtained by combining to be neutral through an alkaline solution, carrying out reduced pressure distillation, evaporating to recover moisture, and obtaining industrial salt and distilled water, wherein the obtained distilled water meets the standard of alkaline washing water for TBEP production;
5) molecular sieve dehydration: at normal temperature, circularly dehydrating the crude ethylene glycol monobutyl ether obtained in the step 3) through a molecular sieve packed tower to obtain an ethylene glycol monobutyl ether finished product with the water content lower than 0.1 percent, wherein the obtained ethylene glycol monobutyl ether finished product meets the use standard of TBEP esterification reaction;
6) preparation of TBEP sodium salt: and 3) adding an alkaline solution into the kettle bottom solution obtained in the step 3) to adjust the pH value to be neutral, putting into a distillation kettle for reduced pressure distillation and dehydration until no water is evaporated, discharging the material in the distillation kettle while the material is hot, and cooling the discharged hot material in a drying oven to 40 ℃ for complete solidification to obtain the solidified TBEP sodium salt.
2. The method for treating wastewater of tris-butoxyethyl phosphate ester according to claim 1, wherein in step 2), the acidic solution is an aqueous hydrochloric acid solution, and the mass fraction of the aqueous hydrochloric acid solution is 15-30%; the stirring and heat preservation reaction time is 0.5-1.5 h.
3. The method for treating wastewater containing tributoxyethyl phosphate according to claim 2, wherein the reaction time is 1 hour.
4. The method for treating tributoxyethyl phosphate wastewater according to claim 1, wherein the temperature for the dehydration by reduced pressure distillation in step 4) is 70 to 80 ℃ and the degree of vacuum is 10kPa or less.
5. The method for treating wastewater containing tributoxyethyl phosphate according to claim 1, wherein in the step 3), the upper oil phase is distilled under reduced pressure into two stages, the first stage is distillation dehydration, the distillation temperature is 70-75 ℃, and the vacuum degree is within 200 Pa; the second stage is to distill and remove ethylene glycol monobutyl ether, the distillation temperature is 145-150 ℃, and the vacuum degree is within 200 Pa.
6. The method for treating wastewater of tributyloxyethyl phosphate according to claim 1, wherein the molecular sieve type used in the molecular sieve packed tower in step 5) is 3A molecular sieve.
7. The method for treating tributoxyethyl phosphate wastewater according to claim 1, wherein in step 6), the temperature for vacuum distillation and dehydration is 145 to 150 ℃ and the vacuum degree is within 6 kPa.
8. The method for treating wastewater containing tributoxyethyl phosphate as claimed in claim 1, wherein in step 6), the obtained TBEP sodium salt is subjected to nuclear magnetic phosphorus spectrum PMNR detection, and the detection results comprise 75-85% of TBEP disodium salt, 10-25% of TBEP monoester disodium salt, 2-5% of water content, less than or equal to 0.1% of sodium chloride by mass, and more than or equal to 94.9% of organophosphorus active ingredient.
9. The method for treating the wastewater of tributoxyethyl phosphate according to claim 1, wherein in the steps 1), 4) and 6), the alkaline solution is an aqueous sodium hydroxide solution, and the mass fraction of the aqueous sodium hydroxide solution is 20-30%.
10. The method for treating wastewater of tributoxyethyl phosphate according to claim 1, wherein the acid solution is added dropwise in step 2).
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