CN109535199B - Method for preparing triphenyl phosphate by extracting phenol from aryl phosphate production wastewater - Google Patents
Method for preparing triphenyl phosphate by extracting phenol from aryl phosphate production wastewater Download PDFInfo
- Publication number
- CN109535199B CN109535199B CN201811633696.6A CN201811633696A CN109535199B CN 109535199 B CN109535199 B CN 109535199B CN 201811633696 A CN201811633696 A CN 201811633696A CN 109535199 B CN109535199 B CN 109535199B
- Authority
- CN
- China
- Prior art keywords
- phenol
- wastewater
- phosphate
- triphenyl phosphate
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 239000002351 wastewater Substances 0.000 title claims abstract description 98
- -1 aryl phosphate Chemical compound 0.000 title claims abstract description 61
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 59
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000010452 phosphate Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 238000000605 extraction Methods 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000005406 washing Methods 0.000 claims abstract description 39
- 238000004821 distillation Methods 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000005886 esterification reaction Methods 0.000 claims abstract description 13
- 239000000047 product Substances 0.000 claims abstract description 13
- 230000018044 dehydration Effects 0.000 claims abstract description 10
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 10
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012043 crude product Substances 0.000 claims abstract description 9
- 230000032050 esterification Effects 0.000 claims abstract description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 9
- 238000005070 sampling Methods 0.000 claims description 4
- BHIIGRBMZRSDRI-UHFFFAOYSA-N [chloro(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(Cl)OC1=CC=CC=C1 BHIIGRBMZRSDRI-UHFFFAOYSA-N 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 13
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 2
- 235000021317 phosphate Nutrition 0.000 description 44
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 6
- 230000000536 complexating effect Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 4
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 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 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
-
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Extraction Or Liquid Replacement (AREA)
- Physical Water Treatments (AREA)
Abstract
The invention discloses a method for preparing triphenyl phosphate by extracting phenol from aryl phosphate production wastewater, which comprises the steps of adding acid into the aryl phosphate alkaline washing wastewater to adjust the pH value to 6-7, stirring, standing for layering to obtain an oil layer and wastewater with the phenol content lower than 25000ppm, adding triphenyl phosphate extractant into the wastewater to perform stirring extraction, transferring an extract phase into a distillation kettle to perform reduced pressure distillation and dehydration, placing the dehydrated extract into an esterification kettle, then adding phosphorus oxychloride and anhydrous magnesium chloride to perform esterification reaction to obtain a triphenyl phosphate crude product, and sequentially performing acid washing, alkaline washing, water washing and distillation on the crude product to obtain a qualified triphenyl phosphate finished product. The invention can solve the phenol recovery problem of various aryl phosphate ester waste water by using triphenyl phosphate with simplest phenol recycling process and least links as an extracting agent in a unified way.
Description
Technical Field
The invention relates to a method for preparing triphenyl phosphate by extracting phenol from aryl phosphate production wastewater.
Background
The aryl phosphate ester flame retardant is an important environment-friendly halogen-free flame retardant, is mainly used for flame retardance of engineering plastics, and commonly comprises bisphenol A-bis (diphenyl phosphate), resorcinol-bis (diphenyl phosphate), hydroquinone bis (diphenyl phosphate), tert-butyl aryl phosphate and the like. Due to the stricter and stricter restrictions on the use of halogen-containing flame retardants in the european and american countries, the market demand for halogen-free aryl phosphate flame retardants has been increasing year by year.
Phenol is mostly used as a final phosphorus oxychloride end-capping reagent in the production of aryl phosphate flame retardants, and in order to ensure that the esterification reaction reaches the end point and obtain a high conversion rate, an excessive phenol method is adopted to ensure that the esterification reaction is smoothly carried out, so that a large amount of phenol exists in alkaline wastewater generated by post-treatment, and the mass concentration of phenol in general alkaline wastewater is at least more than 3%. Phenol is a hazardous substance in wastewater regulated by the country and must therefore be separated from water. In the prior art, common processes for treating wastewater containing phenol in China include physical treatment methods (alkaline distillation, extraction, adsorption and membrane separation), biological treatment methods (activated sludge method and biochemical fluidized bed method), chemical treatment methods (chemical precipitation, incineration and plasma oxidation), wet catalytic oxidation, ultrasonic chemical oxidation and electrochemical oxidation. Most domestic chemical enterprises generally adopt a combined technology, such as an oxidation method, an adsorption method and an activated sludge method, to make wastewater reach the discharge standard.
Aryl phosphate flame retardants also commonly employ a combination of techniques to achieve phenol removal from wastewater, each of which has advantages and disadvantages. Compared with other methods, the extraction method can recover phenol to the reaction, thereby offsetting most of wastewater treatment cost, and the technology is relatively mature and can realize industrialization. Through searching, Chinese patent and journal documents aiming at the extraction and recovery of phenol in the waste water of the production of aryl phosphate ester are not found, so other documents for extracting and recovering phenol from phenol-containing waste water are exemplified.
Patent 1: the patent No. CN105152869A provides a method, which comprises salting out and thickening the waste water produced in phenolic resin production, extracting with organic solvent, and recovering residual phenol after recovering solvent under reduced pressure. The organic solvent extractant is used for extracting phenol, a large amount of solvent is required to be used and distilled and recovered, solvent loss can be continuously generated, organic waste gas emission is increased, a large amount of steam is consumed for distilling the solvent, and the cost is not cost-effective. The same document also contains a document of "research on the properties of dilute phenol solution extracted with n-octanol" published in environmental chemistry Vol.1, 1, 2003.
Patent 2: the literature, "primary amine N1923 complex extraction phenol" reported in the process engineering at vol 4 of 8/12/2012 describes that a complex extraction agent is composed of primary amine N1923 and sulfonated kerosene, petroleum ether, toluene or N-butanol as diluents, phenol-containing simulated wastewater is extracted, and then phenol back-extraction is eluted by using a 20% sodium hydroxide solution, wherein the toluene-primary amine N1923 with the best extraction effect can reach 98.6%; the method has high extraction rate, but back extraction is still needed, sodium phenolate needs to be neutralized and then dehydrated, sodium chloride-containing wastewater is generated more, and the color number of the obtained phenol is generally difficult to control.
Patent 3: chongqing environmental science describes that a fixed bed complexing extraction is carried out on low-concentration simulated wastewater with the phenol concentration of 1000ppm by adopting a stationary phase complexing extraction agent in a document of 'performance research on phenol treatment in water by using the stationary phase complexing extraction agent' at 24 th volume of 2002 of 10 months, 99% of phenol is recovered, and the recovery rate of extraction agent particles is 99.3%. The method uses the macroporous adsorbent to adsorb phenol, combines the efficient extraction effect of the complexing extraction agent on phenol to adsorb phenol, and compared with the liquid complexing extraction agent, the method does not need a container, only needs a fixed bed, is easier to recover solid particles compared with the liquid extraction agent, but only tests low-concentration phenol wastewater, and has a poor effect on the wastewater with the concentration of more than 10000 ppm.
Patent 4: environmental science is in 1995, volume 9, 14, and 5 th document "complex extraction of phenol by tributyl phosphate TBP", in which experimental analysis is performed on the extraction principle of a TBP + kerosene complex extractant on a dilute solution of phenol, the extraction effect of the extractant on phenol by other organic solvents is compared, and the TBP + kerosene complex extractant is proved to have a better extraction effect than a single solvent, and the phenomenon of difficult extraction in a low concentration region existing during actual industrial wastewater extraction is analyzed, and it is considered that wastewater cannot reach the standard and be discharged through single extraction operation. The mixed extractant of the phosphate and the high-boiling point solvent is an extractant with higher relative extraction rate, but the mixed extractant is regenerated to generate a large amount of alkaline or neutral salt-containing wastewater, and the quality of finished products prepared by phenol dehydration is poor.
Similar reports of mixed complex extractants of phosphate and solvent include 'complex extraction method for treating high-concentration phenol wastewater' in volume 44 of Shandong chemical 2015 and 'complex extraction high-concentration phenol-containing wastewater process research' in volume 45 of Guangdong chemical 2018, mainly focusing on the research on the influence factors of the extraction efficiency of phenol, and not much on the problem of wastewater generated in the treatment process which is more concerned by enterprises.
Extraction methods have the following common disadvantages: most of the extractant needs to be regenerated by eluting phenol with an alkaline aqueous solution for reuse, and meanwhile, the eluted phenol needs to be neutralized to be neutral and then is layered and dehydrated to obtain phenol, so that a large amount of waste water containing sodium chloride and a small amount of phenol is generated in the process, and the waste water treatment capacity is increased. Repeated elution causes a gradual reduction in extractant, requiring periodic purchase of supplemental extractant. Meanwhile, the obtained phenol is easy to discolor due to operations such as high-temperature dehydration and the like, and generally only can be degraded for use, so that the application range of the extraction method is influenced.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a method for preparing triphenyl phosphate by extracting phenol from aryl phosphate production wastewater.
A method for preparing triphenyl phosphate by extracting phenol from aryl phosphate production wastewater is characterized by comprising the following steps:
1) adding acid into the aryl phosphate alkaline washing wastewater to adjust the pH value to 6-7, stirring for 0.5-1.5 h at 40-60 ℃, standing for layering, and separating out a lower-layer oil layer and upper-layer wastewater with the phenol content lower than 25000 ppm;
2) adding triphenyl phosphate into the upper-layer wastewater obtained in the step 1), stirring and extracting, then standing and layering, separating out an extraction layer and a water layer with the phenol content lower than 1000ppm, and sequentially carrying out alkaline distillation and macroporous resin adsorption and purification on the water layer to obtain water with the phenol content less than or equal to 10 ppm;
3) transferring the extraction layer obtained in the step 2) into a distillation kettle for reduced pressure distillation and dehydration, and removing until the moisture content is lower than 0.05% to obtain a dehydrated extract;
4) placing the dehydrated extract obtained in the step 3) into an esterification kettle, then adding phosphorus oxychloride and anhydrous magnesium chloride for esterification reaction, sampling and detecting that the residual quantity of the diphenyl phosphoryl chloride intermediate is less than or equal to 0.1%, and then finishing the reaction to obtain a triphenyl phosphate crude product;
5) sequentially carrying out acid washing, alkali washing, water washing and distillation treatment on the triphenyl phosphate crude product obtained in the step 4) to finally obtain a qualified triphenyl phosphate finished product; the water content of the finished product of the triphenyl phosphate is less than or equal to 0.05 percent, the mass content of the phenol is less than or equal to 0.02 percent, and the mass purity is more than 99 percent, and the finished product of the triphenyl phosphate can be reused in the stirring and extracting process of the step 2).
The method for preparing triphenyl phosphate by extracting phenol from aryl phosphate production wastewater is characterized in that in the step 1), the content of phenol in the aryl phosphate alkaline washing wastewater is 25000-35000 ppm, the mass content of aryl phosphate sodium salt is 5-8%, and the pH value is 14.
The method for preparing triphenyl phosphate by extracting phenol from aryl phosphate production wastewater is characterized in that in the step 1), aryl phosphate acid washing wastewater is added into the aryl phosphate alkali washing wastewater to adjust the pH value, and the mass concentration of HCl in the aryl phosphate acid washing wastewater is 16-18%.
The method for preparing triphenyl phosphate by extracting phenol from aryl phosphate production wastewater is characterized in that in the step 2), the feeding mass ratio of the upper layer wastewater to triphenyl phosphate is 10-14: 1, preferably 12: 1; the temperature for stirring and extracting is 50-60 ℃, and the time for stirring and extracting is 0.5-1.5 h, preferably 1 h; the mass content of phenol in the extraction layer is more than or equal to 18 percent.
The method for preparing triphenyl phosphate by extracting phenol from the aryl phosphate production wastewater is characterized in that in the step 3), the temperature for carrying out reduced pressure distillation dehydration is 115-120 ℃, and the vacuum degree for carrying out reduced pressure distillation dehydration is more than or equal to-0.096 MPa; the mass content of phenol in the dehydrated extract is more than or equal to 18 percent.
The method for preparing triphenyl phosphate by extracting phenol from aryl phosphate production wastewater is characterized in that in the step 4), the esterification reaction conditions are as follows: the reaction is carried out for 2-4 h at the temperature of 85-90 ℃, then the temperature is increased to 100-105 ℃, and the reaction is carried out for 2-4 h at the temperature.
The method for preparing triphenyl phosphate by extracting phenol from aryl phosphate production wastewater is characterized in that in the upper layer wastewater in the step 1), the content of phenol is 15000-25000 ppm.
The method for preparing triphenyl phosphate by extracting phenol from aryl phosphate production wastewater is characterized in that in the step 2), the alkaline distillation step is as follows: and adding alkali into the water layer to adjust the pH value to 8-9, transferring the water layer into a distillation kettle, heating to 80 ℃ under vacuum of-0.094 mpa for reduced pressure distillation, evaporating most of water in the water layer, condensing and recovering to obtain distilled condensate water with the phenol content of less than or equal to 100 ppm.
The method for preparing triphenyl phosphate by extracting phenol from aryl phosphate production wastewater is characterized by comprising the following steps of: and (3) keeping the temperature of the distilled condensate water with the phenol content of less than or equal to 100ppm at 30-40 ℃ and sending the distilled condensate water into a packed tower filled with macroporous resin for reflux adsorption of phenol, wherein the water with the phenol content of less than or equal to 10ppm is obtained after the reflux adsorption is carried out for 0.5-1.5 h.
The method for preparing triphenyl phosphate by extracting phenol from aryl phosphate production wastewater is characterized in that the model of the macroporous resin is HPD 100.
Compared with the prior art, the invention has the following beneficial effects:
(1) most of phosphate ester can be used for phenol extraction of aryl phosphate ester waste water, the same aryl phosphate ester which generates waste water is used as an extracting agent to extract phenol, and the phenol is prepared into the phosphate ester through the same esterification and post-treatment processes, the method can avoid extra waste water caused by elution of the phenol from the extracting agent, however, for enterprises with various product types, the number of extraction equipment and equipment for phenol esterification reaction is increased, a plurality of sets of equipment can be needed to treat waste water of a plurality of products, and the investment is huge. The invention can solve the phenol recovery problem of various aryl phosphate ester waste water by using triphenyl phosphate with simplest phenol recycling process and least links as an extracting agent in a unified way.
(2) Phenol in the aryl phosphate production wastewater is mainly from alkaline wastewater generated in an alkaline washing process and mainly exists in the form of sodium phenolate, and the sodium phenolate cannot be extracted from the alkaline wastewater by phosphate esters, and the sodium phenolate needs to be converted into the form of phenol and can be successfully extracted into the phosphate ester under neutral or acidic conditions. Before phenol is extracted, the alkaline waste water is adjusted to be neutral by using the acidic waste water, so that the sodium phenolate is generated into phenol for convenient extraction.
(3) The aryl phosphate production wastewater contains aryl phosphate sodium salt, hydrolyzed aryl phosphate is generated when the wastewater is adjusted to be neutral, the hydrolyzed aryl phosphate has the same extraction effect on phenol, and simultaneously, the concentration of phenol in a water layer and the quality of extractable phenol are reduced due to the addition of acid washing acidic wastewater. The content of the hydrolyzed aryl phosphate in the alkaline wastewater is about 5-10%, 10-20% of the mass of phenol in the original wastewater can be extracted, so that the mass of phenol extracted by triphenyl phosphate is 10-20% less than that of the original phenol in the wastewater.
Aryl phosphates, aryl phosphate sodium salts, hydrolyzed aryl phosphates are exemplified by their molecular structure, resorcinol bis (diphenyl phosphate), abbreviated RDP for example:
the molecular structural formula of the aryl phosphate RDP is as follows:
the molecular structural formula of the sodium salt of the aryl phosphate RDP is as follows:
the molecular structural formula of the hydrolyzed aryl phosphate RDP is as follows:
(4) like other aryl phosphate esters, triphenyl phosphate cannot perform one-time extraction on phenol in wastewater to be qualified (legal discharge standard is less than 10ppm), and usually more than 4 times of extraction is needed to perform qualified discharge, and the production efficiency is reduced after the extraction times are excessive. The invention combines four treatment methods of neutralization-extraction-alkaline distillation-biochemical treatment to discharge the phenol in the treated wastewater up to the standard. The specific method comprises the following steps: the extraction is carried out once, the phenol content of the extracted water layer is lower than 1000ppm, the distilled water is ensured to be distilled and dehydrated under the alkaline condition of an environmental protection station to ensure that the content of the distilled water phenol is less than or equal to 100ppm, then the distilled water is refluxed through a macroporous resin column, and the treated distilled water phenol can reach the standard and be discharged through the adsorption of the macroporous resin to the phenol. Because the phenol content in the water absorbed by the macroporous resin is lower than 100ppm, generally 5-10kg of phenol can be absorbed only when 100 tons of phenol-containing distilled water is treated, the regeneration period of the macroporous resin is much more economical than that of directly treating high-concentration phenol-containing wastewater, and the regeneration of the macroporous resin belongs to a method known by environmental protection technicians.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
In the following examples, alkaline waste water: bisphenol A-bis (diphenyl phosphate) (BDP) alkali washing wastewater, wherein the wastewater contains 31400ppm of phenol, 14 of PH value and 6.39 percent of aryl phosphate sodium salt;
acid wastewater: bisphenol A-bis (diphenyl phosphate) acid-washing wastewater, the concentration of hydrogen chloride is 17.5 percent;
extracting agent: the water content of the finished triphenyl phosphate is 0.05 percent, the phenol content is 200ppm, and the purity is 99.93 percent;
concentrated hydrochloric acid for pickling is 30% reagent grade concentrated hydrochloric acid; the liquid alkali for acid washing is 30 percent sodium hydroxide aqueous solution; the toluene used for the work-up was 99.86% technical grade toluene.
In the following examples,% means mass%.
Example 1
1) Adding 80.8kg of acid washing wastewater into 300kg of alkaline washing wastewater, stirring for 1 hour at 40-60 ℃, adjusting the pH value to 6-7, standing for 1 hour, and separating out 23.3kg of lower-layer oil layer and 355.46kg of upper-layer wastewater; measuring the phenol content of the upper layer wastewater 22188ppm (phenol content detection: liquid chromatography external standard method);
2) adding 29.62kg of triphenyl phosphate extractant into the upper-layer wastewater obtained in the step 1), wherein the addition amount of the extractant is 1/12 which is the mass of the upper-layer wastewater, stirring the mixture for 1 hour at the temperature of between 50 and 60 ℃, then standing the mixture for 1 hour, separating 347.3kg of water layer (the phenol content of the water layer is 887ppm) and 37.42kg of extraction layer, and measuring the phenol content of the extraction layer to be 20152 ppm;
3) transferring the extraction layer obtained in the step 2) into a distillation kettle for carrying out reduced pressure distillation dehydration operation, after distilling out the water under the distillation vacuum degree of-0.096 mpa and the distillation temperature of 115 ℃ and 120 ℃, sampling the extraction layer, detecting the water content of 0.05 percent, detecting the phenol content of 20355ppm, and determining the extraction layer is qualified; to obtain 37kg of dehydrated extract;
4) transferring the dehydrated extract obtained in the step 2) into an esterification kettle, adding 4.04kg of phosphorus oxychloride and 0.012kg of anhydrous magnesium chloride, heating to 85-90 ℃, keeping the temperature for 3 hours, heating to 100-105 ℃, keeping the temperature for 3 hours, detecting the residual amount of the diphenyl phosphoryl chloride intermediate by liquid chromatography, finishing the reaction when the residual amount of phenol is 0.261 percent, and finally obtaining 38.21kg of a crude product of triphenyl phosphate.
5) And (3) sequentially carrying out acid washing, alkali washing, water washing and distillation treatment on the triphenyl phosphate crude product obtained in the step 6) to finally obtain a qualified triphenyl phosphate finished product.
In the step 5), the acid washing method comprises the following steps: 5.6kg of tap water and 4kg of 30% hydrochloric acid are added into the triphenyl phosphate crude product, the mixture is stirred for 2 hours at the temperature of 60-70 ℃, 76.6kg of toluene is added, the mixture is stirred for 1 hour, the mixture is kept stand for 30 minutes and is divided into a triphenyl phosphate layer and a water layer, and the water layer at the lower layer is separated, so that the triphenyl phosphate layer after acid washing is obtained.
In the step 5), the alkali washing method comprises the following steps: adding 8.5kg of tap water and 3kg of 30% liquid alkali into the triphenyl phosphate layer after acid washing, stirring for 2 hours at 60-70 ℃, standing for 30 minutes to separate the triphenyl phosphate layer and the water layer, and separating the water layer at the lower layer to obtain the triphenyl phosphate layer after alkali washing.
In the step 5), the water washing method comprises the following steps: adding 10.2kg of water into the triphenyl phosphate layer after alkali washing, stirring for 2 hours at 60-70 ℃, standing for 30 minutes to separate the triphenyl phosphate layer and the water layer, and separating the water layer on the lower layer to obtain the triphenyl phosphate layer after water washing.
In the step 5), the distillation treatment method comprises the following steps: and (3) distilling the triphenyl phosphate layer subjected to water washing under reduced pressure to remove toluene, keeping the vacuum at the temperature of more than-0.095 mpa and the highest temperature of 130-140 ℃, distilling until no solvent is removed, and finally obtaining 37.65kg of qualified triphenyl phosphate finished product, wherein the triphenyl phosphate finished product returns to an extraction link for extraction, the moisture content is less than or equal to 0.05 percent, the mass content of phenol is less than or equal to 0.02 percent, and the mass purity is more than 99 percent.
6) Transferring 347.3kg of the phenol-containing water layer obtained in the step 2) into a distillation still, adding 0.5kg of 30% sodium hydroxide solution (adjusting the pH value of the water layer to 8-9), gradually heating to 80 ℃ under vacuum of-0.094 mpa for alkaline distillation, distilling 341.1kg of distilled water, and measuring the phenol content to be 75 ppm.
7) Keeping the temperature of the distilled water obtained in the step 6) at 30-40 ℃, sending the distilled water into a packed tower filled with macroporous resin HPD100 for phenol reflux adsorption, and sampling after 1 hour of the reflux adsorption to obtain that the content of phenol in the water is 3ppm, which is qualified.
Example 2 the other steps were the same as in example 1 except that the pH of the wastewater was adjusted to 2 after the acidic wastewater was added in step 1), and the phenol content of the upper wastewater in step 1) was measured to be 20158 ppm.
Example 3 the other steps were the same as in example 1 except that 1/10 was added as an extractant in the proportion of the mass of the aqueous layer in step 2), and finally the phenol content of the aqueous layer in step 2) was measured to be 573 ppm.
Example 4 the other steps were the same as in example 1 except that 1/5 was added as an extractant in the proportion of the mass of the aqueous layer in step 2), and finally the phenol content of the aqueous layer in step 2) was measured to be 415 ppm.
Example 5 the other steps were the same as in example 1 except that 1/13 was added as an extractant in the proportion of the mass of the aqueous layer in step 2) and finally the phenol content of the aqueous layer in step 2) was determined to be 1218 ppm.
Example 6 the other steps were the same as in example 1 except that the extraction temperature in step 2) was changed to 65 to 70 ℃ and the phenol content of the aqueous layer in step 2) was 1005 ppm.
Example 7 the other steps were the same as in example 1 except that the extraction temperature in step 2) was changed to 40 to 45 c and the phenol content of the aqueous layer in step 2) was 1180 ppm.
Comparing example 1 with example 2, it is found that the lower the pH of the waste water is adjusted, the more phenol is extracted from the hydrolyzed phosphoric acid ester, the lower the residual phenol content in the water layer, and the acidity is adjusted to neutrality to perform the next extraction, so the alkaline waste water is adjusted to neutrality.
Comparing examples 1, 3, 4 and 5, it is known that the more the extractant is added to the water layer, the better the extraction effect is, but the increase of phenol quality in the extractant is very limited, and the increase of the extractant amount can cause the decrease of phenol concentration in the extract, which leads to the decrease of production efficiency and the serious cost increase; the addition of the extracting agent is lower than 1/12 of the quality of the water layer, so that the phenol content of the extracted water layer is easily higher than 1000ppm, which is not beneficial to ensuring that the phenol content of the distilled water obtained by alkaline distillation meets the entering requirement of biochemical treatment; therefore, 1/12 is preferably added in an amount to control the quality of the aqueous layer.
Comparing example 1, example 6 and example 7, it is known that both too high and too low temperature during extraction are not favorable for phenol to be extracted into the material layer, which is consistent with the report in the relevant literature about the influence of extraction temperature on the extraction efficiency of phosphate ester extractant, and that too high temperature leads to the increase of phenol solubility in the water layer and too low temperature leads to the increase of phosphate ester viscosity, which is not favorable for being sufficiently mixed with the aqueous solution for extraction. Therefore, it is appropriate to control the temperature at 50 to 60 ℃.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (6)
1. A method for preparing triphenyl phosphate by extracting phenol from aryl phosphate production wastewater is characterized by comprising the following steps:
1) adding acid into the aryl phosphate alkaline washing wastewater to adjust the pH value to 6-7, stirring for 0.5-1.5 h at 40-60 ℃, standing for layering, and separating out a lower-layer oil layer and upper-layer wastewater with the phenol content lower than 25000 ppm;
2) adding triphenyl phosphate into the upper-layer wastewater obtained in the step 1), stirring and extracting, then standing and layering, separating out an extraction layer and a water layer with the phenol content lower than 1000ppm, and sequentially carrying out alkaline distillation and macroporous resin adsorption and purification on the water layer to obtain water with the phenol content less than or equal to 10 ppm;
3) transferring the extraction layer obtained in the step 2) into a distillation kettle for reduced pressure distillation and dehydration, and removing until the moisture content is lower than 0.05% to obtain a dehydrated extract;
4) placing the dehydrated extract obtained in the step 3) into an esterification kettle, then adding phosphorus oxychloride and anhydrous magnesium chloride for esterification reaction, sampling and detecting that the residual quantity of the diphenyl phosphoryl chloride intermediate is less than or equal to 0.1%, and then finishing the reaction to obtain a triphenyl phosphate crude product;
5) sequentially carrying out acid washing, alkali washing, water washing and distillation treatment on the triphenyl phosphate crude product obtained in the step 4) to finally obtain a qualified triphenyl phosphate finished product; the water content of the finished product of the triphenyl phosphate is less than or equal to 0.05 percent, the mass content of the phenol is less than or equal to 0.02 percent, and the mass purity is more than 99 percent, and the finished product of the triphenyl phosphate can be reused in the stirring and extracting process of the step 2);
in the step 2), the feeding mass ratio of the upper-layer wastewater to triphenyl phosphate is 12: 1; the temperature for stirring and extracting is 50-60 ℃, and the time for stirring and extracting is 1 h; the mass content of phenol in the extraction layer is more than or equal to 18 percent.
2. The method for preparing triphenyl phosphate by extracting phenol from aryl phosphate production wastewater according to claim 1, wherein in the aryl phosphate alkaline washing wastewater in the step 1), the phenol content is 25000-35000 ppm, the aryl phosphate sodium salt mass content is 5-8%, and the pH value is 14.
3. The method for preparing triphenyl phosphate by extracting phenol from aryl phosphate production wastewater according to claim 1, wherein in the step 1), aryl phosphate acid washing wastewater is added into the aryl phosphate alkali washing wastewater to adjust the pH value, and the mass concentration of HCl in the aryl phosphate acid washing wastewater is 16-18%.
4. The method for preparing triphenyl phosphate by extracting phenol from aryl phosphate production wastewater according to claim 1, wherein in the step 3), the temperature for performing reduced pressure distillation dehydration is 115-120 ℃, and the vacuum degree for performing reduced pressure distillation dehydration is more than or equal to-0.096 MPa; the mass content of phenol in the dehydrated extract is more than or equal to 18 percent.
5. The method for preparing triphenyl phosphate by extracting phenol from aryl phosphate production wastewater according to claim 1, wherein in the step 4), the esterification reaction is performed under the following conditions: the reaction is carried out for 2-4 h at the temperature of 85-90 ℃, then the temperature is increased to 100-105 ℃, and the reaction is carried out for 2-4 h at the temperature.
6. The method for preparing triphenyl phosphate by extracting phenol from aryl phosphate production wastewater according to claim 1, wherein the content of phenol in the upper layer wastewater of step 1) is 15000-25000 ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811633696.6A CN109535199B (en) | 2018-12-29 | 2018-12-29 | Method for preparing triphenyl phosphate by extracting phenol from aryl phosphate production wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811633696.6A CN109535199B (en) | 2018-12-29 | 2018-12-29 | Method for preparing triphenyl phosphate by extracting phenol from aryl phosphate production wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109535199A CN109535199A (en) | 2019-03-29 |
| CN109535199B true CN109535199B (en) | 2021-01-05 |
Family
ID=65831112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811633696.6A Active CN109535199B (en) | 2018-12-29 | 2018-12-29 | Method for preparing triphenyl phosphate by extracting phenol from aryl phosphate production wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109535199B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111892108B (en) * | 2020-07-27 | 2022-12-23 | 扬州晨化新材料股份有限公司 | Method for reducing content of organic matters in TCPP production wastewater |
| CN112607946B (en) * | 2020-12-17 | 2023-03-24 | 浙江万盛股份有限公司 | Method for recycling organic waste in BDP wastewater |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7700807B2 (en) * | 2003-10-24 | 2010-04-20 | Supresta Llc | Process to prepare alkyl phenyl phosphates |
| CN103214514A (en) * | 2013-04-09 | 2013-07-24 | 天津市联瑞阻燃材料有限公司 | Preparation method of triphenyl phosphate |
| CN106008592A (en) * | 2016-06-01 | 2016-10-12 | 浙江万盛股份有限公司 | Industrial synthesis method of tris(butoxyethyl)phosphate and device thereof |
-
2018
- 2018-12-29 CN CN201811633696.6A patent/CN109535199B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7700807B2 (en) * | 2003-10-24 | 2010-04-20 | Supresta Llc | Process to prepare alkyl phenyl phosphates |
| CN103214514A (en) * | 2013-04-09 | 2013-07-24 | 天津市联瑞阻燃材料有限公司 | Preparation method of triphenyl phosphate |
| CN106008592A (en) * | 2016-06-01 | 2016-10-12 | 浙江万盛股份有限公司 | Industrial synthesis method of tris(butoxyethyl)phosphate and device thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109535199A (en) | 2019-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109535199B (en) | Method for preparing triphenyl phosphate by extracting phenol from aryl phosphate production wastewater | |
| CN108059291B (en) | Method for recovering DMF (dimethyl formamide) and inorganic salt in ceftazidime side chain acid ester wastewater | |
| CN103342626B (en) | Preparation method of chromatographic grade methanol | |
| CN106865675B (en) | Extraction dephenolization method of phenol-containing wastewater | |
| CN103395925A (en) | Treatment method for recycling para-hydroxybenzoic acid wastewater | |
| CN109825322B (en) | Method for extracting phenolic substances from coal tar or direct coal liquefaction oil | |
| CN108794522B (en) | Full continuous flow production process of tris (1-chloro-2-propyl) phosphate | |
| CN107585820B (en) | Extracting agent with high distribution coefficient for polyphenol in phenol-containing wastewater and extracting method | |
| CN111995152B (en) | Method for treating high-concentration wastewater generated in synthesis of anisole from methyl sodium sulfate waste residues | |
| CN111547913A (en) | Method for recovering phenol from phenol-containing wastewater | |
| CN111470997A (en) | Method for recovering DMF waste liquid | |
| CN108211423B (en) | Method for adsorbing and separating phenolic compounds in oil by using biodegradable compound as adsorbent | |
| CN109085260B (en) | Method for purifying pesticide residue grade acetonitrile | |
| CN109232183B (en) | Method for separating dichloropropanol from dichloropropanol hydrochloric acid azeotropic liquid | |
| CN103497214A (en) | Clean preparation method of ethyl chloride with high purity | |
| CN108395367B (en) | Method for separating phenolic compounds from coal tar | |
| CN105947984A (en) | Production process for recycling and producing anhydrous hydrogen fluoride from high-concentration wastewater containing fluoride | |
| CN109912644B (en) | Post-treatment purification process for TCPP (trichloropropylphosphate) production crude product | |
| CN105152874B (en) | A kind of method for producing dipropylene glycol methyl ether | |
| CN107937009A (en) | The separation method of phenolic compound in coal tar and DCL/Direct coal liquefaction product | |
| CN108793304B (en) | Method for extracting phenol-containing coal chemical wastewater | |
| CN110921630A (en) | Method for preparing hydrogen chloride by resolving hydrochloric acid | |
| CN112675574A (en) | Method for extracting and separating phenolic components in phenol oil by using hydroxyl functionalized ionic liquid with double hydrogen bond sites | |
| CN103304398B (en) | A kind of method of purification of carboxylic acid aqueous solution | |
| CN105749877A (en) | Preparation method of adsorbent applied to hydrogen peroxide purification |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |