CN104844424A - Recovery method for tri[2.4-di-tert-butylphenyl]phosphite kettle residue - Google Patents
Recovery method for tri[2.4-di-tert-butylphenyl]phosphite kettle residue Download PDFInfo
- Publication number
- CN104844424A CN104844424A CN201510168090.XA CN201510168090A CN104844424A CN 104844424 A CN104844424 A CN 104844424A CN 201510168090 A CN201510168090 A CN 201510168090A CN 104844424 A CN104844424 A CN 104844424A
- Authority
- CN
- China
- Prior art keywords
- tert
- butyl
- residual
- phenyl
- acid ester
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000011084 recovery Methods 0.000 title claims abstract description 25
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 title abstract 3
- 230000007062 hydrolysis Effects 0.000 claims abstract description 20
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000008346 aqueous phase Substances 0.000 claims abstract description 14
- 238000004821 distillation Methods 0.000 claims abstract description 12
- 239000012074 organic phase Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- -1 [2.4-di-tert-butyl-phenyl] phosphorous acid ester Chemical class 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000001117 sulphuric acid Substances 0.000 claims description 6
- 235000011149 sulphuric acid Nutrition 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 238000013517 stratification Methods 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000002699 waste material Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 150000007522 mineralic acids Chemical class 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 239000003963 antioxidant agent Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 150000008301 phosphite esters Chemical class 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical class CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/005—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by obtaining phenols from products, waste products or side-products of processes, not directed to the production of phenols, by conversion or working-up
- C07C37/009—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by obtaining phenols from products, waste products or side-products of processes, not directed to the production of phenols, by conversion or working-up from waste water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
- C07C37/0555—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group being esterified hydroxy groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a recovery method for tri[2.4-di-tert-butylphenyl]phosphite kettle residue. The method includes the steps of: putting tri[2.4-di-tert-butylphenyl]phosphite kettle residue, water and inorganic acid into a hydrolysis container, conducting heating and stirring to fully mix the materials, carrying out heat preservation hydrolysis, then stopping stirring and conducting standing layering, separating the material into an organic phase and an aqueous phase, discharging the lower layer water when the aqueous phase becomes clear, transferring the organic phase into a distillation apparatus to conduct pressure reduced distillation, maintaining the pressure in the distillation apparatus at 1.00KPa-4.00KPa, and collecting 130-160DEG C fractions, thus obtaining a 2.4-di-tert-butyl phenol product. By means of hydrolysis, distillation and recovery on the kettle residue generated during production of tri[2.4-di-tert-butylphenyl]phosphate, the raw materials can be recovered, the production cost is reduced, change of waste materials into things of value is realized, resources are saved, also waste discharge is reduced, and environmental protection is realized.
Description
Technical field
The present invention relates to the residual recovery method of still produced in a kind of polymkeric substance antioxidant product production process, particularly relate to the recovery method that the still that produces in phosphite ester kind antioxidant production process is residual.More particularly, the present invention relates to the recovery method that the still that produces in phosphorous acid esters three [2.4-di-tert-butyl-phenyl] phosphorous acid ester production process is residual.
Background technology
Three [2.4-di-tert-butyl-phenyl] phosphorous acid ester, be most widely used at present, of paramount importance a kind of outstanding phosphorous acid esters plastics auxiliary antioxidant, colourless dirt, colourless change, high temperature resistant, volatility is low, hydrolytic resistance give prominence to.The change of molecular weight that can prevent polymkeric substance oxidative degradation in the course of processing (as mixture/granulation, secondary processing and recycling) from causing (as chain rupture/crosslinked), prevents colour-change.Excellent processing stability and colour stability can be provided for plastics.Be widely used in the poly-and multipolymer of polyolefine, vinylbenzene list, elastomerics, tackiness agent, engineering plastics (as: PE, PP, PVC, PS, polymeric amide, polycarbonate, ABS) etc. macromolecular material and powder coating, softening agent, commercial fatty, other organic substrate of mineral wet goods.
Three [2.4-di-tert-butyl-phenyl] phosphorous acid ester carries out chemical reaction with 2.4-DI-tert-butylphenol compounds and phosphorus trichloride, reaction mixture through crystallization and purification, then through centrifugal, dry and obtain.In order to enable in phosphorus trichloride molecular structure three chlorine atoms be replaced completely, in blending process, usually allow 2.4-DI-tert-butylphenol compounds little over amount, excessive 2.4-DI-tert-butylphenol compounds and other compositions are removed in later crystallization, rotary process.Crystallisation process solvent for use is generally alcohols, as methyl alcohol, ethanol, Virahol, the trimethyl carbinol etc., in crystallization and centrifugal process, major part three [2.4-di-tert-butyl-phenyl] phosphorous acid ester products crystallization in a solvent, and drying process is entered after centrifugation, rotary process gained filtrate is commonly called mother liquor, although major part three [2.4-di-tert-butyl-phenyl] phosphorous acid ester is centrifuged separation and enters drying process, but have a small amount of three [2.4-di-tert-butyl-phenyl] phosphorous acid ester to be retained in crystalline mother solution with the state of saturated solution, when also having centrifugal, part three [2.4-di-tert-butyl-phenyl] phosphorous acid ester passes filter bag and enters mother liquor because crystal formation is tiny, the 2.4-DI-tert-butylphenol compounds of excessive and non-complete reaction is also comprised in mother liquor, and raw material is brought into and reacts other impurity of generation.Crystalline mother solution proceeds to still kettle by Distillation recovery alcohols recrystallisation solvent, the residue of distilling off solvent claims still residual usually, the still of three [2.4-di-tert-butyl-phenyl] phosphorous acid ester is residual about containing 50-70%2.4-DI-tert-butylphenol compounds, 20-40% tri-[2.4-di-tert-butyl-phenyl] phosphorous acid ester, 10-20% alcoholic solvent and other impurity, 2.4-DI-tert-butylphenol compounds is the important source material of synthesis three [2.4-di-tert-butyl-phenyl] phosphorous acid ester.Reclaim still is residual, not only can obtain a large amount of 2.4-DI-tert-butylphenol compounds, reduce production cost, and residue is made full use of, achieve and turn waste into wealth, decrease environmental pollution.
CN94118738.1, CN201010607161.9 report the mother liquid recovery process of antioxidant 1010, and CN200610118084.4 reports the mother liquid recovery process of oxidation inhibitor 245.Because antioxidant 1010 and oxidation inhibitor 245 are all Hinered phenols antioxidants, the mother liquor of Hinered phenols antioxidant product can generate corresponding alcohol and 3 after alcoholysis, 5-methyl esters, and three [2.4-di-tert-butyl-phenyl] phosphorous acid ester is phosphite ester kind antioxidant, the character that three [2.4-di-tert-butyl-phenyl] phosphorous acid ester still is residual and composition and the former distinguish very large, so Hinered phenols antioxidant mother liquor reclaiming method is not exclusively applicable to the residual recovery of three [2.4-di-tert-butyl-phenyl] phosphorous acid ester stills.Technique for the residual recovery of three [2.4-di-tert-butyl-phenyl] phosphorous acid ester stills has no reported in literature.
Summary of the invention
The invention provides the recovery method that in a kind of phosphorous acid esters three [2.4-di-tert-butyl-phenyl] phosphorous acid ester production process, still is residual, to realize turning waste into wealth, economize on resources, realize environment protection.
Technical scheme of the present invention is:
The recovery method that in a kind of three [2.4-di-tert-butyl-phenyl] phosphorous acid ester production process, still is residual, comprises the following steps:
By residual for three [2.4-di-tert-butyl-phenyl] phosphorous acid ester still, water, mineral acid drops into hydrolysis vessels in setting ratio, heating up and stirring makes material fully mix, insulation hydrolysis, described hydrolysis temperature is 90-100 DEG C, hydrolysis time 30-150 minute, hydrolysis terminates rear stopping and stirring stratification, feed separation is organic phase and aqueous phase, after aqueous phase is limpid, lower floor's aqueous phase is released, organic phase is proceeded to water distilling apparatus underpressure distillation, keep water distilling apparatus internal pressure 1.00 KPa-4.00KPa, collect 130-160 DEG C of cut, namely 2.4-di-tert-butyl phenolic product is obtained.
Described three [2.4-di-tert-butyl-phenyl] phosphorous acid ester still is residual, be made up of the component of following mass percentage: 50-70%2.4-DI-tert-butylphenol compounds, 20-40% tri-[2.4-di-tert-butyl-phenyl] phosphorous acid ester, 10-20% alcoholic solvent and other impurity.
The add-on of described water is the 20-40% of the residual quality of still.
The add-on of described mineral acid is the 0.1-1% of the residual quality of still.
Described mineral acid is mass concentration is 20 ~ 40%(w/w) technical hydrochloric acid, mass concentration be 30 ~ 98%(w/w) industrial sulphuric acid, mass concentration be 30 ~ 70%(w/w) industrial nitric acid or mass concentration be 30 ~ 100%(w/w) the one of industrial phosphoric acid, preferably technical hydrochloric acid or industrial sulphuric acid, particularly preferably be industrial sulphuric acid.
Described alcoholic solvent is the one of methyl alcohol, ethanol, Virahol and the trimethyl carbinol.
The invention has the beneficial effects as follows: oxidation inhibitor three [2.4-di-tert-butyl-phenyl] is not rationally recycled if the still produced in phosphorous acid ester production process is residual, the distillation residue then can only worked as in danger wastes classification transfer to the speciality chemical Hazardous wastes process company of qualification to carry out the burning disposal of specialty, produce the residual oxidation inhibitor manufacturer of still on the one hand and need pay expensive processing costs to chemical hazard disposal company, speciality chemical Hazardous wastes process company still can produce great amount of carbon dioxide in the residual process of this still of process on the other hand, the exhaust gas emissions such as steam, be unfavorable for environment protection, the present invention is by adding the hydrolysis of a small amount of water to the still in three [2.4-di-tert-butyl-phenyl] phosphorous acid ester production process is residual, distillation, carry out innoxious recovery, not only can reclaim a large amount of valuable organic raw material 2, 4-DI-tert-butylphenol compounds, reduce production cost, realization is turned waste into wealth, economize on resources, and reduce waste discharge, realize environment protection.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but be not intended to limit scope of patent protection of the present invention.Under the prerequisite not exceeding technical solution of the present invention, any change that those of ordinary skill in the art made for the present invention easily realize all will fall within scope of patent protection of the present invention.
Embodiment 1
Electric stirring is being housed, thermometer, in the 500ml four-hole boiling flask of condenser, add 20 grams of water, 0.1 gram of concentration is 31%(w/w) technical hydrochloric acid, 100 gram of three [2.4-di-tert-butyl-phenyl] phosphorous acid ester still is residual, this still is residual, and to detect 2.4-DI-tert-butylphenol compounds content through high performance liquid chromatography be 51.8%, three [2.4-di-tert-butyl-phenyl] phosphorous acid ester content is 32.6%, all the other 15.6% are solvent methanol and other impurity, start stirring, be warming up to about 90 DEG C, 90-95 DEG C of insulation hydrolysis 60 minutes, hydrolysis terminates rear sampling and does not detect three [2.4-di-tert-butyl-phenyl] phosphite component through liquid-phase chromatographic analysis, stop stirring, mixture is transferred to separating funnel stratification, after aqueous phase is limpid, lower floor's aqueous phase is released, organic phase is proceeded to water distilling apparatus underpressure distillation, keep water distilling apparatus internal pressure 1.00 KPa-4.00KPa, collect 130-160 DEG C of cut, obtaining 79.6 grams of purity is 99.73%(w/w) 2.4-di-tert-butyl phenolic product, the rate of recovery is 95.91%.
Embodiment 2
Electric stirring is being housed, thermometer, in the 500ml four-hole boiling flask of condenser, add 30 grams of water, 0.5 gram of concentration is 50%(w/w) industrial sulphuric acid, 100 gram of three [2.4-di-tert-butyl-phenyl] phosphorous acid ester still is residual, this still is residual, and to detect 2.4-DI-tert-butylphenol compounds content through high performance liquid chromatography be 67.3%, three [2.4-di-tert-butyl-phenyl] phosphorous acid ester content is 21.8%, all the other 10.9% are solvent methanol and other impurity, start stirring, be warming up to about 100 DEG C, 97-100 DEG C of insulation hydrolysis 30 minutes, hydrolysis terminates rear sampling and does not detect three [2.4-di-tert-butyl-phenyl] phosphite component through liquid-phase chromatographic analysis, stop stirring, mixture is transferred to separating funnel stratification, after aqueous phase is limpid, lower floor's aqueous phase is released, organic phase is proceeded to water distilling apparatus underpressure distillation, keep water distilling apparatus internal pressure 1.00 KPa-4.00KPa, collect 130-160 DEG C of cut, obtaining 86.3 grams of purity is 99.59%(w/w) 2.4-di-tert-butyl phenolic product, the rate of recovery is 97.89%.
Embodiment 3
Electric stirring is being housed, thermometer, in the 500ml four-hole boiling flask of condenser, add 40 grams of water, 0.3 gram of concentration is 85%(w/w) industrial phosphoric acid, 100 gram of three [2.4-di-tert-butyl-phenyl] phosphorous acid ester still is residual, this still is residual, and to detect 2.4-DI-tert-butylphenol compounds content through high performance liquid chromatography be 52.6%, three [2.4-di-tert-butyl-phenyl] phosphorous acid ester content is 38.9%, all the other 8.5% are solvent methanol and other impurity, start stirring, be warming up to about 95 DEG C, 95-100 DEG C of insulation hydrolysis 90 minutes, hydrolysis terminates rear sampling and does not detect three [2.4-di-tert-butyl-phenyl] phosphite component through liquid-phase chromatographic analysis, stop stirring, mixture is transferred to separating funnel stratification, after aqueous phase is limpid, lower floor's aqueous phase is released, organic phase is proceeded to water distilling apparatus underpressure distillation, keep water distilling apparatus internal pressure 1.00 KPa-4.00KPa, collect 130-160 DEG C of cut, obtaining 84.9 grams of purity is 99.91%(w/w) 2.4-di-tert-butyl phenolic product, the rate of recovery is 94.52%.
Claims (7)
1. the recovery method that three [2.4-di-tert-butyl-phenyl] phosphorous acid ester still is residual, is characterized in that, comprise the following steps:
By residual for three [2.4-di-tert-butyl-phenyl] phosphorous acid ester still, water, mineral acid drops into hydrolysis vessels in setting ratio, heating up and stirring makes material fully mix, insulation hydrolysis, described hydrolysis temperature is 90-100 DEG C, hydrolysis time 30-150 minute, hydrolysis terminates rear stopping and stirring stratification, feed separation is organic phase and aqueous phase, after aqueous phase is limpid, lower floor's aqueous phase is released, organic phase is proceeded to water distilling apparatus underpressure distillation, keep water distilling apparatus internal pressure 1.00 KPa-4.00KPa, collect 130-160 DEG C of cut, namely 2.4-di-tert-butyl phenolic product is obtained.
2. the recovery method that three [2.4-di-tert-butyl-phenyl] phosphorous acid ester still as claimed in claim 1 is residual, it is characterized in that, described three [2.4-di-tert-butyl-phenyl] phosphorous acid ester still is residual, be made up of the component of following mass percentage: 50-70%2.4-DI-tert-butylphenol compounds, 20-40% tri-[2.4-di-tert-butyl-phenyl] phosphorous acid ester, 10-20% alcoholic solvent and other impurity.
3. the recovery method that three [2.4-di-tert-butyl-phenyl] phosphorous acid ester still as claimed in claim 1 is residual, it is characterized in that, the add-on of described water is the 20-40% of the residual quality of still.
4. the recovery method that three [2.4-di-tert-butyl-phenyl] phosphorous acid ester still as claimed in claim 1 is residual, it is characterized in that, the add-on of described mineral acid is the 0.1-1% of the residual quality of still.
5. the recovery method that three [2.4-di-tert-butyl-phenyl] phosphorous acid ester still as claimed in claim 1 is residual, it is characterized in that, described mineral acid is the one of technical hydrochloric acid, industrial sulphuric acid, industrial nitric acid or industrial phosphoric acid.
6. the recovery method that three [2.4-di-tert-butyl-phenyl] phosphorous acid ester still as claimed in claim 2 is residual, it is characterized in that, described alcoholic solvent is the one of methyl alcohol, ethanol, Virahol and the trimethyl carbinol.
7. the recovery method that three [2.4-di-tert-butyl-phenyl] phosphorous acid ester still as claimed in claim 5 is residual, it is characterized in that, the mass concentration of described technical hydrochloric acid is 20 ~ 40%, the mass concentration of industrial sulphuric acid is 30 ~ 98%, the mass concentration of industrial nitric acid is 30 ~ 70%, and the mass concentration of industrial phosphoric acid is 30 ~ 100%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510168090.XA CN104844424B (en) | 2015-04-10 | 2015-04-10 | The recovery method that a kind of three [2,4-di-tert-butyl-phenyl] phosphorous acid ester still is residual |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510168090.XA CN104844424B (en) | 2015-04-10 | 2015-04-10 | The recovery method that a kind of three [2,4-di-tert-butyl-phenyl] phosphorous acid ester still is residual |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104844424A true CN104844424A (en) | 2015-08-19 |
| CN104844424B CN104844424B (en) | 2016-04-27 |
Family
ID=53844466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510168090.XA Active CN104844424B (en) | 2015-04-10 | 2015-04-10 | The recovery method that a kind of three [2,4-di-tert-butyl-phenyl] phosphorous acid ester still is residual |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104844424B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108484367A (en) * | 2018-03-14 | 2018-09-04 | 江苏极易新材料有限公司 | A method of recycling 2,4- DI-tert-butylphenol compounds from 168 mother liquor of antioxidant |
| CN110563556A (en) * | 2019-09-26 | 2019-12-13 | 黄河三角洲京博化工研究院有限公司 | method for recovering 2, 4-di-tert-butylphenol from double-helix phosphite antioxidant 626 mother liquor |
| CN114057548A (en) * | 2021-12-03 | 2022-02-18 | 陕西艾科莱特新材料有限公司 | Method for recovering 2, 4-di-tert-butylphenol from antioxidant 168 concentrated mother liquor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798325A (en) * | 2010-03-12 | 2010-08-11 | 江苏工业学院 | Preparation method of antioxidant product with stable performance |
-
2015
- 2015-04-10 CN CN201510168090.XA patent/CN104844424B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798325A (en) * | 2010-03-12 | 2010-08-11 | 江苏工业学院 | Preparation method of antioxidant product with stable performance |
Non-Patent Citations (1)
| Title |
|---|
| 吴松海 等: ""2-4-二叔丁基苯酚连续精馏技术的开发"", 《天津化工》, no. 5, 30 September 2002 (2002-09-30), pages 1 - 3 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108484367A (en) * | 2018-03-14 | 2018-09-04 | 江苏极易新材料有限公司 | A method of recycling 2,4- DI-tert-butylphenol compounds from 168 mother liquor of antioxidant |
| CN108484367B (en) * | 2018-03-14 | 2019-04-30 | 江苏极易新材料有限公司 | A method of recycling 2,4- DI-tert-butylphenol compounds from 168 mother liquor of antioxidant |
| CN110563556A (en) * | 2019-09-26 | 2019-12-13 | 黄河三角洲京博化工研究院有限公司 | method for recovering 2, 4-di-tert-butylphenol from double-helix phosphite antioxidant 626 mother liquor |
| CN114057548A (en) * | 2021-12-03 | 2022-02-18 | 陕西艾科莱特新材料有限公司 | Method for recovering 2, 4-di-tert-butylphenol from antioxidant 168 concentrated mother liquor |
| CN114057548B (en) * | 2021-12-03 | 2024-03-01 | 陕西艾科莱特新材料有限公司 | Method for recovering 2, 4-di-tert-butylphenol from concentrated mother liquor of antioxidant 168 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104844424B (en) | 2016-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104844424B (en) | The recovery method that a kind of three [2,4-di-tert-butyl-phenyl] phosphorous acid ester still is residual | |
| JP4908415B2 (en) | Method for producing useful components from dyed polyester fiber | |
| US7728047B2 (en) | Process for the recycling of expanded polystyrene | |
| JPS6040193A (en) | Manufacture of liquid hydrocarbon | |
| CN108299633B (en) | ferrocene-DOPO double-base polyester type flame-retardant smoke suppressant and preparation method thereof and application of ferrocene-DOPO double-base polyester type flame-retardant smoke suppressant in flame-retardant polymer | |
| JPWO2020213032A1 (en) | Manufacturing method of decolorized polyester, decolorized polyester and decolorizing agent | |
| CN103333052B (en) | Between a kind of separation industries to mixture cresol to prepare the method for pure p-cresol and pure meta-cresol | |
| Saucă et al. | Flame retardant phosphorous-containing polymers obtained by chemically modifying poly (vinyl alcohol) | |
| CN106009041A (en) | Novel organic boron-nitrogen flame retardant and preparation method thereof | |
| SK285553B6 (en) | Method of treatment of halogenous, organic waste material | |
| CN109593099B (en) | Preparation method of high-purity tricresyl phosphate | |
| US3169101A (en) | Purification of impure phenols by distillation with an organic solvent | |
| CN103333188B (en) | A kind of production method of borate | |
| CN106458831A (en) | Process for producing low VOC coalescing aids | |
| JP5178211B2 (en) | Method for recovering dimethyl terephthalate with improved hue from PET bottle waste | |
| JP2005154525A (en) | Method and apparatus for treating polystyrene-based resin composition | |
| CN108707164A (en) | A kind of synthetic method of phosphite ester kind antioxidant 38 | |
| Boukadir et al. | Preparation of a convenient filler for thermoplastics by pyrolysis of rubber powder recovered from tyres | |
| CN101848942A (en) | Partial solvent stripping process for recovering brominated butadiene polymers from solution | |
| US5600003A (en) | Process for isolating tetraphenylborates | |
| CN101671038A (en) | Method for comprehensively utilizing solid waste in methyl carbonate production | |
| CN107445856B (en) | Synthesis process of N-isopropyl acrylamide | |
| CN102060668B (en) | Method for preparing o-xylene-alpha, alpha'-diol | |
| CN114957007B (en) | Method for recycling 3,5 methyl ester through alcoholysis of antioxidant 1010 | |
| CN111635431A (en) | Preparation method of diphenyl phenylphosphonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A method for recovering kettle residue of tri [2,4-di tert butyl phenyl] phosphite Effective date of registration: 20211207 Granted publication date: 20160427 Pledgee: Qilu Bank Co.,Ltd. Linyi Hedong Branch Pledgor: SHANDONG LINYI SUNNY WEALTH CHEMICALS CO.,LTD. Registration number: Y2021980014214 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Granted publication date: 20160427 Pledgee: Qilu Bank Co.,Ltd. Linyi Hedong Branch Pledgor: SHANDONG LINYI SUNNY WEALTH CHEMICALS CO.,LTD. Registration number: Y2021980014214 |