CN101007758B - Crystallized mother liquor recovery process during anti-oxidant production process - Google Patents
Crystallized mother liquor recovery process during anti-oxidant production process Download PDFInfo
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- CN101007758B CN101007758B CN2006101180844A CN200610118084A CN101007758B CN 101007758 B CN101007758 B CN 101007758B CN 2006101180844 A CN2006101180844 A CN 2006101180844A CN 200610118084 A CN200610118084 A CN 200610118084A CN 101007758 B CN101007758 B CN 101007758B
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 238000011084 recovery Methods 0.000 title claims description 27
- 239000012452 mother liquor Substances 0.000 title claims description 15
- 239000003963 antioxidant agent Substances 0.000 title 1
- 230000003078 antioxidant effect Effects 0.000 title 1
- 235000006708 antioxidants Nutrition 0.000 title 1
- 239000007788 liquid Substances 0.000 claims abstract description 35
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 114
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- 238000006136 alcoholysis reaction Methods 0.000 claims description 57
- 238000004821 distillation Methods 0.000 claims description 56
- 239000010413 mother solution Substances 0.000 claims description 47
- 239000000463 material Substances 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 28
- 239000003112 inhibitor Substances 0.000 claims description 24
- 230000003647 oxidation Effects 0.000 claims description 24
- 238000007254 oxidation reaction Methods 0.000 claims description 24
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 21
- 239000012295 chemical reaction liquid Substances 0.000 claims description 20
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 16
- 238000005516 engineering process Methods 0.000 claims description 15
- 239000012074 organic phase Substances 0.000 claims description 12
- 239000012141 concentrate Substances 0.000 claims description 11
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 10
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical class [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 235000019253 formic acid Nutrition 0.000 claims description 8
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052728 basic metal Inorganic materials 0.000 claims description 7
- 150000003818 basic metals Chemical class 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 5
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 claims description 4
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical group CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical group [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 229960004249 sodium acetate Drugs 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 3
- 238000010030 laminating Methods 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 238000009833 condensation Methods 0.000 description 14
- 230000005494 condensation Effects 0.000 description 14
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 7
- 229940017219 methyl propionate Drugs 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 238000001577 simple distillation Methods 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 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 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 description 1
- 235000001018 Hibiscus sabdariffa Nutrition 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 235000005291 Rumex acetosa Nutrition 0.000 description 1
- 240000007001 Rumex acetosella Species 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 235000003513 sheep sorrel Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The invention discloses a recycling technique of crystallized mother liquid in the anti-oxidizer manufacturing course, which comprises the following steps: (1) condensing crystallized mother liquid; (2) alcoholyzing; (3) condensing the alcoholytic liquid; (4) laminating; (5) recycling propionic ester; (6) recycling triglycol.
Description
Technical field
The present invention relates to the recovery technology of crystalline mother solution in a kind of oxidation inhibitor production process, relate in particular to the recovery technology of crystalline mother solution in oxidation inhibitor 245 production processes.
Background technology
Oxidation inhibitor 245, chemical name: triglycol two [β-(3-tertiary butyl-4-hydroxy-5-methyl base phenyl) propionic ester], be to carry out transesterification reaction by β-(3-tertiary butyl-4-hydroxy-5-methyl base phenyl) methyl propionate (or ethyl ester) and triglycol, purify through solvent crystallization then, again through centrifugal (or filtration), dry and get.Used recrystallisation solvent generally is the aqueous solution of lower alcohols, as methyl alcohol, ethanol, Virahol etc.In the crystallization and purification process, most of oxidation inhibitor 245 crystallizations are separated out, but also having considerable a part of oxidation inhibitor 245 still to stay in the solution not crystallization separates out, also comprise unreacted β-(3-tertiary butyl-4-hydroxy-5-methyl base phenyl) methyl propionate (or ethyl ester) and catalyzer completely in the solution, and raw material brings and reacts other impurity of generation into, and this solution is commonly referred to crystalline mother solution.Crystalline mother solution is reclaimed, and the height that not only can reduce cost has reduced environmental pollution simultaneously.
CN91111429.7, CN94118738.1 have reported the mother liquid recovery process of antioxidant 1010.Because the triglycol character that tetramethylolmethane that the antioxidant 1010 alcoholysis generates and oxidation inhibitor 245 alcoholysis generate differs greatly, tetramethylolmethane is crystallizable separates out, by other component separating in modes such as filtration and the alcoholysis liquid, but triglycol is miscible in other composition in the alcoholysis liquid, reclaims so the method that the antioxidant 1010 mother liquor reclaims not exclusively is applicable to oxidation inhibitor 245 mother liquors.Do not see reported in literature at the technology that oxidation inhibitor 245 mother liquors reclaim.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of for the defective that overcomes above-mentioned prior art existence to reduce cost the recovery technology of crystalline mother solution in the oxidation inhibitor production process of protection environment.
Purpose of the present invention can be achieved through the following technical solutions:
The recovery technology of crystalline mother solution is characterized in that in a kind of oxidation inhibitor production process, and this technology may further comprise the steps:
(1) concentrating of crystalline mother solution: the crystalline mother solution in two [β-(3-tertiary butyl-4-hydroxy-5-methyl base phenyl) propionic ester] production processes of oxidation inhibitor triglycol carry out air distillation to 100 earlier～130 ℃, with the most solvent recuperation in the crystalline mother solution, again 100～130 ℃ of following underpressure distillation to pressure 1.013 * 10
-2～1.013 * 10
-3MPa purifies the solvent in the crystalline mother solution, obtains the crystalline mother solution enriched material;
(2) alcoholysis reaction: with the methyl alcohol of the crystalline mother solution enriched material in the step (1) and 0.8～1.5 times of weight, in the presence of catalyzer, closed reactor carried out alcoholysis reaction 5～20 hours in 130～150 ℃, with acid catalyzer is neutralized then, obtain alcoholysis reaction liquid;
(3) concentrate alcoholysis liquid: alcoholysis reaction liquid carry out air distillation to 90 earlier～120 ℃ reclaim methyl alcohol, again 100～130 ℃ of following underpressure distillation to pressure 1.013 * 10
-2～1.013 * 10
-3Mpa purifies methyl alcohol, obtains to concentrate alcoholysis liquid;
(4) layering: add the organic solvent of concentrated alcoholysis liquid weight 20～50% and the water of concentrated alcoholysis liquid weight 10～50%, stir in 80～100 ℃ and washed 0.5～1 hour, standing demix is organic phase and water two portions with feed separation then;
(5) recovery of propionic ester: with the elder generation of the organic phase in the step (4) air distillation to 100～130 ℃ of recovery solvents, underpressure distillation purifies solvent and water again, carry out underpressure distillation or rectifying then and reclaim β-(3-tertiary butyl-4-hydroxy-5-methyl base phenyl) propionic ester, the tower top pressure of rectification under vacuum is 1～5mmHg, 180～220 ℃ of tower still temperature;
(6) recovery of triglycol: the water in the step (4) distilled under normal pressure earlier to 120～140 ℃ remove moisture, triglycol is reclaimed in underpressure distillation or rectifying again.
The terminal temperature of air distillation is 110～130 ℃ in the described step (1), and the temperature of underpressure distillation is 110～130 ℃.
The middle methyl alcohol add-on of described step (2) is 0.9～1.1 times of mother liquor enriched material weight, and the alcoholysis reaction temperature is 130～140 ℃, and the time is 8～16 hours.
Used catalyzer comprises organic tin in the described step (2), alkaline metal salt, the metal-alcoholates class of basic metal and lower alcohol, Lithamide; Catalyst levels is generally 0.5～2% of mother liquor enriched material weight.
Described organic tin catalyzer comprises dibutyltin oxide, the chlorination Monobutyltin; The metal-alcoholates class catalyzer of described basic metal and lower alcohol comprises sodium methylate, sodium ethylate, potassium ethylate, sodium tert-butoxide, potassium tert.-butoxide; Described Lithamide catalyzer comprises Lithamide; The alcoholysis reaction liquid that adopts above-mentioned a few class catalyzer to obtain need cool to 60～70 ℃ add in formic acid or the acetate and after just can enter step (3) and steam methyl alcohol, the add-on of formic acid or acetate is 1～3 times of molar weight of catalyst system therefor mole number.
Described alkaline metal salt catalyzer comprises lithium formate, Lithium Acetate, sodium formiate, sodium-acetate; Can directly enter step (3) behind the alcoholysis reaction liquid that adopts this class catalyzer to obtain and steam methyl alcohol.
The terminal temperature of air distillation is 100～120 ℃ in the described step (3), and the temperature of underpressure distillation is 120～130 ℃.
Concentrate used organic solvent in the alcoholysis liquid water washing process in the described step (4), be meant that boiling spread at 80～120 ℃ alkane or aromatic hydrocarbons, comprises heptane, hexanaphthene, toluene, dimethylbenzene.
The add-on of organic solvent is for concentrating 20～50% of alcoholysis reaction liquid weight in the described step (4), and the add-on of water is for concentrating 10～50% of alcoholysis reaction liquid weight.
The temperature of simple distillation is 100～120 ℃ in the described step (6).
Compared with prior art, the present invention not only can reclaim raw material and reduce cost by the crystalline mother solution in the oxidation inhibitor production process is reclaimed, and has reduced waste discharge simultaneously, helps environment protection.
Embodiment
Embodiment 1
The 4000g crystalline mother solution is added the 2000mL there-necked flask that (branch is adding several times) is equipped with whipping appts, thermometer and had the condensation receiving trap of vacuum suction interface, earlier under normal pressure, steam solvent, outlet temperature is controlled at 120 ℃, after treating not have the phlegma of distillating substantially, the connection vacuum system reduces pressure and purifies solvent, 130 ℃ of outlet temperatures, resulting pressure 2.0 * 10
-3MPa.Obtain mother liquor enriched material 528.3g.The mother liquor enriched material is the sorrel thick liquid, and through liquid-phase chromatographic analysis, composition is:
The 6-tertiary butyl-2-methylphenol 6.14%
β-(3-tertiary butyl-4-hydroxy-5-methyl base phenyl) methyl propionate 25.89%
Impurity 1 0.09%
Two [β-(3-tertiary butyl-4-hydroxy-5-methyl base phenyl) propionic ester] 65.31% of triglycol
Impurity 2 1.50%
Impurity 3 1.06%
Embodiment 2
In the 0.5L autoclave pressure, drop into the mother liquor enriched material 126.3g that embodiment 1 obtains, methyl alcohol 128g, dibutyltin oxide 0.6g, cover kettle cover completely, be warming up to 140 ℃ of timing, 140 ℃ of reactions 8 hours, after being cooled to below 70 ℃, add glacial acetic acid 1mL, stir 15 fens kinds from the autoclave pressure charging opening.
Material is changed in the 500mL there-necked flask, then there-necked flask is loaded onto whipping appts, thermometer and had the condensation receiving trap of vacuum suction interface, stirring intensification is earlier carried out normal pressure and is steamed methyl alcohol, after equitemperature reaches 110 ℃, connect the vacuum system separating methanol that reduces pressure, 120 ℃ of outlet temperatures, resulting pressure 1.013 * 10
-2MPa.After material cooled to 80 ℃, unload the condensation receiving trap, in there-necked flask, add heptane 30g, distilled water 25mL, stirring is warmed up to 80 ℃ of timing, and between 80～90 ℃, continue to stir 0.5 hour, stop to stir standing demix 15 minutes, use the water of suction pipe sucking-off there-necked flask bottom then, water is collected standby with special-purpose bottle.After the bottom water exhaustion, reinstall the condensation receiving trap that has the vacuum suction interface, stirring intensification is earlier carried out normal pressure and is steamed heptane and water, after equitemperature reaches 110 ℃, connecting vacuum system reduces pressure and removes heptane and water, 120 ℃ of outlet temperatures, resulting pressure 1.013 * 10
-2MPa.After temperature reaches 120 ℃, change the receiving bottle that fills heptane and water, change new receiving bottle, continue to heat up and steam, collect the overhead product between the 2～3mmHg, 155～165 ℃, obtain faint yellow transparent thick liquid 109.9g, use liquid-phase chromatographic analysis β-(3-tertiary butyl-4-hydroxy-5-methyl base phenyl) methyl propionate content more than 97%.
Embodiment 3
In the 0.5L autoclave pressure, drop into the mother liquor enriched material 120.3g that embodiment 1 obtains, methyl alcohol 121g, lithium acetate 0.6g covers kettle cover completely, is warming up to 140 ℃ of timing, 140 ℃ of reactions 8 hours, be cooled to below 70 ℃ after.
Material is changed in the 500mL there-necked flask, then there-necked flask is loaded onto whipping appts, thermometer and had the condensation receiving trap of vacuum suction interface, stirring intensification is earlier carried out normal pressure and is steamed methyl alcohol, after equitemperature reaches 110 ℃, connect the vacuum system separating methanol that reduces pressure, 120 ℃ of outlet temperatures, resulting pressure 1.013 * 10
-2MPa.After material cooled to 80 ℃, unload the condensation receiving trap, in there-necked flask, add hexanaphthene 30g, distilled water 25mL, stirring is warmed up to 80 ℃ of timing, and between 80～90 ℃, continue to stir 0.5 hour, stop to stir standing demix 15 minutes, use the water of suction pipe sucking-off there-necked flask bottom then, water is collected standby with special-purpose bottle.After the bottom water exhaustion, reinstall the condensation receiving trap that has the vacuum suction interface, stirring intensification is earlier carried out normal pressure and is steamed hexanaphthene and water, after equitemperature reaches 110 ℃, connecting vacuum system reduces pressure and removes hexanaphthene and water, 120 ℃ of outlet temperatures, resulting pressure 1.013 * 10
-2MPa.After temperature reaches 120 ℃, change the receiving bottle that fills hexanaphthene and water, change new receiving bottle, continue to heat up and steam, collect the overhead product between the 2～3mmHg, 155～165 ℃, obtain faint yellow transparent thick liquid 103.5g, use liquid-phase chromatographic analysis β-(3-tertiary butyl-4-hydroxy-5-methyl base phenyl) methyl propionate content more than 97%.
Embodiment 4
In the 0.5L autoclave pressure, drop into the mother liquor enriched material 131.8g that embodiment 1 obtains, methyl alcohol 128g, Lithamide 0.65g, cover kettle cover completely, be warming up to 140 ℃ of timing, 140 ℃ of reactions 8 hours, after being cooled to below 70 ℃, add glacial acetic acid 1mL, stir 15 fens kinds from the autoclave pressure charging opening.
Material is changed in the 500mL there-necked flask, then there-necked flask is loaded onto whipping appts, thermometer and had the condensation receiving trap of vacuum suction interface, stirring intensification is earlier carried out normal pressure and is steamed methyl alcohol, after equitemperature reaches 110 ℃, connect the vacuum system separating methanol that reduces pressure, 120 ℃ of outlet temperatures, resulting pressure 1.013 * 10
-2MPa.After material cooled to 80 ℃, unload the condensation receiving trap, in there-necked flask, add toluene 35g, distilled water 25mL, stirring is warmed up to 80 ℃ of timing, and between 80～90 ℃, continue to stir 0.5 hour, stop to stir standing demix 15 minutes, use the water of suction pipe sucking-off there-necked flask bottom then, water is collected standby with special-purpose bottle.After the bottom water exhaustion, reinstall the condensation receiving trap that has the vacuum suction interface, stirring intensification is earlier carried out normal pressure and is steamed toluene and water, after equitemperature reaches 110 ℃, connecting vacuum system reduces pressure and removes toluene and water, 120 ℃ of outlet temperatures, resulting pressure 1.013 * 10
-2MPa.After temperature reaches 120 ℃, change the receiving bottle that fills toluene and water, change new receiving bottle, continue to heat up and steam, collect the overhead product between the 2～3mmHg, 155～165 ℃, obtain faint yellow transparent thick liquid 118.6g, use liquid-phase chromatographic analysis β-(3-tertiary butyl-4-hydroxy-5-methyl base phenyl) methyl propionate content more than 97%.
Embodiment 5
In the 0.5L autoclave pressure, drop into the mother liquor enriched material 149.9g that embodiment 1 obtains, methyl alcohol 150g, sodium methylate 0.75g, cover kettle cover completely, be warming up to 140 ℃ of timing, 140 ℃ of reactions 8 hours, after being cooled to below 70 ℃, add glacial acetic acid 1mL, stir 15 fens kinds from the autoclave pressure charging opening.
Material is changed in the 500mL there-necked flask, then there-necked flask is loaded onto whipping appts, thermometer and had the condensation receiving trap of vacuum suction interface, stirring intensification is earlier carried out normal pressure and is steamed methyl alcohol, after equitemperature reaches 110 ℃, connect the vacuum system separating methanol that reduces pressure, 120 ℃ of outlet temperatures, resulting pressure 1.013 * 10
-2MPa.After material cooled to 80 ℃, unload the condensation receiving trap, in there-necked flask, add heptane 30g, distilled water 30mL, stirring is warmed up to 80 ℃ of timing, and between 80～90 ℃, continue to stir 0.5 hour, stop to stir standing demix 15 minutes, use the water of suction pipe sucking-off there-necked flask bottom then, water is collected standby with special-purpose bottle.After the bottom water exhaustion, reinstall the condensation receiving trap that has the vacuum suction interface, stirring intensification is earlier carried out normal pressure and is steamed heptane and water, after equitemperature reaches 110 ℃, connecting vacuum system reduces pressure and removes heptane and water, 120 ℃ of outlet temperatures, resulting pressure 1.013 * 10
-2MPa.After temperature reaches 120 ℃, change the receiving bottle that fills heptane and water, change new receiving bottle, continue to heat up and steam, collect the overhead product between the 2～3mmHg, 155～165 ℃, obtain faint yellow transparent thick liquid 131.8g, use liquid-phase chromatographic analysis β-(3-tertiary butyl-4-hydroxy-5-methyl base phenyl) methyl propionate content more than 97%.
Embodiment 6
The water that standing demix among the embodiment 2～5 is collected, whipping appts, thermometer are being housed and are having in the 250mL there-necked flask of condensation receiving trap of vacuum suction interface, earlier under normal pressure, steam water, after equitemperature reaches 110 ℃, connecting vacuum system reduces pressure and removes water, 120 ℃ of outlet temperatures, resulting pressure 1.013 * 10
-2MPa.After temperature reaches 120 ℃, change the receiving bottle that fills water, change new receiving bottle, continue heating up steams, and collects the overhead product between the 12～15mmHg, 150～160 ℃, obtains colourless transparent liquid 71.2g, with liquid-phase chromatographic analysis triglycol content more than 98%.
Embodiment 7
Crystalline mother solution in two [β-(3-tertiary butyl-4-hydroxy-5-methyl base phenyl) propionic ester] production processes of oxidation inhibitor triglycol is carried out air distillation to 100 ℃ earlier, with the most solvent recuperation in the crystalline mother solution, underpressure distillation to 130 ℃ again, pressure 1.013 * 10
-2MPa purifies the solvent in the crystalline mother solution, obtains the crystalline mother solution enriched material; Again with the methyl alcohol of this crystalline mother solution enriched material and 0.8 times of weight, in the presence of catalyzer, closed reactor carried out alcoholysis reaction 5 hours in 130 ℃, then with acid with the catalyzer neutralization, obtain alcoholysis reaction liquid; This alcoholysis reaction liquid is carried out air distillation to 90 ℃ recovery methyl alcohol earlier, again at 100 ℃, 1.013 * 10
-2Underpressure distillation purifies methyl alcohol under the Mpa, obtains to concentrate alcoholysis liquid; Add the organic solvent of concentrated alcoholysis liquid weight 20% and the water of concentrated alcoholysis liquid weight 10%, stir in 80 ℃ and washed 0.5 hour, standing demix is organic phase and water two portions with feed separation then; Again with organic phase elder generation air distillation to 100 ℃ recovery solvent, underpressure distillation purifies solvent and water again, carry out underpressure distillation or rectifying then and reclaim β-(3-tertiary butyl-4-hydroxy-5-methyl base phenyl) propionic ester, the tower top pressure of rectification under vacuum is 1mmHg, 180 ℃ of tower still temperature; Water earlier under 100 ℃, 1.013MPa condition simple distillation remove moisture, triglycol is reclaimed in underpressure distillation or rectifying again.
Catalyst system therefor comprises organic tin, as dibutyltin oxide, and the chlorination Monobutyltin; The metal-alcoholates class of basic metal and lower alcohol is as sodium methylate, sodium ethylate, potassium ethylate, sodium tert-butoxide, potassium tert.-butoxide etc.; Lithamide; The alcoholysis reaction liquid that adopts above-mentioned a few class catalyzer to obtain need cool to 60～70 ℃ add in formic acid or the acetate and after just can enter step (3) and steam methyl alcohol, the add-on of formic acid or acetate is 1～3 times of molar weight of catalyst system therefor mole number, present embodiment selects for use sodium ethylate as catalyzer, consumption is 2% of a mother liquor enriched material weight, alcoholysis reaction liquid cools to 60 ℃ and adds the formic acid neutralization, and the add-on of formic acid is 1 times of molar weight of catalyst system therefor mole number.
Embodiment 8
Crystalline mother solution in two [β-(3-tertiary butyl-4-hydroxy-5-methyl base phenyl) propionic ester] production processes of oxidation inhibitor triglycol is carried out air distillation to 130 ℃ earlier, with the most solvent recuperation in the crystalline mother solution, underpressure distillation to 100 ℃ again, pressure 1.013 * 10
-3MPa purifies the solvent in the crystalline mother solution, obtains the crystalline mother solution enriched material; With the methyl alcohol of this crystalline mother solution enriched material and 1.5 times of weight, in the presence of catalyzer, closed reactor carried out alcoholysis reaction 20 hours in 150 ℃, then with acid with the catalyzer neutralization, obtain alcoholysis reaction liquid; Alcoholysis reaction liquid is carried out air distillation to 120 ℃ recovery methyl alcohol earlier, again at 130 ℃, 1.013 * 10
-3Underpressure distillation purifies methyl alcohol under the Mpa, obtains to concentrate alcoholysis liquid; Add the organic solvent of concentrated alcoholysis liquid weight 50% and the water of concentrated alcoholysis liquid weight 50% again, stir in 100 ℃ and washed 1 hour, standing demix is organic phase and water two portions with feed separation then; With organic phase elder generation air distillation to 130 ℃ recovery solvent, underpressure distillation purifies solvent and water again, carry out underpressure distillation or rectifying then and reclaim β-(3-tertiary butyl-4-hydroxy-5-methyl base phenyl) propionic ester, the tower top pressure of rectification under vacuum is 5mmHg, 220 ℃ of tower still temperature; Water is earlier at 140 ℃, 1.013 * 10
-2Simple distillation removes moisture under the MPa condition, and triglycol is reclaimed in underpressure distillation or rectifying again.
Used catalyzer comprises organic tin, alkaline metal salt, the metal-alcoholates class of basic metal and lower alcohol, Lithamide; Catalyst levels is generally 0.5～2% of mother liquor enriched material weight, selects Lithamide in the present embodiment for use, and consumption is 0.5% of a mother liquor enriched material weight.
Embodiment 9
Crystalline mother solution in two [β-(3-tertiary butyl-4-hydroxy-5-methyl base phenyl) propionic ester] production processes of oxidation inhibitor triglycol is carried out air distillation to 110 ℃ earlier, with the most solvent recuperation in the crystalline mother solution, underpressure distillation to 110 ℃ again, pressure 1.013 * 10
-2MPa purifies the solvent in the crystalline mother solution, obtains the crystalline mother solution enriched material; With the methyl alcohol of this crystalline mother solution enriched material and 0.9 times of weight, in the presence of catalyzer, closed reactor carried out alcoholysis reaction 8 hours in 140 ℃, then with acid with the catalyzer neutralization, obtain alcoholysis reaction liquid; Alcoholysis reaction liquid is carried out air distillation to 100 ℃ recovery methyl alcohol earlier, again at 120 ℃, 1.013 * 10
-3Underpressure distillation purifies methyl alcohol under the Mpa, obtains to concentrate alcoholysis liquid; Add the organic solvent of concentrated alcoholysis liquid weight 30% and the water of concentrated alcoholysis liquid weight 20%, stir washing 0.5 hour in 80 ℃, standing demix then, with feed separation is organic phase and water two portions, organic phase elder generation air distillation to 100 ℃ recovery solvent, underpressure distillation purifies solvent and water again, carries out underpressure distillation or rectifying then and reclaims β-(3-tertiary butyl-4-hydroxy-5-methyl base phenyl) propionic ester, the tower top pressure of rectification under vacuum is 1mmHg, 180 ℃ of tower still temperature; Water earlier under 100 ℃, 1.013MPa condition simple distillation remove moisture, triglycol is reclaimed in underpressure distillation or rectifying again.
Concentrate used organic solvent in the alcoholysis liquid water washing process, be meant that boiling spread at 80～120 ℃ alkane or aromatic hydrocarbons, as heptane, hexanaphthene, toluene, dimethylbenzene etc., selects hexanaphthene for use in the present embodiment.
Embodiment 10
Crystalline mother solution in two [β-(3-tertiary butyl-4-hydroxy-5-methyl base phenyl) propionic ester] production processes of oxidation inhibitor triglycol is carried out air distillation to 130 ℃ earlier, with the most solvent recuperation in the crystalline mother solution, underpressure distillation to 130 ℃ again, pressure 1.013 * 10
-3MPa purifies the solvent in the crystalline mother solution, obtains the crystalline mother solution enriched material, the methyl alcohol of this crystalline mother solution enriched material and 1.1 times of weight, in the presence of catalyzer, closed reactor carried out alcoholysis reaction 16 hours in 140 ℃, with acid catalyzer is neutralized then, obtain alcoholysis reaction liquid; Alcoholysis reaction liquid is carried out air distillation to 120 ℃ recovery methyl alcohol earlier, again at 130 ℃, 1.013 * 10
-3Underpressure distillation purifies methyl alcohol under the Mpa, obtains to concentrate alcoholysis liquid; Add the organic solvent of concentrated alcoholysis liquid weight 40% and the water of concentrated alcoholysis liquid weight 40%, stir in 100 ℃ and washed 1 hour, standing demix is organic phase and water two portions with feed separation then; Organic phase elder generation air distillation to 130 ℃ recovery solvent, underpressure distillation purifies solvent and water again, carry out underpressure distillation or rectifying then and reclaim β-(3-tertiary butyl-4-hydroxy-5-methyl base phenyl) propionic ester, the tower top pressure of rectification under vacuum is 5mmHg, 220 ℃ of tower still temperature; Water is earlier at 120 ℃, 1.013 * 10
-2Simple distillation removes moisture under the MPa condition, and triglycol is reclaimed in underpressure distillation or rectifying again.
Claims (6)
1. the recovery technology of crystalline mother solution in the oxidation inhibitor production process is characterized in that this technology may further comprise the steps:
(1) concentrating of crystalline mother solution: the crystalline mother solution in two [β-(3-tertiary butyl-4-hydroxy-5-methyl base phenyl) propionic ester] production processes of oxidation inhibitor triglycol carry out air distillation to 100 earlier～130 ℃, with the most solvent recuperation in the crystalline mother solution, again 100～130 ℃ of following underpressure distillation to pressure 1.013 * 10
-2～1.013 * 10
-3MPa purifies the solvent in the crystalline mother solution, obtains the crystalline mother solution enriched material;
(2) alcoholysis reaction: with the methyl alcohol of the crystalline mother solution enriched material in the step (1) and 0.8～1.5 times of weight, in the presence of catalyzer, closed reactor carried out alcoholysis reaction 5～20 hours in 130～150 ℃, with acid catalyzer is neutralized then, obtain alcoholysis reaction liquid;
(3) concentrate alcoholysis liquid: alcoholysis reaction liquid carry out air distillation to 90 earlier～120 ℃ reclaim methyl alcohol, again 100～130 ℃ of following underpressure distillation to pressure 1.013 * 10
-2～1.013 * 10
-3Mpa purifies methyl alcohol, obtains to concentrate alcoholysis liquid;
(4) layering: add the organic solvent of concentrated alcoholysis liquid weight 20～50% and the water of concentrated alcoholysis liquid weight 10～50%, stir in 80～100 ℃ and washed 0.5～1 hour, standing demix is organic phase and water two portions with feed separation then;
(5) recovery of propionic ester: with the elder generation of the organic phase in the step (4) air distillation to 100～130 ℃ of recovery solvents, underpressure distillation purifies solvent and water again, carry out underpressure distillation or rectifying then and reclaim β-(3-tertiary butyl-4-hydroxy-5-methyl base phenyl) propionic ester, the tower top pressure of rectification under vacuum is 1～5mmHg, 180～220 ℃ of tower still temperature;
(6) recovery of triglycol: the water in the step (4) distilled under normal pressure earlier to 120～140 ℃ remove moisture, triglycol is reclaimed in underpressure distillation or rectifying again;
Used catalyzer is an organic tin in the described step (2), alkaline metal salt, the metal-alcoholates class of Lithamide or basic metal and lower alcohol, wherein, the metal-alcoholates class catalyzer of described basic metal and lower alcohol is sodium methylate, sodium ethylate, potassium ethylate, sodium tert-butoxide or potassium tert.-butoxide; Catalyst levels is 0.5～2% of a mother liquor enriched material weight;
Concentrate used organic solvent in the alcoholysis liquid water washing process in the described step (4), be meant that boiling spread is at 80～120 ℃ heptane, hexanaphthene or toluene.
2. the recovery technology of crystalline mother solution is characterized in that in a kind of oxidation inhibitor production process according to claim 1, and the terminal temperature of air distillation is 110～130 ℃ in the described step (1), and the temperature of underpressure distillation is 110～130 ℃.
3. the recovery technology of crystalline mother solution in a kind of oxidation inhibitor production process according to claim 1, it is characterized in that, the middle methyl alcohol add-on of described step (2) is 0.9～1.1 times of mother liquor enriched material weight, and the alcoholysis reaction temperature is 130～140 ℃, and the time is 8～16 hours.
4. the recovery technology of crystalline mother solution is characterized in that in a kind of oxidation inhibitor production process according to claim 1, and described organic tin catalyzer is dibutyltin oxide or chlorination Monobutyltin; The metal-alcoholates class catalyzer of described basic metal and lower alcohol is sodium methylate, sodium ethylate, potassium ethylate, sodium tert-butoxide or potassium tert.-butoxide; Described Lithamide catalyzer is a Lithamide; The alcoholysis reaction liquid that adopts above-mentioned a few class catalyzer to obtain need cool to 60～70 ℃ add in formic acid or the acetate and after just can enter step (3) and steam methyl alcohol, the add-on of formic acid or acetate is 1～3 times of molar weight of catalyst system therefor mole number.
5. the recovery technology of crystalline mother solution is characterized in that in a kind of oxidation inhibitor production process according to claim 1, and described alkaline metal salt catalyzer is lithium formate, Lithium Acetate, sodium formiate or sodium-acetate; Can directly enter step (3) behind the alcoholysis reaction liquid that adopts this class catalyzer to obtain and steam methyl alcohol.
6. the recovery technology of crystalline mother solution is characterized in that in a kind of oxidation inhibitor production process according to claim 1, and the terminal temperature of air distillation is 100～120 ℃ in the described step (3), and the temperature of underpressure distillation is 120～130 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073163A (en) * | 1991-12-09 | 1993-06-16 | 北京化工三厂 | The recovery and treatment method of antioxygen industrial waste liquid |
| CN1053884C (en) * | 1994-12-01 | 2000-06-28 | 中国石油化工总公司 | Process for recovery of crystal mother liquor during the prodn. process of anti-oxidant |
| CN1465559A (en) * | 2002-06-28 | 2004-01-07 | 中国石油天然气股份有限公司 | Recovery and utilization for waste triglycol |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073163A (en) * | 1991-12-09 | 1993-06-16 | 北京化工三厂 | The recovery and treatment method of antioxygen industrial waste liquid |
| CN1053884C (en) * | 1994-12-01 | 2000-06-28 | 中国石油化工总公司 | Process for recovery of crystal mother liquor during the prodn. process of anti-oxidant |
| CN1465559A (en) * | 2002-06-28 | 2004-01-07 | 中国石油天然气股份有限公司 | Recovery and utilization for waste triglycol |
Non-Patent Citations (2)
| Title |
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| 宣晓君.季戊四醇母液回收.化工生产与技术 3.2001,(3),全文. |
| 宣晓君.季戊四醇母液回收.化工生产与技术 3.2001,(3),全文. * |
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