CN1170709A - Method for recovering useful substances from saponified waste alkali liquor - Google Patents
Method for recovering useful substances from saponified waste alkali liquor Download PDFInfo
- Publication number
- CN1170709A CN1170709A CN 96118264 CN96118264A CN1170709A CN 1170709 A CN1170709 A CN 1170709A CN 96118264 CN96118264 CN 96118264 CN 96118264 A CN96118264 A CN 96118264A CN 1170709 A CN1170709 A CN 1170709A
- Authority
- CN
- China
- Prior art keywords
- acid
- waste lye
- saponification waste
- alcohol
- reclaim
- 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
- 239000002699 waste material Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000003513 alkali Substances 0.000 title description 3
- 239000000126 substance Substances 0.000 title description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 12
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims abstract description 9
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 6
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 4
- 238000010992 reflux Methods 0.000 claims abstract description 3
- 238000007127 saponification reaction Methods 0.000 claims description 24
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical group CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 20
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 8
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 5
- 230000032050 esterification Effects 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 229940005605 valeric acid Drugs 0.000 claims description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical group CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical group OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000605 extraction Methods 0.000 abstract description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 abstract description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 abstract 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract 1
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract 1
- 239000011707 mineral Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000001119 stannous chloride Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910001868 water Inorganic materials 0.000 description 10
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229940056729 sodium sulfate anhydrous Drugs 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 150000007520 diprotic acids Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- -1 layering Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229940001516 sodium nitrate Drugs 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for treating and recovering saponified waste lye produced in the process of preparing cyclohexanone by oxidizing cyclohexane, which is characterized by that it uses mineral acid of sulfuric acid or hydrochloric acid or nitric acid, etc. to neutralize saponified waste lye, then uses light oil, etc. to make extraction, and under the conditions of a certain vacuum degree, temp. and reflux ratio the n-butyric acid and n-caproic acid can be recovered, and the recovered dicarboxylic acid can be esterified by alcohol in the presence of stannous chloride to obtain AGS acid ester.
Description
The present invention relates to a kind of processing method that from saponification waste lye, reclaims useful matter.
The manufacturing of hexanolactam generally all will be passed through the intermediate product pimelinketone, and pimelinketone is made through liquid phase air oxidation by hexanaphthene, in this process, the high order deep oxidation by product based on phosphoric acid that produces does not have effective treating method, just with after alkali neutralization, the saponification as alkaline neutralizer, be saponification waste lye, the discharge system discards.
For the discharging that prevents above-mentioned saponification waste lye pollutes environment, simultaneously in order from this saponification waste lye, to extract useful matter, effectively utilize resource, many research reports are arranged both at home and abroad, have plenty of it is handled with incinerating method; The simple method of the usefulness that has reclaims some component wherein etc.
At present, great majority are to adopt burning method to handle above-mentioned saponification waste lye both at home and abroad, though burn favourable to eliminating its pollution to environment.But, burnt considerable resource, introduce 50,000 tons of caprolactam production apparatus with regard to yueyang, hunan hawk mountain petroleum chemical plant and just need 6750 tons of heavy oil for burning 30000 tons of saponification waste lyes every year, 1800 tons of X oil, 30-40 ton liquefied petroleum gas (LPG) is made fuel, not only burnt these fuel, but also burnt about 220 tons of butanic acid, 1540 tons of positive valeric acids, 440 tons of n-caproic acid in 30000 tons of saponification waste lyes, 10000 tons of Sodium sulfate anhydrous.min(99) etc.
In order to effectively utilize above-mentioned resource, and alleviate its pollution to environment, Ube hexanolactam factory has developed a kind of recovery method: at first use in the sulfuric acid saponification deg alkali lye and generation saltcake water and tar, again saltcake water is extracted with lightweight oil and obtain di-carboxylic acid and saltcake solution, then with the di-carboxylic acid recrystallization, reclaim hexanodioic acid, remaining di-carboxylic acid carries out hydrogenation, generates pentanediol and hexylene glycol.Saltcake is reclaimed in the saltcake solution crystallization.
Purpose of the present invention is handled saponification waste lye without burning method, but handles the resource that reclaims in the saponification waste lye with methods such as neutralization, extractions.Turn waste into wealth.
The present invention be achieved in that 1. at first with saponification waste lye with in sulfuric acid or hydrochloric acid or the nitric acid and generate saponified oil and saltcake water or sodium hydride or SODIUMNITRATE and di-carboxylic acid; 2. be 20-40mmhg with above-mentioned saponified oil in vacuum tightness, temperature is 60-140 ℃, distills out butyric acid; In the time of 90-165 ℃, distill out Pentyl alcohol, in the time of 120-190 ℃, distill out n-caproic acid, its reflux ratio is 1: 1-1: 4. saltcake water with lightweight oil and fractionation component, X oil and fractionation component, alkane, alcohol, ketone, acid, ester and derivative and general polar organic solvent as: organic chlorides etc. (form and content: hexanaphthene 3% by lightweight oil, pimelinketone 12%, primary isoamyl alcohol 5%, amylalcohol 30%, epoxy cyclohexane 30%) extract the recovery di-carboxylic acid as extraction agent; 4. di-carboxylic acid carries out esterification with alcohols (as: secondary octanol, 2-Ethylhexyl Alcohol) in the presence of catalyzer such as tin protochloride or sulfuric acid, obtains AGS acid fat (cold resistant plasticizer).
The present invention handles saponification waste lye without burning method, every year, only the fuel economy spending just reached several ten million yuan of coin, moreover, useful matter in its saponification waste lye is reclaimed with the inventive method, from 30000 tons of saponification waste lyes, just can reclaim 220 tons of butanic acids, 1540 tons of positive valeric acids, 440 tons of n-caproic acid.10000 tons of Sodium sulfate anhydrous.min(99) etc. have so not only prevented saponification waste lye to the pollution of environment but also turn waste into wealth, and are that country and enterprise wound is imitated and gained.
Embodiment 1
In the 500ml graduated cylinder, add 200ml saponification waste lye (solid substance 40%), add 40%H
2SO
480ml, layering in 2 minutes obtains oil phase 60ml, 64 grams of weighing, water 220ml, water extracts three times with the 1000ml lightweight oil, layering, oil reservoir reclaims extraction agent with distillation method, must mix di-carboxylic acid 16 grams.Mix di-carboxylic acid and add the secondary octanol of 30 grams under tin protochloride or sulfuric acid catalysis effect, generate AGS acid fat 24 grams, and reclaim secondary octanol.
N
A2SO
4The aqueous solution carries out recrystallization, gets N
A2SO
4Crystal 40 gram, surplus solution is used for diluting 98%H
2SO
4
In and saponification liquor oil phase (saponified oil) 60ml, pour in the 150ml matrass and to add the 20cm fractional column and carry out fractionation and reclaim 98% butanic acid, 3.1 grams at 163-166 ℃, in the time of 184-186 ℃, reclaim positive valeric acid 12 grams, in the time of 203-206 ℃, reclaim n-caproic acid 6 grams, mixing acid 15 grams.
Example 2
Add 200ml saponification waste lye (solid content 35-40%) at the 500ml graduated cylinder, add 30%HCL120ml, layering in 2 minutes obtains oil phase 55ml, 58 grams of weighing, water 225ml.Water extracts 5 times with the 1000ml hexalin.Oil reservoir reclaims extraction agent with distillation method, gets mixed dibasic acid 16 grams.Mix di-carboxylic acid 30 grams, secondary octanol generates AGS acid fat 24 grams and reclaims secondary octanol under solid catalyst such as tin protochloride or effect of sulfuric acid.As follows embodiment 1.
Example 3
Add 200ml saponification waste lye (Gu shape 35-40%) and add 30% nitric acid 100ml in the 500ml graduated cylinder, layering after 2 minutes obtains 60ml, 64 grams of weighing, water 240ml.Water extracts five times with the secondary octanol of 1000ml, layering, oil reservoir reclaim secondary octanol with distillation method and stay a part of secondary octanol, make alcohol: diprotic acid 2: 1, solid catalyst as: generate AGS acid fat 23 grams under tin protochloride or the sulfation catalyst action, and reclaim secondary octanol.As follows embodiment 1.
Claims (3)
1. method that from saponification waste lye, reclaims useful matter, saponification waste lye is extracted recovery hexanodioic acid and saltcake with the sulfuric acid neutralization and with corrective, it is characterized in that, to carry out rectifying with the saponified oil that obtains with saponification waste lye in sulfuric acid or hydrochloric acid or the nitric acid and reclaim butanic acid, positive valeric acid, n-caproic acid, and the di-carboxylic acid in the saponified oil be carried out esterification with alcohol make AGS acid fat in the presence of catalyzer such as tin protochloride or sulfuric acid.
2. method according to claim 1 is characterized in that, to reclaim the vacuum tightness of butanic acid, positive valeric acid, n-caproic acid be 20-40mmhg in rectifying from saponified oil, and temperature is respectively 60-140 ℃, 90-165 ℃, 120-190 ℃, and reflux ratio is 1: 1-1: 4.
3. method according to claim 1 is characterized in that, the used alcohol of esterification can be alcohols such as secondary octanol, 2-Ethylhexyl Alcohol, hexalin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96118264A CN1060758C (en) | 1996-07-15 | 1996-07-15 | Method for recovering useful substances from saponified waste alkali liquor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96118264A CN1060758C (en) | 1996-07-15 | 1996-07-15 | Method for recovering useful substances from saponified waste alkali liquor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1170709A true CN1170709A (en) | 1998-01-21 |
| CN1060758C CN1060758C (en) | 2001-01-17 |
Family
ID=5124939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96118264A Expired - Fee Related CN1060758C (en) | 1996-07-15 | 1996-07-15 | Method for recovering useful substances from saponified waste alkali liquor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1060758C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1125863C (en) * | 1999-10-18 | 2003-10-29 | 中国石油化工股份有限公司巴陵分公司 | Method for evaporating, concentrating and drying saponified waste alkali liquor |
| CN101428915B (en) * | 2008-07-13 | 2010-05-12 | 赵志军 | Method for zero discharge processing of waste saponification lye of cyclohexanone produced by cyclohexane oxidation technology |
| CN102898296A (en) * | 2011-07-29 | 2013-01-30 | 天津赛普泰克科技有限公司 | Separation and recovery technology of monoacids in cyclohexanone by-products |
| CN106966451A (en) * | 2017-04-12 | 2017-07-21 | 赵琪 | A kind of method for solving cyclohexanone saponification waste lye secondary pollution |
| CN108217802A (en) * | 2018-02-05 | 2018-06-29 | 成都普瑞得科技有限公司 | A kind of utilization method of cyclohexanone saponification waste lye utilizes system |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059675C (en) * | 1994-11-25 | 2000-12-20 | 岳阳石油化工总厂研究院 | Method for recovering n-pentanol and cyclohexene oxide from light oil, by-products of cyclohexanol and cyclohexanone preparation by cyclohexane oxidation |
| CN1131654A (en) * | 1995-03-21 | 1996-09-25 | 岳阳昌德化工实业有限公司 | Recovery and usage method for main component of cyclohexane oxidation by-product-X oil |
-
1996
- 1996-07-15 CN CN96118264A patent/CN1060758C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1125863C (en) * | 1999-10-18 | 2003-10-29 | 中国石油化工股份有限公司巴陵分公司 | Method for evaporating, concentrating and drying saponified waste alkali liquor |
| CN101428915B (en) * | 2008-07-13 | 2010-05-12 | 赵志军 | Method for zero discharge processing of waste saponification lye of cyclohexanone produced by cyclohexane oxidation technology |
| CN102898296A (en) * | 2011-07-29 | 2013-01-30 | 天津赛普泰克科技有限公司 | Separation and recovery technology of monoacids in cyclohexanone by-products |
| CN106966451A (en) * | 2017-04-12 | 2017-07-21 | 赵琪 | A kind of method for solving cyclohexanone saponification waste lye secondary pollution |
| CN108217802A (en) * | 2018-02-05 | 2018-06-29 | 成都普瑞得科技有限公司 | A kind of utilization method of cyclohexanone saponification waste lye utilizes system |
| CN108217802B (en) * | 2018-02-05 | 2021-08-10 | 浙江巴陵恒逸己内酰胺有限责任公司 | Utilization method and utilization system of cyclohexanone saponification waste alkali liquor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1060758C (en) | 2001-01-17 |
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