CN102001917B - Method for recovering hydroquinone serving as raw material from waste liquid produced in production process of tert butyl hydroquinone - Google Patents
Method for recovering hydroquinone serving as raw material from waste liquid produced in production process of tert butyl hydroquinone Download PDFInfo
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- CN102001917B CN102001917B CN 201010503970 CN201010503970A CN102001917B CN 102001917 B CN102001917 B CN 102001917B CN 201010503970 CN201010503970 CN 201010503970 CN 201010503970 A CN201010503970 A CN 201010503970A CN 102001917 B CN102001917 B CN 102001917B
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- Prior art keywords
- resorcinol
- waste liquid
- raw material
- production process
- tert
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- 239000002699 waste material Substances 0.000 title claims abstract description 24
- 239000007788 liquid Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000002994 raw material Substances 0.000 title claims abstract description 18
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 title abstract description 15
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 title abstract description 14
- 239000004250 tert-Butylhydroquinone Substances 0.000 title abstract description 8
- 235000019281 tert-butylhydroquinone Nutrition 0.000 title abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 94
- XRCRJFOGPCJKPF-UHFFFAOYSA-N 2-butylbenzene-1,4-diol Chemical compound CCCCC1=CC(O)=CC=C1O XRCRJFOGPCJKPF-UHFFFAOYSA-N 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 239000002932 luster Substances 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019261 food antioxidant Nutrition 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for recovering hydroquinone serving as a raw material from waste liquid produced in a production process of tert butyl hydroquinone. The method comprises the following steps of: adding an acid into the waste liquid produced in a process of producing the tert butyl hydroquinone until the waste liquid is acidic; heating and condensing to remove most solvent; cooling to a room temperature to separate hydroquinone crystals; filtering and collecting the separated hydroquinone crystals; washing the obtained crystals with water; and performing vacuum drying to obtain the hydroquinone. The method has the advantages that: the process is simple, convenient and feasible to operate; the loss of equipment is low; the environment cannot be polluted; and the recovered hydroquinone has high purity and good color and luster, and can be used as the raw material directly after drying.
Description
Technical field
The present invention relates to reclaim in a kind of waste liquid that from the Tert. Butyl Hydroquinone production process, produces the method for raw material Resorcinol.
Background technology
Tert. Butyl Hydroquinone chemical name: 2-Tert. Butyl Hydroquinone
English name: 2-t-butyl-1,4-dihydroxybenzene
Resorcinol chemical name 1, the 4-dihydroxy-benzene
English name hydroquinone
Tert. Butyl Hydroquinone (TBHQ) is a kind of food antioxidant commonly used, and it can be widely used in each field such as food, feed, petroleum products.(BHA BHT) will get well its antioxygen property, and especially the antioxidant effect in grease and goods thereof is best than other like product.The synthesis and production process of present TBHQ is comparative maturity, and state of the art is suitable both at home and abroad.Producing TBHQ is raw material with Resorcinol (HQ) mainly, prepares Tert. Butyl Hydroquinone with trimethyl carbinol generation alkylated reaction with acid as catalyst in organic solvent.The transformation efficiency of raw material Resorcinol is about about 92% in this reaction, and about 8% raw material is reaction not.If it is not discharged with waste liquid is recycled, can waste a lot of raw materials and improve the production cost of TBHQ, in addition, Resorcinol is a kind of Organic Chemicals, has stronger toxicity and can cause more serious pollution to environment with discharging of waste liquid.Therefore, reclaiming unconverted raw material not only can save cost but also can reduce pollution to environment.
Summary of the invention
The object of the present invention is to provide the method that reclaims raw material Resorcinol (HQ) from Tert. Butyl Hydroquinone (TBHQ) production process in a kind of waste liquid that produces, this method is easy and simple to handle, and is not high to equipment requirements, and the treatment time is short, and rate of recovery height.
Purpose of the present invention is achieved by taking following technical scheme:
Reclaim the method for raw material Resorcinol in a kind of waste liquid that from the Tert. Butyl Hydroquinone production process, produces, it is characterized in that, add acid in the waste liquid that produces in the Tert. Butyl Hydroquinone process to acid to producing, reheat concentrates removes most of solvent, be cooled to room temperature and separate out the Resorcinol crystal, filter and collect the Resorcinol crystal of separating out, wash the gained crystal then with water, last vacuum-drying namely obtains Resorcinol.
The used acid of adjustment pH value of solution value of the present invention is acetic acid, hydrochloric acid, phosphoric acid or sulfuric acid, preferred acetic acid or phosphoric acid.
The pH value of solution of the present invention is adjusted into pH=1.0～6.0, preferred pH=2.0～5.0.
Volume is for concentrating preceding 20～60%, preferred 20%～40% after the solution concentration of the present invention.
The quality of washing crystal Resorcinol of the present invention institute water is 10%～70%, preferred 20%～50% of crystal Resorcinol quality.
Dried crystals Resorcinol of the present invention is finished in nitrogen atmosphere.
The drying process of crystal Resorcinol of the present invention is finished under vacuum condition, and vacuum tightness is 0.03～0.1MPa, preferred 0.06～0.09MPa.
The drying temperature of crystal Resorcinol of the present invention is 60～140 ℃, preferred 70～90 ℃.
The invention has the advantages that: technological operation is simple and feasible, and is little to equipment loss, can not pollute environment; The Resorcinol purity height that reclaims, color and luster is good, can directly use as raw material after the drying.
Embodiment
Following examples only are used for setting forth the present invention, and protection scope of the present invention is not only to be confined to following examples.The those of ordinary skill of described technical field all can be realized purpose of the present invention according to above content disclosed by the invention and scope that each parameter is got.
Embodiment 1
Get the waste liquid 1000mL that produces in the Tert. Butyl Hydroquinone production process, add phosphoric acid and adjust its pH to pH=3.5, vigorous stirring 30 minutes, it is 400mL that heating is concentrated into the surplus solution volume, is cooled to room temperature and separates out the Resorcinol crystal, about 25 grams of solid collected by filtration, with 10mL frozen water washing solid, dry crystal Resorcinol 21.8 grams in 0.08MPa, 75 ℃ of nitrogen environments, the GC detected result shows, Resorcinol content 98.8%.
Embodiment 2
Get the waste liquid 1000mL that produces in the Tert. Butyl Hydroquinone production process, add phosphoric acid and adjust its pH to pH=3.5, vigorous stirring 30 minutes, it is 200mL that heating is concentrated into the surplus solution volume, is cooled to room temperature and separates out the Resorcinol crystal, about 37 grams of solid collected by filtration, with 14mL frozen water washing solid, dry crystal Resorcinol 30.6 grams in 0.08MPa, 75 ℃ of nitrogen environments, the GC detected result shows, Resorcinol content 98.4%.
Embodiment 3
Get the waste liquid 1000mL that produces in the Tert. Butyl Hydroquinone production process, add hydrochloric acid and adjust its pH to pH=4.0, vigorous stirring 30 minutes, it is 200mL that heating is concentrated into the surplus solution volume, is cooled to room temperature and separates out the Resorcinol crystal, about 36.2 grams of solid collected by filtration, with 14mL frozen water washing solid, dry crystal Resorcinol 30.3 grams in 0.09MPa, 90 ℃ of nitrogen environments, the GC detected result shows, Resorcinol content 98.5%.
Embodiment 4
Get the waste liquid 1000mL that produces in the Tert. Butyl Hydroquinone production process, add acetic acid and adjust its pH to pH=5.0, vigorous stirring 30 minutes, it is 200mL that heating is concentrated into the surplus solution volume, is cooled to room temperature and separates out the Resorcinol crystal, about 37 grams of solid collected by filtration, with 10mL frozen water washing solid, dry crystal Resorcinol 30.1 grams in 0.07MPa, 75 ℃ of nitrogen environments, the GC detected result shows, Resorcinol content 98.2%.
Embodiment 5
Get the waste liquid 1000mL that produces in the Tert. Butyl Hydroquinone production process, add acetic acid and adjust its pH to pH=5.0, vigorous stirring 30 minutes, it is 200mL that heating is concentrated into the surplus solution volume, is cooled to room temperature and separates out the Resorcinol crystal, about 37 grams of solid collected by filtration, with 10mL frozen water washing solid, dry crystal Resorcinol 30.2 grams in 0.08MPa, 90 ℃ of nitrogen environments, the GC detected result shows, Resorcinol content 98.6%.
Embodiment 6
Get the waste liquid 1000mL that produces in the Tert. Butyl Hydroquinone production process, add phosphoric acid and adjust its pH to pH=3.5, vigorous stirring 30 minutes, it is 300mL that heating is concentrated into the surplus solution volume, is cooled to room temperature and separates out the Resorcinol crystal, about 37 grams of solid collected by filtration, with 10mL frozen water washing solid, dry crystal Resorcinol 30.7 grams in 0.09MPa, 75 ℃ of nitrogen environments, the GC detected result shows, Resorcinol content 98.6%.
Claims (5)
1. reclaim the method for raw material Resorcinol in the waste liquid that from the Tert. Butyl Hydroquinone production process, produces, it is characterized in that, to add acid to the pH value of solution in the waste liquid that produces in the Tert. Butyl Hydroquinone process be 1.0～6.0 to producing, reheat concentrates removes most of solvent, be cooled to room temperature and separate out the Resorcinol crystal, filter and collect the Resorcinol crystal of separating out, wash the gained crystal then with water, last vacuum-drying namely obtains Resorcinol, wherein drying is finished in nitrogen atmosphere, and dry temperature is 60～140 ℃.
2. reclaim the method for raw material Resorcinol in the waste liquid that produces according to claim 1 from the Tert. Butyl Hydroquinone production process, it is characterized in that, adjusting the used acid of pH value of solution value is acetic acid, hydrochloric acid, phosphoric acid or sulfuric acid.
3. reclaim the method for raw material Resorcinol in the waste liquid that from the Tert. Butyl Hydroquinone production process, produces according to claim 1, it is characterized in that, solution concentration is extremely concentrated 20%～60% of front volume.
4. reclaim the method for raw material Resorcinol in the waste liquid that from the Tert. Butyl Hydroquinone production process, produces according to claim 1, it is characterized in that the quality of washing crystal Resorcinol institute water is 10%～70% of crystal Resorcinol quality.
5. reclaim the method for raw material Resorcinol in the waste liquid that from the Tert. Butyl Hydroquinone production process, produces according to claim 1, it is characterized in that the vacuum tightness during the dried crystals Resorcinol is 0.03～0.1MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010503970 CN102001917B (en) | 2010-10-09 | 2010-10-09 | Method for recovering hydroquinone serving as raw material from waste liquid produced in production process of tert butyl hydroquinone |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010503970 CN102001917B (en) | 2010-10-09 | 2010-10-09 | Method for recovering hydroquinone serving as raw material from waste liquid produced in production process of tert butyl hydroquinone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102001917A CN102001917A (en) | 2011-04-06 |
| CN102001917B true CN102001917B (en) | 2013-08-28 |
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| CN 201010503970 Active CN102001917B (en) | 2010-10-09 | 2010-10-09 | Method for recovering hydroquinone serving as raw material from waste liquid produced in production process of tert butyl hydroquinone |
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| CN108721935B (en) * | 2017-04-14 | 2021-02-09 | 上海泰禾国际贸易有限公司 | Trapping device and process for production of o-chlorobenzonitrile |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4323713A (en) * | 1980-11-20 | 1982-04-06 | Uop Inc. | Preparation of mono-tertiary butylhydroquinone |
| CN1699318A (en) * | 2005-05-13 | 2005-11-23 | 广东省食品工业研究所 | Improved process for preparing edible grease antioxidant 2-tert-butyl hydroquinone |
| CN1762945A (en) * | 2005-09-23 | 2006-04-26 | 复旦大学 | Environment friendly 2-tertiary-butyl hydroquinone preparation method |
-
2010
- 2010-10-09 CN CN 201010503970 patent/CN102001917B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4323713A (en) * | 1980-11-20 | 1982-04-06 | Uop Inc. | Preparation of mono-tertiary butylhydroquinone |
| CN1699318A (en) * | 2005-05-13 | 2005-11-23 | 广东省食品工业研究所 | Improved process for preparing edible grease antioxidant 2-tert-butyl hydroquinone |
| CN1762945A (en) * | 2005-09-23 | 2006-04-26 | 复旦大学 | Environment friendly 2-tertiary-butyl hydroquinone preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 叔丁基对苯二酚的合成;夏英姿;《精细石油化工》;20050531(第3期);8-10 * |
| 夏英姿.叔丁基对苯二酚的合成.《精细石油化工》.2005,(第3期),8-10. |
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| CN102001917A (en) | 2011-04-06 |
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Owner name: WENGYUAN GUANGYE QINGYI FOOD TECHNOLOGY CO., LTD. Effective date: 20141115 |
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Effective date of registration: 20141115 Address after: 510308 No. 146 East Xingang Road, Guangdong, Guangzhou Patentee after: Guangdong Prov. Food Industry Inst. Patentee after: Wengyuan Guangye Qingyi Food Technology Co., Ltd. Address before: 510308 No. 146 East Xingang Road, Guangdong, Guangzhou Patentee before: Guangdong Prov. Food Industry Inst. |
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Address after: 510308 No. 146 East Xingang Road, Guangzhou, Guangdong, Haizhuqu District Co-patentee after: Wengyuan Guangye Qingyi Food Technology Co., Ltd. Patentee after: Guangdong Food Industry Research Institute Co Ltd Address before: 510308 No. 146 East Xingang Road, Guangdong, Guangzhou Co-patentee before: Wengyuan Guangye Qingyi Food Technology Co., Ltd. Patentee before: Guangdong Prov. Food Industry Inst. |
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Effective date of registration: 20201021 Address after: 512627, Weng Town Industrial Park, Weng Town, Wengyuan County, Guangdong, Shaoguan Patentee after: L&P FOOD INGREDIENTS Co.,Ltd. Patentee after: GUANGDONG GUANGYE QINGYI FOOD TECHNOLOGY Co.,Ltd. Address before: 510308 No. 146 East Xingang Road, Guangzhou, Guangdong, Haizhuqu District Patentee before: GUANGDONG FOOD INDUSTRY INSTITUTE Co.,Ltd. Patentee before: L&P FOOD INGREDIENTS Co.,Ltd. |
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