CN102381953B - Method for extracting and purifying fluorenone from industrial wastes generated in production of benzoic acid - Google Patents
Method for extracting and purifying fluorenone from industrial wastes generated in production of benzoic acid Download PDFInfo
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- CN102381953B CN102381953B CN 201110263069 CN201110263069A CN102381953B CN 102381953 B CN102381953 B CN 102381953B CN 201110263069 CN201110263069 CN 201110263069 CN 201110263069 A CN201110263069 A CN 201110263069A CN 102381953 B CN102381953 B CN 102381953B
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Abstract
The invention provides a method for extracting and purifying fluorenone from industrial wastes generated in production of benzoic acid, which includes steps of obtaining crude solid fluorenone by means of reaction of crude benzyl ester, water and sodium hydroxide according to a certain proportion after rectification of benzoic acid, and recrystallizing the crude solid fluorenone by ethyl acetate and petroleum ether. Purification of the fluorenone is higher than 98%, and separation efficiency ranges from 60% to 75%. A new technical scheme is provided for further expansion in recycling of industrial wastes generated in production of benzoic acid and for reduction of environment pollution.
Description
Technical field
The present invention relates to the method for aromatic organic compounds separation and Extraction, specifically is a kind of method of extracting the purifying Fluorenone from produce benzoic industrial waste.
Background technology
As important fine-chemical intermediate Fluorenone and derivative thereof, be widely used in fields such as medicine, plastics, dye well electroluminescent organic material.Be important Anticonvulsants as 2-oxyammonia acetyl Fluorenone; The synthetic compound of 2,7 diamin of luorene ketone and azoic coupling component coupling is the disazo dyes that is complementary with present laser apparatus, and good photo-sensitive characteristic is arranged; 2,4,7-trinitro-fluorenone is the light-guide material that is most widely used in the market, can be used for xerox etc.; With the Fluorenone be raw material directly synthetic bisphenol fluorene then be used for modified poly ester, polycarbonate and Resins, epoxy, resin after the modification has that transparency height, specific refractory power height, moulding are good, second-order transition temperature is than characteristics such as height, can be used for opticinstrument, aircraft glass etc., annual demand is huge; On the other hand because fluorenes has higher photo and thermal stability, high fluorescence quantum efficiency and band-gap energy are greater than 2.90eV, thereby become a kind of extremely important and thought by many scholars and to be hopeful business-like blue light material most, along with foundation and the expansion with related industries of developing rapidly of electroluminescent organic material, the demand of Fluorenone is all increasing sharply every year.Therefore, the related production technology of research and development Fluorenone has broad application prospects.
At present, the production technique of relevant report Fluorenone mainly is to obtain by the oxidation fluorenes both at home and abroad, comprises vapour phase oxidation process [ZL96123084.3, ZL99112742.0] and liquid phase oxidation [ZL200410066734.6]; Also have by compound decarboxylations such as biphenyl to prepare certain methods such as Fluorenone, but all be only limited to laboratory study, and the industrialized scale that is unrealized.2007, Shijiangzhuang Oil-Refining Chemical Co., Ltd. and University Of Tianjin have developed the benzoic method in the rectification under vacuum recovery still raffinate of utilizing cooperatively, obtain thick benzyl ester, by products such as coumarone, and the method for utilizing flash distillation is isolated peruscabin and thick Fluorenone from thick benzyl ester, but just mentioning in the relevant report and extracting massfraction is 85% thick Fluorenone [chemical industry and engineering, 2007,24,408-411], the purifying of thick Fluorenone is not done further applied research, also do not set up associated production line, and in actual production process, the content of peruscabin has only about 12% in the thick benzyl ester behind the rectifying phenylformic acid, the content of Fluorenone has then reached 35%-40%, adopts this method can not obtain massfraction greater than 85% thick Fluorenone.
The thick benzyl ester that the present invention reclaims behind the phenylformic acid with Shijiangzhuang Oil-Refining Chemical Co., Ltd. rectifying is research object, and the method success extraction separation by simple hydrolysis goes out purity greater than 98% Fluorenone first, and has finished the pilot scale scale-up.
Summary of the invention
The object of the invention is to provide a kind of method of extracting the purifying Fluorenone from produce benzoic industrial waste, the Fluorenone purity height that this method obtains, yield height.
Production phenylformic acid industrial waste of the present invention refers to the thick benzyl ester behind the rectifying phenylformic acid, the mixture that wherein contains compounds such as benzyl ester, diphenic acid, Fluorenone, as the industrial waste behind Shijiangzhuang Oil-Refining Chemical Co., Ltd.'s rectifying phenylformic acid, wherein contain a large amount of thick benzyl esters.
A kind of method of extracting the purifying Fluorenone from produce the phenylformic acid industrial waste provided by the invention comprises the steps:
(1) with thick benzyl ester, water and sodium hydroxide behind the rectifying phenylformic acid by weight 1: 3-6: 0.15-0.30 joins in the reactor, heating, stir about 1-3h under the 60 ℃～reflux temperature stops heating, is cooled to room temperature, leave standstill 8-14h, suction filtration obtains thick Fluorenone solid and pale brown look filtrate and oily matter, wherein thick Fluorenone purity 80%-92%, yield 25-33%, product appearance: yellow solid;
(2) taking by weighing thick Fluorenone solid joins in the reactor, according to thick Fluorenone solid/g: the ratio of ethyl acetate/mL=1.0: 3.0-6.0, ethyl acetate is joined in the reactor, be heated to Fluorenone and all be dissolved in ethyl acetate, be cooled to room temperature, suction filtration gets yellow filtrate; The underpressure distillation yellow filtrate, 75%-90% ethyl acetate to be recycled stops heating, gets yellow oil; Be cooled to room temperature and leave standstill 1-4h, treat most of Fluorenone crystallization, according to thick Fluorenone solid/g: the ratio of sherwood oil/mL=1.0: 0.8-1.5, sherwood oil is joined in the reactor, stir, suction filtration obtains the Fluorenone filter cake; The Fluorenone filter cake is with the petroleum ether of above-mentioned same consumption, and drying obtains Fluorenone, and purity is greater than 98%, productive rate 80%-88%.Product appearance: yellow crystals.
Step (1) preferred reaction conditions: thick benzyl ester, water and sodium hydroxide are by weight 1: 4-5: 0.2-0.25; Hierarchy of control temperature is 80 ℃～reflux temperature; Reaction times is 1.5-2.0h; Time of repose is 10-12h.
Step (2) preferred reaction conditions: thick Fluorenone solid/g: ethyl acetate/mL=1.0: 3.5-4.5; The ethyl acetate of 80%-85% to be recycled stops heating; Time of repose is 1-2h; Thick Fluorenone solid/g: sherwood oil/mL=1.0: 0.9-1.2.
The content of Fluorenone is 35%-40% in the thick benzyl ester behind Shijiangzhuang Oil-Refining Chemical Co., Ltd.'s rectifying phenylformic acid, and the present invention obtains Fluorenone purity greater than 98%, and separation efficiency is 60-75%.
Do not use any high toxicity organic solvent in the above-mentioned reaction process, need not to add any catalyzer; Purge process is simple to operate, and organic solvent ethyl acetate and sherwood oil involved in the purge process can be by the mode recycles of rectifying, the pale brown look filtrate that produces in the step (1) and oily matter can reclaim by product benzylalcohol and Sodium Benzoate through after further handling.
The present invention has further expanded the scope of utilizing of phenylformic acid manufacture waste material, have easy and simple to handle, the easily separated purifying of product, environmental pollution is little, cost is low, the advantage that economic worth is high.
Embodiment
Embodiment 1
Reagent: the thick benzyl ester behind Shijiangzhuang Oil-Refining Chemical Co., Ltd.'s rectifying phenylformic acid, technical grade; Sodium hydroxide, chemical pure; Ethyl acetate, chemical pure; Sherwood oil, chemical pure.
Operation steps:
With the thick benzyl ester 100g behind Shijiangzhuang Oil-Refining Chemical Co., Ltd.'s rectifying phenylformic acid, water 400mL and sodium hydroxide 20g join in the 1000mL reactor, heating, stir about 2h under the reflux temperature; Stop heating, be cooled to room temperature, leave standstill 12h, suction filtration obtains thick Fluorenone solid 30.5g and pale brown look filtrate and oily matter, thick Fluorenone purity 86.5% wherein, yield 30.5%.
Thick Fluorenone 30.5g and ethyl acetate 120mL are joined in the 250mL reactor, be heated to Fluorenone and all be dissolved in ethyl acetate, be cooled to room temperature, suction filtration gets yellow filtrate; The underpressure distillation yellow filtrate, to be recycled 80% ethyl acetate stops heating, gets yellow oil; Be cooled to room temperature and leave standstill 1.5h, treat that wherein most of Fluorenone crystallizes out, add the 30mL sherwood oil, stir, suction filtration obtains the Fluorenone filter cake; It is 98.8% Fluorenone 26.3g that Fluorenone filter cake 30mL petroleum ether, drying obtain purity, productive rate 86.2%.
The content of Fluorenone is 35.7% in the thick benzyl ester among this embodiment behind Shijiangzhuang Oil-Refining Chemical Co., Ltd.'s rectifying phenylformic acid; Purity of the present invention is that the isolated yield of 86.5% thick Fluorenone is 30.5%; It is that the productive rate of 98.8% Fluorenone is 86.2% that the thick Fluorenone of purifying obtains purity, and overall yield is 26.3%, and separation efficiency is 73.6%.
Embodiment 2
Reagent: with embodiment 1.
Operation steps:
With the thick benzyl ester 100Kg behind Shijiangzhuang Oil-Refining Chemical Co., Ltd.'s rectifying phenylformic acid, water 400L and sodium hydroxide 20kg join in the 1000L reactor, heating, stir about 2h under the reflux temperature; Stop heating, be cooled to room temperature, leave standstill 12h, suction filtration obtains thick Fluorenone solid 32.9kg and pale brown look filtrate and oily matter, thick Fluorenone purity 87.2% wherein, yield 32.9%.
Thick Fluorenone 32.9kg and ethyl acetate 130L are joined in the 500L reactor, be heated to Fluorenone and all be dissolved in ethyl acetate, be cooled to room temperature, suction filtration gets yellow filtrate; The underpressure distillation yellow filtrate, to be recycled 85% ethyl acetate stops heating, gets yellow oil; Be cooled to room temperature and leave standstill 2h, treat that wherein most of Fluorenone crystallizes out, add the 30L sherwood oil, stir, suction filtration obtains the Fluorenone filter cake; It is 98.2% Fluorenone 28.9kg that Fluorenone filter cake 30L petroleum ether, drying obtain purity, productive rate 87.8%.
Among this embodiment behind Shijiangzhuang Oil-Refining Chemical Co., Ltd.'s rectifying phenylformic acid thick benzyl ester in the content of Fluorenone be 38.8%; Purity of the present invention is that the isolated yield of 87.2% thick Fluorenone is 32.9%; It is that the productive rate of 98.2% Fluorenone is 87.8% that the thick Fluorenone of purifying obtains purity, and overall yield is 28.9%, and separation efficiency is 74.5%.
Organic solvent ethyl acetate and sherwood oil involved in above-described embodiment 1 and 2 purge processes can be by the mode recycles of rectifying, the pale brown look filtrate that produces in the reaction process and oily matter can reclaim by product benzylalcohol and Sodium Benzoate through after further handling.
The physical constant of product and spectral data:
Fluorenone
Product appearance: yellow crystals; Fusing point: 83-85 ℃.
1H NMR (300MHz, CDCl
3): δ 7.65 (d, J=7.2Hz, 2H), 7.45-7.48 (m, 4H), 7.28 (d, J=7.0Hz, 2H).
13C NMR (75.5MHz, CDCl
3): δ 193.6,144.3,134.5,134.0,128.9,124.0,120.2.
Claims (8)
1. a method of extracting the purifying Fluorenone from produce the phenylformic acid industrial waste is characterized in that, comprises the steps:
(1) thick benzyl ester, water and sodium hydroxide behind the rectifying phenylformic acid are joined in the reactor by weight 1:3-6:0.15-0.30, heating, stir 1-3h under the 60 ℃～reflux temperature, stop heating, be cooled to room temperature, leave standstill 8-14h, suction filtration obtains thick Fluorenone solid and pale brown look filtrate and oily matter;
(2) taking by weighing thick Fluorenone solid joins in the reactor, according to thick Fluorenone solid/g: the ratio of ethyl acetate/mL=1.0:3.0-6.0, ethyl acetate is joined in the reactor, be heated to Fluorenone and all be dissolved in ethyl acetate, be cooled to room temperature, suction filtration gets yellow filtrate; The underpressure distillation yellow filtrate, 75%-90% ethyl acetate to be recycled stops heating, gets yellow oil; Be cooled to room temperature and leave standstill 1-4h, treat most of Fluorenone crystallization, according to thick Fluorenone solid/g: the ratio of sherwood oil/mL=1.0:0.8-1.5, sherwood oil is joined in the reactor, stir, suction filtration obtains the Fluorenone filter cake; Fluorenone filter cake petroleum ether, drying obtains Fluorenone.
2. a kind of method of extracting the purifying Fluorenone from produce the phenylformic acid industrial waste as claimed in claim 1 is characterized in that, the weight ratio of thick benzyl ester, water and sodium hydroxide is 1:4-5:0.2-0.25 in the step (1).
3. a kind of method of extracting the purifying Fluorenone from produce the phenylformic acid industrial waste as claimed in claim 1 is characterized in that hierarchy of control temperature is 80 ℃～reflux temperature in the step (1), and the reaction times is 1.5-2.0h.
4. a kind of method of extracting the purifying Fluorenone from produce the phenylformic acid industrial waste as claimed in claim 1 is characterized in that time of repose is 10-12h in the step (1).
5. a kind of method of extracting the purifying Fluorenone from produce the phenylformic acid industrial waste as claimed in claim 1 is characterized in that, thick Fluorenone solid/g: ethyl acetate/mL=1.0:3.5-4.5 in the step (2).
6. a kind of method of extracting the purifying Fluorenone from produce the phenylformic acid industrial waste as claimed in claim 1 is characterized in that the ethyl acetate of 80%-85% to be recycled in the step (2) stops heating.
7. a kind of method of extracting the purifying Fluorenone from produce the phenylformic acid industrial waste as claimed in claim 1 is characterized in that time of repose is 1-2h in the step (2).
8. a kind of method of extracting the purifying Fluorenone from produce the phenylformic acid industrial waste as claimed in claim 1 is characterized in that, thick Fluorenone solid/g: sherwood oil/mL=1.0:0.9-1.2 in the step (2).
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| CN 201110263069 CN102381953B (en) | 2011-09-07 | 2011-09-07 | Method for extracting and purifying fluorenone from industrial wastes generated in production of benzoic acid |
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| CN 201110263069 CN102381953B (en) | 2011-09-07 | 2011-09-07 | Method for extracting and purifying fluorenone from industrial wastes generated in production of benzoic acid |
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| CN102381953B true CN102381953B (en) | 2013-07-10 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3875237A (en) * | 1974-03-21 | 1975-04-01 | Gen Electric | Preparation of fluorenone |
| CN1266840A (en) * | 1999-03-15 | 2000-09-20 | 鞍山钢铁集团公司 | Process for preparing fluorenone |
| CN101139277A (en) * | 2007-08-28 | 2008-03-12 | 浙江华联三鑫石化有限公司 | Method for reclaiming terephthalic acid residue |
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2011
- 2011-09-07 CN CN 201110263069 patent/CN102381953B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3875237A (en) * | 1974-03-21 | 1975-04-01 | Gen Electric | Preparation of fluorenone |
| CN1266840A (en) * | 1999-03-15 | 2000-09-20 | 鞍山钢铁集团公司 | Process for preparing fluorenone |
| CN101139277A (en) * | 2007-08-28 | 2008-03-12 | 浙江华联三鑫石化有限公司 | Method for reclaiming terephthalic acid residue |
Non-Patent Citations (4)
| Title |
|---|
| 减压精馏分离苯甲酸釜残液的试验研究;李书奕等;《化学工业与工程》;20070930;第24卷(第5期);408-411 * |
| 李书奕等.减压精馏分离苯甲酸釜残液的试验研究.《化学工业与工程》.2007,第24卷(第5期),408-411. |
| 闪蒸-减压精馏分离苯甲酸废料;韩檬等;《化学工程》;20070731;第35卷(第7期);1-3 * |
| 韩檬等.闪蒸-减压精馏分离苯甲酸废料.《化学工程》.2007,第35卷(第7期),1-3. |
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