CN101348417A - Catalyst glycol antimony preparation - Google Patents
Catalyst glycol antimony preparation Download PDFInfo
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- CN101348417A CN101348417A CNA2008101431983A CN200810143198A CN101348417A CN 101348417 A CN101348417 A CN 101348417A CN A2008101431983 A CNA2008101431983 A CN A2008101431983A CN 200810143198 A CN200810143198 A CN 200810143198A CN 101348417 A CN101348417 A CN 101348417A
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- antimonous oxide
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- ethylene glycol
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a preparation method for catalyst ethylene glycol antimony. The preparation method comprises the following steps that raw materials antimony trioxide and ethylene glycol undergo esterification and dehydration reaction under the conditions of heating and depressurizing according to the weight ratio of 1to between 3 and 20; composite impurity removal discoloring agent, i.e. active carbon and amino polyhydric aid are added and filtered at a late reaction stage; the filtrate undergoes crystallization by cooling at a normal temperature; and a product can be prepared after the crystallized product undergoes centrifuge dripping. The preparation method does not require a cleaning process, a recrystallization process, a drying process and a nitrogen filling protective device and nitrogen, thereby simplifying manufacturing process and greatly reducing production cost; meanwhile, reductive antimony trioxide is eliminated so as to improve the catalytic activity of the product; moreover, the composite impurity removal discoloring agent is added so as to greatly reduce impurity content in the product and to greatly improve product quality.
Description
Technical field
The present invention relates to the preparation method of catalyzer-antimony glycol used in the polyethylene terephthalate polyreaction.
Technical background
The preparation method of existing catalyst glycol antimony.As Chinese patent, in the application number 99122632 " preparation method of glycol antimony catalyst for polyester ", its raw material antimonous oxide and the ethylene glycol weight ratio that feeds intake is 1: 2.5～4, and temperature of reaction is 140～160 ℃, 4～6 hours reaction times.After product filters filtrate is concentrated the back recrystallize with high temperature again, refilter, then vacuum-drying.Need high temperature to concentrate behind this technological reaction, poor product quality when causing crystallization, yield only 88.7%, yield is low.And for example Chinese patent in the application number 001108190 " preparation method of antimony compound of binary alcohol ", when antimonous oxide and ethylene glycol building-up reactions, needs to feed protection of inert gas.Complex process, the production cost height.Chinese patent and for example; in the application number 99114156.3 " a kind of preparation method of high purity antimony glycol "; when antimonous oxide and glycol reaction, feed nitrogen protection; after reaction is filtered; the filtrate crystallisation by cooling refilters; the spent glycol recrystallization is used washing with alcohol after the filtration of recrystallization product, again through centrifuging, vacuum-drying again.This method technology is complicated, needs recrystallization, uses washing with alcohol.Ethanol is inflammable and explosive, worsens environment, and production cost greatly raises simultaneously.Chinese patent and for example, among the application number 02116519-X " preparation method of antimony glycol ", antimonous oxide and ethylene glycol at high temperature react, do not vacuumize the crystallization of slurry filtration postcooling, centrifuging again, carry out recrystallization again, crystallisate washing with alcohol, vacuum-drying again.This method is complicated with sampling technology, needs recrystallization, needs with expensive washing with alcohol, and production cost is higher.
Above technology all needs the vacuum-drying operation, because product can make part Sb in drying process
2(OCH
2CH
2O)
3Be reduced into antimonous oxide, cause that the content of antimony has surpassed theoretical value (57.47%) in the product, thereby the catalytic effect of antimony glycol is affected.Simultaneously, in existing technology in the past, all need washing procedure, use methyl alcohol, ethanol, its toxicity is big, and is inflammable and explosive, and contaminate environment increases potential safety hazard.Need recrystallization in the prior art mostly, inflated with nitrogen is protected, and has increased the complicacy of operation, has also improved production cost greatly.
Summary of the invention
The object of the present invention is to provide a kind of technology simple, can reduce production costs, the preparation method of the antimony glycol that further improves the quality of products.
The present invention includes following steps:
(5) the esterification dehydration reaction of antimonous oxide and ethylene glycol: raw material antimonous oxide and ethylene glycol are by the weight ratio 1: 3～20 that feeds intake, in synthesis reactor, control reaction temperature is 120～200 ℃, be-0.09 at the pressure of reduced vacuum～-condition of 0.02mpa under, esterification dehydration reaction 2-5 hour;
(6) removal of impurities decoloring reaction: add compound removal of impurities discoloring agent gac and amino many hydroxy acids, the add-on of described gac is 0.2～5% of an antimonous oxide input weight, the add-on of the many hydroxy acids of described amino continues reaction 10-20 minute for dropping into 0.1～2% of antimonous oxide weight;
(7) filter, change filtrate over to crystallizer: at room temperature crystallisation by cooling 2-4 hour;
(8) centrifuging is product after drying.
Optimal reaction temperature is 130～150 ℃ in the esterification dehydration reaction of described antimonous oxide and ethylene glycol,
In the esterification dehydration reaction of described antimonous oxide and ethylene glycol best reduced vacuum condition be-0.07～-0.04mpa,
The optimal addn of gac is 1.6～2.5% of a raw material antimonous oxide weight in the described compound removal of impurities discoloring agent,
The optimal addn of amino many hydroxy acids is 0.65～0.9% of a raw material antimonous oxide weight in the described compound removal of impurities discoloring agent.
The present invention has the following advantages:
(1) in reaction process, adds gac and the compound removal of impurities discoloring agent of amino many hydroxy acids, saved washing procedure, save the recrystallization operation, save drying process, saved nitrogen filled protection device and nitrogen, thereby simplified production technique, greatly reduce production cost;
(2) quality product improves greatly, eliminated the reductive antimonous oxide aborning, thereby improved the product catalytic activity, the product antimony content can be controlled in below the theoretical value, be generally 54～55%, owing to added compound removal of impurities discoloring agent, the product foreign matter content reduces greatly, chloride content is dropped to less than 10ppm by 100ppm in the product, iron level is dropped to less than 10ppm by 30ppm, the content of vitriol is dropped to less than 8ppm by 15ppm, and lead content is dropped to less than 8ppm by 15ppm, and arsenic content drops to 15ppm by original 20ppm.Measure through Changsha mining industry research institute X-ray diffraction phase analysis, the result proves high purity antimony glycol.The solvent temperature of product is 30 ℃, and dissolution time is 30 minutes, has reduced by 70 ℃ than solvent temperature 100 degree of in the past drying products.Dissolution time shortens 100 minutes, is user's save energy and time, and is convenient efficient.
(3) owing to saved washing procedure, do not re-use inflammable and explosive methyl alcohol, ethanol, improved the production environment condition yet, eliminated unsafe factor,
Specific embodiments
Embodiment 1
4870 gram ethylene glycol are dropped into when being warmed up to 100 ℃ in the 5000ml four-hole boiling flasks, add antimonous oxide 600 grams, antimonous oxide and ethylene glycol weight ratio 1: 8.1, continue to be warmed up to 135 ℃, the pressure that the unlatching vacuum pump is evacuated down to reduced vacuum is-0.07mpa, keeping temperature of reaction is 135～145 ℃, react after 3 hours, in reaction soln, add 10 gram gacs, gac is 1.67% of an antimonous oxide weight, add the amino many hydroxy acids of 4 grams, amino many hydroxy acids are 0.67% of antimonous oxide weight.Gac and amino many hydroxy acids weight ratio are 2.5, continue 15 minutes after-filtration of reaction, and filtrate is limpid.Change filtrate over to the crystallizer crystallisation by cooling: crystallisation by cooling at room temperature, crystallization time 3 hours.Centrifuging after the crystallization, the crystalline product chemical examination contains Sb54.38%, Pb0.00038, As0.000094, product is measured through Changsha mining industry research institute X-ray diffraction phase analysis, and the result proves high purity antimony glycol.
Embodiment 2
4290 gram ethylene glycol are added when being warmed up to 90 ℃ in the 5000ml four-hole boiling flasks, add antimonous oxide 600 grams, antimonous oxide and ethylene glycol weight ratio 1: 7.15, continue to be warmed up to 130 ℃, the unlatching vacuum pump vacuumizes, keeping temperature of reaction is 135～145 ℃, react after 3 hours, in reaction soln, add gac 15 grams, gac is to drop into 2.5% of antimonous oxide weight, drop into amino many hydroxy acids 5 grams simultaneously in reaction soln, amino many hydroxy acids are to drop into 0.83% of antimonous oxide weight.Gac and amino many hydroxy acids weight ratio are 3, continue 10 minutes after-filtration of reaction, and filtrate is very limpid.Filtrate is changed over to the crystallizer crystallisation by cooling: crystallisation by cooling at room temperature, crystallization time is centrifugal dewatering after 3 hours, measure xln and contain Sb54.65%, contain Pb0.00042, contain As0.00012, sample send Changsha mining industry research institute to carry out the X-ray diffraction phase analysis and measures, and the result proves high purity antimony glycol.
Embodiment 3
In the 2000L reactor, drop into 1970kg ethylene glycol, be warmed to 90 ℃, press antimonous oxide and ethylene glycol weight ratio 1: 7.2 then and drop into the 275kg antimonous oxide, open and stir, be warmed up to 100 ℃ after, open vacuum pump, keeping a jar interior negative pressure is-0.08mpa that temperature is controlled at 135～145 ℃ in the retort, reacts after 3.5 hours, 2% adding 12kg gac by dropping into antimonous oxide weight adds the amino many hydroxy acids of 4.2kg by 0.7% of input antimonous oxide weight simultaneously.Continue reaction 10 minutes, filter then, filtrate is changed over to carry out crystallisation by cooling in the 3000L crystallizer, cool off with tap water, crystallizing at room temperature, crystallization is after 3.5 hours, with the crystal centrifugal dewatering, mother liquor is reused after treatment, and the antimony glycol product after the drying is through checking vacuum packaging, common property goes out the 410kg antimony glycol, and product contains Sb54.32%, contains Pb0.0006%, contain As0.0008, chloride 0.0010%, sulfur-bearing hydrochlorate 0.0009%, the antimony glycol yield is up to 97.28%.Sample carries out the X-ray diffraction phase analysis through Changsha mining industry research institute and identifies that the result proves high purity antimony glycol.
Embodiment 4
2460 gram ethylene glycol are joined in the 3000ml four-hole boiling flask, add antimonous oxide 600 grams when being warmed up to 90 ℃, antimonous oxide and ethylene glycol weight ratio are to continue be warmed up to 130 ℃ at 1: 4.1 to drive vacuum pump and vacuumize 130 ℃ of maintenance temperature.React after 5 hours, add gac 2.7 grams in reaction soln, it is to drop into 0.45% of antimonous oxide weight that gac adds weight, drops into amino many hydroxy acids 1.8 grams simultaneously.Amino many hydroxy acids are to drop into 0.3% of antimonous oxide weight.Continue 20 minutes after-filtration of reaction.Filtrate is very limpid, and filtrate is changed over to crystallisation by cooling in the crystallizer.At room temperature cool off and crystallization, crystallization time centrifugal dewatering after 3 hours is measured crystalline product and is contained Sb54.91%, contains Pb0.00067%, contains As0.00011%.Sample send Changsha mining industry research institute to carry out the X-ray diffraction phase analysis and identifies that the result proves that product is a high purity ethylene glycol.
Embodiment 5
4560 gram ethylene glycol are added in the 5000ml four-hole boiling flasks, add antimonous oxide 300 grams when being warmed up to 90 ℃, antimonous oxide and ethylene glycol weight ratio are 1: 15.2, continue to be warmed up to 130 ℃ and drive vacuum pump and vacuumize 140 ℃ of maintenance temperature.React after 3 hours, add gac 12 grams in reaction soln, it is to drop into 4% of antimonous oxide weight that gac adds weight, drops into amino many hydroxy acids 3 grams simultaneously.Amino many hydroxy acids are to drop into 1% of antimonous oxide weight.Continue 15 minutes after-filtration of reaction.Filtrate is very limpid, and filtrate is changed over to crystallisation by cooling in the crystallizer.At room temperature cool off and crystallization, crystallization time is centrifugal dewatering after 3.5 hours.Measuring crystalline product contains Sb54.76%, contains Pb0.00065%, contains As0.00017%.Sample send Changsha mining industry research institute to carry out the X-ray diffraction phase analysis and identifies that the result proves that product is a high purity ethylene glycol.
Claims (5)
1. the preparation method of a catalyst glycol antimony may further comprise the steps:
(1) the esterification dehydration reaction of antimonous oxide and ethylene glycol: raw material antimonous oxide and ethylene glycol are by the weight ratio 1: 3～20 that feeds intake, in synthesis reactor, control reaction temperature is 120～200 ℃, be-0.09 at the pressure of reduced vacuum～-condition of 0.07mpa under, esterification dehydration reaction 2-5 hour;
(2) removal of impurities decoloring reaction: add compound removal of impurities discoloring agent gac and amino many hydroxy acids, the add-on of described gac is 0.2～5% of an antimonous oxide input weight, the add-on of the many hydroxy acids of described amino was reacted 10-20 minute for dropping into 0.1～2% of antimonous oxide weight;
(3) filter, change filtrate over to crystallizer: at room temperature crystallisation by cooling 2-4 hour;
(4) centrifuging is finished product after drying.
2. the preparation method of catalyst glycol antimony according to claim 1 is characterized in that, the temperature of reaction in the esterification dehydration reaction of described antimonous oxide and ethylene glycol is 130～150 ℃,
3. the preparation method of catalyst glycol antimony according to claim 1 is characterized in that, in the esterification dehydration reaction of described antimonous oxide and ethylene glycol the reduced vacuum condition be-0.07～-0.04mpa,
4. the preparation method of catalyst glycol antimony according to claim 1 is characterized in that, the add-on of gac is 1.6～2.5% of a raw material antimonous oxide weight in the described compound removal of impurities discoloring agent,
5. the preparation method of catalyst glycol antimony according to claim 1 is characterized in that, the add-on of amino many hydroxy acids is 0.65～0.9% of a raw material antimonous oxide weight in the described compound removal of impurities discoloring agent.
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| CNA2008101431983A CN101348417A (en) | 2008-09-12 | 2008-09-12 | Catalyst glycol antimony preparation |
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| CNA2008101431983A CN101348417A (en) | 2008-09-12 | 2008-09-12 | Catalyst glycol antimony preparation |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060666A (en) * | 2011-01-18 | 2011-05-18 | 刘谏文 | Non-drying preparation method of ethylene glycol antimony |
| CN102516037A (en) * | 2011-11-25 | 2012-06-27 | 锡矿山闪星锑业有限责任公司 | Method for preparing ethylene glycol antimony ester by rapid impurity removal and decoloration |
| CN107311841A (en) * | 2017-08-02 | 2017-11-03 | 美轲（广州）化学股份有限公司 | The preparation method of antimony glycol |
| KR101853169B1 (en) * | 2015-11-16 | 2018-04-27 | 단국대학교 산학협력단 | Preparation method for high purity antimony triglycolate |
-
2008
- 2008-09-12 CN CNA2008101431983A patent/CN101348417A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060666A (en) * | 2011-01-18 | 2011-05-18 | 刘谏文 | Non-drying preparation method of ethylene glycol antimony |
| CN102060666B (en) * | 2011-01-18 | 2013-02-13 | 刘谏文 | Non-drying preparation method of ethylene glycol antimony |
| CN102516037A (en) * | 2011-11-25 | 2012-06-27 | 锡矿山闪星锑业有限责任公司 | Method for preparing ethylene glycol antimony ester by rapid impurity removal and decoloration |
| CN102516037B (en) * | 2011-11-25 | 2014-03-19 | 锡矿山闪星锑业有限责任公司 | Method for preparing ethylene glycol antimony ester by rapid impurity removal and decoloration |
| KR101853169B1 (en) * | 2015-11-16 | 2018-04-27 | 단국대학교 산학협력단 | Preparation method for high purity antimony triglycolate |
| CN107311841A (en) * | 2017-08-02 | 2017-11-03 | 美轲（广州）化学股份有限公司 | The preparation method of antimony glycol |
| CN107311841B (en) * | 2017-08-02 | 2020-06-16 | 美轲（广州）化学股份有限公司 | Preparation method of ethylene glycol antimony |
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Open date: 20090121 |