CN102060666B - Non-drying preparation method of ethylene glycol antimony - Google Patents
Non-drying preparation method of ethylene glycol antimony Download PDFInfo
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- CN102060666B CN102060666B CN 201110009826 CN201110009826A CN102060666B CN 102060666 B CN102060666 B CN 102060666B CN 201110009826 CN201110009826 CN 201110009826 CN 201110009826 A CN201110009826 A CN 201110009826A CN 102060666 B CN102060666 B CN 102060666B
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Abstract
The invention provides a non-drying preparation method of ethylene glycol antimony, and relates to a preparation method of antimony-containing compound catalyst which is used in polyester polycondensation reaction. The preparation method is characterized by comprising the following steps: adding antimony trioxide and ethylene glycol in a reaction tank to be subjected to esterification dehydration reaction, wherein the weight ratio of the antimony trioxide to ethylene glycol is 1:(6-7), the temperature in the reaction tank is 135-150 DEG C and the pressure ranges from minus 0.10MPa to minus 0.08MPa; after the reaction, adding a single activated carbon decolouring impurity-removing reagent in the reaction tank for decolouring and impurity removal, then performing circulating filtration, and then filtering again; and then conveying filtrate to a crystallizing tank, crystallizing the filtrate, performing centrifuge dripping, and then directly performing inspection and packaging. In the method provided by the invention, washing and drying are not required, and the chelate structure of the product is not damaged; and the single activated carbon decolouring impurity-removing reagent is used, thus the effects of decolouring and impurity removal are good, the hue value of the product is high, the loss of ethylene glycol is less, the stability of the product quality is good, the operation is simple, and the production cost is low.
Description
Technical field
The present invention relates to a kind of preparation method of the catalyzed with antimony containing compounds agent for the polyester polycondensation.
Background technology
What the production method overwhelming majority of existing antimony glycol adopted is the drying process method, such as Chinese patent, applying date 2001.11.20, application number is the preparation method of a kind of antimony glycol of 01134185, in 120 ℃～180 ℃ temperature range, carry out esterified dehydration reaction with excessive ethylene glycol and antimonous oxide, after filtration, crystallisation by cooling, and spent glycol recrystallization is directly removed ethylene glycol through the decompression heat drying.Owing to be provided with drying process, in drying process, make part Sb
2(OCH
2CH
2O)
3Huge legendary turtle close structure and destroyed, be reduced into antimonous oxide, not only increased the consumption of antimonous oxide, and the catalytic effect of antimony glycol be affected; Owing to be provided with washing procedure, the washings of employing is methyl alcohol or the ethanol that toxicity is large, boiling point is low, Yi Ranyi is sudden and violent in addition, increases production cost and safety cost; And the weak effect of washing decolouring removal of impurities, foreign matter content is high, so that the form and aspect value difference of the polyester product of producing.In order to address these problems, the inventor is the preparation method's of 200710035237.3 crystalline ethylene antimony patent of invention in the application number of invention in 2007, ratio input antimonous oxide and the ethylene glycol by weight 1 ︰ 6～7, under the heating reduced pressure, carry out esterified dehydration reaction, then add gac and heavy metal inhibitor, then carry out circulating filtration, crystallization, behind centrifuge dripping, directly enter again the product quality packing.This application replaces washing decolouring removal of impurities with gac and heavy metal inhibitor decolouring removal of impurities, thereby has saved drying process, has solved because of dry to destroy antimony glycol product huge legendary turtle and close the technical barrier of structure.But, owing to adopt simultaneously gac and heavy metal inhibitor decolouring removal of impurities, have following problem: the one, the removal of impurities of heavy metal inhibitor is influential to the hue value of product, and the whiteness of product and brightness are difficult to further raising; The 2nd, technology controlling and process is relatively more difficult, the poor stability of quality product; The 3rd, the heavy metal inhibitor is expensive, causes production cost higher; The 4th, produced quantity is high, and ethylene glycol consumption is large; The 5th, in the lower situation of the beavy metal impurity content of antimonous oxide, increase the weight of again the metal deactivator removal of impurities, not obvious to improving impurity-eliminating effect.
Summary of the invention
The object of the invention is to disclose a kind of save the heavy metal inhibitor, need not to wash and drying process, do not destroy the product huge legendary turtle close structure, can further reduce product impurity, improve the preparation method that the non-desiccating method product hue value, that reduce ethylene glycol good stability loss, quality product, simple to operate, that production cost is low is produced antimony glycol.
Technical solution of the present invention is: non-desiccating method is produced the preparation method of antimony glycol: the ratio by weight 1 ︰ 6～7 drops into retort with antimonous oxide and ethylene glycol, in retort, carry out esterified dehydration reaction under 135 ℃～150 ℃ of temperature and the reduced pressure, when reaction finishes, add the removal of impurities of decolouring of decolouring cleaner in the retort, then carry out circulating filtration, crystallization, again through directly entering the product quality packing behind the centrifuge dripping, its special character is: described reduced pressure is-0.10～-0.08mpa, described decolouring cleaner adopts single gac, behind circulating filtration, once filter again, then filtered liquid is delivered to crystallizer and makes it crystallization.
The add-on of the gac in the technical solution of the present invention can add in 1～2% the ratio that antimonous oxide drops into weight.
Gac in the technical solution of the present invention can be medical activated carbon.
Circulating filtration can be that the material after the reaction end is exported from retort in the technical solution of the present invention, returns same retort through strainer and pipeline.
The present invention has the following advantages owing to adopted above technical scheme:
1, saved drying process, avoided because of drying to antimony glycol Sb
2(OCH
2CH
2O)
3The destruction of huge legendary turtle zoarium.
2, save washing procedure, avoided using large, the inflammable and explosive methyl alcohol of toxicity and ethanol, improved production environment, eliminated unsafe factor, simplified production technique, reduced safety cost.
3, in reaction process, add single gac and make the decolouring cleaner, decolouring, impurity-eliminating effect is better, the b value 1.0～1.6 of product, the L value is up to 95～98, reduced by 0.3～0.4 than the b value 1.3～2.0 of making the product of decolouring cleaner production with gac and heavy metal inhibitor, than its L value 94～96, improved 1～2, can make the color of polyester textile product purer, brighter, obtained beyond thought technique effect.
4, adopt reduced pressure be-0.10～-0.08mpa so that produced quantity has been dropped to≤70～120 liters by original≤200 liter, greatly reduce the consumption of ethylene glycol.Produced quantity is the mixture of water and ethylene glycol, because it is high to reclaim the cost of ethylene glycol, generally as discharge of wastewater, therefore, produced quantity is lower, and the loss of ethylene glycol is just less.
5, saved the heavy metal inhibitor, not only simplified operating process, and greatly reduced decolouring removal of impurities cost, the ton product can be saved about 1000 yuan of heavy metal inhibitor spendings.
6. once filter again behind the circulating filtration, the product foreign matter content is further reduced, the good stability of quality product.
Embodiment
The present invention is further illustrated below by embodiment:
Embodiment 1: first 1800kg ethylene glycol is dropped into retort, heat 80 ℃, then drop into the 300kg antimonous oxide, begin to stir, 90 rev/mins, pass through 8kg/cm after 10 minutes
2Steam heat, after temperature in the tank reaches 100 ℃, starting vacuum system keeps the interior negative pressure of tank to be-0.099-0.089mpa, temperature is controlled at 135 ℃～140 ℃ in the retort, remain the boiling point state of mixed solution, control produced quantity≤120 liter, 3.5 hours reaction times, after reaction finishes, press antimonous oxide and drop into 1% of weight, add medicinal active carbon discoloring agent, kept 10～15 minutes, carry out circulating filtration under 150 ℃ of conditions, the material after reaction is finished is exported from retort, returns same retort through strainer and pipeline, then with other filtering net antimony glycol liquid is once filtered again, further remove the impurity that in circulating filtration, leaks filter, carry out chilling with the water coolant below 20 ℃ in slow cooling under 30 ℃ the condition after 30 minutes, 3.5 hours cooling times after filtering, make it complete crystallization, xln enters centrigugal swing dryer and dries, and mother liquor is by Returning utilization after processing, and the antimony glycol after the drying directly enters the quality inspection packaging process.The quantum of output 441kg of antimony glycol, product antimony content 54.3%, b value 1.6, L value 96,65 ℃ of temperature, fully dissolving in 20 minutes, solubleness 96%, muriate 10ppm, iron level 8ppm, vitriol 10ppm, lead content 7ppm, arsenic content 10ppm.
Embodiment 2: first 1700kg ethylene glycol is dropped into retort, heat 100 ℃, then drop into the 275kg antimonous oxide, begin to stir, 100 rev/mins, pass through 9kg/cm after 8 minutes
2Steam heat, after temperature in the tank reaches 100 ℃, start vacuum system and keep negative pressure-0.09mpa in the tank, temperature is controlled at 141 ℃～145 ℃ in the retort, remain the boiling point state of mixed solution, control produced quantity≤90 liter, 3.2 hours reaction times, after reaction finishes, press 1.5% of antimonous oxide input weight and add the decolorizing with activated carbon agent, kept 10 minutes, under 150 ℃ of conditions, carry out circulating filtration, material after the reaction end is exported from retort, return same retort through strainer and pipeline, then with other filtering net antimony glycol liquid is once filtered again, further remove the impurity that in circulating filtration, leaks filter, carry out chilling with the water coolant below 20 ℃ 35 ℃ condition slow cooling after 30 minutes after filtering, make it complete crystallization 3 hours cooling times, and xln enters centrigugal swing dryer and dries, mother liquor is by Returning utilization after processing, and the antimony glycol after the drying directly enters the quality inspection packaging process.Quantum of output 404 kg of crystalline ethylene antimony, product antimony content 54.8%, b value 1.3, L value 96.5, fully dissolving in 20 minutes under 65 ℃ of temperature, solubleness 97%, muriate 9ppm, iron level 7ppm, vitriol 10ppm, lead content 8ppm, arsenic content 11ppm.
Embodiment 3: first 1650kg ethylene glycol is dropped into retort, heat 110 ℃, then drop into the 250kg antimonous oxide, begin to stir, 100 rev/mins, steam by 10kg/cm2 after 9 minutes is heated, after temperature in the tank reaches 100 ℃, start vacuum system keep in the tank negative pressure be-0.098～-0.080mpa, the interior temperature of retort is controlled at 145 ℃～150 ℃, remains the boiling point state of mixed solution, control produced quantity≤70 liter, in 2.8 hours reaction times, after reaction finishes, press antimonous oxide and drop into 2.5% of weight.Add medicinal active carbon discoloring agent, medicinal active carbon discoloring agent preferably, kept 12 minutes, under 150 ℃ of conditions, carry out circulating filtration, material after the reaction end is exported from retort, return same retort through strainer and pipeline, then with other filtering net antimony glycol liquid is once filtered again, further remove the impurity that in circulating filtration, leaks filter, after filtering antimony glycol liquid is carried out chilling with the water coolant below 20 ℃ 40 ℃ condition slow cooling after 30 minutes, 2.5 hours cooling times, make it complete crystallization, xln enters centrigugal swing dryer and dries, and mother liquor is by Returning utilization after processing, and the antimony glycol after the drying directly enters the quality inspection packaging process.Quantum of output 371 kg of crystalline ethylene antimony, product antimony content 55%, b value 1.0, L value 98, muriate 8ppm, iron level 6ppm, vitriol 9ppm, lead content 8ppm, arsenic content 10ppm.
Claims (6)
1. non-desiccating method is produced the preparation method of antimony glycol, ratio by weight 1:6～7 drops into retort with antimonous oxide and ethylene glycol, 135 ℃～150 ℃ of temperature and reduced pressure-0.10 in retort～-carry out esterified dehydration reaction under the 0.08MPa, when reaction finishes, add the removal of impurities of decolouring of decolouring cleaner in the retort, then carry out circulating filtration, filtered liquid is delivered to crystallizer makes it crystallization, again through directly entering the product quality packing behind the centrifuge dripping, it is characterized in that: described decolouring cleaner adopts single gac, the add-on of gac adds in 1～2.5% the ratio that antimonous oxide drops into weight, described circulating filtration is that the material after reaction is finished is exported from retort, return same retort through strainer and pipeline, behind circulating filtration, with other filtering net antimony glycol liquid is once filtered again.
2. non-desiccating method according to claim 1 is produced the preparation method of antimony glycol, and it is characterized in that: described gac is medical activated carbon.
3. non-desiccating method according to claim 1 is produced the preparation method of antimony glycol, it is characterized in that: described reduced pressure is-0.096～-0.085MPa.
4. non-desiccating method according to claim 3 is produced the preparation method of antimony glycol, it is characterized in that: described reduced pressure is-0.098～-0.088MPa.
5. non-desiccating method according to claim 1 is produced the preparation method of antimony glycol, it is characterized in that: the add-on of described gac drops into 1.5～2% ratio adding of weight by antimonous oxide.
6. non-desiccating method according to claim 5 is produced the preparation method of antimony glycol, it is characterized in that: the add-on of described gac drops into 1.6～1.8% ratio adding of weight by antimonous oxide.
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| CN103044200B (en) * | 2013-01-18 | 2014-03-05 | 湖南辰州矿业股份有限公司 | Preparation method of ethylene glycol antimony |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317473A (en) * | 2001-03-26 | 2001-10-17 | 辽阳市宏伟区合成催化剂厂 | Process for preparing glycol antimony catalyst |
| CN101074186A (en) * | 2007-06-26 | 2007-11-21 | 安化县文威化工有限公司 | Production of crystalline ethylene antimony |
| CN101348417A (en) * | 2008-09-12 | 2009-01-21 | 长沙烨星电子材料有限公司 | Catalyst glycol antimony preparation |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317473A (en) * | 2001-03-26 | 2001-10-17 | 辽阳市宏伟区合成催化剂厂 | Process for preparing glycol antimony catalyst |
| CN101074186A (en) * | 2007-06-26 | 2007-11-21 | 安化县文威化工有限公司 | Production of crystalline ethylene antimony |
| CN101348417A (en) * | 2008-09-12 | 2009-01-21 | 长沙烨星电子材料有限公司 | Catalyst glycol antimony preparation |
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Effective date of registration: 20160429 Address after: 413001 26F Huachang company, Century Towers,, 1089 Yiyang Avenue, Hunan, Yiyang Patentee after: Yiyang Huachang Antimony catalyst Co., Ltd. Address before: 413500 Hunan County, Yiyang City, Hunan Province, Anhua County, East Ping Town unitary Industrial Zone Anhua County Wei Chemical Co., Ltd. Patentee before: Liu Jianwen |