CN104478691B - A kind of method of aqueous phase one-step synthesis calcium stearate - Google Patents
A kind of method of aqueous phase one-step synthesis calcium stearate Download PDFInfo
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- CN104478691B CN104478691B CN201410685213.2A CN201410685213A CN104478691B CN 104478691 B CN104478691 B CN 104478691B CN 201410685213 A CN201410685213 A CN 201410685213A CN 104478691 B CN104478691 B CN 104478691B
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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Abstract
The present invention relates to a kind of method of aqueous phase one-step synthesis calcium stearate, with stearic acid and calcium hydroxide for raw material, utilizing hydrogen peroxide and alcohol to be composite catalyst, is in the aqueous phase of 1:7 ~ 15 in solid-to-liquid ratio, reacts 1 ~ 3 hour at 60 ~ 80 DEG C.The advantage of this method is that reaction efficiency is high, and filter cake moisture content is low, and be easy to dry, production cost is low; Synthesis technique is simple, can directly utilize existing double decomposition production unit to carry out industrial production; Filtrate can be recycled, and avoids the discharge of waste water.
Description
Technical field
The invention belongs to the preparing technical field of metallic soap, be specifically related to the method for stearic acid one-step synthesis calcium stearate.
Background technology
Calcium stearate is the one of metallic soap of stearic acid, has been widely used in fields such as plastics, detergents and cosmetic, coating.At present, the synthetic method of calcium stearate mainly contains: double decomposition, scorification and aqueous phase single stage method.The technique of double decomposition is the most ripe, the method that Ye Shi domestic enterprise generally adopts.But there is the defects such as quality product is poor, production cost is higher, brine waste quantity discharged is large in double decomposition.Scorification be with stearic acid and calcium hydroxide (or calcium oxide) for raw material, under melting condition, synthesize calcium stearate.The advantage of scorification (CN102344354) is non-wastewater discharge in production process, and product water ratio is low, without the need to drying process.But because the fusing point of calcium stearate is higher, temperature of reaction is usually more than 150 DEG C, and product is easily oxidized flavescence, and carry out along with reaction, reaction system viscosity increases, and not exclusively, product free acid content is higher in reaction.
Patent (CN101117312, CN101353300) discloses a kind of method of aqueous phase one-step synthesis calcium stearate.Implementation step comprises: first, and the mixed system of stearic acid and water is heated to 70 ~ 75 DEG C, then adds ammoniacal liquor, the ammonium stearate of generation can be used as emulsifying agent, makes stearic acid and water form emulsion; Secondly, calcium hydroxide is pulled an oar, and joins in stearic acid late, stirring reaction certain hour at 90 ~ 100 DEG C; Then, CaCl is added
2solution, makes ammonium stearate be converted into calcium stearate, reaches the effect of breakdown of emulsion.Finally, through centrifuge dehydration, drying, finished product is obtained.Compared with double decomposition, this approach reduce production cost, decrease the content of soluble salt in waste water.But this method still exists operating process complexity, containing a small amount of soluble salt in waste water, cannot really realize reusing of waste water.
In addition, Guo Lixin etc. (additives for plastics, 2006,5,29-31) report stearic acid and calcium hydroxide under the katalysis of hydrogen peroxide in aqueous phase the technique of one-step synthesis calcium stearate.But, (fine chemical material and intermediate, 2011 such as Wu Shugang, 9,3-6) find that the catalytic reaction effect that hydrogen peroxide synthesizes calcium stearate to stearic acid and calcium hydroxide is unsatisfactory, there is speed of response slow, the problems such as material easily wraps up, and product free acid is high, and solid accumulation density is large.Take quaternary amine as catalyzer, then can obtain the good product of quality, but there is the problems such as quaternary amine price is higher, the reaction times is longer.Wu Maoying etc. (daily chemical industry, 2003,5,292-294), by a kind of specific processing method, make stearic acid and calcium hydroxide one-step synthesis calcium stearate in aqueous phase.But Wu Maoying etc. do not disclose this specific processing method, and need to cross 200 object high quality calcium hydroxides for raw material, the reaction times is also longer.Hu Guohua etc. (Chemical Industry in Guangzhou, 2013,9,199-201) improve the equipment that double decomposition produces calcium stearate, achieve aqueous phase one-step synthesis calcium stearate, but do not mention the quality index such as the bulk density of product in the middle of document.
In sum, develop and be a kind ofly easy to realize efficient, the low cost of industrialization, the calcium stearate one-step method for synthesizing of environmental protection on existing double decomposition production unit, remain the technical problem that the researchist in this field is in the urgent need to address.
Summary of the invention
For solving above technical problem, the object of the present invention is to provide and a kind ofly be easy to realize efficient, the low cost of industrialization, the calcium stearate synthetic method of environmental protection on existing double decomposition production unit.
For solving the problems of the technologies described above, the invention provides a kind of method of aqueous phase one-step synthesis calcium stearate, the method is made up of following steps:
Be that stearic acid and the water of 1:7 ~ 15 adds in reactor by mass ratio, stir and be warming up to 60 ~ 80 DEG C; Add hydrogen peroxide and alcohol as composite catalyst, control hydrogen peroxide and stearic mass ratio is 1:4 ~ 10, alcohol and stearic mass ratio are 1:10 ~ 30; Add calcium hydroxide, control calcium hydroxide and stearic mass ratio are 1:6.9 ~ 7.2; React after 1 ~ 3 hour, cooled by reaction solution, centrifugal, gained solids is calcium stearate after drying; Filtrate can be recycled.
Described alcohol be in glycerol, ethanol, propyl alcohol, ethylene glycol and propylene glycol any one or multiple.
Compared with prior art, the method for aqueous phase one-step synthesis calcium stearate provided by the invention has the following advantages: the hydrogen peroxide used in reaction and alcohol have synergy, and reaction efficiency is high; The product particle obtained after centrifugation is thin, and filter cake moisture content is low, and be easy to dry, the bulk density of finished product is little; Synthesis technique is simple, can directly utilize existing double decomposition production unit to carry out industrial production; Filtrate can be recycled, and avoids the discharge of waste water.
Embodiment
Below the specific embodiment of the present invention is described in further detail.For person of ordinary skill in the field, from detailed description of the invention, above and other object of the present invention, feature and advantage will be apparent.
Embodiment 1:
13.65g stearic acid and 150g water are added in reaction vessel, is heated to 60 DEG C, after stearic acid all dissolves, open and stir, add 3g hydrogen peroxide and 0.68g glycerol, then add 1.98g calcium hydroxide in batches, react 2 hours.After having reacted, product, through centrifugation, drying, pulverizing, gets product.The quality test results of product is as shown in table 1.
Embodiment 2:
13.65g stearic acid and 200g water are added in reaction vessel, is heated to 70 DEG C, after stearic acid all dissolves, open and stir, add 3g hydrogen peroxide and 1.0g ethanol, then add 1.90g calcium hydroxide in batches, react 3 hours.After having reacted, product, through centrifugation, drying, pulverizing, gets product.The quality test results of product is as shown in table 1.
Embodiment 3:
13.65g stearic acid and 120g water are added in reaction vessel, is heated to 80 DEG C, after stearic acid all dissolves, open and stir, add 2g hydrogen peroxide and 0.8g propyl alcohol, then add 1.95g calcium hydroxide in batches, react 1 hour.After having reacted, product, through centrifugation, drying, pulverizing, gets product.The quality test results of product is as shown in table 1.
Embodiment 4:
13.65g stearic acid and 160g water are added in reaction vessel, is heated to 60 DEG C, after stearic acid all dissolves, open and stir, add 3g hydrogen peroxide and 0.7g ethylene glycol, then add 1.98g calcium hydroxide in batches, react 2 hours.After having reacted, product, through centrifugation, drying, pulverizing, gets product.The quality test results of product is as shown in table 1.
Embodiment 5:
13.65g stearic acid and 130g water are added in reaction vessel, is heated to 60 DEG C, after stearic acid all dissolves, open and stir, add 1.5g hydrogen peroxide and 0.5g glycerol, then add 1.95g calcium hydroxide in batches, react 3 hours.After having reacted, product, through centrifugation, drying, pulverizing, gets product.The quality test results of product is as shown in table 1.
Embodiment 6(amplification test):
Amplification test directly adopts original double decomposition production unit, without the need to improving equipment.136.5Kg stearic acid and 1400Kg water are added in reaction vessel, is heated to 60 DEG C, after stearic acid all dissolves, open and stir, add 25Kg hydrogen peroxide and 6Kg glycerol, then add 19.5Kg calcium hydroxide in batches, react 2 hours.After having reacted, product, through centrifugation, drying, pulverizing, gets product.The quality test results of product is as shown in table 1.
Embodiment 7(amplification test):
The filtrate 1100Kg of 136.5Kg stearic acid and embodiment 6 is added in reaction vessel, adds water 300Kg and glycerine 0.8Kg, be heated to 60 DEG C, after stearic acid all dissolves, open and stir, add 25Kg hydrogen peroxide, add 19.5Kg calcium hydroxide more in batches, react 2 hours.After having reacted, product, through centrifugation, drying, pulverizing, gets product.The quality test results of product is as shown in table 1.
Comparative example 1:
13.65g stearic acid and 150g water are added in reaction vessel, is heated to 60 DEG C, after stearic acid all dissolves, open and stir, add 1.98g calcium hydroxide in batches, react 2 hours.After having reacted, product, through centrifugation, drying, pulverizing, gets product.The quality test results of product is as shown in table 1.
Comparative example 2:
13.65g stearic acid and 150g water are added in reaction vessel, is heated to 60 DEG C, after stearic acid all dissolves, open and stir, add 3g hydrogen peroxide, then add 1.98g calcium hydroxide in batches, react 2 hours.After having reacted, product, through centrifugation, drying, pulverizing, gets product.The quality test results of product is as shown in table 1.
Comparative example 3:
13.65g stearic acid and 150g water are added in reaction vessel, is heated to 60 DEG C, after stearic acid all dissolves, open and stir, add 0.68g glycerol, then add 1.98g calcium hydroxide in batches, react 2 hours.After having reacted, product, through centrifugation, drying, pulverizing, gets product.The quality test results of product is as shown in table 1.
Table 1: the quality test results of calcium stearate product.
Test-results shows: according to the method for aqueous phase one-step synthesis calcium stearate provided by the invention, with hydrogen peroxide and alcohol for composite catalyst, the quality product of producing can reach the premium grads standard that industry standard HG/T2424-2012 specifies, product bulk density is little, and cake moisture is low, particle is tiny, is easy to dry.Compared with method provided by the invention, do not add catalyzer, separately with hydrogen peroxide or alcohol for catalyzer time, the reaction of stearic acid and calcium hydroxide is difficult to completely, and the free acid of product is higher, and comparatively greatly, bulk density is also higher for product grain.Therefore, hydrogen peroxide and alcohol demonstrate good synergy in the reaction of aqueous phase one-step synthesis calcium stearate, and this is core innovation of the present invention just also.
Be to be understood that; although the present invention is clearly demonstrated by above embodiment; but when not deviating from the present invention's spirit and essence thereof; person of ordinary skill in the field is when making various corresponding change and correction according to the present invention, but these changes accordingly and correction all should belong to the protection domain of claim of the present invention.
Claims (1)
1. a method for aqueous phase one-step synthesis calcium stearate, is characterized in that, with hydrogen peroxide and alcohol for composite catalyst, and the one-step synthesis calcium stearate in water by stearic acid and calcium hydroxide, reactions steps is as follows:
(1) be that the stearic acid of 1:7 ~ 15 and water add in reactor by mass ratio, stir and be warming up to 60 ~ 80 DEG C;
(2) hydrogen peroxide and alcohol is added as composite catalyst, described alcohol be in glycerol, propyl alcohol, ethylene glycol and propylene glycol any one or multiple, control hydrogen peroxide and stearic mass ratio are 1:4 ~ 10, and alcohol and stearic mass ratio are 1:10 ~ 30;
(3) add calcium hydroxide, control calcium hydroxide and stearic mass ratio are: 1:6.9 ~ 7.2;
(4) react after 1 ~ 3 hour, cooled by reaction solution, centrifugation, gained solids is calcium stearate after drying; Filtrate can be recycled.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2124495C1 (en) * | 1997-06-10 | 1999-01-10 | Стерлитамакский ЗАО "Каустик" | Calcium stearate production method |
| RU2259993C1 (en) * | 2004-03-29 | 2005-09-10 | Закрытое акционерное общество "Каустик" | Method for preparing calcium stearate |
| CN102041152A (en) * | 2010-09-29 | 2011-05-04 | 上海东升新材料有限公司 | Metal stearate lubricating agent and preparation method and application thereof |
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2014
- 2014-11-25 CN CN201410685213.2A patent/CN104478691B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2124495C1 (en) * | 1997-06-10 | 1999-01-10 | Стерлитамакский ЗАО "Каустик" | Calcium stearate production method |
| RU2259993C1 (en) * | 2004-03-29 | 2005-09-10 | Закрытое акционерное общество "Каустик" | Method for preparing calcium stearate |
| CN102041152A (en) * | 2010-09-29 | 2011-05-04 | 上海东升新材料有限公司 | Metal stearate lubricating agent and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 直接法工艺合成硬脂酸钙的工业化研究;郭立新登;《塑料助剂》;20061020(第5期);第29-31页 * |
| 直接法工艺合成硬脂酸钙的研究及工业化生产;郭立新等;《化工文摘》;20060601(第3期);第37-38页 * |
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