CN101914008B - Method for recycling catalyst in process of preparing dichloropropanol by using glycerol method - Google Patents
Method for recycling catalyst in process of preparing dichloropropanol by using glycerol method Download PDFInfo
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- CN101914008B CN101914008B CN2010102500757A CN201010250075A CN101914008B CN 101914008 B CN101914008 B CN 101914008B CN 2010102500757 A CN2010102500757 A CN 2010102500757A CN 201010250075 A CN201010250075 A CN 201010250075A CN 101914008 B CN101914008 B CN 101914008B
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- catalyzer
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- preparing dichloropropanol
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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
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a method for recycling a catalyst in a process of preparing dichloropropanol by using a glycerol method, which comprises the steps of: carrying out decompression and distillation on a kettle bottom solution for preparing the dichloropropanol by using the glycerol method to obtain residual slag of the kettle bottom solution, adding water for refluxing and hydrolyzing adipate in the residual slag, wherein the mass ratio of the kettle bottom solution and the water during the hydrolysis is 1:1.5-3, the reflux time is 4-6h; cooling a hydrolysis product, crystallizing and filtering, collecting crystals, standing and demixing filtrate to obtain an organic layer and a water layer; standing the water layer for 10-20h, crystallizing and then filtering and collecting crystals; preparing alkali liquor with mass concentration of 20-40 percent and the organic layer, mixing, refluxing and hydrolyzing, wherein the reflux time is 1-2h; adding acid in a hydrolyzed product for keeping controlling the temperature and acidizing within a pH value range of 2-3; cooling, crystallizing, filtering and collecting crystals after evaporating and condensing an acidic solution; and merging the crystals collected in three times and then washing with water and purifying to obtain adipic acid crystals. The invention has the advantages of short hydrolysis time and high adipic acid yield.
Description
Technical field
The invention belongs to a kind of method that from the preparing dichloropropanol by using glycerol method kettle base solution, reclaims the catalyzer hexanodioic acid.
Background technology
Along with the rise of Biodiesel and the recovery of oil prodution industry, by-product a large amount of cheap glycerine, so the method for coming synthesizing dichloropropanol take glycerine as raw material and then preparing epoxy chloropropane is risen again.The reaction that the glycerine chloro generates dichlorohydrine is to realize under the effect of the catalyzer such as organic carboxyl acid, and hexanodioic acid has showed higher catalytic activity and the high (T of its boiling point as a kind of SOLID ORGANIC carboxylic acid in the glycerin catalytic chlorination prepares the reaction of dichlorohydrine
b=332.7 ℃), therefore be applied widely.
But in this reaction process, the catalyst system therefor hexanodioic acid participates in reaction, be embodied in catalyzer in reaction process with glycerine, glycerine monochlorohydrin, the dichlorohydrine generation ester that reacts, increase along with the catalytic agent reuse number of times, the content of adipic acid ester constantly rises, thereby cause its catalytic activity to reduce gradually, therefore in order to guarantee that its catalytic activity reduces the three wastes simultaneously, be necessary afterwards it to be hydrolyzed to reclaim the catalyzer hexanodioic acid several times at catalytic agent reuse.
Patent US20070112224 discloses the method that reclaims the catalyzer hexanodioic acid in a kind of preparing dichloropropanol by using glycerol method kettle base solution.Reactor substrate and certain density mixed in hydrochloric acid, back hydrolysis, then decrease temperature crystalline filters and obtains adipic acid crystals.This patent employing acidic hydrolysis method reclaims hexanodioic acid wherein, and hydrolysis time is longer, and has hydrolysising balance, so the hexanodioic acid rate of recovery is lower.
Summary of the invention:
The objective of the invention is the above-mentioned shortcoming for the acidic hydrolysis existence, provide a kind of hydrolysis time short, the recovery method that adipic acid yield is high.
The solubleness temperature influence of hexanodioic acid in water is violent, is soluble in hot water, descends rapidly along with temperature reduces its solubleness.The solubleness of hexanodioic acid in room temperature (25 ℃) Shi Zaishui is 2.3g/100g water, and the solubleness in water is 160g/100g water in the time of 100 ℃, therefore can come hexanodioic acid in the crystal water solution system by the method that cools, not need to add in addition crystallization auxiliary.The present invention has utilized the characteristic of above-mentioned hexanodioic acid.
Recovery method of the present invention may further comprise the steps:
(1) the preparing dichloropropanol by using glycerol method kettle base solution is carried out underpressure distillation to remove dichlorohydrine and glycerine monochlorohydrin wherein, obtain the kettle base solution residue;
(2) in the kettle base solution residue, add entry wherein adipic acid ester is carried out back hydrolysis; The mass ratio of kettle base solution residue and water is during hydrolysis: the kettle base solution residue: water=1: 1.5～3; Return time is 4～6h;
(3) to hydrolysate lower the temperature, crystallization filters, and collects crystal, the filtrate standing demix obtains organic layer and water layer; Water layer filters the collection crystal after leaving standstill 10～20h crystallization again;
(4) the preparation mass concentration is 20～40% alkali lye and the middle organic layer mixing back hydrolysis that produces of step (3), return time 1～2h;
(5) adding acid in the product after hydrolysis keeps pH to carry out the temperature control acidifying in 2～3 scope;
(6) with after the acidizing fluid evaporation concentration, lower the temperature, crystallization, filtration, collect crystal;
(7) with washing purifying after three collected crystal merging, obtain adipic acid crystals.
Comprise glycerine, glycerine monochlorohydrin, dichlorohydrine, hexanodioic acid, glycerine monochlorohydrin adipate monoester, two-(glycerine monochlorohydrin)-adipic acid ester, dichlorohydrine adipate monoester, two-(dichlorohydrine)-adipic acid ester, high boiling chloro by product etc. in the described preparing dichloropropanol by using glycerol method kettle base solution.
Described alkali can be alkali metal hydroxide or alkaline earth metal hydroxides, such as being sodium hydroxide, potassium hydroxide, calcium hydroxide etc.
During the middle organic layer mixing back hydrolysis that produces of described alkali lye and step (3), first organic layer is measured its saponification value, required theoretical alkali number when calculating alkaline hydrolysis according to saponification value, actual adding alkali number are 1.1～1.3 times of theoretical alkali number.
Temperature during described temperature control acidifying is 55～75 ℃.Described acid is a kind of in nitric acid, sulfuric acid, the hydrochloric acid.
Preferred bases of the present invention is sodium hydroxide, and acid is nitric acid.
Crystallization in described step (3) and (6) only needs under agitation hydrolysate slowly to be cooled to room temperature, just can separate out adipic acid crystals, does not need to add in addition crystallization auxiliary.
The kettle base solution that the present invention is produced when being suitable for processing take hexanodioic acid as catalyzer by preparing dichloropropanol by using glycerol method especially is fit to process the kettle base solution of catalyzer hexanodioic acid through producing behind the cyclically utilizing repeatedly.
The present invention has following advantage:
1. adopt the method for two one-step hydrolysis, improved the rate of recovery of catalyzer hexanodioic acid;
2. be hydrolyzed simultaneously other chloro by product in the system.
3. reduced the content of chlorinatedorganic in the Recycling of waste liquid
Specific embodiment:
The following examples are to illustrate of the present inventionly, rather than limit of the present invention.
Embodiment 1
(hexanodioic acid exists with the form of adipic acid ester in the kettle base solution to get preparing dichloropropanol by using glycerol method kettle base solution 400g, converted herein and be hexanodioic acid 130.72g) add in the four-hole bottle, remove dichlorohydrine and glycerine monochlorohydrin through underpressure distillation, obtain residue 300g. and be cooled to adding 450g water in the backward residue of room temperature, back hydrolysis 6h.Hydrolysate under agitation is cooled to room temperature, filters behind the 2h and obtain first crystal 72.69g; The filtrate layering obtains water layer 510g and organic layer 95g.The water layer of 510g filters water layer through after leaving standstill 10h, isolates second batch crystal 3 5.22g; In the organic layer of 95g, add behind the sodium hydroxide solution that 420g concentration is 20wt% back hydrolysis 2h in four-hole bottle, then be cooled to 55 ℃ and drip nitric acid maintenance ph=2 reaction 1h, after the evaporation concentration, be cooled to room temperature under stirring, the 3rd crowd of crystal 3 8.52g filtered to get in crystallization.After first crystal, second batch crystal and the 3rd batch of crystal merged, with 100ml water washing twice, obtain adipic acid crystals 117.4g (hexanodioic acid wt%=95.6%).Be 86.22% through adipic acid yield behind two one-step hydrolysis.
Embodiment 2
(hexanodioic acid exists with the form of adipic acid ester in the kettle base solution to get preparing dichloropropanol by using glycerol method kettle base solution 400g, converted herein and be hexanodioic acid 131.26g) add in the four-hole bottle, remove dichlorohydrine and glycerine monochlorohydrin through underpressure distillation, obtain residue 304g. and be down to adding 500g water in the backward residue of room temperature, back hydrolysis 5.5h.Hydrolysate under agitation is cooled to room temperature, filters behind the 2h and obtain first crystal 70.34g; The filtrate layering, water layer 548g and organic layer 87g, water layer isolate second batch crystal 3 1.06g after leaving standstill 20h; In the 87g organic layer, add behind the sodium hydroxide that 260g concentration is 30wt% back hydrolysis 2.5h in four-hole bottle, then be cooled to 60 ℃ and regulate ph=3 reaction 1h with nitric acid, under agitation be cooled to room temperature after the evaporation concentration, the 3rd crowd of crystal 3 6.52g filtered to get in crystallization.After first crystal, second batch crystal and the 3rd batch of crystal merged, with 100ml water washing twice, obtain adipic acid crystals 114.3g (hexanodioic acid wt%=96.2%).Be 83.77% through adipic acid yield behind two one-step hydrolysis.
Embodiment 3
(hexanodioic acid exists with the form of adipic acid ester in the kettle base solution to get preparing dichloropropanol by using glycerol method kettle base solution 400g, converted herein and be hexanodioic acid 128.47g) add in the four-hole bottle, remove dichlorohydrine and glycerine monochlorohydrin through underpressure distillation, obtain residue 306g and be cooled to adding 900g water in the backward residue of room temperature, back hydrolysis 4h.Hydrolysate under agitation is cooled to room temperature, filters behind the 2h and obtain first crystal 71.86g; The filtrate layering obtains water layer 956g and organic layer 81g.The water layer of 956g filters water layer through after leaving standstill 15h, isolates second batch crystal 3 4.12g; In the organic layer of 81g, add behind the sodium hydroxide that 180g concentration is 40wt% back hydrolysis 3h in four-hole bottle, then be cooled to 70 ℃ and drip nitric acid maintenance ph=2 reaction 1h, after the evaporation concentration, be cooled to room temperature under stirring, the 3rd crowd of crystal 3 8.52g filtered to get in crystallization.After first crystal, second batch crystal and the 3rd batch of crystal merged, with 100ml water washing twice, obtain adipic acid crystals 116.2g (hexanodioic acid wt%=95.8%).Be 86.65% through adipic acid yield behind two one-step hydrolysis.
Comparative Examples:
(hexanodioic acid exists with the form of adipic acid ester in the kettle base solution to get preparing dichloropropanol by using glycerol method kettle base solution 400g, converted herein and be hexanodioic acid 129.63g) place the four-hole bottle with water trap, azeotropic hydrogenchloride (HCL%=20.02%) 160.3g and water 58.2g are joined in the flask back-mixing compound backflow 10h.In water trap, obtain 86.6g and contain the organic layer of 83% dichlorohydrine and 17% water and the water layer that 165.8g contains 15% dichlorohydrine, contain the 319.2g hydrolysate in the four-hole bottle.Hydrolysate under agitation is cooled to room temperature, filters to get first crystal 80.62g behind the 2h, filtrate obtains second batch crystal 3 9.86g after leaving standstill 20h.After first crystal and the merging of second batch crystal, with 100ml water washing twice, obtain adipic acid crystals 93.90g (hexanodioic acid wt%=94.7%).Adipic acid yield is 68.60% behind the process back hydrolysis.
Claims (10)
1. the recovery method of catalyzer in the process of preparing dichloropropanol by using glycerol method is characterized in that comprising the steps:
(1) the preparing dichloropropanol by using glycerol method kettle base solution is carried out underpressure distillation to remove dichlorohydrine and glycerine monochlorohydrin wherein, obtain the kettle base solution residue;
(2) in the kettle base solution residue, add entry wherein adipic acid ester is carried out back hydrolysis; The mass ratio of kettle base solution residue and water is during hydrolysis: the kettle base solution residue: water=1: 1.5～3; Return time is 4～6h;
(3) to hydrolysate lower the temperature, crystallization filters, and collects crystal, the filtrate standing demix obtains organic layer and water layer; Water layer filters the collection crystal after leaving standstill 10～20h crystallization again;
(4) the preparation mass concentration is 20～40% alkali lye and the middle organic layer mixing back hydrolysis that produces of step (3), return time 1～2h;
(5) adding acid in the product after hydrolysis keeps pH to carry out the temperature control acidifying in 2～3 scope;
(6) with after the acidizing fluid evaporation concentration, lower the temperature, crystallization, filtration, collect crystal;
(7) with washing purifying after three collected crystal merging, obtain adipic acid crystals.
2. the recovery method of catalyzer in a kind of process of preparing dichloropropanol by using glycerol method as claimed in claim 1 is characterized in that comprising in the described preparing dichloropropanol by using glycerol method kettle base solution glycerine, glycerine monochlorohydrin, dichlorohydrine, hexanodioic acid, glycerine monochlorohydrin adipate monoester, two one (glycerine monochlorohydrin) adipic acid ester, dichlorohydrine adipate monoester, two one (dichlorohydrine) adipic acid ester and high boiling chloro by product.
3. the recovery method of catalyzer in a kind of process of preparing dichloropropanol by using glycerol method as claimed in claim 1 is characterized in that described alkali is alkali metal hydroxide or alkaline earth metal hydroxides.
4. the recovery method of catalyzer in a kind of process of preparing dichloropropanol by using glycerol method as claimed in claim 3 is characterized in that described alkali metal hydroxide is sodium hydroxide or potassium hydroxide.
5. the recovery method of catalyzer in a kind of process of preparing dichloropropanol by using glycerol method as claimed in claim 3 is characterized in that described alkaline earth metal hydroxides is calcium hydroxide.
6. the recovery method of catalyzer in a kind of process of preparing dichloropropanol by using glycerol method as claimed in claim 1, during the organic layer mixing back hydrolysis that it is characterized in that producing in the alkali lye of described step (4) and the step (3), first organic layer is measured its saponification value, required theoretical alkali number when calculating alkaline hydrolysis according to saponification value, actual adding alkali number are 1.1～1.3 times of theoretical alkali number.
7. the recovery method of catalyzer in a kind of process of preparing dichloropropanol by using glycerol method as claimed in claim 1, the temperature when it is characterized in that described temperature control acidifying is 55～75 ℃.
8. the recovery method of catalyzer in a kind of process of preparing dichloropropanol by using glycerol method as claimed in claim 1 is characterized in that described acid is a kind of in nitric acid, sulfuric acid or the hydrochloric acid.
9. the recovery method of catalyzer in a kind of process of preparing dichloropropanol by using glycerol method as claimed in claim 1 is characterized in that described alkali is sodium hydroxide, and acid is nitric acid.
10. the recovery method of catalyzer in a kind of process of preparing dichloropropanol by using glycerol method as claimed in claim 1, it is characterized in that the crystallization in described step (3) and (6) only needs under agitation hydrolysate slowly to be cooled to room temperature, just separates out adipic acid crystals.
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| CN103524729B (en) * | 2013-10-17 | 2015-09-16 | 宁波环洋化工有限公司 | A kind of production method of mortar concrete admixture |
| CN105237354B (en) * | 2014-10-24 | 2018-07-03 | 连云港环海化工有限公司 | The recoverying and utilizing method of glycerin chlorination raffinate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1882522A (en) * | 2003-11-20 | 2006-12-20 | 索尔维公司 | Process for producing dichloropropanol from glycerol, the glycerol coming eventually from the conversion of animal fats in the manufacture of biodiesel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1882522A (en) * | 2003-11-20 | 2006-12-20 | 索尔维公司 | Process for producing dichloropropanol from glycerol, the glycerol coming eventually from the conversion of animal fats in the manufacture of biodiesel |
| CN101284764A (en) * | 2003-11-20 | 2008-10-15 | 索尔维公司 | Process for producing epoxy resin |
Non-Patent Citations (2)
| Title |
|---|
| 甘油氯化制备二氯丙醇过程中副产物处理的研究;程晓曦等;《化工时刊》;20100202;第24卷(第2期);21-24 * |
| 程晓曦等.甘油氯化制备二氯丙醇过程中副产物处理的研究.《化工时刊》.2010,第24卷(第2期),21-24. |
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