CN101570470B - Method for preparing dichloropropanol by glycerin chlorination - Google Patents

Abstract

The invention relates to a method for preparing dichloropropanol by glycerin chlorination, comprising the following steps: guiding chlorine hydride to the glycerin for reaction under the catalysis of naphthenic acid functioning as catalyst, and collecting the dichloropropanol as the product of the reaction after the reaction is finished. Compared with the prior method for preparing dichloropropanol, the method for preparing the dichloropropanol by glycerin chlorination has the advantages that the catalyst can be reutilized, has high activity and good selectivity and less byproducts of reactionare generated.

Description

A kind of method for preparing dichlorohydrine through glycerin chlorination

Technical field

The present invention relates to a kind of method of producing fine chemicals.Specifically, the present invention provides a kind of method by the glycerine synthesizing dichloropropanol.

Background technology

Dichlorohydrine comprises that dichlorohydrine has two kinds of isomer, promptly 1, and 3-two chloro-2-propyl alcohol and 2,3-two trimethylewne chlorohydrin 3-s, their topmost purposes are the synthesizing epoxy chloropropanes.Epoxy chloropropane is one of principal monomer of producing epoxy resin, and global YO is all produced through dichlorohydrine more than 1,500,000 tons.Main industrial process is propylene high-temperature chlorination and allyl acetate method.The propylene high-temperature chlorination is raw material with the propylene, at high temperature generates chlorallylene with chlorine reaction, and again with hypochlorous acid reacted dichlorohydrine, last saponification obtains epoxy chloropropane.This technology is the mainstream technology of producing epoxy chloropropane at present, and technology maturation, the subject matter of existence are that three wastes discharge amount is big especially, is difficult for administering the environmental pollution especially severe.The allyl acetate method is that propylene and acetic acid oxidation under palladium catalysis generate allyl acetate, is hydrolyzed to vinyl carbinol again, and vinyl carbinol is a dichlorohydrine through chlorination, and last saponification obtains epoxy chloropropane.This method decreases than propylene high-temperature chlorination on three waste discharge, but technical process is long, and facility investment is big.These two kinds of method common ground all be with propylene with chlorine be raw material, by product is many, environmental pollution is serious.

Since earlier 1900s, another kind of synthetic route is disclosed: with hydrogenchloride or hydrochloric acid with the glycerin catalytic chlorination, referring to German Patent GB1973081906 number.Compile at H. lid Germania A. Bo Late, organic teaching and research group of department of chemistry of Nanjing University translates " organic synthesis " first collection (Science Press, nineteen fifty-seven) the 234th～235 page and has reported the method for glycerine, hydrogenchloride synthesizing dichloropropanol in the presence of acetic acid, propionic acid catalyzer.Existing many pieces of publication documents such as WO2005/021476, WO2005/054167, WO2006/020234, CN101029000 etc. have reported that glycerine chlorination reaction under the condition that catalyzer such as aliphatic carboxylic acid, acid anhydrides, acyl chlorides, lactone, acid amides, organic nitrile exist generates the method for dichlorohydrine.

The catalyst type that existing bibliographical information adopts has lipid acid, like acetic acid, propionic acid, butyric acid, caproic acid, and polycarboxylic acid such as hexanodioic acid etc. or their mixture; Acyl chlorides such as Acetyl Chloride 98Min., 6-hydroxyl caproyl chloride, or their mixture; The ester class is a ritalin, vinyl acetic monomer, methyl propionate, ethyl propionate etc.; Organic nitrile is acetonitrile, propionitrile, vinyl cyanide, isopropyl cyanide, and succinonitrile, adiponitrile or their mixture, fragrant nitrile are cyanobenzene, benzyl cyanide and substituted benzene formonitrile HCN, benzyl cyanide etc.The boiling point that these catalyzer have is low, in reaction process, for improving the transformation efficiency of glycerine, need constantly steam the water that generates in the reaction process, causes catalyst loss easily; The boiling point that has is high, has overcome the catalyst loss problem, but active low, long reaction time.

Summary of the invention

The present invention is directed to the problem that exists in the prior art, a kind of method that adopts naphthenic acid to prepare dichlorohydrine as the glycerin catalytic chlorination catalyst is provided.

Method provided by the invention comprises: in the presence of the naphthenic acid catalyzer, hydrogenchloride is passed into reacts in the glycerine, reaction finishes and collects the product dichlorohydrine.

Said naphthenic acid is selected from a kind of in ring butyric acid, chaulmoogric acid, the cyclohexylenedinitrilotetraacetic acid or their mixture.The mol ratio of naphthenic acid and glycerine can be 0.001～1: 1, and suitable mol ratio is 0.01～0.5: 1, preferred 0.02～0.2: 1.

Hydrogenchloride and glycerine mol ratio can be 1～10: 1, and suitable mol ratio is 2～6: 1.

Method provided by the invention can be carried out under normal pressure, also can carry out adding to depress.The temperature that the present invention is suitable for is between 30 ℃～160 ℃, and more suitable temperature of reaction is 50～140 ℃, and preferable reaction temperature is 80～120 ℃.Reaction times was generally 1～20 hour, was preferably 3～12 hours.

According to the inventive method, reaction finishes and obtains chlorated liquid in the afterreaction still, also possibly obtain acid distillate through distillation in the reaction process simultaneously, and purpose product dichlorohydrine promptly is present in chlorated liquid and the acid distillate.If separating dichloropropanol can be carried out underpressure distillation with chlorated liquid, obtain reduced pressure distillate and cauldron bottom residue, acid distillate and reduced pressure distillate are merged, add in the alkali and divide water-yielding stratum and oil reservoir with the back, oil reservoir is dichlorohydrine.Cauldron bottom residue is a small amount of unreacted glycerine, glycerine monochlorohydrin, catalyzer and other by product.If reacted cauldron bottom residue is joined continuation reaction in the glycerine, can no longer add catalyzer.

The present invention has no particular limits the source and the purity of raw material glycerine; The source of glycerine can be the glycerine of a day chemical industry, Triple Pressed Stearic Acid production and production of biodiesel by-product; Also can be glycerine from biological fermentation and chemosynthesis; Especially preparing the glycerine of biofuel institute by-product through greasy transesterification reaction, is renewable resources, meets the requirement and the direction of contemporary chemical industry development.Glycerine can be the raw glycerine of refining glycerine or purity 40～99%, and contained impurity should be not and hcl reaction in the glycerine, and can separate with the final product dichlorohydrine easily.Can contain glycerine monochlorohydrin in the glycerine.

Reaction of the present invention and last handling process can be intermittently batch treatments, also can serialization handle.

The dichlorohydrine that the present invention obtains can be applied to prepare epoxy chloropropane.

Compare with existing method, method characteristics provided by the invention are following:

(1) boiling point of catalyzer is higher than the boiling point of dichlorohydrine; Reaction finishes the back and from reaction product, steams dichlorohydrine; Chloro by products such as remaining catalyzer and glycerine monochlorohydrin add glycerine and are used further to chlorination reaction, can have been improved utilization ratio of raw materials by directly recycling.

(2) catalyst activity is high, and speed of response is fast.

(3) selectivity is high, under identical glycerol conversion yield, has improved the yield of dichlorohydrine.

(4) the byproduct of reaction kind is less.

Description of drawings

The color atlas of the reaction product that Fig. 1 embodiment 1 obtains, analytical results sees the following form.

RT (min)	5.448	6.332	8.148	9.615	10.748	13.632	15.998
								Material	1,3-two chloro-2-propyl alcohol	2,3-two trimethylewne chlorohydrin 3-s	Chaulmoogric acid	3-chloro-1, the 2-Ucar 35	Glycerin	Glycerine	Chaulmoogric acid-3-chloro-2-hydroxy propyl ester

The color atlas of the reaction product that Fig. 2 Comparative Examples 1 obtains, analytical results sees the following form.

RT (min)	3.348	4.448	5.565	6.465	8.682	9.248	9.782	10.898	13.815
										Material	Acetic acid	Acetic acid-1,3-two chloro-2-propyl ester	1,3-two chloro-2-propyl alcohol	2,3-two trimethylewne chlorohydrin 3-s	Acetic acid-3-chloro-2-hydroxy propyl ester,	Acetic acid-2-chloro-3-hydroxy propyl ester	3-chloro-1, the 2-Ucar 35	2-chloro-1, the 3-Ucar 35	Glycerine

Embodiment

Following embodiment is used for explaining the present invention, rather than restriction the present invention.

Embodiment 1

In the there-necked flask that has stirring and reflux; Add 92.05g (1.00mol) glycerine and 11.43g (0.10mol) chaulmoogric acid and (claim cyclopentyl formic acid again; English name: cyclopentanecarboxylic acid, lark prestige chemical reagents corporation provides), be heated to 110 ℃; Feed hydrogen chloride gas, the flow of hydrogen chloride gas is 200ml/min.Reacted 8 hours, and obtained chlorated liquid 112.18g, condensing reflux obtains acid distillate 73.87g in the reaction process, and the transformation efficiency that obtains glycerine through stratographic analysis is 99.68%.Chlorated liquid is adopted underpressure distillation, the fraction 69.20g that obtains reducing pressure, cauldron bottom residue 42.98g merges acid distillate and decompression fraction.Obtain the dichlorohydrine total recovery through stratographic analysis: 73.76%, the glycerine monochlorohydrin total recovery: 19.13%, the reaction product composition sees the following form 1:

Table 1

Embodiment 2

In the there-necked flask that has stirring and reflux, add the 42.98g cauldron bottom residue that 92.25g (1.002mol) glycerine and embodiment 1 obtain, be heated to 110 ℃, feed hydrogen chloride gas, the flow of hydrogen chloride gas is 200ml/min.Reacted 8 hours, and obtained chlorated liquid 146.32g, condensing reflux obtains acid distillate 68.90g in the reaction process, and the transformation efficiency that obtains glycerine through stratographic analysis is 99.58%.Chlorated liquid is adopted underpressure distillation, the fraction 94.35g that obtains reducing pressure, cauldron bottom residue 51.97g merges acid distillate and decompression fraction.Obtain the dichlorohydrine total recovery through stratographic analysis: 82.61%, the glycerine monochlorohydrin total recovery: 15.28%, the reaction product composition sees the following form 2:

Table 2

Embodiment 3

In the there-necked flask that has stirring and reflux, add the 51.97g cauldron bottom residue that 92.21g (1.002mol) glycerine and embodiment 2 obtain, be heated to 110 ℃, feed hydrogen chloride gas, the flow of hydrogen chloride gas is 200ml/min.Reacted 8 hours, and obtained chlorated liquid 161.02g, condensing reflux obtains acid distillate 68.60g in the reaction process, and the transformation efficiency that obtains glycerine through stratographic analysis is 99.49%.Chlorated liquid is adopted underpressure distillation, the fraction 101.85g that obtains reducing pressure, cauldron bottom residue 59.17g merges acid distillate and decompression fraction.Obtain the dichlorohydrine total recovery through stratographic analysis: 87.91%, the glycerine monochlorohydrin total recovery: 11.88%, the reaction product composition sees the following form 3:

Table 3

Embodiment 4

In the there-necked flask that has stirring and reflux, add the 59.17g cauldron bottom residue that 93.87g (1.019mol) glycerine and embodiment 3 obtain, be heated to 110 ℃, feed hydrogen chloride gas, the flow of hydrogen chloride gas is 200ml/min.Reacted 8 hours, and obtained chlorated liquid 181.02g, condensing reflux obtains acid distillate 53.15g in the reaction process, and the transformation efficiency that obtains glycerine through stratographic analysis is 99.48%.Chlorated liquid is carried out underpressure distillation, the fraction 110.92g that obtains reducing pressure, cauldron bottom residue 70.10g merges acid distillate and decompression fraction.Obtain the dichlorohydrine total recovery through stratographic analysis: 80.04%, the glycerine monochlorohydrin total recovery: 13.28%, reaction product is formed as follows

Table 4

Embodiment 5

In the there-necked flask that has stirring and reflux; Add 93.25g (1.014mol) glycerine and 12.95g (0.102mol) cyclohexylenedinitrilotetraacetic acid and (claim hexahydrobenzoic acid again; English name: cyclohexanecarboxylic acid, lark prestige chemical reagents corporation provides), be heated to 110 ℃; Feed hydrogen chloride gas, the flow of hydrogen chloride gas is 200ml/min.Reacted 8 hours, and obtained chlorated liquid 109.78g, condensing reflux obtains acid liquid 70.21g in the reaction process; The transformation efficiency that obtains glycerine through stratographic analysis is 99.52%; The dichlorohydrine total recovery is 67.72%, and the glycerine monochlorohydrin total recovery is 24.43%, and the reaction product composition sees the following form 5:

Table 5

Name of material	Weight (g)	1,3-two chloro-2-propyl alcohol (g)	2,3-two trimethylewne chlorohydrin 3-s (g)	3-chloro-1,2-Ucar 35 (g)	2-chloro-1,3-Ucar 35 (g)	Acidity (mmolNaOH/100g)
							Acid distillate	70.21	25.76	0.37	0.52	0.01	339.20
Chlorated liquid	109.78	60.33	2.12	19.67	7.18	147.25

Embodiment 6

In the there-necked flask that has stirring and reflux, add 92.87g (1.019mol) glycerine and 6.23g (0.050mol) cyclohexylenedinitrilotetraacetic acid, be heated to 100 ℃, feed hydrogen chloride gas, the flow of hydrogen chloride gas is 200ml/min.Reacted 8 hours, and obtained chlorated liquid 167.55g, because temperature of reaction is low, the acid distillate that condensing reflux obtains in the reaction process is 0.The transformation efficiency that obtains glycerine through stratographic analysis is 99.38%, and the dichlorohydrine total recovery is 58.95%, and the glycerine monochlorohydrin total recovery is 32.91%, and the reaction product composition sees the following form 6:

Table 6

Name of material	Weight (g)	1,3-two chloro-2-propyl alcohol (g)	2,3-two trimethylewne chlorohydrin 3-s (g)	3-chloro-1,2-Ucar 35 (g)	2-chloro-1,3-Ucar 35 (g)	Acidity (mmolNaOH/100g)
							Chlorated liquid	167.55	74.81	1.93	29.51	7.12	263.75

Comparative Examples 1

In the there-necked flask that has stirring and reflux, add 92.50g (1.005mol) glycerine and 6.07g (0.101mol) acetic acid, be heated to 110 ℃, feed hydrogen chloride gas, the flow of hydrogen chloride gas is 200ml/min.Reacted 8 hours, and obtained chlorated liquid 128.85g, condensing reflux obtains acid liquid 44.64g in the reaction process; The transformation efficiency that obtains glycerine through stratographic analysis is 99.62%; The dichlorohydrine total recovery is 65.02%, and the glycerine monochlorohydrin total recovery is 24.18%, and the reaction product composition sees the following form 7:

Table 7

Name of material	Weight (g)	1,3-two chloro-2-propyl alcohol (g)	2,3-two trimethylewne chlorohydrin 3-s (g)	3-chloro-1,2-Ucar 35 (g)	2-chloro-1,3-Ucar 35 (g)	Acidity (mmolNaOH/100g)
							Acid distillate	44.64	7.22	0.34	0.65	0	371.50
Chlorated liquid	128.85	75.01	1.41	21.04	4.92	106.25

Claims (9)

1. method for preparing dichlorohydrine through glycerin chlorination; Comprise: in the presence of the naphthenic acid catalyzer; Hydrogenchloride is passed in the glycerine reacts; Reaction finishes and collects the product dichlorohydrine, and said naphthenic acid is selected from a kind of in ring butyric acid, chaulmoogric acid and the cyclohexylenedinitrilotetraacetic acid or their mixture.

2. according to the described method of claim 1, it is characterized in that the mol ratio of naphthenic acid and glycerine is 0.001～1: 1.

3. according to the described method of claim 1, it is characterized in that the mol ratio of naphthenic acid and glycerine is 0.01～0.5: 1.

4. according to the described method of claim 1, it is characterized in that the mol ratio of naphthenic acid and glycerine is 0.02～0.2: 1.

5. according to the described method of claim 1, it is characterized in that the mol ratio of hydrogenchloride and glycerine is 1～10: between 1.

6. according to the described method of claim 1, it is characterized in that the mol ratio of hydrogenchloride and glycerine is 2～6: 1.

7. according to the described method of claim 1, it is characterized in that temperature of reaction is between 30 ℃～160 ℃.

8. according to the described method of claim 1, it is characterized in that temperature of reaction is 50～140 ℃.

9. according to the described method of claim 1, it is characterized in that temperature of reaction is 80～120 ℃.

Images