CN86102942A - Dichlorohydrine is synthetic to be reached-footwork hydrolysis system glycerine - Google Patents
Dichlorohydrine is synthetic to be reached-footwork hydrolysis system glycerine Download PDFInfo
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- CN86102942A CN86102942A CN86102942.9A CN86102942A CN86102942A CN 86102942 A CN86102942 A CN 86102942A CN 86102942 A CN86102942 A CN 86102942A CN 86102942 A CN86102942 A CN 86102942A
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- dichlorohydrine
- glycerine
- propenyl chloride
- butyl hypochlorate
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Abstract
The present invention is to be raw material with propenyl chloride, t-butyl hypochlorate, water, produces the commercial run of glycerine through dichlorohydrine.Its technical process is: the t-butyl hypochlorate that will be made by chlorine, the trimethyl carbinol and aqueous sodium hydroxide solution reaction and propenyl chloride react generation concentration in the aqueous solution be dichlorohydrine more than 80%.Again this dichlorohydrine one-step hydrolysis in basic solution is made concentration and is rare glycerine of 13～15%.After purify, concentrate, vacuum distilling etc. handled, obtain the pure glycerin more than 99%.
Description
The invention belongs to organic chemistry filed.
Glycerine (glycerol) is a kind of organic compound of having many uses, and is used for chemistry, food, braiding, printing, light industry, fiery explosive and other industrial sectors in a large number.Glycerine and Tetra hydro Phthalic anhydride condensation synthetic alkyd resin are a kind of maximum purposes of glycerine.Industry such as urethane foam, makeup, medicine (comprising toothpaste) and tobacco processing are also very big to the demand of glycerine; Wherein the demand growth in recent years of polyurethane foam industry is the fastest.
The industrial preparation of synthetic glycerine generally adopts traditional chlorine alcoholization process, promptly carries out chlorohydrin action by hypochloric acid water solution and propenyl chloride, obtains the corresponding chloropharin (being generally 4～5%) of lower concentration.Again through cyclisation, refining obtain the pure product of epoxy chloropropane, hydrolysis makes glycerine in basic solution then.The main drawback of this method is a long flow path, and yield is low, produces the sewage that contains organic muriate, alcohol and inorganic salt in a large number in cyclization process, and 1 ton of glycerine of every production produces 60 tons of sewage approximately, must the huge sewage biochemical treatment facility of configuration.
For avoiding large amount of sewage, improve the chlorohydrination yield, adopted the closed loop chlorohydrination as U.S. Lu Musi company (Lummus Co.) abroad, but suitability for industrialized production not as yet.(as United States Patent (USP) U.S.P.4,008,133(1977); U.S.P.4,126,526(1978); U.S.P.4,496,753(1985)) to adopt t-butyl hypochlorate to replace the hypochlorous acid of lower concentration be the chlorohydrin action raw material in improved technical process, thereby improved chloropharin concentration (being about 30% weight).The saline sewage that reaction produces in the whole process is treated remove organic impurity after, return electrolyzer and recycle.Therefore, this technology has eliminated that traditional chlorohydrination produces contains CaCl in a large number
2Sewage.But the processing of saline sewage and recycling certainly will increase power consumption.
The present invention is directed to above-mentioned shortcoming improves.Improved technology is earlier to make concentration with t-butyl hypochlorate, water and propenyl chloride to reach dichlorohydrine more than 80%, is raw material with this dichlorohydrine then, without cyclisation and treating process directly in basic solution hydrolysis make glycerine.The present invention has the following advantages:
1. because flow process without the cyclisation stage, thereby does not produce a large amount of saline sewages, eliminated pollution.
2. improved the yield of dichlorohydrine and glycerine.The chlorohydrination yield is 94～98%, improves 6～8% than traditional method; The hydrolysis yield is that 87～88%(is in dichlorohydrine), the glycerine total recovery is compared with traditional method and is improved 16～18%.
3. owing to saved the huge cyclisation device and the biochemical treatment system of epoxy chloropropane refining system and sewage, thereby shorten flow process, saving equipment reduces investment.
In addition, estimate industrial production of the present invention after, its power consumption, raw materials consumption etc. can be lower than traditional method, production cost is compared with present advanced index, approximately can descend 25～30%.
Except that above advantage, equipment used in the present invention is easy to processing, and engineering problems such as the corrosion of equipment are resolved by test.
Generally speaking, be dissolved with the free chlorine (Cl of some amount in the synthetic t-butyl hypochlorate
2), this free chlorine and t-butyl hypochlorate have the ability of carrying out chemical reaction with propenyl chloride equally, are referred to as reactive chlorine.Following reaction then takes place in the entry when the t-butyl hypochlorate that contains free chlorine adds:
Newly-generated hypochlorous acid runs into propenyl chloride chlorohydrin action generation dichlorohydrine then takes place, and reaction formula is as follows:
Experimental result shows that generally speaking, HOCl and alkene or alkene derivatives are inoperative, only reacts in acidic medium and just can carry out, and therefore above-mentioned chlorohydrin action must carry out in acidic aqueous solution.
Be dissolved in the free chlorine (Cl in the t-butyl hypochlorate
2) and H
2O reaction, major part change HOCl into has participated in chlorohydrin action generation dichlorohydrine; Portion C l
2Participate in reaction and generate trichloropropane and other side reaction things.The yield that how much affects chlorohydrin action and the selectivity of free chlorine.Free chlorine is too many, can reduce reaction yield; Free chlorine then reacts and can not carry out very little.Therefore, to improve the chlorohydrination yield significantly and reduce the side reaction deposits yields, then must strictly control the concentration of free chlorine in water and the acidity of solution, promptly control the cl content that dissociates in the prepared t-butyl hypochlorate below 1%, control the mol ratio of t-butyl hypochlorate and propenyl chloride and the pH value of regulating the aqueous solution simultaneously.
Experiment showed, to add the acidity that strong acid such as sulfuric acid or nitric acid are regulated the aqueous solution in the system, the control pH value is below 5, and then the chlorohydrination yield can reach 96～97%, Cl in the reaction solution
-Content below 1000ppm, Cl in the circulation fluid
-Do not have a large amount of accumulation, thereby guaranteed normally carrying out of reaction.
The present invention has made concentration according to above principle and has reached dichlorohydrine crude product more than 80%, and makes glycerine as raw material one one-step hydrolysis.Dichlorohydrine hydrolysis in basic solution makes rare glycerine of 13～15%.Rare glycerine obtains concentration after purifying, concentrating be glycerine more than 80%.Again after vacuum distilling, gac and treatment on ion exchange columns, can obtain purity and be 99.5% glycerine.
Dichlorohydrine hydrolysis in basic solution is produced the reaction mechanism of glycerine basically with identical by epoxy chloropropane hydrolysis system glycerine, and different is that two reactions of the present invention are carried out in same hydrolysis kettle.After dichlorohydrine and NaOH reaction generate epoxy chloropropane, then continue in basic solution, to react generating glycerine.Reaction formula is as follows:
Except that above-mentioned main reaction, remain in other side reactions, generate Polyglycerine as glycerine and epoxy chloropropane polymerization, epoxy chloropropane and HCl reaction generate 1,3-dichlorohydrine etc., wherein main side reaction is to generate two Polyglycerine.
The technical process that the present invention adopts is as follows: at first by the synthetic t-butyl hypochlorate of the trimethyl carbinol, chlorine and aqueous sodium hydroxide solution.Then, the ratio of components of stipulating according to the present invention drips new synthetic t-butyl hypochlorate and propenyl chloride continuously in the chlorohydrination reactor that fills distilled water (being preheating to 40 ℃), start agitator simultaneously, and add the pH value of small amounts of inorganic acid-conditioning solution.Strict control rate of addition, reinforced finishing fully stirred 10～15 minutes in 1 hour; Question response finishes, and stops to stir, and leaves standstill 10～15 minutes, and dichlorohydrine promptly generates.In this process, temperature of reaction can be controlled in 10～70 ℃ of scopes, is the best with 35～50 ℃; Reaction can be carried out adding to depress, and also can carry out under normal pressure.This chlorohydrin action is two alternate contact reactss, and the mixing efficiency of reactor is very important, and generally speaking, as long as t-butyl hypochlorate and propenyl chloride must be got well in aqueous phase emulsification, reaction just can normally be carried out.Mol ratios such as the ratio of components of t-butyl hypochlorate and propenyl chloride generally is defined as or propenyl chloride are more excessive slightly.The ratio of components that the present invention adopts is a t-butyl hypochlorate: propenyl chloride=1: 0.98～1.01(mole).
Reacted chloropharin hydrorrhea flows into quantizer, tells the organic layer dichlorohydrine from the bottom, and this organic layer dichlorohydrine is sent into the dichlorohydrine tower.Cat head is told the trimethyl carbinol, and treated removing returned the t-butyl hypochlorate reactor after the objectionable impurities and used; What obtain at the bottom of the tower is dichlorohydrine.Remove the later dichlorohydrine concentration of the trimethyl carbinol and can reach more than 80%, yield generally reaches 94%(in propenyl chloride), reach as high as 98%, the by product trichloropropane in the reaction can reduce to minimum.
The dichlorohydrine that comes out from dichlorohydrine Tata underflow enters hydrolysis kettle, and adds alkali lye continuously, and dichlorohydrine is hydrolyzed to react in basic solution and obtains aqueous glycerin solution.This glycerin liquid through in and still send into stripping tower after regulating pH value and remove volatile impurity, reclaim organism such as trichloropropane, obtain 13～15% rare glycerine at the tower still.Rare glycerine is glycerine more than 80% through purifying, obtain after the concentration concentration, and separates out salt.Through washing, centrifuging, reclaim sugar water and sodium-chlor again.This sodium-chlor can use for industry, the sugar water retrieval system again with or send vaporizer recovery glycerine.Enumerate embodiment below and further set forth characteristics of the present invention.Percentage ratio used among the embodiment is weight percentage.
Embodiment 1
Get one 3 liter glass there-necked flasks, at first add 2004 gram water, start agitator, be heated to about 40 ℃; Respectively ratio of components drip chloro propylene and t-butyl hypochlorate in accordance with regulations drip 8 times continuously then, till dichlorohydrine begins to separate out, and standing demix then.Each add-on: propenyl chloride (98%) is 9.8 milliliters, and t-butyl hypochlorate (98%) is 13.5 milliliters.After, the time that whenever adds propenyl chloride and t-butyl hypochlorate is about 10 minutes, stirs 10 minutes, leaves standstill 10 minutes, then, emits organic layer (containing dichlorohydrine) from the bottom, is collected in the bottle.This test reinforced 30 times altogether, amount to propenyl chloride (100%) 174 gram, t-butyl hypochlorate (98%) 259 gram, obtain organic layer dichlorohydrine (60.29%) 189 gram, remove after the trimethyl carbinol, the concentration of dichlorohydrine reaches more than 80%, water layer dichlorohydrine (7.17%) 2259 gram.Calculating total recovery is that 93.98%(is in propenyl chloride).
Embodiment 2
In 5 liter reactors and dichlorohydrine settlement separator, add reacted water layer last time, and add small amount of H
2SO
4, to regulate pH value below 2.Start agitator and recycle pump.With well heater preheating reactor, temperature of charge is risen to about 40 ℃, continuously drip chloro propylene (98%) and t-butyl hypochlorate (94.4%).Strict control rate of addition, keeping the ratio of components of two kinds of materials is 1: the 1.012(mole).The input speed of propenyl chloride is 56 milliliters/hour.T-butyl hypochlorate is 82 milliliters/hour, 30 milliliters/hour in water.Temperature of reaction is 49～52 ℃, about 20 minutes of the residence time.Regularly emit the organic layer dichlorohydrine, and be collected in the bottle from the settlement separator bottom.This test adds propenyl chloride (98%) 573 gram altogether, and t-butyl hypochlorate (94.40%) 855 gram obtains organic layer dichlorohydrine (48.98%) 1816 gram, removes after the trimethyl carbinol, and dichlorohydrine concentration reaches more than 80%.Calculated yield is that 93.95%(is in propenyl chloride).Table 1 has been listed the test-results of continuous processing dichlorohydrine.
Embodiment 3
Take by weighing 200 gram water, 230 gram thick dichlorohydrines (containing 80.7%), and add in the hydrolysis kettle respectively.Start agitator, and be warming up to 40～50 ℃.Take by weighing the 95%NaOH61 gram again, be dissolved in the alkaligenous aqueous solution of preparation in the 98 gram water; When temperature rises to 40～50 ℃, alkali lye is splashed in the hydrolysis kettle, the dropping time is about 30 minutes.Claim 95%NaOH16 gram, Na again
2CO
362 restrain, and are dissolved in the 306 gram water being mixed with mixed alkali lye.When treating that the still temperature reaches more than 80 ℃, begin to drip mixed alkali lye, and continue to heat up, in 30 minutes, dropwise.Continue to be warmed up to 105 ℃ again, reaction is proceeded 4～5 hours; After the cooling, emit material, weigh.This material is 13.2% rare glycerine, and weight is 944 grams, and calculating the hydrolysis yield is that 90.20%(is in dichlorohydrine).Adopt the testing data of technical process synthetic glycerine of the present invention to list table 2 in.
Claims (9)
1, the present invention be a kind of be raw material with propenyl chloride, t-butyl hypochlorate, water, the commercial run for preparing glycerine through dichlorohydrine, its characteristics are to produce by the yield that improves dichlorohydrine the dichlorohydrine of high density, an one-step hydrolysis synthetic glycerine in basic solution then.
2, a kind of commercial run of preparation glycerine as claimed in claim 1, wherein dichlorohydrine system carries out chlorohydrin action with propenyl chloride by t-butyl hypochlorate and makes in water medium, it is characterized in that reclaiming that to obtain concentration behind the trimethyl carbinol be dichlorohydrine more than 80%, yield reaches as high as 98%(in propenyl chloride more than or equal to 94%).
3, a kind of commercial run of preparation glycerine as claimed in claim 1 is characterized in that dichlorohydrine and mixed alkali (NaOH+Na
2CO
3) equivalence ratio be 1: 2～2.05; Mix NaOH and Na in the alkali
2CO
3Equivalence ratio be 0.25～0.75.
4, a kind of commercial run of preparation glycerine as claimed in claim 1 is characterized in that chemical reaction can carry out in intermittent process or successive processes, hydrolysis temperature is at 80～150 ℃, and pressure is normal pressure or pressurization.
5, a kind of dichlorohydrine synthesis technique as claimed in claim 2, its characteristics are that the mol ratio of t-butyl hypochlorate and propenyl chloride is 1: 0.98～1.01.
6, a kind of dichlorohydrine synthesis technique as claimed in claim 2, its characteristics are to react and can carry out under normal pressure, and temperature of reaction is controlled at 10～70 ℃.
7, a kind of dichlorohydrine synthesis technique as claimed in claim 2, its characteristics are to add small amounts of inorganic acid or organic acid in reaction process, the pH value of control solution is below 5.
8, a kind of as claim 2 or 5 described dichlorohydrine synthesis techniques, its characteristics are to require that the content of free chlorine is controlled at 1%(weight in the t-butyl hypochlorate) below.
9, a kind of as claim 2 or 8 described synthesis techniques, it is characterized in that the small amounts of inorganic acid that adds in the reaction process can be sulfuric acid, nitric acid, hydrochloric acid or their nitration mixture; Organic acid can be acetic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86102942.9A CN1006062B (en) | 1986-04-28 | 1986-04-28 | Synthesis of dichloro-propyl-alcohol and prepn. of glycerol by one-step hyd rolysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86102942.9A CN1006062B (en) | 1986-04-28 | 1986-04-28 | Synthesis of dichloro-propyl-alcohol and prepn. of glycerol by one-step hyd rolysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86102942A true CN86102942A (en) | 1987-11-11 |
| CN1006062B CN1006062B (en) | 1989-12-13 |
Family
ID=4801891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86102942.9A Expired CN1006062B (en) | 1986-04-28 | 1986-04-28 | Synthesis of dichloro-propyl-alcohol and prepn. of glycerol by one-step hyd rolysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1006062B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219643A (en) * | 2011-04-15 | 2011-10-19 | 刘景全 | Environment-friendly glycerol and preparation method thereof |
| CN102603481A (en) * | 2012-02-07 | 2012-07-25 | 江苏安邦电化有限公司 | Micro reaction system and method for chlorohydrination of chloropropene |
-
1986
- 1986-04-28 CN CN86102942.9A patent/CN1006062B/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219643A (en) * | 2011-04-15 | 2011-10-19 | 刘景全 | Environment-friendly glycerol and preparation method thereof |
| CN102219643B (en) * | 2011-04-15 | 2013-08-14 | 刘景全 | Environment-friendly glycerol and preparation method thereof |
| CN102603481A (en) * | 2012-02-07 | 2012-07-25 | 江苏安邦电化有限公司 | Micro reaction system and method for chlorohydrination of chloropropene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1006062B (en) | 1989-12-13 |
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