GB2168341A - Method of producing dichloropropanols - Google Patents
Method of producing dichloropropanols Download PDFInfo
- Publication number
- GB2168341A GB2168341A GB08431376A GB8431376A GB2168341A GB 2168341 A GB2168341 A GB 2168341A GB 08431376 A GB08431376 A GB 08431376A GB 8431376 A GB8431376 A GB 8431376A GB 2168341 A GB2168341 A GB 2168341A
- Authority
- GB
- United Kingdom
- Prior art keywords
- water
- dichloropropanols
- allyl chloride
- chlorine
- calcium hydroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 27
- XEPXTKKIWBPAEG-UHFFFAOYSA-N 1,1-dichloropropan-1-ol Chemical class CCC(O)(Cl)Cl XEPXTKKIWBPAEG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000460 chlorine Substances 0.000 claims abstract description 23
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 22
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 18
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 239000011541 reaction mixture Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000013067 intermediate product Substances 0.000 abstract 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 12
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 12
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 9
- 235000011941 Tilia x europaea Nutrition 0.000 description 9
- 239000004571 lime Substances 0.000 description 9
- 239000008267 milk Substances 0.000 description 9
- 210000004080 milk Anatomy 0.000 description 9
- 235000013336 milk Nutrition 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- -1 chlorocarbonyl compounds Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- AVGQTJUPLKNPQP-UHFFFAOYSA-N 1,1,1-trichloropropane Chemical compound CCC(Cl)(Cl)Cl AVGQTJUPLKNPQP-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical class ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- ATADHKWKHYVBTJ-UHFFFAOYSA-N hydron;4-[1-hydroxy-2-(methylamino)ethyl]benzene-1,2-diol;chloride Chemical compound Cl.CNCC(O)C1=CC=C(O)C(O)=C1 ATADHKWKHYVBTJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000012451 post-reaction mixture Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/64—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by simultaneous introduction of -OH groups and halogens
- C07C29/66—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by simultaneous introduction of -OH groups and halogens by addition of hypohalogenous acids, which may be formed in situ, to carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
In a method of producing dichloropropanols (an intermediate product for the synthesis of epichlorohydrin) from allyl chloride, chlorine and water, an aqueous solution or suspension of calcium hydroxide, ally chloride and water, if necessary, is introduced into a circulating stream at a temperature of 33 - 43 DEG C, the said calcium hydroxide being introduced in an amount such that the pH-value of the stream is 2 - 7, and the sequence of addition being such that, after introducing the aqueous solution or suspension of calcium hydroxide into the circulating stream by means of a suction conduit of the circulation forcing pump, liquid allyl chloride is added, and only then chlorine (and water, if necessary) is batched through a pressure conduit of the circulation forcing pump into thus obtained mixture.
Description
SPECIFICATION
Method of producing dichloropropanols
This invention relates to producing dichloropropanols, which are intermediates for the synthesis of epichlorohydrin, from allyl chloride, chlorine and water.
It is known to produce dichloropropanols from allyl chloride and hypochlorous acid obtained by dissolving chlorine in water. To obtain a sufficient concentration of hypochlorous acid various conditions of production are used. According to L. A. Osin, Promyslennye chlororganiceskie produkty, Moskwa, 1978, hypochlorous acid is prepared at a temperature of 18-20"C in a separate column supplied with aqueous sodium carbonate solution and gaseous chlorine, the pH of the aqueous solution of hypochlorous acid being maintained within the range of 4.7 - 5.2. In an alternative to this method, aqueous sodium hydroxide solution is used in place of sodium carbonate.Another known method for preparing an aqueous solution of hypochlorous acid is described in USSR patent specification No. 289078, in which gaseous chlorine is introduced into a separately obtained aqueous calcium hypochlorite solution having a temperature of 6-8"C. The aqueous solution of hypochlorous acid thus prepared is fed into a chlorohydroxylation reaction system, supplied with allyl chloride. The greater portion of the reaction mixture circulates and the amount removed from the cycle corresponds to the amount of hypochlorous acid solution and allyl chloride introduced. The shortcoming of the method is that hypochlorous acid has to be produced in a separate apparatus, which is easily corroded, thus causing environmental problems, and needs cooling, thus increasing production costs.
Polish patent specification No. 50365 and F.R.G. patent specification No. 1960064 describe a method in which the chlorohydroxylation reaction is carried out at a temperature of 45-70"C and gaseous allyl chloride is introduced into a solution of hypochlorous acid that has been previously produced. A disadvantage of such a method is the large consumption of energy needed for evaporating the allyl chloride and maintaining the elevated process temperature. In processes known so far, allyl chloride is introduced into a solution of hypochlorous acid prepared in a separate reactor or in an independent unit of a complex reactor system.
From the description of Polish application No. P-222445 titled 'Method of producing dichloropropanols' (published in Polish Patent Office Bulletin No. 19 of September 18th 1981) a process is known in which allyl chloride, water and chlorine are proportioned into a circulating reaction mixture. According to this method an aqueous solution or suspension of calcium hydroxide is dosed into circulating stream in an amount such that pH-value of the stream is 2-7, and then allyl chloride, chlorine and if necessary more water, are fed.
The present invention provides a process for producing dichloropropanols which comprises forming a mixture of calcium hydroxide, allyl chloride and water, and then introducing chlorine into the said mixture at a temperature in said mixture of 33-43"C, the amount of calcium hydroxide used being sufficient to maintain a pH of 2-7 in the reaction mixture.
The idea of this invention is as follows. In the production of dichloropropanols from allyl chloride and hypochlorous acid prepared from water and chlorine, allyl chloride, water and chlorine are dosed into the reaction mixture subjected to forced circulation, and an aqueous solution or suspension of calcium hydroxide, allyl chloride and, if necessary, water, is introduced into the circulating stream at a temperature of 33-43"C, said stream containing water, dichloropropanols, hydrogen chloride and by-products such as trichloropropane, chlorocarbonyl compounds and chloroethers, the said calcium hydroxide being introduced in an amount such that pH-value of the stream is 2-7.The particular reactants are proportioned in such a sequence that, after introducing the aqueous solution or suspension of calcium hydroxide into the circulating stream by a suction conduit of the circulation forcing pump, liquid allyl chloride is added, and then chlorine and, if necessary, water are dosed through a pressure conduit of the circulation forcing pump into thus-obtained mixture.
Unexpectedly, it has been found, that dichloropropanols can be obtained with a yield of 94-97% without a necessity to produce hypochlorous acid before, if the lime milk and liquid allyl chloride are at first introduced into the circulating stream of reaction mixture and only then chlorine and, if necessary, water, are added. In processes which have been known so far, the yield of dichloropropanols was lower by about 5% if first lime milk and chlorine and the allyl chloride and water were introduced into a circulating reaction mixture. However, in a process without lime milk addition the yield of dichloropropanols was lower by about 10%.Moreover, the method according to the present invention assures a high dichloropropanol yield with a small amount of by-products such as trichloropropane, chlorocarbonyl compounds and chloroethers, without the need for evaporating allyl chloride and producing hydrochlorous acid solution in a separate apparatus. The addition of calcium hydroxide markedly decreases corrosion problems in the reaction system, and the said hydroxide is not lost because a process commonly used for processing dichloropropanols to give epichlorohydrin is conducted at a pH-value of 10-12, which is attained by the addition of lime milk.
The following Examples illustrate the invention.
Example I
The chlorohydroxylation reaction of allyl chloride to dichloropropanols was carried out in a circulating system composed of a reactor with a capacity of 50 dcm3, a pump and heat exchanger. Lime milk with a concentration of 2-9% Ca(OH)2 was continuously measured from a tank into the circulating reaction mixture, and process water and ally chloride were added from other tanks, and gaseous chlorine from a gas cylinder.
No. of Temp. pH of Allyl Chlorine Process Re
Run in reactor circ. chloride dosage, yields marks OC mixture dosage, g/h
g/h
1 38.7 1.2 1990 1849 85.7% No Ca(OH)2 batched
2 37.6 2.4 2205 2087 93.2%
3 38.6 3.7 1897 1796 96.7%
4 35 6.6 2187 2070 93.1%
5 37.5 2.8 2148 1995 89.6% calculated as the ratio of mole amount of formed dichloropropanols to the mole amount of introduced allyl chloride.
Five series of tests were conducted in which the chlorohydroxylation reaction was maintained at a temperature within the range of 33-43"C, the points of introducing chlorine and allyl chloride were changed and pH of reaction was changed from 1-7. To emulsify both streams, lime milk and allyl chloride were supplied at the suction side of pump in experiments 2-4. However, gaseous chlorine and water were introduced into the conduit at the pressing side of the pump. Lime milk was not batched in the series 1, and lime milk and chlorine were introdcued at the suction side of the pump in series 5, while allyl chloride and water were fed into a pressure conduit. A constant amount of circulating reaction mixture equal to 2 m3/h was maintained in all series.
An assumed pH-value was maintained in each series by batching a proper amount of lime milk, and the concentration of dichloropropanols in the reaction mixture was kept equal to 2 wt.% by proportioning an appropriate amount of water. The excess of post-reaction mixture was taken off from the reactor into a product container.
Example Il The chlorohydroxylation of allyl chloride to dichloropropanols was carried out in a circulating system composed of a reactor with the working capacity of 65 m3, a pump and heat exchanger. A suspension of calcium hydroxide with a concentration of 17-20 wt.%Ca(OH)2 and liquid chloride were supplied continuously, through a suction conduit of the pump, into a circulating reaction mixture, whereas chlorine and water were introduced by a pressure conduit of the pump. The process temperature was maintained in the range from 33 to 43 C by controlling the heat exchanger. The pH of the reaction mixture was adjusted by the amount of calcium hydroxide suspension added, and the dichloropropanol concentration was maintained in the range of 2.1 - 2.5 wt.% by means of the flow of water. The flow intensity of the stream of circulating reaction mixture varied between 7000,000 kg/h and 900,000 kg/h.
Under those conditions, when the reactor system was supplied with chlorine in the amount of 2,3002,600 kg/h and allyl chloride in the amount of 2,500-2,800 kg/h in a molar ratio Clz: Ac of 1.01-1, the obtained yield of conversion of allyl chloride to dichloropropanols was in the range of 94 to 95.5%.
Claims (5)
1. A process for producing dichloropropanols which comprises forming a mixture cf calcium hydroxide, allyl chloride and water, and then introducing chlorine into the said mixture at a temperature in said mixture of 33-43"C, the amount of calcium hydroxide used being sufficient to maintain a pH of 2-7 in the reaction mixture.
2. A process according to Claim 1 in which the process is operated continuously.
3. A process according to Claim 2 in which the reaction mixture is fed through a circulation forcing pump, the calcium hydroxide is introduced as an aqueous solution or suspension into a suction conduit of the said pump, liquid allyl chloride is added, and chlorine and optionally more water are introduced through a pressure conduit of the circulation forcing pump.
4. A process according to Claim 1 substantially as described in Example I or II.
5. Dichloropropanols when produced by the process of any of Claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08431376A GB2168341B (en) | 1984-12-12 | 1984-12-12 | Method of producing dichloropropanols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08431376A GB2168341B (en) | 1984-12-12 | 1984-12-12 | Method of producing dichloropropanols |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8431376D0 GB8431376D0 (en) | 1985-01-23 |
| GB2168341A true GB2168341A (en) | 1986-06-18 |
| GB2168341B GB2168341B (en) | 1988-06-22 |
Family
ID=10571073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08431376A Expired GB2168341B (en) | 1984-12-12 | 1984-12-12 | Method of producing dichloropropanols |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2168341B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2223256C2 (en) * | 2002-01-28 | 2004-02-10 | Закрытое акционерное общество "Каустик" | Method for preparing dichloropropanols |
| CN116836042A (en) * | 2023-07-05 | 2023-10-03 | 宁波环洋新材料股份有限公司 | Method for preparing dichloropropanol by low-temperature catalysis |
-
1984
- 1984-12-12 GB GB08431376A patent/GB2168341B/en not_active Expired
Non-Patent Citations (2)
| Title |
|---|
| PL APPLICATION P-222445 * |
| SU 289078 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2223256C2 (en) * | 2002-01-28 | 2004-02-10 | Закрытое акционерное общество "Каустик" | Method for preparing dichloropropanols |
| CN116836042A (en) * | 2023-07-05 | 2023-10-03 | 宁波环洋新材料股份有限公司 | Method for preparing dichloropropanol by low-temperature catalysis |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8431376D0 (en) | 1985-01-23 |
| GB2168341B (en) | 1988-06-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |