CN104557442B - The method of comprehensive utilization of carbon trichloride - Google Patents
The method of comprehensive utilization of carbon trichloride Download PDFInfo
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- CN104557442B CN104557442B CN201310491639.XA CN201310491639A CN104557442B CN 104557442 B CN104557442 B CN 104557442B CN 201310491639 A CN201310491639 A CN 201310491639A CN 104557442 B CN104557442 B CN 104557442B
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Abstract
The present invention is the method for comprehensive utilization of the accessory substance carbon trichloride on dichloroethanes chlorination.Carbon trichloride solution, glycerine, hydrogenation catalyst and chlorination catalyst are added in autoclave, feeds intake and finishes under certain temperature and Hydrogen Vapor Pressure while carrying out hydrogenation-dechlorination and glycerin chlorination reaction, reaction is finished, room temperature is down to after insulation 4h；Then hydrogenation catalyst is filtered to isolate, reaction solution obtains containing in solvent layer and glycerin layer, solvent layer by layering contains glycerine, dichlorohydrin, water, chlorination catalyst and glycerine monochlorohydrin in solvent, pentachloroethane and tetrachloro-ethylene, trichloroethanes, glycerin layer.
Description
Technical field
The present invention is the method for comprehensive utilization of the accessory substance carbon trichloride on dichloroethanes chlorination.
Background technology
Carbon trichloride is also known as perchloroethane, is replaced the compound generated by chlorine for whole hydrogen atoms in ethane molecule, point
Minor CCl3CCl3.Carbon trichloride has camphor fragrance, can directly be distilled without melting；186~187 DEG C of fusing point（Tube sealing
In）, 186 DEG C of boiling point（777 millimetress of mercury）, relative density 2.091；It is water insoluble, it is dissolved in ethanol, ether, benzene, chloroform etc. organic
Solvent.Lube oil additive can be made, also available for manufacture insecticide, pest repellant, smoke screen etc..
Dichloroethanes chlorination generally generates the mixture of tetrachloroethanes, pentachloroethane and carbon trichloride, wherein tetrachloroethanes
It is mainly used in synthesis trichloro ethylene and tetrachloro-ethylene with pentachloroethane.And carbon trichloride is the maximum one kind of chlorohydrocarbon Poisoning,
Maximum permissible concentration is 1ppm in the toxic effect of nervous centralis to people, air.Therefore the chlordene that dichloroethanes chlorination is generated
Ethane has to comprehensively utilize or carries out environmental protection treatment, and otherwise the harm to environment is quite big.
Patent CN201120046267.6, CN201110078335.1, CN201110078334.7,
CN201120269554.3 and CN201110212452.2, has been directed to the recovery method of carbon trichloride, mainly using liter
Two kinds of techniques of China and distillation, reclaim carbon trichloride and are recycled, but be not directed to the method for comprehensive utilization of carbon trichloride.
US5099084, introduces a kind of carbon trichloride method of comprehensive utilization, using carbon trichloride and methane at 400-700 DEG C
Lower carry out cracking reaction, generation tetrachloro-ethylene, chloromethanes and hydrogen chloride；US5097083 and US4899000 also give
Method similar US5099084, difference is that selected solvent is different, and what US5097083 was selected is ethane, raw after reaction
Into vinyl chloride, US4899000 generates chloropropene after selecting propylene, reaction.Three United States Patent (USP)s of the above are all to use Pintsch process
Process synthesis utilize carbon trichloride, Pintsch process mainly has two big shortcomings：1., cracking reaction temperature is high, and equipment requirement is harsh；
2., pyrolysis product is more, and poor selectivity, separating difficulty is big.
The content of the invention
The purpose of the present invention is：A kind of method of comprehensive utilization of carbon trichloride is provided, carbon trichloride hydrogenation-dechlorination is changed
For pentachloroethane, the hydrogen chloride and glycerine reaction by-product dichlorohydrin of generation.
The preparation method of the present invention and technological process：
Certain density carbon trichloride solution, a certain amount of glycerine, hydrogenation catalyst and chlorination is added in autoclave to urge
Agent.Carry out hydrogenation-dechlorination and glycerin chlorination reaction, insulation a period of time, reaction simultaneously under certain temperature and Hydrogen Vapor Pressure
Finish, cooling.Hydrogenation catalyst is filtered to isolate, reaction solution is obtained in solvent layer and glycerin layer, solvent layer containing molten by layering
Agent, pentachloroethane and a small amount of tetrachloro-ethylene, trichloroethanes etc., contain glycerine, dichlorohydrin, water, chlorination catalysis in glycerin layer
Agent and a small amount of glycerine monochlorohydrin.
In above-mentioned steps, the concentration of carbon trichloride solution（Carbon trichloride/（Carbon trichloride+solvent））It is excellent for 5~80wt%
Select 10~60wt%, best 20~40wt%；Solvent can be alcohols（Such as methanol, ethanol）, esters（Such as ethyl acetate, second
Acid butyl ester etc.）, aromatics（Chlorine benzene,toluene,xylene etc.）Deng；The mol ratio of glycerine and carbon trichloride is 1:2~1:10, preferably
1:2~1:5, best 1:2~1:3；Hydrogenation catalyst can be activated carbon supported noble metal catalyst such as platinum carbon, palladium carbon etc.,
It can be nickel catalyst；The bullion content of activated carbon supported noble metal catalyst can be 1-5wt%, preferably 1-4wt%, most
Good 1-2wt%；Noble metal catalyst consumption can be the 0.5-5wt%, preferably 1-3wt%, best 1-2%, nickel of carbon trichloride quality
Catalyst amount can be that carbon trichloride quality can be 1-10wt%, preferably 2-8wt%, best 3-5wt%；Chlorination catalyst
Can be binary acid such as succinic acid, glutaric acid, adipic acid etc., or monoacid, such as acetic acid；The consumption of chlorination catalyst
Can be the 0.5-6wt%, preferably 1-5wt%, best 2-4wt% of qualities of glycerin；Reaction temperature is 50-250 DEG C, preferably 80-180
DEG C, optimal 100-150 DEG C；Hydrogen Vapor Pressure is 0.2-4.0MPa, preferably 0.5-3.0MPa, optimal 1.0-2.0MPa.
The solvent layer is mainly containing solvent, pentachloroethane and a small amount of tetrachloro-ethylene, trichloroethanes etc..Wherein five in solvent layer
The content of chloroethanes（Deduct after solvent）For 90-95wt%, tetrachloro-ethylene 3-6wt%, trichloroethanes 1-2wt%；The glycerin layer master
Contain unreacted glycerine, dichlorohydrin, water and a small amount of glycerine monochlorohydrin and chlorination catalyst.In glycerin layer（Deduct solvent
Afterwards）, dichloropropanol content is 90wt%, glycerine monochlorohydrin content 7-8wt%.
Biggest advantage of the present invention is exactly that the poisonous by-product carbon trichloride for producing dichloroethanes chlorination is comprehensively utilized,
It is changed into valuable pentachloroethane, while the hydrogen chloride by-product dichlorohydrin, the chlorine that generate using glycerine absorbing reaction the third two
Alcohol, the three wastes problem for not only having improved value-added content of product but also having solved.
Embodiment
Embodiment 1
150g carbon trichlorides, 600g toluene, 0.75g5% palladium-carbon catalysts are added in 2L autoclaves（Butt）, 35g glycerine
With 0.8g adipic acids.Feed intake complete, replaced 3-4 times with 0.4MPa hydrogen, reacted under 100 DEG C and 1.0MPa Hydrogen Vapor Pressures,
After heat-insulation pressure keeping reaction 4hr, cooling.Palladium-carbon catalyst is filtered to isolate, reaction solution is divided into 45.8g glycerin layers and 712g solvents
Layer, the content of pentachloroethane wherein in solvent layer（Deduct after solvent）About 92.57wt%, tetrachloro-ethylene about 5.64wt%, three chloroethenes
Alkane about 1.02wt%；In glycerin layer（Deduct after solvent）, dichloropropanol content 92.14wt%, glycerine monochlorohydrin content 6.59wt%.
Embodiment 2
150g carbon trichlorides, 600g ethanol, 1g5% palladium-carbon catalysts are added in 2L autoclaves（Butt）, 40g glycerine and
1.2g glutaric acid.Feed intake complete, replaced 3-4 times with 0.4MPa hydrogen, reacted under 120 DEG C and 1.0MPa Hydrogen Vapor Pressures, protected
After warm pressurize reaction 4hr, cooling.Palladium-carbon catalyst is filtered to isolate, reaction solution is divided into 51.2g glycerin layers and 715.1g solvents
Layer, the content of pentachloroethane wherein in solvent layer（Deduct after solvent）91.24wt%, tetrachloro-ethylene 6.34wt%, trichloroethanes
1.57wt%；In glycerin layer（Deduct after solvent）, dichloropropanol content 93.57wt%, glycerine monochlorohydrin content 4.69wt%.
Embodiment 3
120g carbon trichlorides, 500g ethyl acetate, 12g Raney's nickel catalysts are added in 2L autoclaves（Butt）, 30g is sweet
Oil and 1.5g acetic acid.Feed intake complete, replaced 3-4 times with 0.4MPa hydrogen, reacted under 110 DEG C and 0.8MPa Hydrogen Vapor Pressures,
After heat-insulation pressure keeping reaction 4hr, cooling.Raney nickel is filtered to isolate, reaction solution is divided into 39.8g glycerin layers and 598.6g solvents
Layer, the content of pentachloroethane wherein in solvent layer（Deduct after solvent）92.34wt%, tetrachloro-ethylene 6.59wt%, trichloroethanes
0.67wt%；In glycerin layer（Deduct after solvent）, dichloropropanol content 94.57wt%, glycerine monochlorohydrin content 3.67wt%.
Embodiment 4
120g carbon trichlorides, 600g dimethylbenzene, 1.5g2% platinum carbon catalyst are added in 2L autoclaves（Butt）, 30g is sweet
Oil and 1.5g adipic acids.Feed intake complete, replaced 3-4 times with 0.4MPa hydrogen, carried out under 120 DEG C and 1.6MPa Hydrogen Vapor Pressures anti-
Should, after heat-insulation pressure keeping reaction 4hr, cooling.Platinum carbon catalyst is filtered to isolate, reaction solution is divided into 40.1g glycerin layers and 695.1g
The content of pentachloroethane in solvent layer, wherein solvent layer（Deduct after solvent）92.67wt%, tetrachloro-ethylene 5.34wt%, three chloroethenes
Alkane 1.37wt%；In glycerin layer（Deduct after solvent）, dichloropropanol content 94.31wt%, glycerine monochlorohydrin content 4.52wt%.
Embodiment 5
180g carbon trichlorides, 500g dimethylbenzene, 1.5g3% palladium-carbon catalysts are added in 2L autoclaves（Butt）, 45g is sweet
Oil and 1.5g adipic acids.Feed intake complete, replaced 3-4 times with 0.4MPa hydrogen, carried out under 120 DEG C and 1.4MPa Hydrogen Vapor Pressures anti-
Should, after heat-insulation pressure keeping reaction 4hr, cooling.Palladium-carbon catalyst is filtered to isolate, reaction solution is divided into 55.6g glycerin layers and 635.4g
The content of pentachloroethane in solvent layer, wherein solvent layer（Deduct after solvent）92.49wt%, tetrachloro-ethylene 5.68wt%, three chloroethenes
Alkane 1.26wt%；In glycerin layer（Deduct after solvent）, dichloropropanol content 93.5wt%, glycerine monochlorohydrin content 4.97wt%.
Embodiment 6
150g carbon trichlorides, 600g toluene, 0.9g5% palladium-carbon catalysts are added in 2L autoclaves（Butt）, 35g glycerine
With 1g acetic acid.Feed intake complete, replaced 3-4 times with 0.4MPa hydrogen, reacted under 150 DEG C and 1.5MPa Hydrogen Vapor Pressures, is incubated
After pressurize reaction 4hr, cooling.Palladium-carbon catalyst is filtered to isolate, reaction solution is divided into 44.9g glycerin layers and 712.4g solvent layers,
The content of pentachloroethane wherein in solvent layer（Deduct after solvent）93.21wt%, tetrachloro-ethylene 5.61wt%, trichloroethanes
1.46wt%；In glycerin layer（Deduct after solvent）, dichloropropanol content 94.37wt%, glycerine monochlorohydrin content 4.64wt%.
Embodiment 7
150g carbon trichlorides, 600g toluene, 15g amorphous nickel catalyst are added in 2L autoclaves（Butt）, 35g glycerine
With 1g adipic acids.Feed intake complete, replaced 3-4 times with 0.4MPa hydrogen, reacted under 180 DEG C and 1.0MPa Hydrogen Vapor Pressures, protected
After warm pressurize reaction 4hr, cooling.Raney nickel is filtered to isolate, reaction solution is divided into 45.9g glycerin layers and 711.9g solvent layers,
The content of pentachloroethane wherein in solvent layer（Deduct after solvent）92.97wt%, tetrachloro-ethylene 6.12wt%, trichloroethanes
0.24wt%；In glycerin layer（Deduct after solvent）, dichloropropanol content 93.12wt%, glycerine monochlorohydrin content 5.1wt%.
Embodiment 8-13
Experimentation be the same as Example 1, difference is：Hydrogenation catalyst has carried out five batches and applied mechanically.
Claims (10)
1. a kind of method of comprehensive utilization of carbon trichloride, it is characterised in that added in autoclave carbon trichloride solution, glycerine,
Hydrogenation catalyst and chlorination catalyst, feed intake and finish under certain temperature and Hydrogen Vapor Pressure while carrying out hydrogenation-dechlorination and glycerin chlorination
Reaction, reaction is finished, and room temperature is down to after insulation 4h；Then hydrogenation catalyst is filtered to isolate, reaction solution obtains solvent by layering
Contain in layer and glycerin layer, solvent layer and contain glycerine, dichloro in solvent, pentachloroethane and tetrachloro-ethylene, trichloroethanes, glycerin layer
Propyl alcohol, water, chlorination catalyst and glycerine monochlorohydrin；The concentration of carbon trichloride solution be 10~40wt%, solvent be alcohols solvent,
Esters solvent, aromatic solvents；The mol ratio of glycerine and carbon trichloride is 1:2~1:3；Hydrogenation catalyst is activated carbon supported expensive
Metallic catalyst or nickel catalyst；Bullion content in activated carbon supported noble metal catalyst is 1-5wt%；Activated carbon is born
Supported noble metal catalyst consumption is the 0.5-5wt% of carbon trichloride quality, and nickel catalyst consumption is the 1- of carbon trichloride quality
10wt%；Chlorination catalyst is binary acid or monoacid；The consumption of chlorination catalyst is the 0.5-6wt% of qualities of glycerin；Reaction
Temperature is 50-250 DEG C, and Hydrogen Vapor Pressure is 0.2-4.0MPa, and the activated carbon supported noble metal catalyst is platinum carbon catalyst, palladium
C catalyst.
2. the method for comprehensive utilization of a kind of carbon trichloride according to claim 1, it is characterised in that alcohols solvent is first
Alcohol, ethanol；Esters solvent is ethyl acetate, butyl acetate；Aromatic solvents are chlorine benzene,toluene,xylene.
3. the method for comprehensive utilization of a kind of carbon trichloride according to claim 1, it is characterised in that the binary acid is fourth
Diacid, glutaric acid, adipic acid, monoacid are acetic acid.
4. the method for comprehensive utilization of a kind of carbon trichloride according to claim 1, it is characterised in that the solvent layer is deducted
The content of pentachloroethane is 90-95wt%, tetrachloro-ethylene 3-6wt%, trichloroethanes 1-2wt% after solvent；The glycerin layer button
Except dichloropropanol content is 90wt%, glycerine monochlorohydrin content 7-8wt% after solvent.
5. a kind of method of comprehensive utilization of carbon trichloride according to claim 1, it is characterised in that your activated carbon supported gold
Bullion content in metal catalyst is 1-4wt%；Activated carbon supported noble metal catalyst consumption is the 1- of carbon trichloride quality
3wt%, nickel catalyst consumption is the 2-8wt% of carbon trichloride quality.
6. a kind of method of comprehensive utilization of carbon trichloride according to claim 5, it is characterised in that your activated carbon supported gold
Bullion content in metal catalyst is 1-2wt%；Activated carbon supported noble metal catalyst consumption is the 1- of carbon trichloride quality
2wt%, Raney nickel consumption is the 3-5wt% of carbon trichloride quality.
7. a kind of method of comprehensive utilization of carbon trichloride according to claim 1, it is characterised in that the use of chlorination catalyst
Measure the 1-5wt% for qualities of glycerin.
8. a kind of method of comprehensive utilization of carbon trichloride according to claim 7, it is characterised in that the use of chlorination catalyst
Measure the 2-4wt% for qualities of glycerin.
9. the method for comprehensive utilization of a kind of carbon trichloride according to claim 1, it is characterised in that reaction temperature is 80-
180 DEG C, Hydrogen Vapor Pressure is 0.5-3.0MPa.
10. a kind of method of comprehensive utilization of carbon trichloride according to claim 9, it is characterised in that reaction temperature is
100-150 DEG C, Hydrogen Vapor Pressure is 1.0-2.0MPa.
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| CN1845888A (en) * | 2003-09-01 | 2006-10-11 | 化学和冶金生产联合体股份公司 | Method of preparing dichloropropanols from glycerine |
| CN1974511A (en) * | 2003-11-20 | 2007-06-06 | 索尔维公司 | Process for producing organic compounds |
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| CN1845888A (en) * | 2003-09-01 | 2006-10-11 | 化学和冶金生产联合体股份公司 | Method of preparing dichloropropanols from glycerine |
| CN1974511A (en) * | 2003-11-20 | 2007-06-06 | 索尔维公司 | Process for producing organic compounds |
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| 甘油氯化制备二氯丙醇工艺的研究;宗敏等;《应用化工》;20080229;第37卷(第2期);第162-164页 * |
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