CN100388976C - Catalyst for dehydrochlorination of chloralkane to produce chloroalkene and its preparation method - Google Patents
Catalyst for dehydrochlorination of chloralkane to produce chloroalkene and its preparation method Download PDFInfo
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- CN100388976C CN100388976C CNB2006101012571A CN200610101257A CN100388976C CN 100388976 C CN100388976 C CN 100388976C CN B2006101012571 A CNB2006101012571 A CN B2006101012571A CN 200610101257 A CN200610101257 A CN 200610101257A CN 100388976 C CN100388976 C CN 100388976C
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Abstract
The present invention relates to a catalyst for the dehydrochlorination of chloralkane to produce chloroalkene and a preparation method thereof. The present invention is characterized in that a main active ingredient of the catalyst is the chloride of Fe, Co, Ni, Pd, Cu, Zn or Hg. The weight of the main active ingredient is 0.1 to 15% of the total weight of the catalyst. The catalyst also comprises a cocatalyst and a carrier. The ingredient of the cocatalyst is the hydroxide of Na, K, Ca or Mg, and the weight of the cocatalyst is 0.1 to 5% of the total weight of the catalyst. The carrier which is grainy or broken activated carbon, and specific surface area of the carrier is 600 to 2000m<2>/g. The catalyst of the present invention is used for the dehydrochlorination of chloralkane to produce chloroalkene, the reaction of the catalyst has the advantages of high feed stock conversion, target product selectivity, simple preparation method, low cost and high stability.
Description
Technical field
The present invention relates to a kind of catalyst of dehydrochlorination of chloralkane to produce chloroalkene, and this Preparation of catalysts method.
Background technology
Chloro-alkenes such as trichloro-ethylene are a kind of important organochlorine products, are widely used as degreasing metal agent, metal cleaner, metal parts finished surface inorganic agent, solvent, organic extractant, fabric and wool dry cleaning agent; Also can be used for the agricultural chemicals preparation, organic synthesis raw material (synthetic cold-producing medium HFC-134a, 1,1,1,2-HFC-134a, CFC alternative-12, dicholorodifluoromethane), medical material etc.
The production method of trichloro-ethylene mainly contains (Zhang Huimin, the production of trichloro-ethylene and application present situation, Chinese chlor-alkali, 2004, (8): 17-19) such as acetylene method, ethene direct chlorination method, process for oxychlorination of ethylene.Acetylene method comprises three kinds of technologies: (1) saponification method: adopt catalyst to make acetylene and chlorine generation addition reaction under reduced pressure, generate tetrachloroethanes, tetrachloroethanes and milk of lime reaction then generates trichloro-ethylene and calcium chloride.This technological reaction mild condition is to realize industrialized method the earliest.Shortcoming is to produce the saponification waste liquid that trichloro-ethylene per ton produces 5～8 tons, wherein contains the chlorohydrocarbon of about 5% calcium chloride and a great deal of, and calcium chloride is not easy to be recycled; (2) pyrolysismethod: make the tetrachloroethanes thermal cracking remove hydrogen chloride under 400～500 ℃ of conditions, shortcoming is that reaction temperature is higher, and selectivity of product is low; (3) catalysis dechlorination hydrogen method: adopt catalyst to make tetrachloroethanes remove hydrogen chloride under 200～300 ℃ of conditions, advantage is no residue discharging, and by-product hydrochloric acid, weak point is low (the industrial technology introduction of trichloro-ethylene of catalyst activity, the chemical industry economic technology information, 2005, (3): 14-17).In addition, 1,2-dichloroethanes or other C
2The halogenated hydrocarbons raw material under 340～385 ℃ of conditions, also can generate trichloro-ethylene and tetrachloro-ethylene through chlorination, cracking reaction, simultaneously by-product hydrochloric acid.Because the continuous rise of oil price, this technology is affected thereupon.
The yearly productive capacity of China's trichloro-ethylene is about 40,000 tons at present, and supply falls short of demand in market, mainly adopts acetylene method.
Summary of the invention
One of purpose of the present invention is at the deficiency of catalyst performance in the existing acetylene method dehydrochlorination steps, and a kind of highly active catalyst is provided, and two of purpose provides above-mentioned Preparation of catalysts method.
Technical scheme of the present invention is:
A kind of catalyst of dehydrochlorination of chloralkane to produce chloroalkene, its special feature are that the catalyst activity sexual element is the chloride of iron, cobalt, nickel, palladium, copper, zinc or mercury.
Wherein active ingredient accounts for 0.1～15% of total catalyst weight.
Also include co-catalyst, wherein the co-catalyst composition is the hydroxide of sodium, potassium, calcium or magnesium, and it accounts for 0.1～5% of total catalyst weight.
Also include carrier, wherein carrier is granular or broken active carbon, and its specific area is 600～2000m
2/ g.
Further, wherein carrier is active carbon from coal or plant base active carbon.
A kind of method for preparing catalyst of dehydrochlorination of chloralkane to produce chloroalkene, its special feature are, the active ingredient incipient impregnation to absorbent charcoal carrier, was made 110～130 ℃ of dryings then at least in 12 hours.
Wherein active ingredient is main active component, i.e. the chloride of iron, cobalt, nickel, palladium, copper, zinc or mercury.
The another kind of selection be, wherein active ingredient is that main active component adds co-catalyst, i.e. the chloride of iron, cobalt, nickel, palladium, copper, zinc or mercury is added the hydroxide of sodium, potassium, calcium or magnesium.
With hydrochloric acid absorbent charcoal carrier is carried out preliminary treatment before the dipping, this preliminary treatment be with absorbent charcoal carrier in 2～4 centinormal 1 hydrochloric acid solutions in 70～90 ℃ of reflow treatment 4～8 hours, solid-to-liquid ratio is 1: 5～1: 10g/mL, washing is extremely neutral then, and gets final product in 4～8 hours in 180～200 ℃ of vacuum drying.
Catalyst of the present invention is applied to dehydrochlorination of chloralkane to produce chloroalkene, wherein chloralkane comprises tetrachloroethanes, pentachloroethane, dichloroethanes and trichloroethanes, chloro-alkenes is a trichloro-ethylene, vinyl chloride, dichloroethylene and tetrachloro-ethylene, chloralkane generation elimination reaction, remove hydrogen chloride and generate corresponding chloro-alkenes, its reaction temperature is 200～300 ℃, use catalyst of the present invention to carry out the reaction that chloralkane gas phase dehydrochlorination generates chloro-alkenes, have high feed stock conversion and target product selectivity, method for preparing catalyst is simple, with low cost, have high stability simultaneously.
The specific embodiment
Embodiment 1
Adopt 4 equivalent concentration hydrochloric acid 85 ℃ of reflow treatment granular activated carbons (AC, active carbon from coal, 20～40 orders, its BET specific area is 764m
2/ g) 6 hours, solid-to-liquid ratio is 1: 5 (g/mL), washs to neutrality, 190 ℃ of vacuum drying 6 hours with deionized water.Adopt equi-volume impregnating to prepare NiCl
2/ AC catalyst, raw material is for analyzing pure nickel chloride, and immersion solvent is a deionized water, NiCl
2Account for 1% of total catalyst weight, 120 ℃ of dryings 12 hours, make required catalyst then.
(450 * 12mm carries out on i.d.) the dehydrochlorination reaction active testing of catalyst at continuous fixed bed reactor.Reaction condition is: the raw material chloralkane is a technical grade, and wherein tetrachloroethanes, pentachloroethane content are respectively 96.8%, 1.29%, and flow velocity is 2mL/h, and preheat temperature is 220 ℃, and carrier gas is N
2, flow velocity is 10mL/min, catalyst amount is 2g, W/F=100ghmol
-1, reaction temperature is 200 ℃, reaction pressure is 0.2MPa.The reaction procatalyst is at N
2In 200 ℃ of maintenances 2 hours, switch the importing raw material in the gas, reacted 6 hours, the conversion ratio of tetrachloroethanes is 87%, and the selectivity of trichloro-ethylene is 98%.
Embodiment 2
Adopt 2 equivalent concentration hydrochloric acid 70 ℃ of reflow treatment granular activated carbons (AC, coal-based granular active carbon, 20～40 orders, its BET specific area is 687m
2/ g) 4 hours, solid-to-liquid ratio is 1: 5 (g/mL), washs to neutrality, 180 ℃ of vacuum drying 4 hours with deionized water.Adopt equi-volume impregnating to prepare NiCl
2/ AC catalyst, raw material is for analyzing pure nickel chloride, and immersion solvent is a deionized water, NiCl
2Account for 0.1% of catalyst weight, 110 ℃ of dryings 12 hours, make required catalyst then.Testing active result according to embodiment 1 step is 83% for the conversion ratio of tetrachloroethanes, and the selectivity of trichloro-ethylene is 97.5%.
Embodiment 3
Adopt 3 equivalent concentration hydrochloric acid 80 ℃ of reflow treatment granular activated carbons (AC, coal-based broken shaped activated carbon, 20～40 orders, its BET specific area is 799m
2/ g) 6 hours, solid-to-liquid ratio is 1: 7 (g/mL), washs to neutrality, 190 ℃ of vacuum drying 6 hours with deionized water.Adopt equi-volume impregnating to prepare NiCl
2/ AC catalyst, raw material is for analyzing pure nickel chloride, and immersion solvent is a deionized water, NiCl
2Account for 8% of catalyst weight, 120 ℃ of dryings 20 hours, make required catalyst then.Testing active result according to embodiment 1 step is 65% for the conversion ratio of tetrachloroethanes, and the selectivity of trichloro-ethylene is 97.6%.
Embodiment 4
Adopt 2 equivalent concentration hydrochloric acid 90 ℃ of reflow treatment granular activated carbons (AC, the broken shaped activated carbon of coconut husk base, 20～40 orders, its BET specific area is 1420m
2/ g) 8 hours, solid-to-liquid ratio is 1: 10 (g/mL), washs to neutrality, 200 ℃ of vacuum drying 8 hours with deionized water.Adopt equi-volume impregnating to prepare NiCl
2/ AC catalyst, raw material is for analyzing pure nickel chloride, and immersion solvent is a deionized water, NiCl
2Account for 15% of catalyst weight, 130 ℃ of dryings 24 hours, make required catalyst then.Testing active result according to embodiment 1 step is 59% for the conversion ratio of tetrachloroethanes, and the selectivity of trichloro-ethylene is 97%.
Embodiment 5
Adopt 4 equivalent concentration hydrochloric acid 85 ℃ of reflow treatment granular activated carbons (AC, active carbon from coal, 20～40 orders, its BET specific area is 764m
2/ g) 6 hours, solid-to-liquid ratio is 1: 5 (g/mL), washs to neutrality, 190 ℃ of vacuum drying 6 hours with deionized water.Adopt equi-volume impregnating to prepare NiCl
2-Ca (OH)
2/ AC catalyst, wherein NiCl
2Load capacity is 1%, Ca (OH)
2Load capacity is 0.1%.Ca (OH)
2Raw material is for analyzing pure cerium hydroxide calcium saturated solution, and immersion solvent is a deionized water, and dipping preparation successively at twice 110 ℃ of dryings 12 hours, is made required catalyst then.Testing active result according to embodiment 1 step is 90% for the conversion ratio of tetrachloroethanes, and the selectivity of trichloro-ethylene is 98.5%.Compare with embodiment 1, the stability of catalyst improves.
Embodiment 6
With granular activated carbon (AC, active carbon from coal, 20～40 orders, its BET specific area is 764m
2/ g) 120 ℃ of dryings 12 hours, without the salt acid treatment, adopting and analyzing pure nickel chloride is raw material, and deionized water is an immersion solvent, and equi-volume impregnating prepares NiCl
2/ AC catalyst, NiCl
2Load capacity is 10%, 120 ℃ of dryings 12 hours, makes required catalyst then.Carry out active testing result contrast according to embodiment 1 step, the conversion ratio of tetrachloroethanes is 27%, and the selectivity of trichloro-ethylene is 96%.
Embodiment 7
Coal-based granular activated carbon is carried out drying according to embodiment 6 described methods handle, adopting and analyzing pure nickel chloride is raw material, and deionized water is an immersion solvent, and equi-volume impregnating prepares NiCl
2/ AC catalyst, NiCl
2Load capacity is 0.5%, 120 ℃ of dryings 12 hours, makes required catalyst then.Testing active result according to embodiment 1 step is 43% for the conversion ratio of tetrachloroethanes, and the selectivity of trichloro-ethylene is 98%.
Embodiment 8
Coal-based granular activated carbon is carried out drying according to embodiment 6 described methods handle, adopting raw material is raw material for the pure nickel chloride of analysis, potassium hydroxide, and deionized water is an immersion solvent, and equi-volume impregnating prepares NiCl
2-KOH/AC catalyst, NiCl
2Load capacity is 10%, and the KOH load capacity is 1%, and dipping preparation successively at twice 120 ℃ of dryings 12 hours, is made required catalyst then.Testing active result according to embodiment 1 step is 33% for the conversion ratio of tetrachloroethanes, and the selectivity of trichloro-ethylene is 98.5%.Compare with embodiment 6, the stability of catalyst improves.
Embodiment 9
Coal-based granular activated carbon is carried out drying according to embodiment 6 described methods handle, adopting and analyzing pure ferric trichloride is raw material, and deionized water is an immersion solvent, and equi-volume impregnating prepares FeCl
3/ AC catalyst, FeCl
3Load capacity is 5%, 120 ℃ of dryings 12 hours, makes required catalyst then.Testing active result according to embodiment 1 step is 25% for the conversion ratio of tetrachloroethanes, and the selectivity of trichloro-ethylene is 97%.
Embodiment 10
Coal-based granular activated carbon is carried out drying according to embodiment 6 described methods handle, adopting and analyzing pure cobalt chloride is raw material, and deionized water is an immersion solvent, and equi-volume impregnating prepares CoCl
2/ AC catalyst, cobalt chloride load capacity are 10%, 120 ℃ of dryings 12 hours, make required catalyst then.Testing active result according to embodiment 1 step is 19% for the conversion ratio of tetrachloroethanes, and the selectivity of trichloro-ethylene is 93%.
Embodiment 11
Coal-based granular activated carbon is carried out drying according to embodiment 6 described methods handle, adopting and analyzing pure stannous chloride is raw material, and concentrated ammonia liquor is an immersion solvent; equi-volume impregnating prepares the CuCl/AC catalyst; the stannous chloride load capacity is 5%, 120 ℃ of dryings 12 hours, makes required catalyst then.Testing active result according to embodiment 1 step is 40% for the conversion ratio of tetrachloroethanes, and the selectivity of trichloro-ethylene is 97%.
Embodiment 12
Coal-based granular activated carbon is carried out drying according to embodiment 6 described methods handle, adopting and analyzing pure zinc chloride is raw material, and deionized water is an immersion solvent, and equi-volume impregnating prepares ZnCl
2/ AC catalyst, zinc chloride load capacity are 5%, 120 ℃ of dryings 12 hours, make required catalyst then.Testing active result according to embodiment 1 step is 33% for the conversion ratio of tetrachloroethanes, and the selectivity of trichloro-ethylene is 96.5%.
Claims (7)
1. the catalyst of a dehydrochlorination of chloralkane to produce chloroalkene is characterized in that:
The catalyst activity sexual element is the chloride of iron, cobalt, nickel, palladium, copper, zinc or mercury, and wherein active ingredient accounts for 0.1～15% of total catalyst weight, also includes carrier, and wherein carrier is granular or broken active carbon, and its specific area is 600～2000m
2/ g.
2. the catalyst of a kind of dehydrochlorination of chloralkane to produce chloroalkene as claimed in claim 1 is characterized in that:
Also include co-catalyst, wherein the co-catalyst composition is the hydroxide of sodium, potassium, calcium or magnesium, and it accounts for 0.1～5% of total catalyst weight.
3. the catalyst of a kind of dehydrochlorination of chloralkane to produce chloroalkene as claimed in claim 1 is characterized in that:
Wherein carrier is active carbon from coal or plant base active carbon.
4. the method for preparing catalyst of a dehydrochlorination of chloralkane to produce chloroalkene is characterized in that:
The active ingredient incipient impregnation to absorbent charcoal carrier, was made 110～130 ℃ of dryings then at least in 12 hours.
5. the method for preparing catalyst of a kind of dehydrochlorination of chloralkane to produce chloroalkene as claimed in claim 4 is characterized in that:
Wherein active ingredient is main active component, i.e. the chloride of iron, cobalt, nickel, palladium, copper, zinc or mercury.
6. the method for preparing catalyst of a kind of dehydrochlorination of chloralkane to produce chloroalkene as claimed in claim 4 is characterized in that:
Wherein active ingredient is that main active component adds co-catalyst, i.e. the chloride of iron, cobalt, nickel, palladium, copper, zinc or mercury is added the hydroxide of sodium, potassium, calcium or magnesium.
7. the method for preparing catalyst of a kind of dehydrochlorination of chloralkane to produce chloroalkene as claimed in claim 4 is characterized in that:
With hydrochloric acid absorbent charcoal carrier is carried out preliminary treatment before the dipping, this preliminary treatment be with absorbent charcoal carrier in 2～4 centinormal 1 hydrochloric acid solutions in 70～90 ℃ of reflow treatment 4～8 hours, solid-to-liquid ratio is 1: 5～1: 10g/mL, washing is extremely neutral then, and gets final product in 4～8 hours in 180～200 ℃ of vacuum drying.
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| CNB2006101012571A CN100388976C (en) | 2006-07-07 | 2006-07-07 | Catalyst for dehydrochlorination of chloralkane to produce chloroalkene and its preparation method |
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| CNB2006101012571A CN100388976C (en) | 2006-07-07 | 2006-07-07 | Catalyst for dehydrochlorination of chloralkane to produce chloroalkene and its preparation method |
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| CN100388976C true CN100388976C (en) | 2008-05-21 |
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