CN104289247A - Catalyst applied to preparation of vinyl chloride by catalytic cracking of 1,2-dichloroethane as well as preparation method and application of catalyst - Google Patents
Catalyst applied to preparation of vinyl chloride by catalytic cracking of 1,2-dichloroethane as well as preparation method and application of catalyst Download PDFInfo
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Abstract
The invention relates to a nitrogen-doped active carbon catalyst applied to preparation of vinyl chloride by catalytic cracking of 1,2-dichloroethane and in particular relates to active carbon, wherein the inner surface and the outer surface of the active carbon are doped with nitrogen; the doping content of nitrogen is 0.1-10wt%; furthermore, meal is loaded on the nitrogen-doped active carbon catalyst and exists in the form of a metal compound; the loading content of the metal compound is 0.1-10wt%. According to the catalyst, the preparation method is simple, the process is short, materials are easily available, and the cost is relatively low; the nitrogen doped in the active carbon has a small possibility of losing and inactivating; the nitrogen is doped in the nitrogen-doped active carbon catalyst loaded with the metal compound, so that the dispersion of the metal component on the active carbon can be effectively improved; the catalytic activity is improved; the cracking temperature of dichloroethane can be greatly reduced under the catalytic action of the catalyst prepared by the method.
Description
Technical field
The present invention relates to and prepare chloroethylene catalyst and preparation method thereof and application for 1,2-dichloroethanes catalytic pyrolysis, belong to catalyst for cracking field.
Background technology
Polyvinyl chloride (PVC) is world's second largest resins for universal use, and vinyl chloride (VCM) is the important monomer of synthesis PVC.Vinyl chloride is produced and is mainly contained two kinds of industrial product routes: carbide route and ethylene process route.In carbide, vinyl chloride is obtained by mercury chloride catalyzing acetylene hydrochlorinate; In ethylene process, vinyl chloride is obtained by 1,2-dichloroethanes cracking.
The whole world is prohibited mercury treaty " water Wu pact " and is strictly limited and will prohibit the use mercury catalyst, makes China's carbide produce vinyl chloride route and is subject to very big restriction, develop green vinyl chloride production line imperative.
Dichloroethanes cracking is for the industrial employing thermal cracking of vinyl chloride, and reaction temperature controls at about 500 DEG C, to improve dichloroethanes conversion ratio.This route reaction temperature is high, and energy consumption is large, easily occurs the problem such as coking, carbon distribution, and research and development catalyst reduces cracking temperature, and raising cracking is selective very necessary.
Just start to carry out the research of 1,2-dichloroethanes catalytic pyrolysis as far back as the forties in 20th century, find that activated carbon supported barium chloride, lanthanum chloride, barium chloride etc. all have catalytic action to this reaction.The zeolite molecular sieve etc. such as polypropylene cyanogen carbon fiber active carbon and ZSM-5 is also found there is catalytic action to this reaction in addition.These catalyst can reduce dichloroethanes cracking temperature to a certain extent, but because catalyst activity is inadequate, the life-span is shorter and be difficult to the problems such as regeneration, also have with a certain distance from commercial Application.
N doping catalyst in the present invention, nitrogen-atoms inside is entrained in carbon atom, has very excellent catalytic activity, can greatly reduce dichloroethanes cracking temperature, improves the life-span of catalyst.
Summary of the invention
The object of the invention is to overcome in existing dichloroethanes cracking vinyl chloride technology, reaction temperature is high, and energy consumption is large, the problems such as easy coking, carbon distribution, provides a kind of 1,2-dichloroethanes catalytic pyrolysis to prepare chloroethylene catalyst and preparation method thereof and application.
The present invention is achieved by the following technical solutions:
One provided by the invention is used for 1,2-dichloroethanes catalytic pyrolysis and prepares the nitrating activated-carbon catalyst of vinyl chloride, be specially a kind of at surfaces externally and internally all doped with the active carbon of nitrogen element.
Preferably, described nitrating activated-carbon catalyst load can have metal component.
Preferably, described metal exists with the form of metallic compound.
Preferably, in described nitrating activated-carbon catalyst, the doping of nitrogen element is 0.1-10wt%.
Preferably, the specific area of described active carbon is 700 ~ 2000m
2/ g, particle diameter is 0.05 ~ 1cm, and pore volume is 0.4 ~ 0.7m
3/ g; Be selected from carbo lignius, coal-based carbon and fruit shell carbon.Wherein, described fruit shell carbon namely with shells such as coconut husk, peach shell, walnut shell, jujube shells for raw material, active carbon adopts the techniques such as charing, activation, superheated vapor catalysis to refine and forms, and outward appearance is black indefinite form particle, through a kind of active carbon of produced in series processes.
Preferably, described metallic compound is selected from the form of metal compound such as metal oxide, chloride, sulfate, phosphate, nitrate; Be more preferably the chloride of metal.
Preferably, described metal is selected from calcium, barium, lanthanum, copper etc.
Preferably, the load capacity of described metallic compound is 0.1-10wt%.
The present invention is the open described preparation method preparing the nitrating activated-carbon catalyst of vinyl chloride for 1,2-dichloroethanes catalytic pyrolysis further, comprises the following steps:
(1) get active carbon to carry out immersion treatment with removal of impurities and dredge duct, then after filtration, washing, dry after for subsequent use;
(2) the obtained described nitrating activated-carbon catalyst preparing vinyl chloride for 1,2-dichloroethanes catalytic pyrolysis of any one nitrogen element acquisition methods following is used:
Method one: get the active carbon after step (1) process, be placed in nitrogenous active gases and carry out N doping;
Method two: get the active carbon after step (1) process, the aqueous solution being placed in nitrogen-containing compound carries out impregnation process, after then filtering, drying, then carbonization under an inert atmosphere.
Wherein,
Preferably, in step (1), the soak of shown immersion treatment is the aqueous solution of hydrochloric acid, nitric acid, hydrogen peroxide or NaOH etc.
Preferably, in described soak, the concentration of solute is 0.5-5mol/L, is preferably 1-2.5 mol/L; The volume ratio of active carbon and soak is 1:1.1 ~ 1.5; The time of immersion treatment is 1-24 hour.
Preferred, in step (1), the soak of described immersion treatment is hydrochloric acid or nitre aqueous acid.
Preferably, the mode isolated by filtration of centrifuge dripping is adopted.
Preferably, for the situation of pickling, described washing spends deionized water to faintly acid.
Preferably, drying described in step (1) is 80 ~ 150 DEG C, and the time is 2 ~ 24 hours.
Method one for step (2):
Preferably, in the method one of step (2), described N doping is: described active carbon after step (1) process is placed in tube furnace, 400 ~ 1000 DEG C are warming up under inert atmosphere, then nitrogenous active gases 4 ~ 20 hours are passed into 10 ~ 100ml/min speed, then be cooled to room temperature, stop again afterwards passing into described nitrogenous active gases.
Preferably, described nitrogenous active gases is the gaseous mixture of ammonia and hydrogen, and the ratio of ammonia and hydrogen volume flow is 2-7:1; Be more preferably 5:1.
For the active carbon of 50g after step (1) process, then can pass into ammonia and hydrogen with the speed of 50ml/min and 10ml/min respectively simultaneously.
Preferably, described inert atmosphere is selected from nitrogen, helium.
Method two for step (2):
Preferably, in the method two of step (2), described nitrogen-containing compound is selected from pyridine, piperidines, polyacrylamide, polyvinylpyrrolidone and melamine etc.
Preferably, in the method two of step (2), the concentration of the aqueous solution of described nitrogen-containing compound is 0.1 ~ 3mol/L.
Preferably, described impregnation process, the active carbon after step (1) process and nitrogen-containing compound aqueous solution volume ratio are 1:1.1 ~ 1.5.
Preferably, described dipping is vacuum impregnation, and dip time is 2 ~ 20 hours.
Preferably, described vacuum-impregnated pressure is-0.1MPa.
Preferably, the temperature of described oven dry is 80 ~ 150 DEG C, and the time is 2 ~ 24 hours.
Preferably, in the method two of step (2), described carbonization is, the active carbon after impregnation process and filtration, oven dry is placed in tube furnace, is warming up to 400 ~ 1000 DEG C under an inert atmosphere, carbonization 4 ~ 20 hours.
Preferably, described inert atmosphere is selected from nitrogen, helium.
If desired, the operating procedure of repetition methods two, can obtain the activated-carbon catalyst that N doping amount is higher.
When described for 1, when the nitrating activated-carbon catalyst load that 2-dichloroethanes catalytic pyrolysis prepares vinyl chloride has a metal, the preparation method of described catalyst is as follows: impregnated in the aqueous solution of the metallic compound of described carried metal by the nitrating activated-carbon catalyst obtained through preceding method, and then after filtration, dry obtained described load has the nitrating activated-carbon catalyst of metal.
Preferably, the concentration of the aqueous solution of described metallic compound is 0.1-2.5mol/L; The volume ratio 1:1.1-1.5 of the nitrating activated-carbon catalyst metallizing thing aqueous solution; Dip time is 2-8 hour.
Preferably, the temperature of described drying is 80 ~ 150 DEG C, and the time is 2 ~ 24 hours.
The present invention also provides described one for 1,2-dichloroethanes catalytic pyrolysis prepares the application of vinyl chloride nitrating activated-carbon catalyst, be specially and described nitrating activated-carbon catalyst inserted in fixed bed reactors, raw material dichloroethanes through pre-thermal evaporation laggard enter fixed bed reactors bed carry out catalytic cracking reaction generate vinyl chloride.
Preferably, the pressure of described catalytic cracking reaction is normal pressure, and temperature is 220 ~ 350 DEG C, and air speed is 10 ~ 200 h
-1; Be more preferably 220-290 DEG C.
Technique effect of the present invention and advantage are:
Nitrating catalyst provided by the invention or load have the nitrating catalyst of metal compared with prior art, and preparation technology is simple, and flow process is short, and material is easy to get, and cost is lower; Be entrained in the nitrogen element in active carbon, not easily run off inactivation; Load to have in the nitrating activated-carbon catalyst of metallic compound N doping can effective reinforcement metal component dispersiveness on the activated carbon, improves catalytic activity; Under the catalytic action of the catalyst prepared in the present invention, dichloroethanes cracking temperature significantly reduces.When cracking temperature is 290 DEG C, the cleavage rate of dichloroethanes can reach more than 90%, and the selective of vinyl chloride reaches 99%.
Detailed description of the invention
Below by way of specific instantiation, technical scheme of the present invention is described.Should be understood that one or more method steps that the present invention mentions do not repel and before and after described combination step, also to there is additive method step or can also insert additive method step between these steps clearly mentioned; Should also be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.And, except as otherwise noted, the numbering of various method steps is only the convenient tool differentiating various method steps, but not be ordering or the enforceable scope of restriction the present invention of restriction various method steps, the change of its relativeness or adjustment, when changing technology contents without essence, when being also considered as the enforceable category of the present invention.
The invention provides a kind of nitrating activated-carbon catalyst preparing vinyl chloride for 1,2-dichloroethanes catalytic pyrolysis, be specially a kind of at surfaces externally and internally all doped with the active carbon of nitrogen element, the doping of nitrogen element is 0.1-10wt%;
A kind of preferable case, the load of described nitrating activated-carbon catalyst has metal, and described metal exists with the form of metallic compound, and becket compound load capacity is at 0.1-10wt%; Described metal is selected from calcium, barium, lanthanum, copper etc.; Described metallic compound is selected from the form of metal compound such as metal oxide, chloride, sulfate, phosphate, nitrate, is preferably chloride and the oxide of metal.
The corresponding preparation method also providing above-mentioned nitrating activated-carbon catalyst of the present invention, generally comprises following steps:
Step (1): get active carbon and carry out immersion treatment with removal of impurities and dredge duct, then after filtration, washing, dry after for subsequent use;
Under preferable case, described soak is selected from the aqueous solution of sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid and NaOH, and concentration, at 0.5-5mol/L, is preferably 1-2.5 mol/L; Immersion process, active carbon and soak 1:1.1 ~ 1.5 by volume during immersion; Immersion treatment 1-24 hour.This step object is the impurity that the mode of employing immersion removes in activated carbon raw material.Therefore, in the scope that those skilled in the art can understand, any immersion scheme that can reach removal of impurities object all belongs to the category of the present invention's protection; The mode of preferred use centrifuge dripping carries out Separation of Solid and Liquid.Then 80 ~ 150 DEG C of dryings are for subsequent use after 2 ~ 24 hours.
Step (2): use the obtained described nitrating activated-carbon catalyst preparing vinyl chloride for 1,2-dichloroethanes catalytic pyrolysis of any one nitrogen element acquisition methods following:
Method one: get the active carbon after step (1) process, be placed in nitrogenous active gases and carry out N doping;
Under preferable case: method one, described active carbon after step (1) process is placed in tube furnace, 400 ~ 1000 DEG C are warming up under inert atmosphere, then nitrogenous active gases 4 ~ 20 hours are passed into 10 ~ 100ml/min speed, then room temperature is cooled to, stop again afterwards passing into described nitrogenous active gases, namely obtain nitrating active carbon;
Wherein inert gas can select nitrogen or helium; Described nitrogenous active gases is the mixture of ammonia and hydrogen; Under preferable case, ammonia and hydrogen are that 2-7:1 passes into simultaneously by the ratio of flow; The ratio being more preferably 5:1 passes into simultaneously.
As a kind of preferred embodiment, for the active carbon of 50g after step (1) process, pass into ammonia and hydrogen with the speed of 50ml/min and 10ml/min respectively simultaneously.
Method two: get the active carbon after step (1) process, the aqueous solution being placed in nitrogen-containing compound carries out impregnation process, after then filtering, drying, then carbonization under an inert atmosphere, namely obtain nitrogen-dopped activated carbon;
Preferably, in method two, described nitrogen-containing compound is selected from the nitrogen-containing compounds such as pyridine, piperidines, polyacrylamide, polyvinylpyrrolidone and melamine.Under preferable case, the concentration of the aqueous solution of nitrogen-containing compound is 0.1 ~ 3mol/L.Impregnation process process, the active carbon after step (1) process and the nitrogen-containing compound aqueous solution carry out 1:1.1 ~ 1.5 by volume.Preferably, described dipping is vacuum impregnation, and pressure is-0.1MPa, and dip time is 2 ~ 20 hours.Then carbonization is carried out after drying 2 ~ 24 hours at 80 ~ 150 DEG C.
Preferably, the carbonisation of method two is: the active carbon after impregnation process and filtration, oven dry is placed in tube furnace, is warming up to 400 ~ 1000 DEG C under an inert atmosphere, carbonization 4 ~ 20 hours.Wherein inert gas is selected from nitrogen, helium.If desired, the operating procedure of repetition methods two, can obtain the active carbon that N doping amount is higher.
When described for 1, when the nitrating activated-carbon catalyst load that 2-dichloroethanes catalytic pyrolysis prepares vinyl chloride has a metal, the preparation method of described catalyst is as follows: impregnated in the aqueous solution of the metallic compound of described carried metal by the nitrating activated-carbon catalyst obtained through preceding method, and then after filtration, dry obtained described load has the nitrating activated-carbon catalyst of metal.
As preferred performance, during dipping, the concentration of the aqueous solution of described metallic compound is 0.1-2.5mol/L; The by volume ratio 1:1.1-1.5 of the nitrating activated-carbon catalyst metallizing thing aqueous solution floods; Dipping 2-8 hour.
As preferred performance, the temperature of described drying is 80 ~ 150 DEG C, and the time is 2 ~ 24 hours.
The present invention also provides described one for 1,2-dichloroethanes catalytic pyrolysis prepares the application of vinyl chloride nitrating activated-carbon catalyst, be specially and described nitrating activated-carbon catalyst inserted in fixed bed reactors, raw material dichloroethanes through pre-thermal evaporation laggard enter fixed bed reactors bed carry out catalytic cracking reaction generate vinyl chloride.
As preferred performance, the pressure of described catalytic cracking reaction is normal pressure, and temperature is 220 ~ 350 DEG C, and air speed is 10 ~ 200 h
-1.Experiment proves, under the above-described reaction conditions, catalyst of the present invention has higher catalytic activity, and dichloroethanes cracking temperature significantly reduces.When cracking temperature is 290 DEG C, the cleavage rate of dichloroethanes can reach more than 90%, and the selective of vinyl chloride reaches 99%.
Below by way of specific embodiment, the present invention is further described, but does not therefore limit the present invention.Wherein example 1-6 is for preparing nitrogen-dopped activated carbon catalyst; Example 7-10 is for preparing metal load type nitrogen-dopped activated carbon catalyst; And provide comparative example 1-3 there is no the example in contrast of the activated-carbon catalyst of N doping.The catalytic applications performance of the catalyst sample of preparation is in table 1
Embodiment 1
Prepare sample 1: the N doping coal-based carbon catalyst taking ammonia as nitrogenous source
Concrete preparation process is: 500g coal-based carbon being joined 1000ml concentration is in the hydrochloric acid solution of 2mol/L, and soaking at room temperature is centrifuge dripping after 12 hours, spends deionized water to faintly acid, and in 120 DEG C of dryings 10 hours.Get the active carbon that 50g handles well and put into tube furnace, in nitrogen atmosphere after raised temperature to 500 DEG C, pass into ammonia and hydrogen respectively with the speed of 50ml/min and 10ml/min simultaneously, heating is stopped to be cooled to room temperature after 6 hours, and close ammonia and hydrogen, obtain the nitrogen-dopped activated carbon catalyst that the total doping of surfaces externally and internally nitrogen is 1.1wt%.
Embodiment 2
Prepare sample 2: the N doping coal-based carbon catalyst taking polyacrylamide as nitrogenous source.
Concrete preparation process is: get 2g polyacrylamide-300 (analyzing pure, molecular weight) and join in 100g deionized water, and at 60 DEG C, heating is stirred to and dissolves completely.Add wherein by 50g embodiment 1 with the coal-based carbon after HCl treatment, under-0.1MPa, vacuum soaks 2h, crosses and to filter after unnecessary solution at 80 DEG C vacuum drying 10 hours.Dried active carbon is put into tube furnace, and under nitrogen protection in 600 DEG C of carbonizations 10 hours, obtain the N doping coal-based carbon catalyst that polyacrylamide is nitrogenous source, N doping amount meets between 0.1-10%.
Embodiment 3
Prepare sample 3: the N doping coal-based carbon catalyst taking polyvinylpyrrolidone as nitrogenous source.
With reference to the method in embodiment 2, get 2g polyvinyl pyrilodone K30 (analyzing pure) and join in 100g deionized water, stirred at ambient temperature is to dissolving completely.Add wherein by 50g embodiment 1 with the coal-based carbon after HCl treatment, under-0.1MPa, vacuum soaks 2h, crosses and to filter after unnecessary solution at 80 DEG C vacuum drying 10 hours.Dried active carbon is put into tube furnace, and under nitrogen protection in 700 DEG C of carbonizations 10 hours, obtain the nitrogen-dopped activated carbon catalyst that polyvinylpyrrolidone is nitrogenous source, N doping amount meets between 0.1-10%.
Embodiment 4
Prepare sample 4: the N doping coconut husk Pd/carbon catalyst taking polyvinylpyrrolidone as nitrogenous source.
Concrete preparation process: 500g coconut carbon being joined 1000ml concentration is in the salpeter solution of 2mol/L, and soaking at room temperature is centrifuge dripping after 12 hours, spends deionized water to faintly acid, and for subsequent use in 120 DEG C of dryings 10 hours.Getting 4g PVP K30 (analyzing pure) joins in 100g deionized water, and stirred at ambient temperature is to dissolving completely.Add wherein by the coconut carbon after above-mentioned for 50g nitric acid treatment, under-0.1MPa, vacuum soaks 2h.Cross and to filter after unnecessary solution at 80 DEG C vacuum drying 10 hours.Dried active carbon is put into tube furnace, and under nitrogen protection in 700 DEG C of carbonizations 10 hours, obtain the N doping coconut husk Pd/carbon catalyst that polyvinylpyrrolidone is nitrogenous source, N doping amount meets between 0.1-10%.
Embodiment 5
Prepare sample 5: the N doping coal-based carbon catalyst taking melamine as nitrogenous source.
With reference to the method in embodiment 2, get 3g melamine (analyzing pure) and join in 100g deionized water, be stirred at 80 DEG C and dissolve completely.Add wherein by 50g embodiment 1 with the coal-based carbon after HCl treatment, under-0.1MPa, vacuum soaks 2h.Cross and to filter after unnecessary solution in 80 DEG C of vacuum drying chambers dry 10 hours.Dried active carbon is put into tube furnace, and under nitrogen protection in 700 DEG C of carbonizations 10 hours, obtain the nitrogen-dopped activated carbon catalyst that melamine is nitrogenous source, N doping amount meets between 0.1-10%.
Embodiment 6
Prepare sample 6: employing pyridine is the N doping coconut carbon catalyst of nitrogenous source.
With reference to the method in embodiment 2, get 8g pyridine (analyzing pure) and join in 100g deionized water, stirred at ambient temperature 10 minutes.Add wherein by 50g embodiment 4 by the coconut carbon after nitric acid treatment, under-0.1MPa, vacuum soaks 2h.Cross and to filter after unnecessary solution in 80 DEG C of vacuum drying chambers dry 10 hours.Dried active carbon is put into tube furnace, and under nitrogen protection in 700 DEG C of carbonizations 10 hours, obtain the nitrogen-dopped activated carbon catalyst that pyridine is nitrogenous source, N doping amount meets between 0.1-10%.
Embodiment 7
Prepare sample 7: the N doping coal-based carbon catalyst of load barium chloride.
Getting 0.8g barium chloride (analyzing pure) is dissolved in 40g deionized water, stirs the nitrogen-dopped activated carbon added until completely dissolved in 20g embodiment 2.Room temperature immersion puts into 120 DEG C of drying boxes after 4 hours dries 10 hours, and obtain barium chloride load N doping coal-based carbon catalyst, barium chloride doping meets between 0.1-10wt%.
Embodiment 8
Prepare sample 8: the N doping coal-based carbon catalyst of load lanthanum chloride
Getting 1.2g seventy flavors pearl pill (analyzing pure) is dissolved in 40g deionized water, stirs the nitrogen-dopped activated carbon added until completely dissolved in 20g embodiment 3.Room temperature immersion puts into 120 DEG C of drying boxes after 4 hours dries 10 hours, and obtain lanthanum chloride load N doping coal-based carbon catalyst, lanthanum chloride doping meets between 0.1-10wt%.
Embodiment 9
Prepare sample 9: the N doping coconut husk Pd/carbon catalyst of load copper chloride
Getting 1.9g copper chloride dihydrate (analyzing pure) is dissolved in 40g deionized water, stirs the nitrogen-dopped activated carbon added until completely dissolved in 20g embodiment 4.Room temperature immersion puts into 120 DEG C of drying boxes after 4 hours dries 10 hours, and obtain copper chloride load N doping coal-based carbon catalyst, copper chloride doping meets between 0.1-10wt%.
Embodiment 10
Prepare sample 10: the N doping coconut husk Pd/carbon catalyst of load calcium chloride
Getting 9g calcium chloride (analyzing pure) is dissolved in 40g deionized water, stirs the nitrogen-dopped activated carbon added until completely dissolved in 15g embodiment 4.Room temperature immersion puts into 120 DEG C of drying boxes after 4 hours dries 10 hours, and obtain copper chloride load N doping coal-based carbon catalyst, calcium chloride doping meets between 0.1-10wt%.
Comparative example 1
Comparative catalyst 1: HCl treatment active carbon from coal (processing mode is example 1 simultaneously).
Comparative example 2
Comparative catalyst 2: barium chloride load coal-based carbon catalyst.
Getting 0.8g barium chloride (analyzing pure) is dissolved in 40g deionized water, stir the salt acid soak added until completely dissolved in 20g embodiment 1 clean after active carbon.Room temperature immersion puts into 120 DEG C of drying boxes after 2 hours dries 10 hours, obtains barium chloride supported active Pd/carbon catalyst.
Comparative example 3
Comparative example catalyst 3: calcium chloride load coconut husk Pd/carbon catalyst.
Get 0.8g calcium chloride to be dissolved in 50g deionized water, after being stirred to dissolving completely, add the coconut husk charcoal in 20g embodiment 4 after nitric acid treatment.Room temperature immersion puts into 120 DEG C of drying boxes after 2 hours dries 10 hours, obtains calcium chloride load coconut husk Pd/carbon catalyst.
Catalyst performance evaluation and test experiment
It is in the quartz tube reactor of 16mm that 15g catalyst sample is loaded internal diameter, is heated to by quartz tube reactor and reacts temperature required and keep 20min under 30ml/min nitrogen protection.Close nitrogen, open dichloroethanes sampling valve, pump into dichloroethanes carry out catalyst activity investigation with 10ml/min flow velocity, now reaction velocity is 87 h
-1.Under different catalysts catalytic action the conversion ratio of 1,2-dichloroethanes and vinyl chloride selective as shown in table 1.
The catalytic performance of table 1 sample
Result shows, adopts the selective far above normal load type activated carbon catalysis of its low temperature of N doping catalysis of preparing of the inventive method and high temperature active and vinyl chloride.
Claims (18)
1. prepare the nitrating activated-carbon catalyst of vinyl chloride for 1,2-dichloroethanes catalytic pyrolysis for one kind, be specially a kind of at surfaces externally and internally all doped with the active carbon of nitrogen element, the doping of described nitrogen element is 0.1 ~ 10wt%.
2. as claimed in claim 1 for 1,2-dichloroethanes catalytic pyrolysis prepares the nitrating activated-carbon catalyst of vinyl chloride, it is characterized in that, the load of described nitrating activated-carbon catalyst has metal, described metal exists with the form of metallic compound, and the load capacity of described metallic compound is 0.1 ~ 10wt%.
3. the nitrating activated-carbon catalyst preparing vinyl chloride for 1,2-dichloroethanes catalytic pyrolysis as claimed in claim 1 or 2, it is characterized in that, the specific area of described active carbon is 700 ~ 2000m
2/ g, particle diameter is 0.05 ~ 1cm, and pore volume is 0.4 ~ 0.7m
3/ g.
4. the nitrating activated-carbon catalyst preparing vinyl chloride for 1,2-dichloroethanes catalytic pyrolysis as claimed in claim 1 or 2, it is characterized in that, described active carbon is selected from carbo lignius, coal-based carbon and fruit shell carbon.
5. the nitrating activated-carbon catalyst preparing vinyl chloride for 1,2-dichloroethanes catalytic pyrolysis as claimed in claim 2, it is characterized in that, described metal is selected from calcium, barium, lanthanum and copper etc.
6. the nitrating activated-carbon catalyst preparing vinyl chloride for 1,2-dichloroethanes catalytic pyrolysis as claimed in claim 2, it is characterized in that, described metallic compound is selected from metal oxide, chloride, sulfate, phosphate and nitrate etc.
7. the preparation method preparing the nitrating activated-carbon catalyst of vinyl chloride for 1,2-dichloroethanes catalytic pyrolysis as claimed in claim 1, comprises the following steps:
(1) get active carbon to carry out immersion treatment with removal of impurities and dredge duct, then after filtration, washing, dry after for subsequent use;
(2) the obtained described nitrating activated-carbon catalyst preparing vinyl chloride for 1,2-dichloroethanes catalytic pyrolysis of any one nitrogen element acquisition methods following is used:
Method one: get the active carbon after step (1) process, be placed in nitrogenous active gases and carry out N doping;
Method two: get the active carbon after step (1) process, the aqueous solution being placed in nitrogen-containing compound carries out impregnation process, after then filtering, drying, then carbonization under an inert atmosphere.
8. preparation method as claimed in claim 7, it is characterized in that, in step (1), the soak of shown immersion treatment is the aqueous solution of hydrochloric acid, nitric acid, hydrogen peroxide or NaOH etc.
9. preparation method as claimed in claim 7, it is characterized in that, in described soak, the concentration of solute is 0.5-5mol/L; The volume ratio of active carbon and soak is 1:1.1 ~ 1.5; The time of immersion treatment is 1 ~ 24 hour.
10. preparation method as claimed in claim 7, it is characterized in that, in the method one of step (2), described N doping process is: described active carbon after step (1) process is placed in tube furnace, after being warming up to 400-1000 DEG C under inert atmosphere, then pass into nitrogenous active gases 4 ~ 20 hours with 10 ~ 100ml/min speed, be then cooled to room temperature, stop again afterwards passing into described nitrogenous active gases.
11. preparation methods as claimed in claim 10, it is characterized in that, described nitrogenous active gases is the gaseous mixture of ammonia and hydrogen, and ammonia is 2 ~ 7:1 with the ratio of hydrogen volume flow.
12. preparation methods as claimed in claim 7, it is characterized in that, in the method two of step (2), described nitrogen-containing compound is selected from pyridine, piperidines, polyacrylamide, polyvinylpyrrolidone and melamine.
13. preparation methods as claimed in claim 7, is characterized in that, in the method two of step (2), the concentration of aqueous solution of described nitrogen-containing compound is 0.1 ~ 3mol/L; Described dipping is vacuum impregnation, and the time of dipping is 2 ~ 10 hours; Dipping process, the active carbon after step (1) process and nitrogen-containing compound aqueous solution volume ratio are 1:1.1 ~ 1.5.
14. preparation methods as claimed in claim 7, is characterized in that, in the method two of step (2), described carbonization is, active carbon after impregnation process and washing, oven dry is placed in tube furnace, is warming up to 400 ~ 1000 DEG C under an inert atmosphere, carbonization 4 ~ 20 hours.
15. is as claimed in claim 2 for 1,2-dichloroethanes catalytic pyrolysis prepares the preparation method of the nitrating activated-carbon catalyst of vinyl chloride, it is characterized in that, getting the nitrating activated-carbon catalyst that the arbitrary preparation method of claim 7-14 obtains impregnated in the aqueous solution of the metallic compound of described carried metal, then after filtration, dry after obtained load have the nitrating activated-carbon catalyst of metal.
16. preparation methods as claimed in claim 15, is characterized in that, the concentration of the aqueous solution of described metallic compound is 0.1-2.5mol/L; The volume ratio 1:1.1-1.5 of the nitrating activated-carbon catalyst metallizing thing aqueous solution; Dip time is 2-8 hour.
17. as described in right 1 or 2 for 1, the nitrating activated-carbon catalyst that 2-dichloroethanes catalytic pyrolysis prepares vinyl chloride is used as 1,2-dichloroethanes catalytic pyrolysis prepares the purposes of vinyl chloride catalysts, for described nitrating activated-carbon catalyst is inserted in fixed bed reactors, raw material dichloroethanes through pre-thermal evaporation laggard enter fixed bed reactors bed carry out catalytic cracking reaction generate vinyl chloride.
18. purposes as claimed in claim 17, is characterized in that, the pressure of described catalytic cracking reaction is normal pressure, and temperature is 180 ~ 350 DEG C, and air speed is 10 ~ 200h
-1.
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Cited By (13)
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| CN105833892A (en) * | 2016-04-22 | 2016-08-10 | 辽宁石油化工大学 | Catalyst for preparing vinyl chloride by cracking 1,2-dichloroethane as well as preparation method and application of catalyst |
| TWI577446B (en) * | 2016-03-31 | 2017-04-11 | 臺灣塑膠工業股份有限公司 | Cracking catalyst of 1,2-dichloroethane, method of producing the same and application thereof |
| CN106732682A (en) * | 2015-11-25 | 2017-05-31 | 上海氯碱化工股份有限公司 | The catalyst and preparation method of trichloroethanes liquid-phase catalysis cracking preparing vinylidene chloride |
| CN109433239A (en) * | 2018-10-23 | 2019-03-08 | 重庆师范大学 | A kind of preparation method and application for the platinum carbon catalyst that Fe-N is modified |
| CN109926081A (en) * | 2017-12-15 | 2019-06-25 | 中国科学院大连化学物理研究所 | A kind of catalyst, preparation and regeneration method for 1,2- dichloroethanes cracking preparing chloroethylene |
| CN110975855A (en) * | 2019-12-18 | 2020-04-10 | 浙江工业大学 | Catalyst for preparing tetrafluoroethylene and hexafluoropropylene by catalytic cracking of monochlorodifluoromethane, preparation method and application thereof |
| CN111454122A (en) * | 2019-01-22 | 2020-07-28 | 中国科学院上海有机化学研究所 | Method for eliminating hydrogen chloride by catalytic cracking of chloralkane |
| WO2020220312A1 (en) * | 2019-04-30 | 2020-11-05 | 中国科学院大连化学物理研究所 | Catalyst for preparing vinyl chloride by cracking 1,2-dichloroethane and preparation and regeneration methods therefor |
| CN112316968A (en) * | 2020-11-13 | 2021-02-05 | 中国石油大学(北京) | Crude terephthalic acid hydrofining catalyst and preparation method and application thereof |
| JP2021525162A (en) * | 2019-04-30 | 2021-09-24 | 中国科学院大▲連▼化学物理研究所Ｄａｌｉａｎ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｃｈｅｍｉｃａｌ Ｐｈｙｓｉｃｓ，Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ | Manufacturing method of supported carbon catalyst, supported carbon catalyst and its use |
| CN113634272A (en) * | 2021-07-26 | 2021-11-12 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Acetylene hydrochlorination catalyst of N-P modified activated carbon and preparation method thereof |
| CN113731460A (en) * | 2021-07-21 | 2021-12-03 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | N-P modified acetylene hydrochlorination non-noble metal catalyst and preparation method and application thereof |
| CN114177924A (en) * | 2021-12-27 | 2022-03-15 | 贵州重力科技环保有限公司 | Catalyst for preparing trichloroethylene by eliminating hydrogen chloride with tetrachloroethane and preparation method thereof |
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| CN106732682A (en) * | 2015-11-25 | 2017-05-31 | 上海氯碱化工股份有限公司 | The catalyst and preparation method of trichloroethanes liquid-phase catalysis cracking preparing vinylidene chloride |
| TWI577446B (en) * | 2016-03-31 | 2017-04-11 | 臺灣塑膠工業股份有限公司 | Cracking catalyst of 1,2-dichloroethane, method of producing the same and application thereof |
| CN106732772A (en) * | 2016-03-31 | 2017-05-31 | 台湾塑胶工业股份有限公司 | Cracking catalyst for 1, 2-dichloroethane, process for producing the same and use thereof |
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| CN109926081A (en) * | 2017-12-15 | 2019-06-25 | 中国科学院大连化学物理研究所 | A kind of catalyst, preparation and regeneration method for 1,2- dichloroethanes cracking preparing chloroethylene |
| CN109433239A (en) * | 2018-10-23 | 2019-03-08 | 重庆师范大学 | A kind of preparation method and application for the platinum carbon catalyst that Fe-N is modified |
| CN111454122B (en) * | 2019-01-22 | 2021-09-03 | 中国科学院上海有机化学研究所 | Method for eliminating hydrogen chloride by catalytic cracking of chloralkane |
| CN111454122A (en) * | 2019-01-22 | 2020-07-28 | 中国科学院上海有机化学研究所 | Method for eliminating hydrogen chloride by catalytic cracking of chloralkane |
| WO2020220312A1 (en) * | 2019-04-30 | 2020-11-05 | 中国科学院大连化学物理研究所 | Catalyst for preparing vinyl chloride by cracking 1,2-dichloroethane and preparation and regeneration methods therefor |
| JP2021525161A (en) * | 2019-04-30 | 2021-09-24 | 中国科学院大▲連▼化学物理研究所Ｄａｌｉａｎ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｃｈｅｍｉｃａｌ Ｐｈｙｓｉｃｓ，Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ | A catalyst for thermally decomposing 1,2-dichloroethane to produce vinyl chloride, and a method for producing and regenerating the catalyst. |
| JP2021525162A (en) * | 2019-04-30 | 2021-09-24 | 中国科学院大▲連▼化学物理研究所Ｄａｌｉａｎ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｃｈｅｍｉｃａｌ Ｐｈｙｓｉｃｓ，Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ | Manufacturing method of supported carbon catalyst, supported carbon catalyst and its use |
| JP7003223B2 (en) | 2019-04-30 | 2022-02-21 | 中国科学院大▲連▼化学物理研究所 | A catalyst for thermally decomposing 1,2-dichloroethane to produce vinyl chloride, and a method for producing and regenerating the catalyst. |
| JP7034256B2 (en) | 2019-04-30 | 2022-03-11 | 中国科学院大▲連▼化学物理研究所 | Manufacturing method of supported carbon catalyst, supported carbon catalyst and its use |
| US11338276B2 (en) | 2019-04-30 | 2022-05-24 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Catalyst for preparing chloroethylene by cracking 1,2-dichloroethane and a preparation and regeneration method thereof |
| CN110975855A (en) * | 2019-12-18 | 2020-04-10 | 浙江工业大学 | Catalyst for preparing tetrafluoroethylene and hexafluoropropylene by catalytic cracking of monochlorodifluoromethane, preparation method and application thereof |
| CN112316968A (en) * | 2020-11-13 | 2021-02-05 | 中国石油大学(北京) | Crude terephthalic acid hydrofining catalyst and preparation method and application thereof |
| CN113731460A (en) * | 2021-07-21 | 2021-12-03 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | N-P modified acetylene hydrochlorination non-noble metal catalyst and preparation method and application thereof |
| CN113634272A (en) * | 2021-07-26 | 2021-11-12 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Acetylene hydrochlorination catalyst of N-P modified activated carbon and preparation method thereof |
| CN114177924A (en) * | 2021-12-27 | 2022-03-15 | 贵州重力科技环保有限公司 | Catalyst for preparing trichloroethylene by eliminating hydrogen chloride with tetrachloroethane and preparation method thereof |
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