CN114367296A - Catalyst for hydrodechlorination of chlorinated aromatic hydrocarbon and preparation method and application thereof - Google Patents
Catalyst for hydrodechlorination of chlorinated aromatic hydrocarbon and preparation method and application thereof Download PDFInfo
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- CN114367296A CN114367296A CN202011104607.6A CN202011104607A CN114367296A CN 114367296 A CN114367296 A CN 114367296A CN 202011104607 A CN202011104607 A CN 202011104607A CN 114367296 A CN114367296 A CN 114367296A
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- hydrodechlorination
- nickel
- chlorinated aromatic
- aromatic hydrocarbon
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 39
- 238000001354 calcination Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 21
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000005416 organic matter Substances 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 30
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract description 30
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- -1 nickel nitride Chemical class 0.000 abstract description 12
- 239000003575 carbonaceous material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000006298 dechlorination reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/24—Nitrogen compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to the field of catalyst materials, and provides a preparation method of a catalyst for hydrodechlorination of chlorinated aromatic hydrocarbon. According to the invention, by adopting a calcining mode, nickel nitride is prepared, and the carbon material converted from the nitrogen-containing organic matter in the calcining process is used as a catalyst carrier, so that the catalyst has the characteristics of large specific surface area and many active sites, and the activity of the prepared catalyst is improved by combining the active component nickel nitride with the carbon material carrier; and meanwhile, the stability of the catalyst is improved by the calcining mode. When the catalyst obtained by the preparation method provided by the invention is used in the process of hydrodechlorination of chlorinated aromatic hydrocarbon, the chlorobenzene conversion rate and benzene selectivity are both over 65%; moreover, the highest chlorobenzene conversion rate can reach 98.4%, the highest benzene selectivity can reach 99.3%, and the performance of the catalyst is not obviously changed after the catalyst is recycled for 5 times.
Description
Technical Field
The invention relates to the field of catalyst materials, in particular to a catalyst for hydrodechlorination of chlorinated aromatic hydrocarbon and a preparation method and application thereof.
Background
Chlorinated aromatic hydrocarbons and derivatives thereof are used as chemical raw materials in a large number in the fields of agricultural chemicals, medicines, chemical industry, and the like. Such organic substances have good thermal and chemical stability, are not easily naturally or biologically degraded, and are enriched in the topmost birds, fish and humans of the food chain by the food chain. Chlorinated aromatic hydrocarbons and their derivatives are highly toxic, highly carcinogenic, and significantly inhibitory to living organisms, and thus can pose serious harm to animals and humans. Therefore, the method has important significance for processing the chlorinated aromatic hydrocarbon and the derivatives thereof in the environment.
At present, the main treatment methods for chlorinated aromatic hydrocarbons and derivatives thereof are as follows: adsorption, photocatalytic degradation, biodegradation, oxidation, combustion, catalytic chlorination, and dechlorination. However, adsorption methods do not fundamentally address chlorinated organics; photocatalytic degradation and biodegradation have the problems of low efficiency and long period; the oxidation method and the combustion method can cause secondary pollution; the catalytic hydrodechlorination method is the most common method at present, and is simple, efficient and safe. In the prior art, a nickel-containing catalyst is generally used for catalytic hydrodechlorination of chlorinated aromatic hydrocarbon and derivatives thereof, and under the condition that noble metals are omitted, newly prepared nickel is often used as a catalyst for reaction by a reduction method in order to improve the conversion rate of raw materials and the selectivity of products, but the catalytic effect is still not ideal, the conversion rate of the raw materials is usually more than 40%, and the selectivity is also more than 50%.
Disclosure of Invention
In view of the above, the present invention aims to provide a catalyst for hydrodechlorination of chlorinated aromatic hydrocarbons, and a preparation method and an application thereof, wherein the preparation method of the catalyst provided by the present invention does not use noble metals, the prepared catalyst is used for the catalytic reaction of hydrodechlorination of chlorinated aromatic hydrocarbons, and the conversion rate of raw materials and the selectivity of products can be above 60% at the same time.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a catalyst for hydrodechlorination of chlorinated aromatic hydrocarbon, which comprises the following steps:
mixing the nickel precursor, the nitrogen-containing organic matter and the solvent, and calcining to obtain the catalyst for hydrodechlorination of chlorinated aromatic hydrocarbon.
Preferably, the nickel precursor includes at least one of nickel nitrate hexahydrate, nickel acetate, nickel chloride, and nickel acetylacetonate.
Preferably, the nitrogen-containing organic substance includes at least one of urea, dicyandiamide, and melamine.
Preferably, the solvent comprises at least one of methanol, ethanol and water.
Preferably, the ratio of the amounts of the nickel precursor and the nitrogen-containing organic substance is 0.01-0.03.
Preferably, the ratio of the amount of the substance of the nickel precursor to the volume of the solvent is
0.08～0.12mmol/mL。
Preferably, the calcining temperature is 600-1000 ℃, and the calcining time is 1-4 h.
Preferably, the atmosphere of the calcination is an inert atmosphere.
The invention also provides the catalyst for hydrodechlorination of chlorinated aromatic hydrocarbons, which is prepared by the preparation method in the technical scheme.
The invention also provides the application of the catalyst in the technical scheme in the chlorinated aromatic hydrocarbon hydrodechlorination reaction.
The invention provides a preparation method of a catalyst for hydrodechlorination of chlorinated aromatic hydrocarbon, which is characterized in that a nickel precursor, a nitrogen-containing organic matter and a solvent are mixed and calcined to obtain the catalyst for hydrodechlorination of chlorinated aromatic hydrocarbon. The invention prepares nickel nitride (Ni) by calcining3N), the carbon material converted from the nitrogen-containing organic matter in the calcining process is used as the carrier of the nickel nitride, and has the characteristics of large specific surface area and more active sites, and the activity of the prepared catalyst is improved by combining the active component nickel nitride with the carbon material carrier; and meanwhile, the stability of the catalyst is improved by the calcining mode. The results of the examples show that when the catalyst prepared by the preparation method provided by the invention is used in the process of hydrodechlorination of chlorinated aromatic hydrocarbon, the chlorobenzene conversion rate and benzene selectivity are both over 65%; the highest chlorobenzene conversion rate can reach 98.4%, the highest benzene selectivity can reach 99.3%, and the catalyst can be recycled for 5 timesNo significant change was observed. Therefore, compared with the nickel-containing catalyst without noble metal in the prior art (the conversion rate of the raw material is only more than 40%, and the selectivity is also more than 50%), the catalyst obtained by the preparation method provided by the invention has better catalytic performance.
Detailed Description
The invention provides a preparation method of a catalyst for hydrodechlorination of chlorinated aromatic hydrocarbon, which comprises the following steps:
and mixing the nickel precursor, the nitrogen-containing organic matter and the solvent, and calcining to obtain the catalyst for hydrodechlorination of chlorinated aromatic hydrocarbon.
In the present invention, the nickel precursor preferably includes at least one of nickel nitrate hexahydrate, nickel acetate, nickel chloride, and nickel acetylacetonate, and more preferably, nickel nitrate hexahydrate. In the invention, the nickel nitride obtained by using the nickel nitrate hexahydrate as a nickel precursor has low impurity content, and the catalyst has good catalytic performance.
In the present invention, the nitrogen-containing organic substance preferably includes at least one of urea, dicyandiamide, and melamine, and more preferably melamine. In the invention, the nitrogen-containing organic matter provides nitrogen atoms in the prepared nickel nitride and provides carrier carbon required by the catalyst, and when melamine is used as a nitrogen source and a catalyst carrier, the obtained catalyst has better catalytic performance.
In the present invention, the solvent preferably includes at least one of methanol, ethanol and water, and more preferably ethanol. In the invention, the ethanol is easier to volatilize in the preparation process, and the influence of the solvent on the performance of the catalyst is reduced.
In the present invention, the ratio of the amounts of the nickel precursor and the nitrogen-containing organic substance is preferably 0.01 to 0.03, and more preferably 0.02. In the invention, the ratio of the amounts of the nickel precursor and the nitrogen-containing organic substance is controlled within the above range, and the obtained catalyst has good catalytic performance.
In the present invention, the ratio of the amount of the nickel precursor to the volume of the solvent is preferably 0.08 to 0.12mmol/mL, and more preferably 0.1 mmol/mL. In the invention, the ratio of the material amount of the nickel precursor to the volume of the solvent is controlled in the above range, and the obtained catalyst has good catalytic performance.
In the present invention, it is preferable that the mixing of the nickel precursor, the nitrogen-containing organic substance, and the solvent further includes drying. The drying method is not particularly limited in the present invention, and the solvent in the mixture can be removed by a drying method well known to those skilled in the art.
In the invention, the drying temperature is preferably 60-100 ℃, and more preferably 80 ℃. In the invention, the temperature of the drying temperature is controlled within the range, so that the solvent of the mixed species can be completely removed, and the influence of the solvent on the performance of the prepared catalyst in the later calcining process is avoided.
In the invention, the calcining temperature is preferably 600-1000 ℃, and more preferably 800-900 ℃; the calcination time is preferably 1-4 h, and more preferably 2-3 h. In the present invention, the calcination temperature and calcination time are controlled within the above ranges, and the obtained catalyst has good catalytic performance.
In the present invention, the atmosphere of the calcination is preferably an inert atmosphere. In the present invention, the gas of the inert atmosphere preferably includes at least one of argon, nitrogen, helium, and neon, and more preferably nitrogen. In the invention, the nitrogen is a common gas provider with inert atmosphere, so that the influence of oxygen in the air on the performance of the catalyst in the calcining process can be avoided, and the catalytic capability of the catalyst is improved.
The preparation method provided by the invention not only prepares nickel nitride (Ni) in a calcining way3N), the carbon material converted from the nitrogen-containing organic matter in the calcining process is used as the carrier of the nickel nitride catalyst, and has the characteristics of large specific surface area and many active sites, and the activity of the prepared catalyst is improved by the combination of the active component nickel nitride and the carbon material carrier; and meanwhile, the stability of the catalyst is improved by the calcining mode.
The invention also provides a catalyst for hydrodechlorination of chlorinated aromatic hydrocarbons, which is prepared by the preparation method. In the present invention, the catalytic component of the catalyst is preferably nickel nitride, and the support is preferably a carbon material generated during calcination.
The invention also provides the application of the catalyst in the hydrogenation and dechlorination reaction of chlorinated aromatic hydrocarbon.
The invention has no special regulation on the conditions of the hydrogenation and dechlorination reaction of the chlorinated aromatic hydrocarbon, and the reaction can be carried out by adopting the reaction conditions which are well known to the technical personnel in the field.
In the invention, the mass ratio of the chlorinated aromatic hydrocarbon to the catalyst is preferably (0.8-1.2): 1, and more preferably 1: 1.
The catalyst obtained by the preparation method provided by the invention is used in the process of hydrodechlorination of chlorinated aromatic hydrocarbon, and the chlorobenzene conversion rate and benzene selectivity are both over 65%; moreover, the highest chlorobenzene conversion rate can reach 98.4%, the highest benzene selectivity can reach 99.3%, and the performance of the catalyst is not obviously changed after the catalyst is recycled for 5 times. Therefore, compared with the nickel-containing catalyst without noble metal in the prior art (the conversion rate of the raw material is only more than 40%, and the selectivity is also more than 50%), the catalyst obtained by the preparation method provided by the invention has better catalytic performance.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
1) 1mmol of nickel nitrate hexahydrate and 50mmol of melamine are placed in 10mL of ethanol and stirred for 4h to give a viscous mixture. (the ratio of the amounts of the nickel precursor and the nitrogen-containing organic substance was 0.02, and the ratio of the nickel precursor and the solvent was 0.1mmol/mL)
2) The viscous mixture obtained in step 1 was evaporated to dryness at a high temperature of 80 ℃ to obtain a solid powder.
3) Calcining the solid powder obtained in the step 2 for 2 hours at the high temperature of 800 ℃ in a nitrogen atmosphere to obtain a catalyst; the catalyst is used for the hydrogenation and dechlorination of the chlorinated aromatic hydrocarbon.
Example 2
1) 1mmol of nickel nitrate hexahydrate and 50mmol of melamine are placed in 10mL of ethanol and stirred for 4h to give a viscous mixture. (the ratio of the amounts of the nickel precursor and the nitrogen-containing organic substance was 0.02, and the ratio of the nickel precursor and the solvent was 0.1mmol/mL)
2) The viscous mixture obtained in step 1 was evaporated to dryness at a high temperature of 80 ℃ to obtain a solid powder.
3) Calcining the solid powder obtained in the step 2 for 2 hours at the high temperature of 700 ℃ in a nitrogen atmosphere to obtain a catalyst; the catalyst is used for the hydrogenation and dechlorination of the chlorinated aromatic hydrocarbon.
Example 3
1) 1mmol of nickel nitrate hexahydrate and 50mmol of melamine are placed in 10mL of ethanol and stirred for 4h to give a viscous mixture. (the ratio of the amounts of the nickel precursor and the nitrogen-containing organic substance was 0.02, and the ratio of the nickel precursor and the solvent was 0.1mmol/mL)
2) The viscous mixture obtained in step 1 was evaporated to dryness at a high temperature of 80 ℃ to obtain a solid powder.
3) Calcining the solid powder obtained in the step 2 for 2 hours at the high temperature of 900 ℃ in a nitrogen atmosphere to obtain a catalyst; the catalyst is used for the hydrogenation and dechlorination of the chlorinated aromatic hydrocarbon.
Comparative example 1
Adding 530.3mg of anhydrous nickel nitrate and 10ml of water into 1g of activated carbon, stirring for 4 hours, and reducing by using 0.2M sodium borohydride to obtain the catalyst.
Performance testing
The catalysts prepared in examples 1-3 and comparative example 1 were respectively filled in a high pressure reactor, ethanol was used as a solution, the temperature was 80 ℃, the reaction pressure was 2bar hydrogen, and the mass ratio of chlorobenzene to catalyst was 1:1, carrying out catalytic hydrogenation and dechlorination reaction on chlorobenzene.
The catalysts prepared in examples 1 to 3 and comparative example 1 were used to hydrodechlorinate chlorobenzene, and the results of the catalytic performance tests are shown in table 1.
TABLE 1 data of catalytic Performance test of catalysts prepared in examples 1-3 and comparative example 1
As can be seen from Table 1, the catalyst provided by the invention has chlorobenzene conversion rate and benzene selectivity of over 65 percent in the process of performing hydrodechlorination reaction on chlorinated aromatic hydrocarbon; the highest chlorobenzene conversion rate can reach 98.4 percent, and the highest benzene selectivity can reach 99.3 percent; when the reaction was carried out using the newly prepared nickel catalyst alone, the chlorobenzene conversion was only 45.1% and the benzene selectivity was only 56.5%. Therefore, compared with the nickel-containing catalyst without noble metal in the prior art, the catalyst obtained by the preparation method provided by the invention has better catalytic performance.
Chlorobenzene was hydrodechlorinated using the catalyst prepared in example 1, and the stability of the catalyst was evaluated, and the test results are shown in table 2.
Table 2 catalyst cyclability test prepared in example 1
| Number of tests | Chlorobenzene conversion | Benzene selectivity |
| 1 | 98.4％ | 99.3％ |
| 2 | 99.1％ | 98.7％ |
| 3 | 97.9％ | 98.2％ |
| 4 | 98.5％ | 99.2％ |
| 5 | 98.25 | 98.5％ |
As can be seen from Table 2, the performance of the catalyst prepared in example 1 is not significantly changed after the chlorobenzene is subjected to hydrodechlorination reaction for 5 times. Therefore, the catalyst for the hydrodechlorination of chlorinated aromatic hydrocarbon, which is obtained by the preparation method provided by the invention, has better stability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a catalyst for hydrodechlorination of chlorinated aromatic hydrocarbon comprises the following steps:
and mixing the nickel precursor, the nitrogen-containing organic matter and the solvent, and calcining to obtain the catalyst for hydrodechlorination of chlorinated aromatic hydrocarbon.
2. The production method according to claim 1, wherein the nickel precursor includes at least one of nickel nitrate hexahydrate, nickel acetate, nickel chloride, and nickel acetylacetonate.
3. The method according to claim 1, wherein the nitrogen-containing organic substance comprises at least one of urea, dicyandiamide, and melamine.
4. The method of claim 1, wherein the solvent comprises at least one of methanol, ethanol, and water.
5. The method according to claim 1, wherein the ratio of the amounts of the nickel precursor and the nitrogen-containing organic substance is 0.01 to 0.03.
6. The method according to claim 1, wherein the ratio of the amount of the substance of the nickel precursor to the volume of the solvent is (0.08 to 0.12) mmol/mL.
7. The preparation method according to claim 1, wherein the calcination temperature is 600-1000 ℃ and the calcination time is 1-4 h.
8. The method according to claim 1, wherein the atmosphere for calcination is an inert atmosphere.
9. The catalyst for hydrodechlorination of chlorinated aromatic hydrocarbon prepared by the preparation method of any one of claims 1 to 8.
10. Use of the catalyst according to claim 9 in the hydrodechlorination of chlorinated aromatic hydrocarbons.
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| JPH09194401A (en) * | 1996-01-19 | 1997-07-29 | Kansai Tec:Kk | Hydrodechlorination treatment of polychlorivated aromatic compound |
| CN1548226A (en) * | 2003-05-14 | 2004-11-24 | 中国科学院大连化学物理研究所 | Catalyst for hydrodehalogenation of arene halide and its prepn and application |
| RU2402512C1 (en) * | 2009-03-23 | 2010-10-27 | Ордена Трудового Красного Знамени Институт физики металлов УрО РАН | Method of hydrodechlorinating chloroaromatic compounds |
| CN104815681A (en) * | 2015-03-13 | 2015-08-05 | 洛阳瑞泽石化工程有限公司 | Hydrodechlorination catalyst, preparation method and application thereof |
| CN107032326A (en) * | 2017-04-19 | 2017-08-11 | 广东工业大学 | A kind of method that solid catalysis prepares spiral carbon nano pipe |
| CN107570192A (en) * | 2017-08-21 | 2018-01-12 | 东莞理工学院 | A kind of nickel filling nitrogen doped carbon nanotube and its preparation method and application |
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