CN114367296B - 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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- CN114367296B CN114367296B CN202011104607.6A CN202011104607A CN114367296B CN 114367296 B CN114367296 B CN 114367296B CN 202011104607 A CN202011104607 A CN 202011104607A CN 114367296 B CN114367296 B CN 114367296B
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- aromatic hydrocarbon
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 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
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 17
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000005416 organic matter Substances 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 27
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract description 26
- -1 nickel nitride Chemical class 0.000 abstract description 12
- 239000003575 carbonaceous material Substances 0.000 abstract description 7
- 239000004480 active ingredient Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 description 16
- 239000000203 mixture Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 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
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000006298 dechlorination reaction Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction 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
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000006978 adaptation Effects 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
- YXGWBKCOOBHTPT-UHFFFAOYSA-N benzene;chlorobenzene Chemical compound C1=CC=CC=C1.ClC1=CC=CC=C1 YXGWBKCOOBHTPT-UHFFFAOYSA-N 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 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
- 238000006731 degradation 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
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification 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
- 239000000575 pesticide Substances 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
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, through a calcination mode, nickel nitride is prepared, and a carbon material converted from a nitrogen-containing organic matter in the calcination process is used as a catalyst carrier, so that the catalyst has the characteristics of large specific surface area and more active sites, and the activity of the prepared catalyst is improved by combining active ingredients of the nickel nitride with the carbon material carrier; the calcination mode also improves the stability of the catalyst. The catalyst obtained by the preparation method is used in the process of hydrodechlorination of chlorinated aromatic hydrocarbon, and the chlorobenzene conversion rate and benzene selectivity are both above 65%; and the conversion rate of chlorobenzene can be up to 98.4%, the selectivity of benzene can be up to 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, a preparation method and application thereof.
Background
Chlorinated aromatic hydrocarbons and derivatives thereof are widely used as chemical raw materials in the fields of pesticides, medicines, chemical industry and the like. The organic matters have good thermal stability and chemical stability, are not easy to be naturally degraded or biodegraded, and are enriched in the topmost birds, fish and human bodies of the food chain through the food chain. Chlorinated aromatic hydrocarbons and their derivatives have high toxicity, high carcinogenicity and obvious inhibition to organisms, so that the chlorinated aromatic hydrocarbons and their derivatives cause serious harm to animals and human bodies. Therefore, the method has important significance for the treatment of 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, biological degradation, oxidation, combustion, catalytic chlorination and dechlorination. However, adsorption methods do not fundamentally address chlorinated organics; the problems of low efficiency and long period of photocatalytic degradation and biodegradation exist; secondary pollution can be caused by an oxidation method and a combustion method; the catalytic hydrodechlorination method is the most commonly used 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 in order to improve the conversion rate of raw materials and the selectivity of products under the condition of omitting noble metal, a reduction method is often adopted to prepare newly prepared nickel as a catalyst for reaction, but the catalytic effect is still unsatisfactory, and the conversion rate of raw materials is only above 40% and the selectivity is only above 50%.
Disclosure of Invention
In view of the above, the invention aims to provide a catalyst for hydrodechlorination of chlorinated aromatic hydrocarbon, and a preparation method and application thereof, and the preparation method of the catalyst does not use noble metal, and the prepared catalyst is used for hydrodechlorination catalytic reaction of chlorinated aromatic hydrocarbon, and the conversion rate of raw materials and the selectivity of products can be more than 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:
and mixing the nickel precursor, the nitrogen-containing organic matter and the solvent, and calcining to obtain the catalyst for hydrodechlorination of the chlorinated aromatic hydrocarbon.
Preferably, the nickel precursor comprises at least one of nickel nitrate hexahydrate, nickel acetate, nickel chloride, and nickel acetylacetonate.
Preferably, the nitrogen-containing organic matter comprises at least one of urea, dicyandiamide and melamine.
Preferably, the solvent includes at least one of methanol, ethanol, and water.
Preferably, the ratio of the amounts of the nickel precursor and the nitrogen-containing organic matter is 0.01 to 0.03.
Preferably, the ratio of the amount of the material of the nickel precursor to the solvent volume is
0.08～0.12mmol/mL。
Preferably, the calcination temperature is 600-1000 ℃ and the calcination time is 1-4 h.
Preferably, the calcined atmosphere is an inert atmosphere.
The invention also provides a catalyst for hydrodechlorination of the chlorinated aromatic hydrocarbon, which is prepared by the preparation method.
The invention also provides application of the catalyst in the hydrogenation dechlorination reaction of the chlorinated aromatic hydrocarbon.
The invention provides a preparation method of a catalyst for hydrodechlorination of chlorinated aromatic hydrocarbon, which comprises the steps of mixing a nickel precursor, a nitrogen-containing organic matter and a solvent, and calcining to obtain the catalyst for hydrodechlorination of chlorinated aromatic hydrocarbon. The invention prepares nickel nitride (Ni 3 N), and the carbon material converted from the nitrogen-containing organic matters in the calcination process is used as a nickel nitride carrier, so that the catalyst 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 ingredient nickel nitride with the carbon material carrier; the calcination mode also improves the stability of the catalyst. The results of the examples show that the catalyst obtained by the preparation method provided by the invention is used in the hydrodechlorination process of the chlorinated aromatic hydrocarbon, and the chlorobenzene conversion rate and the benzene selectivity are both above 65%; and the conversion rate of chlorobenzene can be up to 98.4%, the selectivity of benzene can be up to 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 raw materials is only more than 40 percent, and the selectivity is also only more than 50 percent), 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 the 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 nitrate hexahydrate used as the nickel precursor has the advantages of low content of nickel nitride impurities and good catalytic performance of the catalyst.
In the present invention, the nitrogen-containing organic matter preferably includes at least one of urea, dicyandiamide, and melamine, more preferably melamine. In the invention, the nitrogen-containing organic matter provides nitrogen atoms in the prepared nickel nitride, and simultaneously provides carrier carbon required by the catalyst, and when melamine is used as a nitrogen source and a provider of the 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, more preferably ethanol. In the invention, the ethanol is easier to volatilize in the preparation process, so that the influence of the solvent on the catalyst performance 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, more preferably 0.02. In the present invention, the ratio of the amounts of the nickel precursor and the nitrogen-containing organic matter is controlled within the above range, and the catalyst obtained has good catalytic performance.
In the present invention, the ratio of the amount of the substance of the nickel precursor to the volume of the solvent is preferably 0.08 to 0.12mmol/mL, more preferably 0.1mmol/mL. In the invention, the ratio of the amount of the substance of the nickel precursor to the solvent volume is controlled in the above range, and the catalytic performance of the obtained catalyst is good.
In the present invention, the mixing of the nickel precursor, the nitrogen-containing organic compound and the solvent preferably further comprises drying. The drying mode is not particularly limited in the present invention, and the solvent in the mixture may be removed by drying modes well known to those skilled in the art.
In the present invention, the drying temperature is preferably 60 to 100 ℃, more preferably 80 ℃. In the invention, the temperature of the drying temperature is controlled in 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 calcination process is avoided.
In the present invention, the temperature of the calcination is preferably 600 to 1000 ℃, more preferably 800 to 900 ℃; the calcination time is preferably 1 to 4 hours, more preferably 2 to 3 hours. In the invention, the calcination temperature and the calcination time are controlled in the above ranges, and the catalyst obtained has good catalytic performance.
In the present invention, the calcined atmosphere is preferably an inert atmosphere. In the present invention, the inert atmosphere gas preferably includes at least one of argon, nitrogen, helium and neon, more preferably nitrogen. In the invention, the nitrogen is a common gas provider in inert atmosphere, so that the influence of oxygen in air on the performance of the catalyst in the calcination process can be avoided, and the catalytic capability of the catalyst is improved.
The preparation method provided by the invention not only prepares the nickel nitride (Ni 3 N), and the carbon material converted from the nitrogen-containing organic matters in the calcination process is used as a carrier of the nickel nitride catalyst, so that the catalyst has the characteristics of large specific surface area and more active sites, and the combination of the active ingredient nickel nitride and the carbon material carrier improves the activity of the prepared catalyst; the calcination mode also improves the stability of the catalyst.
The invention also provides a catalyst for hydrodechlorination of chlorinated aromatic hydrocarbon, which is prepared by the preparation method. In the present invention, the catalytic component of the catalyst is preferably nickel nitride, and the carrier is preferably a carbon material generated during calcination.
The invention also provides application of the catalyst in the hydrodechlorination reaction of the chlorinated aromatic hydrocarbon.
The conditions for the hydrodechlorination reaction of the chlorinated aromatic hydrocarbon are not particularly limited, and the reaction is carried out under reaction conditions well known to those skilled in the art.
In the present invention, the mass ratio of the chlorinated aromatic hydrocarbon to the catalyst is preferably (0.8 to 1.2): 1, 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 above 65%; and the conversion rate of chlorobenzene can be up to 98.4%, the selectivity of benzene can be up to 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 raw materials is only more than 40 percent, and the selectivity is also only more than 50 percent), the catalyst obtained by the preparation method provided by the invention has better catalytic performance.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
1) 1mmol of nickel nitrate hexahydrate and 50mmol of melamine were put into 10mL of ethanol and stirred for 4 hours to give a viscous mixture. (the ratio of the amounts of the nickel precursor and the nitrogen-containing organic matters was 0.02, and the ratio of the nickel precursor and the solvent was 0.1 mmol/mL)
2) Evaporating the viscous mixture obtained in the step 1 at a high temperature of 80 ℃ to dryness to obtain 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 the catalyst for hydrodechlorination of chlorinated aromatic hydrocarbon.
Example 2
1) 1mmol of nickel nitrate hexahydrate and 50mmol of melamine were put into 10mL of ethanol and stirred for 4 hours to give a viscous mixture. (the ratio of the amounts of the nickel precursor and the nitrogen-containing organic matters was 0.02, and the ratio of the nickel precursor and the solvent was 0.1 mmol/mL)
2) Evaporating the viscous mixture obtained in the step 1 at a high temperature of 80 ℃ to dryness to obtain solid powder.
3) Calcining the solid powder obtained in the step 2 for 2 hours in a high-temperature nitrogen atmosphere at 700 ℃ to obtain a catalyst; the catalyst is the catalyst for hydrodechlorination of chlorinated aromatic hydrocarbon.
Example 3
1) 1mmol of nickel nitrate hexahydrate and 50mmol of melamine were put into 10mL of ethanol and stirred for 4 hours to give a viscous mixture. (the ratio of the amounts of the nickel precursor and the nitrogen-containing organic matters was 0.02, and the ratio of the nickel precursor and the solvent was 0.1 mmol/mL)
2) Evaporating the viscous mixture obtained in the step 1 at a high temperature of 80 ℃ to dryness to obtain solid powder.
3) Calcining the solid powder obtained in the step 2 for 2 hours in a high-temperature nitrogen atmosphere at 900 ℃ to obtain a catalyst; the catalyst is the catalyst for hydrodechlorination of chlorinated aromatic hydrocarbon.
Comparative example 1
1g of activated carbon was added with 530.3mg of anhydrous nickel nitrate and 10ml of water, stirred for 4 hours, and reduced with 0.2M sodium borohydride to obtain a catalyst.
Performance testing
The catalysts prepared in examples 1 to 3 and comparative example 1 were respectively charged into a high-pressure reaction vessel with ethanol as a solution, and the mass ratio of chlorobenzene to catalyst was 1 at a reaction pressure of 2bar hydrogen at a temperature of 80 ℃: and (1) carrying out chlorobenzene catalytic hydrogenation dechlorination reaction under the condition.
The catalysts prepared in examples 1-3 and comparative example 1 were used for hydrodechlorination of chlorobenzene, and the results of the catalytic performance tests are shown in Table 1.
Table 1 catalytic performance test data for the catalysts prepared in examples 1 to 3 and comparative example 1
As can be seen from Table 1, in the process of carrying out the hydrodechlorination reaction of the chlorinated aromatic hydrocarbon by using the catalyst provided by the invention, the chlorobenzene conversion rate and the benzene selectivity are both above 65%; 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 freshly prepared nickel catalyst alone, the conversion of chlorobenzene 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.
The catalyst prepared in example 1 was used for hydrodechlorination of chlorobenzene, and the stability of the catalyst was evaluated, and the test results are shown in table 2.
TABLE 2 catalyst cycle performance test prepared in example 1
| Number of tests | Conversion of chlorobenzene | 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 catalyst prepared in example 1 was subjected to hydrodechlorination reaction for 5 times, and the properties were not significantly changed. Therefore, the catalyst for hydrodechlorination of the chlorinated aromatic hydrocarbon, which is obtained by the preparation method, has better stability.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (2)
1. Use of a catalyst in a hydrodechlorination reaction of chlorinated aromatic hydrocarbons, the method of preparing the catalyst comprising:
mixing a nickel precursor, a nitrogen-containing organic matter and a solvent, and calcining to obtain a catalyst for hydrodechlorination of chlorinated aromatic hydrocarbon;
the nickel precursor is nickel nitrate hexahydrate;
the nitrogen-containing organic matter is melamine;
the solvent is ethanol;
the ratio of the amounts of the nickel precursor and the substances containing nitrogen organic matters is 0.01-0.03;
the calcination temperature is 800 ℃, and the calcination time is 2 hours;
the calcined atmosphere is an inert atmosphere.
2. The use according to claim 1, characterized in that the ratio of the amount of the substance of the nickel precursor to the volume of the solvent is (0.08-0.12) mmol/mL.
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| 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 |
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2020
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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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