CN111450860A - Nitrogen-doped carbon catalyst based on biomass and preparation method and application thereof - Google Patents

Nitrogen-doped carbon catalyst based on biomass and preparation method and application thereof Download PDF

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CN111450860A
CN111450860A CN201910056498.6A CN201910056498A CN111450860A CN 111450860 A CN111450860 A CN 111450860A CN 201910056498 A CN201910056498 A CN 201910056498A CN 111450860 A CN111450860 A CN 111450860A
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biomass
nitrogen
doped carbon
carbon catalyst
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姜标
沈兆兵
刘悦
邢萍
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Shanghai Institute of Organic Chemistry of CAS
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Shanghai Institute of Organic Chemistry of CAS
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    • 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
    • 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
    • C07C1/30—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 by splitting-off the elements of hydrogen halide from a single molecule
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • 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 discloses a nitrogen-doped carbon catalyst based on biomass and a preparation method and application thereof. The biomass-based nitrogen-doped carbon catalyst is prepared by carbonizing biomass or a mixture of the biomass and a nitrogen source at 400-1000 ℃, wherein the biomass is selected from at least one of bamboo processing leftovers, wood processing leftovers, plant straws, plant leaves, cereals, beans, cereal processing leftovers, bean processing leftovers and livestock manure. The catalyst provided by the invention does not contain heavy metals such as mercury and the like, is environment-friendly, excellent in catalytic performance, good in catalytic activity, low in cost and easy for large-scale production, and can be used as a catalyst for eliminating hydrogen chloride reaction by cracking chloralkane, reaction for preparing chloroalkene by hydrochlorinating alkyne or reaction for preparing chloroethylene by a ginger clock method.

Description

Nitrogen-doped carbon catalyst based on biomass and preparation method and application thereof
Technical Field
The invention relates to a catalyst, a preparation method and application thereof, in particular to a biomass-based nitrogen-doped carbon catalyst, a preparation method and application thereof, and belongs to the technical field of catalysis.
Background
Olefins and chlorinated olefins are very important chemical feedstocks, for example: vinyl chloride, vinylidene chloride, trichloroethylene, tetrachloroethylene, propylene, trichloropropylene, tetrachloropropylene, butene, pentene, hexene and the like are used in a wide variety of chemical and material synthesis industries.
The existing olefin is mainly prepared by the reaction of alkyl halide and sodium hydroxide alcoholic solution, and can also be prepared by the dehydration of alcohol or the reaction of o-alkyl halide and zinc, wherein small molecular olefin such as ethylene propylene and the like is mainly prepared by petroleum cracking, the former is not suitable for industrial production, and the latter petroleum cracking needs to consume a large amount of petroleum resources, but China belongs to oil-poor countries and is in short supply of petroleum resources.
The existing preparation methods of chlorinated alkene mainly comprise an alkyne method, an alkene method and the like, and no matter what preparation method is adopted, a catalyst is a key factor.
The alkyne method mainly adopts an alkyne hydrochlorination method, such as: although the acetylene hydrochlorination method belongs to a mature technology, the method mainly uses a mercuric chloride catalyst in the reaction process, the mercuric chloride catalyst is easy to sublimate and run off and has serious environmental pollution, and some mercuric-free catalysts are developed at present, but the mercury-free catalysts at present mainly are noble metal catalysts, such as noble metal chlorides, such as gold tetrachloride, platinum chloride and the like, are expensive and easy to inactivate, so that the industrial production is difficult to realize. In addition, for the preparation of vinyl chloride, there are reports (for example, CN201010149180.1, CN201110330158.1, and CN201210191433.0) related to the preparation of vinyl chloride by using the zingiber officinale method (i.e., the reaction of acetylene and dichloroethane to prepare vinyl chloride), in which activated carbon-supported barium chloride is used to replace mercury chloride catalyst, so as to reduce environmental pollution, but the activity of the catalyst needs to be improved, and usually at a high temperature of above 250 ℃, the acetylene conversion rate is only about 80%. Therefore, the preparation of the mercury-free catalyst with low price and good catalytic performance is the important content for preparing the chloro-alkene by the improved alkyne method at present.
The olefin method mainly adopts an olefin oxychlorination method, such as an ethylene oxychlorination method, has large consumption on petroleum resources, is mainly suitable for oil-rich national regions, can not avoid the reaction of eliminating hydrogen chloride by chloralkane in the reaction process, although the preparation of corresponding chlorinated olefin by eliminating hydrogen chloride through chloralkane cracking belongs to a mature technology, the method of eliminating hydrogen chloride by chloralkane mainly adopts a high-temperature cracking mode, and chloralkane is cracked into corresponding olefin, hydrogen chloride and other byproducts at 500-550 ℃. Therefore, the preparation of the high-efficiency catalyst reduces the temperature of the chloralkane cracking reaction, and the improvement of the selectivity of the reaction is the important content of the improvement of the chloralkane cracking process at present.
Angelo J.Magistro et al found that chlorides and oxides of lanthanum, praseodymium, neodymium, cerium and the like in lanthanide elements have better activity for preparing vinyl chloride by catalytic cracking of dichloroethane, wherein the activity of lanthanum chloride is highest; the reaction is carried out at 300 ℃ and the retention time of 10.9 seconds by using HZF-33 zeolite loaded with lanthanum chloride as a catalyst, the conversion rate of dichloroethane is 35.8 percent, and the selectivity of chloroethylene is 90.1 percent.
In the research of preparing vinyl chloride by catalytic cracking of 1, 2-dichloroethane dehydrochlorination, the Wangwenxin compares the performances of chloride catalysts of barium, copper, cobalt, nickel and bismuth loaded on activated carbon, and the results show that the performance of copper chloride is optimal, the copper chloride loading rate is 11 percent, the activated carbon catalyst is used for catalytic cracking of gas-phase dichloroethane under the conditions that the temperature is 340 ℃ and the flow rate of 1, 2-dichloroethane is 0.66 ml/min, and the dichloroethane conversion rate is 79.64 percent.
Isao Mochida et al of Japan uses polyacrylonitrile-based activated carbon fiber (PAN-ACF) as a catalyst, catalyzes the cracking reaction of 1, 2-dichloroethane at the reaction temperature of 300 ℃ and 325 ℃, the conversion rate of raw materials is 21-63%, the selectivity of vinyl chloride is more than 99%, and the service life of the catalyst is 100 hours.
In patent CN201010555844.4, activated alumina is used as a carrier, and one or more of cesium chloride, potassium chloride or magnesium chloride is used as an active component to prepare a catalyst, and at a reaction temperature of 115-250 ℃, trichloroethane is catalyzed to perform catalytic cracking to prepare vinylidene chloride, the conversion rate of trichloroethane can reach above 53%, and the selectivity of vinylidene chloride can reach above 90%.
However, the metal oxide, chloride, non-metal PAN-ACF catalyst or supported catalyst reported at present is low in conversion rate, high in reaction temperature or easy to sinter and deactivate, and is not suitable for industrial application.
Nitrogen doping is a common method for modifying and improving catalysts, nitrogen-doped catalysts generally have better catalytic activity, and related reports that nitrogen-doped catalysts are used for preparing chlorinated olefins currently exist, such as: patents CN201510006144.2, CN201410532264.1, and CN201410532152.6 disclose applications of nitrogen-doped catalysts in preparation of vinyl chloride by reaction of acetylene and hydrogen chloride, preparation of vinyl chloride by reaction of acetylene and dichloroethane, and preparation of vinyl chloride by cracking of 1, 2-dichloroethane, respectively.
However, the existing nitrogen-doped catalysts are all prepared by using active carbon as a carrier, immersing the active carbon carrier in a nitrogen-containing immersion liquid, and then calcining at high temperature, wherein the active carbon is a black porous solid carbon, and is produced by crushing and molding coal or carbonizing and activating uniform coal particles, so the active carbon can be classified as a nitrogen-doped coal-based catalyst, a large amount of non-renewable coal is inevitably used in the preparation process, the resource waste is caused, and the activity of the prepared catalyst is low, and the prepared catalyst is not enough to meet the requirement of actual production.
The biobase is a sustainable renewable resource, the price is low, the biomass resource in China is rich, but the energy utilization rate is low. The total amount of biomass resources available nationwide is about 4.6 million tons of standard coal every year, wherein the standard coal comprises crop straws, agricultural product processing residues, forestry residues, energy crops, domestic garbage, organic wastes and the like, and the environmental protection pressure is caused by excessive accumulation of the biomass wastes. However, in 2015, the biomass utilization amount of the China is about 3500 million tons of standard coal, and only about 50% of the biomass can be commercially utilized.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a biomass-based nitrogen-doped carbon catalyst, and a preparation method and an application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a nitrogen-doped carbon catalyst based on biomass is obtained by carbonizing biomass or a mixture of the biomass and a nitrogen source (preferably the mixture of the biomass and the nitrogen source) at 400-1000 ℃, wherein the biomass is selected from at least one of bamboo processing leftovers, wood processing leftovers, plant straws (such as corn straws), plant leaves (such as lettuce leaves), grains (such as corns), beans (such as soybeans and peanuts), grain processing leftovers, bean processing leftovers (such as bean pulp and peanut shells) and livestock manure (such as cow manure).
In one embodiment, the biomass-based nitrogen-doped carbon catalyst is prepared by impregnating and modifying biomass with an aqueous solution containing a nitrogen source and an activating agent, carbonizing at 400-1000 ℃, and then cooling, washing and drying.
In one embodiment, the biomass-based nitrogen-doped carbon catalyst is prepared by impregnating and modifying biomass with an aqueous solution containing an activating agent, carbonizing the biomass at 400-1000 ℃ in an inert gas or ammonia (preferably ammonia) atmosphere, and then cooling, washing and drying the biomass-based nitrogen-doped carbon catalyst.
Preferably, the nitrogen source is at least one selected from the group consisting of acrylamide, urea, melamine, pyridine, pyrrole, imidazole, ammonium chloride, ammonium sulfate, and ammonia.
Preferably, the activating agent is selected from any one of zinc chloride, sodium hydroxide and potassium hydroxide.
A method of making a biomass-based nitrogen-doped carbon catalyst as described in the present invention, comprising the steps of:
1) cleaning, drying and crushing the biomass for later use;
2) mixing the biomass obtained in the step 1) with a nitrogen source and an activating agent, adding water, stirring uniformly, soaking, and then concentrating and drying a soaking system to obtain a soaking modified substance;
3) carbonizing the impregnated modified substance for 1-12 hours at 400-1000 ℃ in an inert gas atmosphere, and then cooling, washing and drying to obtain the biomass-based nitrogen-doped carbon catalyst.
Preferably, in the step 1), the biomass is crushed to 10-30 meshes.
Preferably, in the step 2), the mass ratio of the nitrogen source to the biomass is (0-10): 1 (preferably 0.1 to 3): 1).
Preferably, in the step 2), the mass ratio of the activating agent to the biomass is (0.1-10): 1 (preferably 0.1 to 5): 1).
Preferably, in the step 2), the biomass obtained in the step 1) is mixed with a nitrogen source and an activating agent, water is added, the mixture is uniformly stirred, vacuum impregnation is performed for 1-24 hours, then the impregnation system is subjected to reduced pressure concentration, and the obtained concentrate is dried at 120-200 ℃ to obtain the impregnation modified substance.
Preferably, in step 3), the washing operation is as follows: the cooled carbonized product is washed with an acidic aqueous solution (until the concentration of metal ions in the carbonized product is less than 100ppm), and then washed with water to be neutral.
Preferably, in the step 3), the drying temperature is 120-200 ℃.
Another method of making a biomass-based nitrogen-doped carbon catalyst as described in the present invention comprises the steps of:
a) cleaning, drying and crushing the biomass for later use;
b) mixing the biomass obtained in the step 1) with an activating agent, adding water, stirring uniformly, soaking, and then concentrating and drying a soaking system to obtain a soaking modified substance;
c) carbonizing the impregnated modifier at 400-1000 ℃ for 1-12 hours in an inert gas or ammonia gas (preferably ammonia gas) atmosphere, and then cooling, washing and drying to obtain the biomass-based nitrogen-doped carbon catalyst.
Preferably, in the step b), the mass ratio of the activating agent to the biomass is (0.1-10): 1 (preferably 0.1 to 5): 1).
Preferably, in the step b), the biomass obtained in the step 1) is mixed with an activating agent, water is added to the mixture and stirred uniformly, the mixture is vacuumized and impregnated for 1 to 24 hours, then the impregnation system is subjected to reduced pressure concentration, and the obtained concentrate is dried at 120 to 200 ℃ to obtain the impregnation modified substance.
As a preferred scheme, in the step c), the impregnated modifier is placed in a tubular furnace, inert gas or ammonia gas (preferably ammonia gas) is introduced on line, carbonization is carried out for 1-12 hours at 400-1000 ℃, and then cooling, washing and drying are carried out, so as to obtain the biomass-based nitrogen-doped carbon catalyst.
As a further preferable scheme, in the step c), the flow rate of the gas used by the hundred grams of biomass is 10-100 ml/min.
The biomass-based nitrogen-doped carbon catalyst can be used as a reaction for eliminating hydrogen chloride by cracking chlorinated alkane (preferably C2-C6 reaction for eliminating hydrogen chloride by cracking chlorinated alkane, such as the reaction for eliminating hydrogen chloride by cracking 1, 2-dichloroethane to prepare vinyl chloride, the reaction for eliminating hydrogen chloride by cracking 1-chloropropane to prepare propylene, the reaction for eliminating hydrogen chloride by using tetrachloropropane to prepare trichloropropene, the reaction for eliminating hydrogen chloride by using pentachloropropane to prepare tetrachloropropene, the reaction for eliminating hydrogen chloride by using 1-chlorobutane to prepare 1-butene, the reaction for eliminating hydrogen chloride by cracking 1-chloropentane to prepare 1-pentene, the reaction for eliminating hydrogen chloride by using 1-chlorohexane to prepare 1-hexene, and the like), the catalyst for the reaction of hydrochlorination of alkyne to produce chloro-alkene (preferably the reaction of hydrochlorination of acetylene or propyne to produce chloro-alkene, for example, the reaction of acetylene and hydrogen chloride to produce vinyl chloride) or the reaction of preparing vinyl chloride by using a ginger-clock method (namely the reaction of acetylene and dichloroethane to produce vinyl chloride).
Compared with the prior art, the invention has the following remarkable beneficial effects:
the biomass-based nitrogen-doped carbon catalyst provided by the invention does not contain heavy metals such as mercury and the like, is environment-friendly and excellent in catalytic performance, can be used as a catalyst for eliminating hydrogen chloride reaction by cracking chloroalkane, reaction for preparing chloroalkene by hydrochlorinating alkyne or reaction for preparing chloroethylene by using a Zingiber officinale method, and has the advantages of high selectivity and conversion rate and good catalytic activity; in addition, the nitrogen-doped carbon catalyst based on the biomass takes renewable biomass as a raw material, the variety of selectable biomass is various, the raw material source is wide, the cost is low, the environmental protection pressure caused by excessive accumulation of biomass waste can be solved, a new way is provided for deep utilization of biomass resources, besides chemical bonds formed by nitrogen and carbon atoms, the surface of the prepared catalyst is also rich in oxygen atoms, trace metal elements and the like, and the synergistic effect of the atoms enables the catalyst to have better catalytic activity compared with the traditional nitrogen-doped coal-based catalyst; in addition, the preparation method disclosed by the invention has the advantages of simple preparation process (only one-step carbonization), easiness in obtaining raw materials, low cost, strong process controllability, easiness in large-scale production and the like, and has significant progress and industrial application value compared with the prior art.
Detailed Description
The technical scheme of the invention is further detailed and completely explained by combining the embodiment, the comparative example and the application example.
Example 1
1) Washing bamboo processing leftovers, drying, and pulverizing to 20 mesh for later use;
2) mixing 10g of bamboo powder, 10g of acrylamide and 10g of zinc chloride, adding water with the same volume, uniformly stirring, vacuumizing and soaking for 10 hours, then concentrating a soaking system under reduced pressure, and drying a concentrate at 120 ℃ to obtain a soaking modified substance;
3) carbonizing the impregnated modified substance at 1000 ℃ for 2 hours in the nitrogen gas atmosphere, cooling to room temperature, washing the cooled carbonized product with 10% dilute hydrochloric acid (to remove redundant zinc chloride until the concentration of zinc ions in the carbonized product is lower than 100ppm), washing with deionized water to be neutral, and drying at 120 ℃ to obtain the biomass-based nitrogen-doped carbon catalyst, which is abbreviated as C-1.
Example 2
1) Cleaning, drying and crushing the wood processing leftovers into 20 meshes for later use;
2) mixing 10g of wood powder, 5g of urea and 15g of zinc chloride, adding water with the same volume, uniformly stirring, vacuumizing and impregnating for 10 hours, then concentrating an impregnation system under reduced pressure, and drying a concentrate at 120 ℃ to obtain an impregnation modified substance;
3) carbonizing the impregnated modified substance at 800 ℃ for 4 hours in the nitrogen gas atmosphere, cooling to room temperature, washing the cooled carbonized product with 10% dilute hydrochloric acid (to remove redundant zinc chloride until the concentration of zinc ions in the carbonized product is lower than 100ppm), then washing with deionized water to be neutral, and then drying at 120 ℃ to obtain the biomass-based nitrogen-doped carbon catalyst, which is abbreviated as C-2.
Example 3
1) Cleaning, drying and crushing the corn straws to 20 meshes for later use;
2) mixing 10g of straw powder, 2g of ammonium chloride and 20g of sodium hydroxide, adding water with the same volume, uniformly stirring, vacuumizing and soaking for 10 hours, then concentrating a soaking system under reduced pressure, and drying a concentrate at 120 ℃ to obtain a soaking modified substance;
3) carbonizing the impregnated modified substance at 600 ℃ for 6 hours in the nitrogen gas atmosphere, cooling to room temperature, washing the cooled carbonized product with 10% dilute hydrochloric acid (to remove redundant sodium hydroxide until the concentration of sodium ions in the carbonized product is lower than 100ppm), washing with deionized water to be neutral, and drying at 120 ℃ to obtain the biomass-based nitrogen-doped carbon catalyst, which is abbreviated as C-3.
Example 4
1) Cleaning corn, oven drying, and pulverizing to 20 mesh;
2) mixing 10g of corn flour, 20g of imidazole and 5g of potassium hydroxide, adding water with the same volume, uniformly stirring, vacuumizing and impregnating for 10 hours, then concentrating an impregnation system under reduced pressure, and drying the concentrate at 120 ℃ to obtain an impregnation modified substance;
3) carbonizing the impregnated modified substance at 500 ℃ for 8 hours in the nitrogen gas atmosphere, cooling to room temperature, washing the cooled carbonized product with 10% dilute hydrochloric acid (to remove redundant potassium hydroxide until the concentration of potassium ions in the carbonized product is lower than 100ppm), washing with deionized water to be neutral, and drying at 120 ℃ to obtain the biomass-based nitrogen-doped carbon catalyst, which is abbreviated as C-4.
Example 5
1) Cleaning, drying and crushing soybeans to 20 meshes for later use;
2) mixing 10g of soybean meal, 30g of pyrrole and 30g of zinc chloride, adding water with the same volume, uniformly stirring, vacuumizing and impregnating for 10 hours, then concentrating an impregnation system under reduced pressure, and drying a concentrate at 120 ℃ to obtain an impregnation modified substance;
3) carbonizing the impregnated modified substance at 400 ℃ for 10 hours in the nitrogen gas atmosphere, cooling to room temperature, washing the cooled carbonized product with 10% dilute hydrochloric acid (to remove redundant zinc chloride until the concentration of zinc ions in the carbonized product is lower than 100ppm), then washing with deionized water to be neutral, and then drying at 120 ℃ to obtain the biomass-based nitrogen-doped carbon catalyst, which is abbreviated as C-5.
Example 6
1) Cleaning, drying and crushing the soybean meal into 20 meshes for later use;
2) mixing 10g of soybean meal powder, 5g of melamine and 20g of potassium chloride, adding water with the same volume, uniformly stirring, vacuumizing and impregnating for 10 hours, then concentrating an impregnation system under reduced pressure, and drying a concentrate at 120 ℃ to obtain an impregnation modified substance;
3) carbonizing the impregnated modifier at 400 ℃ for 10 hours in a nitrogen gas atmosphere, cooling to room temperature, washing the cooled carbonized product with 10% dilute hydrochloric acid (to remove redundant potassium chloride until the concentration of potassium ions in the carbonized product is lower than 100ppm), washing with deionized water to be neutral, and drying at 120 ℃ to obtain the biomass-based nitrogen-doped carbon catalyst, which is abbreviated as C-6.
Example 7
1) Cleaning waste lettuce leaves in a vegetable field, drying and crushing the lettuce leaves to 20 meshes for later use;
2) mixing 10g of lettuce leaf powder, 20g of ammonium sulfate and 40g of potassium hydroxide, adding water with the same volume, uniformly stirring, vacuumizing and soaking for 10 hours, then concentrating a soaking system under reduced pressure, and drying a concentrate at 120 ℃ to obtain a soaking modified substance;
3) carbonizing the impregnated modified substance at 700 ℃ for 5 hours in the nitrogen gas atmosphere, cooling to room temperature, washing the cooled carbonized product with 10% diluted hydrochloric acid (to remove redundant potassium hydroxide until the concentration of potassium ions in the carbonized product is lower than 100ppm), washing with deionized water to be neutral, and drying at 120 ℃ to obtain the biomass-based nitrogen-doped carbon catalyst, which is abbreviated as C-7.
Example 8
1) Cleaning peanut shells, drying and crushing the peanut shells to 20 meshes for later use;
2) mixing 10g of peanut shell powder and 30g of sodium hydroxide (no additional nitrogen source is needed), adding water with the same volume, uniformly stirring, vacuumizing and impregnating for 10 hours, then concentrating an impregnation system under reduced pressure, and drying a concentrate at 120 ℃ to obtain an impregnation modified substance;
3) and (3) introducing ammonia gas (50 ml/min) into the immersed modified substance tube furnace on line, carbonizing the immersed modified substance tube furnace at 700 ℃ for 5 hours, cooling the immersed modified substance tube furnace to room temperature, washing the cooled carbonized product with 10% dilute hydrochloric acid (to remove redundant sodium hydroxide until the concentration of sodium ions in the carbonized product is lower than 100ppm), washing the carbonized product with deionized water to neutrality, and drying the carbonized product at 120 ℃ to obtain the biomass-based nitrogen-doped carbon catalyst, which is abbreviated as C-8.
Example 9
1) Cleaning cow dung, drying and crushing to 20 meshes for later use;
2) mixing 10g of dry cow dung and 40g of zinc chloride (no additional nitrogen source is needed), adding water with the same volume, uniformly stirring, vacuumizing and dipping for 10 hours, then concentrating a dipping system under reduced pressure, and drying a concentrate at 120 ℃ to obtain a dipping modifier;
3) and (2) introducing ammonia gas (50 ml/min) into the immersed modified substance tube furnace on line, carbonizing the immersed modified substance tube furnace at 700 ℃ for 5 hours, cooling the immersed modified substance tube furnace to room temperature, washing the cooled carbonized product with 10% dilute hydrochloric acid (to remove redundant zinc chloride until the concentration of zinc ions in the carbonized product is lower than 100ppm), washing the carbonized product with deionized water to neutrality, and drying the carbonized product at 120 ℃ to obtain the biomass-based nitrogen-doped carbon catalyst, which is abbreviated as C-9.
Comparative example
1) Soaking coal-based carbon in 2N hydrochloric acid, cleaning, drying, and pulverizing to 20 mesh;
2) putting 10g of coal-based carbon powder into a reactor, adding 60ml of aqueous solution containing 10% acrylamide, uniformly stirring, soaking for 10 hours, then concentrating the soaking system under reduced pressure, and drying the concentrate at 120 ℃ to obtain a comparative soaking modifier;
3) carbonizing the comparative impregnation modifier at 1000 ℃ for 2 hours in a nitrogen gas atmosphere, cooling to room temperature, washing the cooled carbonized product to be neutral by using deionized water, and drying at 120 ℃ to obtain the nitrogen-doped coal-based catalyst, which is abbreviated as D-1.
Application example 1: application of nitrogen-doped carbon catalyst in reaction for preparing chloroethylene by using Zingiber officinale method
The catalytic performance of the biomass-based nitrogen-doped carbon catalysts prepared in examples 1 to 9 and the nitrogen-doped coal-based catalyst prepared in the comparative example in the reaction of producing vinyl chloride by the zingiber process (i.e., the reaction of dichloroethane and acetylene to produce vinyl chloride) was examined using a fixed bed reactor: the reaction raw materials are dichloroethane and acetylene; the fixed bed reactor is a quartz tube with the inner diameter of 6 mm, and dichloroethane and acetylene enter a catalyst bed layer for reaction after being fully premixed; condensing the reaction tail gas to collect unreacted dichloroethane, and analyzing the gas phase product by gas chromatography; the reaction conditions are as follows: the volume space velocity of the acetylene is 16-64h-1And the molar ratio of dichloroethane to acetylene in the mixed gas is 1.2: the reaction temperature is 180-260 ℃, the catalytic performance of the catalyst is considered under the conditions, and the reaction results are shown in table 1 (in the table, the acetylene conversion rate is the initial highest conversion rate).
Table 1 catalytic performance of biomass-based nitrogen-doped carbon catalysts prepared in examples 1 to 9 and nitrogen-doped coal-based catalysts prepared in comparative example in reaction of producing vinyl chloride by zingiber process
Figure BDA0001952650500000081
Figure BDA0001952650500000091
As can be seen from table 1: compared with a nitrogen-doped coal-based catalyst, the biomass-based nitrogen-doped carbon catalyst prepared by the embodiment of the invention has more excellent catalytic performance in a method for preparing vinyl chloride by a Zingiber officinale method in a low-temperature range of 180-260 ℃, and has remarkable progress compared with the traditional coal-based carbon catalyst.
Application example 2: application of nitrogen-doped carbon catalyst in reaction for preparing vinyl chloride by hydrochlorinating acetylene
The catalytic performance of the biomass-based nitrogen-doped carbon catalysts prepared in examples 1 to 9 and the nitrogen-doped coal-based catalyst prepared in the comparative example in the preparation of vinyl chloride by acetylene hydrochlorination was examined using a fixed bed reactor: the reaction raw materials are acetylene and hydrogen chloride; the fixed bed reactor is a quartz tube with the inner diameter of 6 mm, and acetylene and hydrogen chloride enter a catalyst bed layer for reaction after being fully premixed; analyzing the gas phase product by gas chromatography; the reaction conditions are as follows: the volume space velocity of the acetylene is 16-128h-1And the molar ratio of hydrogen chloride to acetylene in the mixed gas is 1.2: the reaction temperature is 160-250 ℃, the catalytic performance of the catalyst is considered under the above conditions, and the reaction results are shown in table 2 (in the table, the acetylene conversion rate is the initial highest conversion rate).
Table 2 catalytic performance of biomass-based nitrogen-doped carbon catalysts prepared in examples 1 to 9 and nitrogen-doped coal-based catalyst prepared in comparative example in preparation of vinyl chloride through hydrochlorination of acetylene
Figure BDA0001952650500000101
As can be seen from table 2: compared with a nitrogen-doped coal-based catalyst, the biomass-based nitrogen-doped carbon catalyst prepared by the embodiment of the invention has more excellent catalytic performance in the preparation of chloroethylene through acetylene hydrochlorination in the low-temperature range of 160-250 ℃, and has significant progress compared with the traditional coal-based carbon catalyst.
Application example 3: application of nitrogen-doped carbon catalyst in reaction for preparing chloroethylene by cracking dichloroethane
The biomass-based nitrogen-doped carbon catalysts prepared in examples 1 to 9 and the nitrogen-doped coal-based catalyst prepared in the comparative example were examined for their catalytic performance in the preparation of vinyl chloride by a dichloroethane cracking reaction using a fixed-bed reactor, in which the dichloroethane was used as a raw material and a quartz tube having an inner diameter of 6 mm, and unreacted dichloroethane was collected by condensation under the conditions of a liquid hourly space velocity of 0.5 to 4m L/h/g and a reaction temperature of 200 ℃ and 300 ℃ under which the catalytic performance of the catalysts was examined, and the reaction results are shown in Table 3.
Table 3 catalytic performance of biomass-based nitrogen-doped carbon catalysts prepared in examples 1 to 9 and nitrogen-doped coal-based catalysts prepared in comparative example in preparation of vinyl chloride through dichloroethane cracking reaction
Figure BDA0001952650500000111
Figure BDA0001952650500000121
As can be seen from table 3: compared with a nitrogen-doped coal-based catalyst, the biomass-based nitrogen-doped carbon catalyst prepared by the embodiment of the invention has more excellent catalytic performance in preparing chloroethylene by dichloroethane cracking reaction in the low temperature range of 200-300 ℃, and has significant progress compared with the traditional coal-based carbon catalyst.
Application example 4: application of biomass-based nitrogen-doped carbon catalyst in reaction for preparing propylene through catalytic cracking of 1-chloropropane
And (2) vaporizing 1-chloropropane, introducing the vaporized 1-chloropropane into fixed bed reactors respectively filled with the biomass-based nitrogen-doped carbon catalyst prepared in the embodiment and the nitrogen-doped coal-based catalyst prepared in the comparative example, and reacting, wherein the liquid hourly space velocity of the 1-chloropropane is 0.5-4m L/h/g, the reaction temperature is 200-300 ℃, the reaction effluent is cooled to room temperature, the fixed bed reactor used in the reaction process is a quartz tube with the inner diameter of 6 mm, and the reaction result is shown in table 4 (the conversion rate of the 1-chloropropane is the initial highest conversion rate).
Table 4 results of catalyzing 1-chloropropane cleavage reaction using the biomass-based nitrogen-doped carbon catalyst prepared in example and the nitrogen-doped coal-based catalyst prepared in comparative example
Figure BDA0001952650500000122
Figure BDA0001952650500000131
As can be seen from table 4: the 1-chloropropane cracking reaction has high 1-chloropropane conversion rate and high propylene selectivity when propylene is prepared under the catalytic action of the biomass-based nitrogen-doped carbon catalyst, and the biomass-based nitrogen-doped carbon catalyst has excellent catalytic activity, particularly low-temperature (200-300 ℃) catalytic activity, and has significant progress compared with the traditional coal-based carbon catalyst.
Application example 5 application of the biomass-based nitrogen-doped carbon catalyst in the reaction of preparing 1-butene through catalytic cracking of 1-chlorobutane, 1-chlorobutane is vaporized and then introduced into a fixed bed reactor respectively filled with the biomass-based nitrogen-doped carbon catalyst prepared in the examples and the nitrogen-doped coal-based catalyst prepared in the comparative examples to react, the liquid hourly space velocity of the 1-chlorobutane is 0.5-4m L/h/g, the reaction temperature is 200-300 ℃, the reaction effluent is cooled to room temperature, the fixed bed reactor used in the reaction process is a quartz tube with the inner diameter of 6 mm, and the reaction results are shown in table 5 (in the table, the conversion rate of the 1-chlorobutane is the initial highest conversion rate).
TABLE 5 results of catalyzing 1-chlorobutane cracking reaction using the biomass-based nitrogen-doped carbon catalyst prepared in example and the nitrogen-doped coal-based catalyst prepared in comparative example
Figure BDA0001952650500000132
Figure BDA0001952650500000141
As can be seen from table 5: when the 1-chlorobutane cracking reaction is used for preparing propylene under the catalytic action of the biomass-based nitrogen-doped carbon catalyst, the 1-chlorobutane conversion rate and the butene selectivity are high, the biomass-based nitrogen-doped carbon catalyst has excellent catalytic activity, particularly low-temperature (200-300 ℃) catalytic activity, and the catalytic activity is remarkably improved compared with that of a traditional coal-based carbon catalyst.
Application example 6: application of nitrogen-doped carbon catalyst in reaction for preparing 1-pentene by catalytic cracking of 1-chloropentane
1-chloropentane is vaporized and then introduced into fixed bed reactors respectively filled with biomass-based nitrogen-doped carbon catalysts prepared in the examples and nitrogen-doped coal-based catalysts prepared in the comparative examples for reaction, the liquid hourly space velocity of the 1-chloropentane is 0.5-4m L/h/g, the reaction temperature is 200-300 ℃, the reaction effluent is cooled to room temperature, the fixed bed reactor used in the reaction process is a quartz tube with the inner diameter of 6 millimeters, and the reaction results are shown in table 6 (the conversion rate of the 1-chloropentane is the initial highest conversion rate).
TABLE 6 results of 1-chloropentane cleavage reaction catalyzed by biomass-based nitrogen-doped carbon catalyst prepared in example and nitrogen-doped coal-based catalyst prepared in comparative example
Figure BDA0001952650500000151
Figure BDA0001952650500000161
As can be seen from table 6: the 1-chloropentane cracking reaction has high 1-chloropentane conversion rate and high pentene selectivity when the 1-pentene is prepared under the catalytic action of the biomass-based nitrogen-doped carbon catalyst, the biomass-based nitrogen-doped carbon catalyst has excellent catalytic activity, particularly low-temperature (200-300 ℃) catalytic activity, and the catalyst has significant progress compared with the traditional coal-based carbon catalyst.
Application example 7: application of nitrogen-doped carbon catalyst in reaction for preparing 1-hexene through catalytic cracking of 1-chlorohexane
The method comprises the following steps of vaporizing 1-chlorohexane, introducing the vaporized 1-chlorohexane into fixed bed reactors respectively filled with biomass-based nitrogen-doped carbon catalysts prepared in examples and nitrogen-doped coal-based catalysts prepared in comparative examples, reacting, wherein the liquid hourly space velocity of the 1-chlorohexane is 0.5-4m L/h/g, the reaction temperature is 200-300 ℃, the reaction effluent is cooled to room temperature, the fixed bed reactor used in the reaction process is a quartz tube with the inner diameter of 6 mm, and the reaction result is shown in table 7 (in the table, the conversion rate of the 1-chlorohexane is the initial highest conversion rate).
TABLE 7 results of 1-chlorohexane cracking reaction catalyzed by biomass-based nitrogen-doped carbon catalyst prepared in example and nitrogen-doped coal-based catalyst prepared in comparative example
Figure BDA0001952650500000162
Figure BDA0001952650500000171
As can be seen from table 7: the 1-chlorohexane cracking reaction has high 1-chlorohexane conversion rate and high hexene selectivity when the 1-hexene is prepared under the catalytic action of the biomass-based nitrogen-doped carbon catalyst, and the biomass-based nitrogen-doped carbon catalyst has excellent catalytic activity, particularly low-temperature (200-300 ℃) catalytic activity, and has significant progress compared with the traditional coal-based carbon catalyst.
From Table 1 to Table 7, it can be seen that: the biomass-based nitrogen-doped carbon catalyst can be used as a catalyst for eliminating hydrogen chloride reaction by cracking chloralkane, preparing chloroalkene by hydrochlorination of alkyne or preparing chloroethylene by a Zingzhong method, has the advantages of high selectivity and conversion rate, good catalytic activity, particularly better catalytic activity in a low temperature range, excellent catalytic effect under the condition of low catalytic amount, and has remarkable improvement compared with the traditional nitrogen-doped coal-based catalyst.
Finally, it should be pointed out here that: the above is only a part of the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention, and the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above description are intended to be covered by the present invention.

Claims (10)

1. A nitrogen-doped carbon catalyst based on biomass is characterized in that: the biomass is obtained by carbonizing biomass or a mixture of the biomass and a nitrogen source at 400-1000 ℃, wherein the biomass is selected from at least one of bamboo processing leftovers, wood processing leftovers, plant straws, plant leaves, cereals, beans, cereal processing leftovers, bean processing leftovers and livestock manure.
2. The biomass-based nitrogen-doped carbon catalyst of claim 1, wherein: the biomass is obtained by performing impregnation modification on biomass by using an aqueous solution containing a nitrogen source and an activating agent, carbonizing at 400-1000 ℃, and then cooling, washing and drying.
3. The biomass-based nitrogen-doped carbon catalyst of claim 1, wherein: the biomass is subjected to impregnation modification by an aqueous solution containing an activating agent, then is carbonized at 400-1000 ℃ in an inert gas or ammonia atmosphere, and then is cooled, washed and dried to obtain the biomass-based catalyst.
4. The biomass-based nitrogen-doped carbon catalyst according to any one of claims 1 to 3, wherein: the nitrogen source is at least one selected from acrylamide, urea, melamine, pyridine, pyrrole, imidazole, ammonium chloride, ammonium sulfate and ammonia water.
5. The biomass-based nitrogen-doped carbon catalyst according to any one of claims 1 to 3, wherein: the activating agent is any one of zinc chloride, sodium hydroxide and potassium hydroxide.
6. A method of making the biomass-based nitrogen-doped carbon catalyst of claim 1, comprising the steps of:
1) cleaning, drying and crushing the biomass for later use;
2) mixing the biomass obtained in the step 1) with a nitrogen source and an activating agent, adding water, stirring uniformly, soaking, and then concentrating and drying a soaking system to obtain a soaking modified substance;
3) carbonizing the impregnated modified substance for 1-12 hours at 400-1000 ℃ in an inert gas atmosphere, and then cooling, washing and drying to obtain the biomass-based nitrogen-doped carbon catalyst.
7. The method of claim 6, wherein: the mass ratio of the nitrogen source to the biomass is (0-10): 1; the mass ratio of the activating agent to the biomass is (0.1-10): 1.
8. a method of making the biomass-based nitrogen-doped carbon catalyst of claim 1, comprising the steps of:
a) cleaning, drying and crushing the biomass for later use;
b) mixing the biomass obtained in the step 1) with an activating agent, adding water, stirring uniformly, soaking, and then concentrating and drying a soaking system to obtain a soaking modified substance;
c) carbonizing the impregnated modified substance at 400-1000 ℃ for 1-12 hours in an inert gas or ammonia atmosphere, and then cooling, washing and drying to obtain the biomass-based nitrogen-doped carbon catalyst.
9. The method of claim 8, wherein: the mass ratio of the activating agent to the biomass is (0.1-10): 1.
10. use of a biomass-based nitrogen-doped carbon catalyst according to any one of claims 1 to 3, characterized in that: the biomass-based nitrogen-doped carbon catalyst is used as a catalyst for a reaction of eliminating hydrogen chloride by cracking chlorinated alkane, a reaction of preparing chlorinated alkene by hydrochlorinating alkyne or a reaction of preparing vinyl chloride by a Zingiber officinale method.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113106491A (en) * 2021-04-30 2021-07-13 佛山仙湖实验室 Preparation method of nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electro-catalytic material, product and application thereof
CN113120898A (en) * 2021-05-20 2021-07-16 四川大学 Nitrogen-doped formed biochar and preparation method and application thereof
CN114057165A (en) * 2021-12-02 2022-02-18 中国科学院青岛生物能源与过程研究所 Method for separating and recovering hydrogen chloride gas in chloro-olefin production
WO2022052539A1 (en) * 2020-09-10 2022-03-17 中国矿业大学 Crop straw-based nitrogen-doped porous carbon material preparation method and application thereof
CN116272943A (en) * 2023-03-24 2023-06-23 遵义医科大学 Carbon-based nonmetallic catalyst and preparation method and application thereof

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104289254A (en) * 2014-10-11 2015-01-21 中国科学院上海高等研究院 Nitrogen-modified catalyst applied to preparation of vinyl chloride and preparation method of nitrogen-modified catalyst
CN104475143A (en) * 2014-12-26 2015-04-01 中国科学院上海高等研究院 Nitrogen-doped activated carbon catalyst and application thereof
CN104525237A (en) * 2015-01-07 2015-04-22 中国科学院上海高等研究院 Nitrogen-doped active carbon catalyzer and application thereof in chloroethylene synthesis
CN105819443A (en) * 2016-03-04 2016-08-03 四川大学 Active carbon prepared from waste plant-based biomass, and preparation method thereof
CN105983428A (en) * 2015-01-30 2016-10-05 天津大学 Catalyst used in low-temperature removal of hydrogen chloride from dichloroethane for preparation of vinyl chloride, and preparation method and application thereof
CN106831289A (en) * 2017-02-09 2017-06-13 中国科学院上海高等研究院 A kind of non-metallic catalyst and its application in chloropropane elimination reaction is catalyzed
CN106914265A (en) * 2017-03-06 2017-07-04 南京师范大学 A kind of method for preparing N doping porous nano carbon material as carbon source gel method with biomass
CN106955668A (en) * 2017-04-01 2017-07-18 东北农业大学 A kind of method that fuse salt assisted with high-temperature charring prepares N doping multiporous biological charcoal
CN107115883A (en) * 2017-05-16 2017-09-01 浙江工业大学 A kind of starch base N doping mesopore forming charcoal and preparation method and application
KR20170103113A (en) * 2016-03-03 2017-09-13 성균관대학교산학협력단 Carbon composite, method of manufacturing the carbon composite, sodium-ion capacitor electrode including the carbon composite, and carbon-dioxide absorbent
WO2018120067A1 (en) * 2016-12-30 2018-07-05 The University Of Hong Kong Waste biomass-derived metal-free catalysts for oxygen reduction reaction
CN108262077A (en) * 2017-01-03 2018-07-10 中国科学院大连化学物理研究所 One kind has multi-stage porous high intensity N doping charcoal monoblock type catalysis material and preparation method and catalytic applications
CA3055280A1 (en) * 2017-04-06 2018-10-11 Ipr Holding As Method for producing activated carbon

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104289254A (en) * 2014-10-11 2015-01-21 中国科学院上海高等研究院 Nitrogen-modified catalyst applied to preparation of vinyl chloride and preparation method of nitrogen-modified catalyst
CN104475143A (en) * 2014-12-26 2015-04-01 中国科学院上海高等研究院 Nitrogen-doped activated carbon catalyst and application thereof
CN104525237A (en) * 2015-01-07 2015-04-22 中国科学院上海高等研究院 Nitrogen-doped active carbon catalyzer and application thereof in chloroethylene synthesis
CN105983428A (en) * 2015-01-30 2016-10-05 天津大学 Catalyst used in low-temperature removal of hydrogen chloride from dichloroethane for preparation of vinyl chloride, and preparation method and application thereof
KR20170103113A (en) * 2016-03-03 2017-09-13 성균관대학교산학협력단 Carbon composite, method of manufacturing the carbon composite, sodium-ion capacitor electrode including the carbon composite, and carbon-dioxide absorbent
CN105819443A (en) * 2016-03-04 2016-08-03 四川大学 Active carbon prepared from waste plant-based biomass, and preparation method thereof
WO2018120067A1 (en) * 2016-12-30 2018-07-05 The University Of Hong Kong Waste biomass-derived metal-free catalysts for oxygen reduction reaction
CN108262077A (en) * 2017-01-03 2018-07-10 中国科学院大连化学物理研究所 One kind has multi-stage porous high intensity N doping charcoal monoblock type catalysis material and preparation method and catalytic applications
CN106831289A (en) * 2017-02-09 2017-06-13 中国科学院上海高等研究院 A kind of non-metallic catalyst and its application in chloropropane elimination reaction is catalyzed
CN106914265A (en) * 2017-03-06 2017-07-04 南京师范大学 A kind of method for preparing N doping porous nano carbon material as carbon source gel method with biomass
CN106955668A (en) * 2017-04-01 2017-07-18 东北农业大学 A kind of method that fuse salt assisted with high-temperature charring prepares N doping multiporous biological charcoal
CA3055280A1 (en) * 2017-04-06 2018-10-11 Ipr Holding As Method for producing activated carbon
CN107115883A (en) * 2017-05-16 2017-09-01 浙江工业大学 A kind of starch base N doping mesopore forming charcoal and preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHAOBING SHEN ET.AL: "Mercury-free nitrogen-doped activated carbon catalyst: an efficient catalyst for the catalytic coupling reaction of acetylene and ethylene dichloride to synthesize the vinyl chloride monomer", 《REACTION CHEMISTRY & ENGINEERING》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022052539A1 (en) * 2020-09-10 2022-03-17 中国矿业大学 Crop straw-based nitrogen-doped porous carbon material preparation method and application thereof
GB2603717A (en) * 2020-09-10 2022-08-10 Univ China Mining Crop straw-based nitrogen-doped porous carbon material preparation method and application thereof
GB2603717B (en) * 2020-09-10 2023-03-22 Univ China Mining Crop straw-based nitrogen-doped porous carbon material preparation method and application thereof
CN113106491A (en) * 2021-04-30 2021-07-13 佛山仙湖实验室 Preparation method of nitrogen-doped mesoporous hollow carbon sphere loaded platinum-cobalt oxide composite electro-catalytic material, product and application thereof
CN113120898A (en) * 2021-05-20 2021-07-16 四川大学 Nitrogen-doped formed biochar and preparation method and application thereof
CN114057165A (en) * 2021-12-02 2022-02-18 中国科学院青岛生物能源与过程研究所 Method for separating and recovering hydrogen chloride gas in chloro-olefin production
CN116272943A (en) * 2023-03-24 2023-06-23 遵义医科大学 Carbon-based nonmetallic catalyst and preparation method and application thereof

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