CN111454122B - Method for eliminating hydrogen chloride by catalytic cracking of chloralkane - Google Patents
Method for eliminating hydrogen chloride by catalytic cracking of chloralkane Download PDFInfo
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Abstract
The invention discloses a method for eliminating hydrogen chloride by catalytic cracking of chloralkane, which comprises the steps of enabling the chloralkane to have cracking reaction to eliminate the hydrogen chloride to prepare corresponding olefin under the action of a nitrogen-doped carbon catalyst based on biomass; 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 method has the advantages of simple preparation process, easily obtained raw materials, low cost, strong process controllability, easy large-scale production, high conversion rate of catalytic cracking of the chloralkane, high product selectivity, low energy consumption and the like.
Description
Technical Field
The invention relates to a method for eliminating hydrogen chloride by catalytic cracking of chloralkane, belonging to the technical field of halogenated hydrocarbon elimination reaction.
Background
Olefins and chlorinated olefins are very important chemical feedstocks, for example: vinyl chloride, vinylidene chloride, trichloroethylene, tetrachloroethylene, propylene, chloropropene, dichloropropene, trichloropropene, tetrachloropropene, pentachloropropene, butene, pentene, hexene and the like are widely used in the chemical and material synthesis industries.
At present, the elimination of hydrogen chloride by cracking chlorinated alkanes to prepare corresponding alkenes is a well established technology, for example: the ethylene dichloride is cracked to prepare the vinyl chloride, the 1-chloropropane is cracked to prepare the propylene, and the like. However, the existing method for eliminating hydrogen chloride by cracking chloralkane mainly adopts a high-temperature cracking mode, the cracking temperature is usually higher than 500 ℃, the whole production process has high temperature and high energy consumption, a large amount of coking can be generated in the reaction process, and great influence is caused on the production. Therefore, the preparation of the high-efficiency catalyst reduces the cracking reaction temperature of the chloralkane, and the improvement of the reaction selectivity is the important content of improving 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%. Chinese patent CN201680054571.0 discloses pentachlorideThe catalyst used in the patent is transition metal oxide, metal catalyst, aluminum fluoride and combination thereof, the reaction temperature is 250-300 ℃, and the highest conversion rate of the raw material is 98-99%. Chinese patent CN201711170169.1 discloses a method for preparing 1-chloropropene by catalytic dehydrochlorination of 1, 2-dichloropropane, wherein the catalyst used in the patent comprises an active component and a carrier, and the active component is M1-M2-M3Wherein M is1Is a chloride of Fe or Co, M2A compound of Pt or Pd, M3Chloride of Ce or La; the carrier is gamma-Al2O3Molecular sieve or active carbon, the reaction temperature is 300-400 ℃, the conversion rate of 1, 2-dichloropropane is 85.7-90.6%, and the selectivity of 1-chloropropene is 99.2-99.6%. 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 a catalyst, the nitrogen-doped catalyst generally has better catalytic activity, and related reports that the nitrogen-doped catalyst is used for preparing chlorinated olefin exist at present. Chinese patent CN201410532152.6 discloses a nitrogen modified catalyst for preparing vinyl chloride and a preparation method thereof, wherein the nitrogen modified catalyst uses active carbon as a carrier, and loads a metal salt compound and a nitrogen-containing compound; the patent dissolves a metal salt compound and a nitrogen-containing compound in deionized water to prepare an impregnating solution; then dipping the activated carbon carrier subjected to acid cleaning and drying treatment in prepared dipping liquid, and then carrying out activation treatment (calcination at 800 ℃ under 200-; the prepared nitrogen modified catalyst not only reduces the cracking temperature, but also keeps higher 1, 2-dichloroethane conversion rate and chloroethylene selectivity in the reaction of preparing chloroethylene by catalytically cracking 1, 2-dichloroethane.
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 method for eliminating hydrogen chloride by catalytic cracking of chlorinated alkane.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for eliminating hydrogen chloride by catalytic cracking of chloralkane is characterized in that the chloralkane is subjected to cracking reaction under the action of a nitrogen-doped carbon catalyst based on biomass to eliminate hydrogen chloride and prepare corresponding olefin; the biomass-based nitrogen-doped carbon catalyst 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).
As an embodiment, the method is in a nitrogen-doped carbon catalyst based on biomassUnder the action of the catalyst, the molecular formula is CnClxHySubjecting chlorinated alkane (such as chloroethane, dichloroethane, trichloroethane, tetrachloroethane, pentachloroethane, chloropropane, dichloropropane, trichloropropane, tetrachloropropane, pentachloropropane, hexachloropropane, heptachloropropane, 1-chlorobutane, 1-chloropentane and 1-chlorohexane) to cracking reaction to remove hydrogen chloride to obtain CnClx-1Hy-1Wherein n is an integer of 2 to 6, x is an integer of 1 to 7, y is 2(n +1) -x, and y is not less than 1.
Preferably, the method is to lead the molecular formula to be C under the action of a nitrogen-doped carbon catalyst based on biomass2ClxHyThe preparation of the molecular formula C by eliminating hydrogen chloride through the cracking reaction of chloroethane2Clx-1Hy-1Wherein x is an integer of 1 to 5, y is 2(n +1) -x, and y is not less than 1.
As a further preferred scheme, the chloroethane includes but is not limited to chloroethane, dichloroethane (preferably 1, 2-dichloroethane), trichloroethane (preferably 1,1, 2-trichloroethane), tetrachloroethane and pentachloroethane.
As a further preferable scheme, the method is to make dichloroethane undergo cracking reaction to eliminate hydrogen chloride to prepare vinyl chloride under the action of a nitrogen-doped carbon catalyst based on biomass.
As a further preferable scheme, the method is to make the 1,1, 2-trichloroethane undergo cracking reaction to eliminate hydrogen chloride to prepare the vinylidene chloride under the action of a nitrogen-doped carbon catalyst based on biomass.
In a further preferable mode, the method is used for preparing trichloroethylene by carrying out cracking reaction on tetrachloroethane under the action of a nitrogen-doped carbon catalyst based on biomass to eliminate hydrogen chloride.
As a further preferable scheme, the method is to make pentachloroethane undergo cracking reaction to eliminate hydrogen chloride under the action of a nitrogen-doped carbon catalyst based on biomass so as to prepare tetrachloroethylene.
Preferably, the method is carried out under the action of nitrogen-doped carbon catalyst based on biomassThen, the molecular formula is C3ClxHyThe chloropropane is subjected to cracking reaction to eliminate hydrogen chloride and prepare the molecular formula C3Clx-1Hy-1Wherein x is an integer of 1 to 7, y is 2(n +1) -x, and y is not less than 1.
As a further preferable scheme, the chloropropanes include, but are not limited to, chloropropane (preferably 1-chloropropane), dichloropropane, trichloropropane, tetrachloropropane (preferably 1,1,1, 3-tetrachloropropane), pentachloropropane (preferably 1,1,1,3,3, -pentachloropropane), hexachloropropane (preferably 1,1,1,3,3, 3-hexachloropropane), heptachloropropane.
In a further preferable mode, the method is used for preparing the 1,1, 3-trichloropropene by eliminating hydrogen chloride through the cracking reaction of the 1,1,1, 3-tetrachloropropane under the action of a nitrogen-doped carbon catalyst based on biomass.
As a further preferable scheme, the method is to make 1,1,1,3, 3-tetrachloropropene by cracking 1,1,1,3, 3-pentachloropropane under the action of a nitrogen-doped carbon catalyst based on biomass to eliminate hydrogen chloride.
In one embodiment, the temperature of the cracking reaction is 140 to 400 deg.C (preferably 200 to 300 deg.C, more preferably 250 to 300 deg.C).
In one embodiment, the liquid hourly space velocity of the chlorinated alkane is 0.1-5 mL/h/g (preferably 0.5-4mL/h/g, more preferably 1-4 mL/h/g).
As an embodiment, the biomass-based nitrogen-doped carbon catalyst is prepared by impregnating and modifying biomass with a nitrogen-containing source and an aqueous solution of an activating agent, carbonizing at 400-1000 ℃, and then cooling, washing and drying; or the biomass is soaked and modified by aqueous solution containing an activating agent, then carbonized at 400-1000 ℃ in inert gas or ammonia (preferably ammonia) atmosphere, and then cooled, washed and dried to obtain the biomass-based 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 one or more selected from zinc chloride, sodium hydroxide and potassium hydroxide.
Preferably, the preparation of the nitrogen-doped carbon catalyst based on biomass comprises the following steps:
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.
In a further preferable scheme, in the step 1), the biomass is crushed to 10-30 meshes.
As a further preferable scheme, in the step 2), the mass ratio of the nitrogen source to the biomass is (0-10): 1 (preferably 0.1 to 3): 1).
In a further preferable scheme, 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).
As a further preferable scheme, in the step 2), the biomass obtained in the step 1) is mixed with a nitrogen source and an activating agent, water is added and 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 an impregnation modified substance.
As a further preferable mode, in the 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 to 200 ℃.
Preferably, the preparation of the nitrogen-doped carbon catalyst based on biomass comprises the following steps:
1) cleaning, drying and crushing the biomass for later use;
2) 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;
3) 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.
In a further preferable scheme, 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). As a further preferable scheme, in the step 2), the biomass obtained in the step 1) is mixed with an activating agent, water is added to the mixture and 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 an impregnation modified substance.
As a further preferable scheme, in the step 3), 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 3), the flow rate of the gas used by the hundred grams of biomass is 10-100 ml/min.
As a further preferable mode, in the 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.
Compared with the prior art, the invention has the following remarkable beneficial effects:
the biomass-based nitrogen-doped carbon catalyst used in the method does not contain heavy metals such as mercury and the like, is environment-friendly, has excellent catalytic performance, has the advantages of high catalytic cracking conversion rate of chlorinated alkane and high product selectivity, and has good catalytic activity; in addition, the nitrogen-doped carbon catalyst based on the biomass, which is used by the invention, takes renewable biomass as a raw material, has various selectable biomass types, wide raw material sources and low cost, can solve the environmental protection pressure caused by excessive accumulation of biomass wastes, provides a new way for deep utilization of biomass resources, and has rich oxygen atoms, trace metal elements and the like on the surface of the prepared catalyst besides chemical bonds formed by nitrogen and carbon atoms, and the catalyst has better catalytic activity compared with the traditional nitrogen-doped coal-based catalyst due to the synergistic effect of the oxygen atoms and the trace metal elements; in addition, the method provided by the invention has the advantages of simple preparation process, readily available raw materials, low cost, strong process controllability, easiness for large-scale production, high conversion rate of catalytic cracking of the chlorinated alkane, high product selectivity, low energy consumption 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 and the comparative example.
Example 1: preparation of nitrogen-doped carbon catalyst based on biomass
Example 1.1
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 1.2
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 1.3
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 1.4
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 1.5
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 1.6
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 1.7
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 1.8
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 1.9
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.
Example 2: preparation of chloroethylene by dichloroethane catalytic cracking
Dichloroethane is vaporized and then introduced into fixed bed reactors respectively filled with the biomass-based nitrogen-doped carbon catalyst prepared in example 1 and the nitrogen-doped coal-based catalyst prepared in the comparative example to react, the liquid hourly space velocity of the dichloroethane is 0.5-4mL/h/g, the reaction temperature is 200-300 ℃, the reaction effluent is cooled to room temperature, and liquid vinyl chloride can be obtained, wherein 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 1.
TABLE 1 results of preparing vinyl chloride by catalyzing a dichloroethane cracking reaction using the biomass-based nitrogen-doped carbon catalyst prepared in example and the nitrogen-doped coal-based catalyst prepared in comparative example
As can be seen from table 1: the dichloroethane cracking reaction has high dichloroethane conversion rate and high chloroethylene selectivity when the biomass-based nitrogen-doped carbon catalyst is used for preparing chloroethylene under the catalytic action, 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.
Example 3: preparation of vinylidene chloride by catalytic cracking of 1,1, 2-trichloroethane
The method comprises the steps of vaporizing 1,1, 2-trichloroethane, introducing the vaporized 1,1, 2-trichloroethane into fixed bed reactors respectively filled with the biomass-based nitrogen-doped carbon catalyst prepared in example 1 and the nitrogen-doped coal-based catalyst prepared in a comparative example, reacting, wherein the liquid hourly space velocity of the 1,1, 2-trichloroethane is 0.5-4mL/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 result is shown in table 2 (the conversion rate of the 1,1, 2-trichloroethane is the initial highest conversion rate).
Table 2 results of catalyzing 1,1, 2-trichloroethane cracking reaction using the biomass-based nitrogen-doped carbon catalyst prepared in example and the nitrogen-doped coal-based catalyst prepared in comparative example
As can be seen from table 2: when the pyrolysis reaction of the 1,1, 2-trichloroethane is used for preparing the vinylidene chloride under the catalytic action of the biomass-based nitrogen-doped carbon catalyst, the conversion rate of the 1,1, 2-trichloroethane is higher, the biomass-based nitrogen-doped carbon catalyst has excellent catalytic activity, particularly low-temperature (200-300 ℃) catalytic activity, and the method is remarkably improved compared with the traditional coal-based carbon catalyst.
Example 4: preparation of trichloroethylene by tetrachloroethane catalytic cracking
The tetrachloroethane was vaporized and then introduced into fixed bed reactors respectively containing the biomass-based nitrogen-doped carbon catalyst prepared in example 1 and the nitrogen-doped coal-based catalyst prepared in the comparative example to react, the liquid hourly space velocity of the tetrachloroethane was 0.5 to 4mL/h/g, the reaction temperature was 200 to 300 ℃, the reaction effluent was cooled to room temperature, the fixed bed reactor used in the reaction process was a quartz tube having an inner diameter of 6 mm, and the reaction results were as shown in table 3 (the tetrachloroethane conversion rate in the table was the initial highest conversion rate).
Table 3 results of catalyzing tetrachloroethane cracking reaction using biomass-based nitrogen-doped carbon catalyst prepared in example and nitrogen-doped coal-based catalyst prepared in comparative example
As can be seen from table 3: the pyrolysis reaction of tetrachloroethane has higher tetrachloroethane conversion rate and high selectivity of trichloroethylene when the vinylidene chloride is prepared by adopting 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 remarkable progress compared with the traditional coal-based carbon catalyst.
Example 5: preparation of tetrachloroethylene by catalytic cracking of pentachloroethane
The pentachloroethane is vaporized and then introduced into fixed bed reactors respectively filled with the biomass-based nitrogen-doped carbon catalyst prepared in example 1 and the nitrogen-doped coal-based catalyst prepared in the comparative example for reaction, the liquid hourly space velocity of the pentachloroethane is 0.5-4mL/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 (in the table, the conversion rate of the pentachloroethane is the initial highest conversion rate).
TABLE 4 results of catalyzing pentachloroethane cracking reactions using the biomass-based nitrogen-doped carbon catalyst prepared in example and the nitrogen-doped coal-based catalyst prepared in comparative example
As can be seen from table 4: the cracking reaction of pentachloroethane has higher pentachloroethane conversion rate and high tetrachloroethylene selectivity when vinylidene chloride is prepared by adopting the biomass-based nitrogen-doped carbon catalyst of the invention under the catalytic action, and the biomass-based nitrogen-doped carbon catalyst has excellent catalytic activity, especially low-temperature (200-300 ℃) catalytic activity, and has significant progress compared with the traditional coal-based carbon catalyst.
Example 6: preparation of propylene by catalytic cracking of 1-chloropropane
1-chloropropane is vaporized and then introduced into a fixed bed reactor respectively filled with the biomass-based nitrogen-doped carbon catalyst prepared in example 1 and the nitrogen-doped coal-based catalyst prepared in a comparative example for reaction, wherein the liquid hourly space velocity of 1-chloropropane is 0.5-4mL/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 5 (the conversion rate of 1-chloropropane is the initial highest conversion rate).
TABLE 5 results of catalyzing 1-chloropropane cracking reaction using the biomass-based nitrogen-doped carbon catalyst prepared in example and the nitrogen-doped coal-based catalyst prepared in comparative example
As can be seen from table 5: the 1-chloropropane cracking reaction has high 1-chloropropane conversion rate and high propylene selectivity when the vinylidene chloride 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.
Example 7: preparation of 1,1, 3-trichloropropene by catalytic cracking of 1,1,1, 3-tetrachloropropane
The method comprises the steps of vaporizing 1,1,1, 3-tetrachloropropane, introducing the vaporized 1,1,1, 3-tetrachloropropane into fixed bed reactors respectively filled with the biomass-based nitrogen-doped carbon catalyst prepared in example 1 and the nitrogen-doped coal-based catalyst prepared in a comparative example, and reacting, wherein the liquid hourly space velocity of the 1,1,1, 3-tetrachloropropane is 0.5-4mL/h/g, the reaction temperature is 200-300 ℃, the reaction effluent is cooled to room temperature, and then liquid 1,1, 3-trichloropropene can be obtained, 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 6.
TABLE 6 results of preparing 1,1, 3-trichloropropene by catalyzing 1,1,1, 3-tetrachloropropane cracking reaction using the biomass-based nitrogen-doped carbon catalyst prepared in example and the nitrogen-doped coal-based catalyst prepared in comparative example
As can be seen from table 6: the cracking reaction of the 1,1,1, 3-tetrachloropropane has high raw material conversion rate and high product selectivity when the 1,1, 3-trichloropropene is prepared by adopting 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 remarkable progress compared with the traditional coal-based carbon catalyst.
Example 8: preparation of 1,1,3, 3-tetrachloropropene by catalytic cracking of 1,1,1,3, 3-pentachloropropane
Vaporizing 1,1,1,3, 3-pentachloropropane, and introducing the vaporized 1,1,1,3, 3-pentachloropropane into fixed bed reactors respectively filled with the biomass-based nitrogen-doped carbon catalyst prepared in example 1 and the nitrogen-doped coal-based catalyst prepared in the comparative example for reaction, wherein the liquid hourly space velocity of the 1,1,1,3, 3-pentachloropropane is 0.5-4mL/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 7.
TABLE 7 results of catalytic cracking reaction of 1,1,1,3, 3-pentachloropropane using the biomass-based nitrogen-doped carbon catalyst prepared in example and the nitrogen-doped coal-based catalyst prepared in comparative example
As can be seen from table 7: when 1,1,1,3, 3-pentachloropropane cracking reaction is used for preparing 1,1,3, 3-tetrachloropropene under the catalytic action of the biomass-based nitrogen-doped carbon catalyst, the raw material conversion rate is 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 the traditional coal-based carbon catalyst.
Example 9: 1,1,1,3, 3-pentachloropropene prepared by catalytic cracking of 1,1,1,3, 3-hexachloropropane
After vaporizing 1,1,1,3,3, 3-hexachloropropane, the vaporized 1,1,1,3, 3-hexachloropropane was introduced into fixed bed reactors respectively containing the biomass-based nitrogen-doped carbon catalyst prepared in example 1 and the nitrogen-doped coal-based catalyst prepared in the comparative example to react, the liquid hourly space velocity of 1,1,1,3,3, 3-hexachloropropane was 0.5-4mL/h/g, the reaction temperature was 200-300 ℃, the reaction effluent was cooled to room temperature, the fixed bed reactor used in the reaction process was a quartz tube with an inner diameter of 6 mm, and the reaction results are shown in table 8.
Table 8 results of catalyzing 1,1,1,3,3, 3-hexachloropropane cracking reaction using the biomass-based nitrogen-doped carbon catalyst prepared in example and the nitrogen-doped coal-based catalyst prepared in comparative example
As can be seen from table 8: when the 1,1,1,3,3, 3-hexachloropropane cracking reaction is used for preparing 1,1,1,3, 3-pentachloropropene under the catalytic action of the biomass-based nitrogen-doped carbon catalyst, the raw material conversion rate and the product selectivity are higher, the biomass-based nitrogen-doped carbon catalyst has excellent catalytic activity, particularly low-temperature (200-300 ℃) catalytic activity, and the method has remarkable progress compared with the traditional coal-based carbon catalyst.
Example 10: preparation of 1-butene by catalytic cracking of 1-chlorobutane
The method comprises the steps of vaporizing 1-chlorobutane, introducing the vaporized 1-chlorobutane 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-chlorobutane is 0.5-4mL/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 9 (in the table, the conversion rate of the 1-chlorobutane is the initial highest conversion rate).
TABLE 9 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
As can be seen from table 9: 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.
Example 11: preparation of 1-pentene by catalytic cracking of 1-chloropentane
1-chloropentane is vaporized and then introduced into fixed bed reactors 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-chloropentane is 0.5-4mL/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 result is shown in table 10 (in the table, the conversion rate of the 1-chloropentane is the initial highest conversion rate).
TABLE 10 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
As can be seen from table 10: 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.
Example 12: preparation of 1-hexene by 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 0.5-4mL/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 11 (in the table, the conversion rate of the 1-chlorohexane is the initial highest conversion rate).
TABLE 11 results of catalyzing 1-chlorohexane cracking reaction using the biomass-based nitrogen-doped carbon catalyst prepared in example and the nitrogen-doped coal-based catalyst prepared in comparative example
As can be seen from table 11: 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 11, it can be seen that: the biomass-based nitrogen-doped carbon catalyst can be used for cracking chloralkane to eliminate hydrogen chloride reaction, has the advantages of high conversion rate of catalytic cracking of chloralkane and high selectivity of products, and has good catalytic activity in a low temperature range; in addition, the method provided by the invention has the advantages of simple preparation process, readily available raw materials, low cost, strong process controllability, easiness for large-scale production, high conversion rate of catalytic cracking of the chlorinated alkane, high product selectivity, low energy consumption and the like, and has significant progress and industrial application value compared with the prior art.
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 (6)
1. A method for eliminating hydrogen chloride by catalytic cracking of chloralkane is characterized in that: the method is to lead the molecular formula to be C under the action of a nitrogen-doped carbon catalyst based on biomassnClxHyThe preparation of the molecular formula C by eliminating hydrogen chloride through the cracking reaction of chloralkanenClx-1Hy-1Wherein n is an integer of 2-6, x is an integer of 1-7, y is 2(n +1) -x, and y is not less than 1; the biomass-based nitrogen-doped carbon catalyst is prepared by impregnating and modifying biomass with a nitrogen-containing source and an aqueous solution of an activator, carbonizing the biomass at 400-1000 ℃ in an inert gas atmosphere, and then cooling, washing and drying the biomass-based nitrogen-doped carbon catalyst; or the biomass is subjected to impregnation modification by an aqueous solution containing an activating agent, then is carbonized at 400-1000 ℃ in an ammonia atmosphere, and then is cooled, washed and dried to obtain the biomass-based catalyst; 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 activating agent is selected from one or more of zinc chloride, sodium hydroxide and potassium hydroxide.
2. The method of claim 1, wherein: the cracking reaction temperature is 140-400 ℃.
3. The method of claim 1, wherein: the liquid hourly space velocity of the chloralkane is 0.1-5 mL/h/g.
4. The method of claim 1, 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 method according to any one of claims 1 to 4, wherein the preparation of the biomass-based nitrogen-doped carbon catalyst comprises the following steps:
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.
6. The method according to any one of claims 1 to 4, wherein the preparation of the biomass-based nitrogen-doped carbon catalyst comprises the following steps:
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 ammonia atmosphere, and then cooling, washing and drying to obtain the biomass-based nitrogen-doped carbon catalyst.
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CN104289247A (en) * | 2014-10-11 | 2015-01-21 | 中国科学院上海高等研究院 | Catalyst applied to preparation of vinyl chloride by catalytic cracking of 1,2-dichloroethane as well as preparation method and application of catalyst |
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 |
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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 |
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