CN107573968B - Method for preparing high-purity bio-alkane by using waste oil - Google Patents
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Abstract
The invention discloses a method for preparing high-purity bio-alkane by using waste oil, which comprises the following steps: removing water impurities from the waste oil, carrying out hydrodeoxygenation and denitrification modification under the action of a modification catalyst to obtain a crude bio-alkane product, and carrying out oil-water separation on the crude bio-alkane product to obtain a product which is high-purity long-chain straight-chain alkane of C13-C22. The method can remove nitrogen and oxygen in the grease to saturate C = C chemical bonds in unsaturated double bonds of long-chain aliphatic hydrocarbon chains of the grease in the hydrogenation reaction process, and obtain a high-purity biomass long-chain straight-chain alkane oil product which is generated by sulfur-free, benzene, nitrogen oxide, aromatization and isomerization with the content of C13-C22 of more than 99%, the oil product is an important organic chemical raw material, has very wide application and plays a very important role in national economy, the development of the oil product drives the development of other basic organic chemical products, and the oil product has an energy function and can be used for producing substances such as biochemical products and the like.
Description
Technical Field
The invention relates to the field of biological new energy, in particular to a method for producing high-purity bio-alkane by using waste oil.
Background
The alkane is a saturated hydrocarbon under hydrocarbons, mainly comes from the fractionation of petroleum, the content of the alkane in the petroleum is about 54%, the straight-chain alkane obtained by the fractionation is generally 28-32%, the purity of the straight-chain alkane is not more than 96%, and toxic residues such as aromatic hydrocarbons, benzene, sulfur and the like exist. At present, the world straight-chain alkane is mainly derived from petroleum fractionation, the production capacity is about 380 million tons/year, the straight-chain alkane is mainly distributed in nearly 20 countries and regions such as the United states, Western Europe, Asia and the like, and the supply is extremely short and in short supply.
In China, as a new automotive diesel standard is implemented, diesel indexes are developed towards low sulfur, low nitrogen, low aromatic hydrocarbon, low density and high cetane number, the stability problem and the environmental protection problem of diesel are solved actively, the combustion quality and efficiency are solved, the quality of the existing diesel is upgraded, hydrogen in fuel gas is used as a hydrogen source to reform, catalyze and crack oil products, alkane in petroleum is reformed, catalytically and cracked to produce high-quality and high-octane oil products along with the processing of the oil products, so that the alkane derived from petroleum fractionation is tensed and in short supply, particularly along with the increasing depletion of crude oil in the world, for China with the dependence of petroleum import exceeding 60%, the supply and demand of the alkane derived from petroleum fractionation is more prominent, the contradiction is caught, a new way for developing diversified alkane sources is urgently needed, and the complete dependence on petroleum import is eliminated. According to the method, petroleum resources are removed, the waste oil is used, the purity of the biomass straight-chain alkane prepared by removing nitrogen oxide through hydrogenation modification under the action of the modified catalyst reaches more than 99%, and sulfur, benzene and nitrogen oxide are not generated, and aromatization and isomerization are not performed.
The waste oil is used as the raw material to produce the biomass alkane, and the source is very rich in China. The waste oil is used as a raw material, the urban area of developed areas is excluded, 3229 large, medium and small cities above county level in China are totally included, the population is more than 13.6 hundred million people, the dining rooms of the dialogistic institutions are excluded, nearly 350 million registered hotels and restaurants exist, more than 6000 million tons of kitchen waste are generated every year, particularly, the content of the waste oil in the restaurants of the hotels is more than 30%, and about 1800 million tons of waste oil and 'swill-cooked dirty oil' are generated in the kitchen waste more than 6000 million tons every year. However, for a long time, the treatment of kitchen waste in China is always in an unordered state, the kitchen waste goes deep into the town from the city, most of the kitchen waste is treated in various modes such as landfill, composting and incineration, the utilization rate is low, resources are wasted, secondary pollution and toxic and harmful substances are easy to generate, the health of people are endangered, especially, gutter oil with toxicity being one hundred times that of arsenic is extremely bad and impatient to prevention, even about 200-300 million tons of the kitchen waste enters supermarkets from various channels and is led to common people dining tables every year, and great harm is generated to the health and life safety of people, so that the kitchen waste is highly valued by the nation and the people in China, comprehensive utilization of high and new technologies is urgently needed, a sustainable development circular economy industry is constructed, and high added value products are produced by changing waste into valuable. In addition, the invention can also utilize biomass energy non-edible oil and fat as raw materials, and utilize the land resource available in China to be about 6750 ten thousand square hectares and can produce more than 2 hundred million tons of biomass energy vegetable oil and fat. However, for a long time, due to the lack of technical development of high value-added products for biomass energy crops in China, the lack of powerful support of a market platform for fruits of the biomass energy crops, the enthusiasm for farmers to plant cannot be guaranteed, large-area waste of forestry land in China is caused, and industrialized high-tech and new channels for oil utilization are urgently needed.
The method for producing the bio-alkane by using the waste oil opens up a new way for utilizing the oil, has energy function as a new biological energy source, can be used for the physical production of biochemical products and the like, has reproducibility and low CO2Emission and no SO2The biomass fuel has the basic characteristics of wide distribution, diversified use forms, rich total amount of biomass fuel and the like, can relieve the pressure of energy and environment, and is a biomass fuelThe renewable energy source is the only renewable carbon source, is an urgent need for realizing the strategic development of the national new energy industry, and has great significance for economic sustainable development, reduction of petroleum resource consumption, reduction of environmental pressure, control of atmospheric pollution, improvement of social and economic benefits and the like.
The bio-alkane is used as a biomass fuel, and compared with the traditional petroleum-based fuel, the emission of carbon dioxide can be reduced by more than 55-90%; compared with naphtha, the cracking raw material for the industrial production of olefins has the advantages that the yield of trienes (ethylene, propylene and butadiene) is improved by more than 30%, the cracking temperature is reduced by more than 80 ℃, the carbon dioxide emission and the energy consumption are reduced by about 20%, a technical route of high product yield, long operation period, low energy consumption and carbon dioxide emission is expanded for the olefin industry, environment-friendly high-quality raw materials which are inexhaustible, inexhaustible and renewable are developed, the olefin industry can get rid of complete dependence on petroleum resource import, and the cracking raw material is a major revolution of raw materials for the production of the olefin industry in China. The method is used for other related industries such as chlorinated paraffin, plasticizer and the like, the biological alkane opens up a new channel for the requirement of raw materials, the biomass nontoxic long-chain straight-chain alkane is provided, and the contradiction between supply and demand of the related industries in the current serious shortage of petrochemical straight-chain alkane raw materials is relieved. In particular to high-purity long-chain straight-chain alkane with C18-C22, which is used for producing alpha-olefin and is a natural raw material which is difficult to obtain poly alpha-olefin (lubricating oil is never replaced).
At present, the basic idea of people for researching the preparation of alkane by grease or fatty acid methyl ester hydrodeoxygenation is to use a catalytic system for removing elements such as N, S, O and the like by oil product hydrofining, the adopted catalysts mainly comprise two categories of transition metal supported catalysts and noble metal supported catalysts, and from the research result, the problems of large carbon chain loss, large hydrogen consumption, serious isomerization, poor catalyst stability and the like caused by large cracking reaction depth exist in the hydrodeoxygenation reaction process.
Specifically, there are several problems in the following areas:
1. acidity and acid content of catalyst
The cracking reaction is caused by strong acidity or large acid amount on the surface of the catalyst; the weak acidity or small amount of acid affects the hydrodeoxygenation activity of the catalyst.
2. Water-resistant stability of the catalyst
A large amount of water is generated in the hydrodeoxygenation reaction of grease or fatty acid methyl ester, and due to the existence of water in a reaction system, the structure of the carrier Al2O3 is induced to be changed from gamma type to alpha type, so that the framework structure of the catalyst is damaged, and the hydrothermal stability of the catalyst is reduced.
3. Tolerance of catalyst to impurities in feedstock
Phosphorus-containing compounds, alkaline earth elements and alkali metal elements contained in the grease or fatty acid methyl ester raw materials are enriched on the surface of the catalyst to cover the active sites of the catalyst, so that the surface carbon deposition and the activity stability of the catalyst are reduced in the reaction process.
4. Removal of trace nitrogen-containing compounds from fats and oils or fatty acid methyl esters
The adsorption and removal by using a conventional strong acid adsorbent have no effect basically; if the acidic carrier is used for loading transition metal oxide for hydrogenation removal, normal paraffin cracking and isomerization reaction can be caused, so that the yield of the target product is low, and the product quality is influenced.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing high-purity bio-alkane by directly hydrogenating waste oil. By adopting a high-selectivity hydrodeoxygenation modification and non-alkaline denitrifier moderate hydrogenation process for the waste oil, nitrogen and oxygen in the oil can be removed, so that unsaturated double bonds of long-chain aliphatic hydrocarbon chains of the oil are saturated by C = C chemical bonds in the hydrogenation reaction process, and a high-purity biomass long-chain straight-chain alkane oil product which is generated by sulfur-free, benzene, nitrogen oxides, aromatization and isomerization and has the content of C13-C22 of more than 99% is obtained.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a method for preparing high-purity bio-alkane by using waste oil is characterized by comprising the following steps: removing water impurities from the waste oil, carrying out hydrodeoxygenation and denitrification modification under the action of a modification catalyst to obtain a crude bio-alkane product, and carrying out oil-water separation on the crude bio-alkane product to obtain a product which is high-purity long-chain straight-chain alkane of C13-C22.
The waste oil mainly comprises catering waste oil, acidified oil, industrial palm oil, oil processing plant leftovers and the like.
The water impurities in the waste grease are removed by separating the water in the waste grease, and then continuously filtering the waste grease by using a pipeline filter to remove impurities such as mud, sand, metal fragments and the like.
The modified catalyst for hydrodeoxygenation can be modified by adopting a common transition metal hydrodeoxygenation catalyst, the components comprise nickel, nickel-molybdenum, nickel-cobalt, nickel-tungsten and cobalt-molybdenum, and the carrier is selected from oxides, activated carbon, molecular sieves and the like. The volume ratio of hydrogen to oil subjected to hydrodeoxygenation is 20-1000, and the airspeed is 1.0h-1The reaction pressure is 0.5-16Mpa, and the reaction temperature is 150-350 ℃.
The hydrodenitrogenation modified catalyst can be modified by adopting a common denitrification catalyst, the components comprise nickel, molybdenum, cobalt, tungsten and other compositions, and the carrier is selected from oxides, activated carbon and molecular sieves. The volume ratio of hydrogen to oil for hydrodenitrogenation is 10-500, and the airspeed is 0.5-3h-1The reaction pressure is 0.5-5Mpa, and the reaction temperature is 150-300 ℃.
The reaction temperature of the hydrodeoxygenation is 2.0MPa at the reaction pressure and the liquid hourly space velocity of 1.0h-1Under the condition of a hydrogen-oil volume ratio of 700, when the reaction temperature is 310-450 ℃, the generation amount of heavy components can be reduced by increasing the temperature. When the reaction temperature is 260-350 ℃, the reaction conversion rate and selectivity reach the optimum, then the reaction product is isomerized when the reaction temperature is continuously increased, and the generation amount of isoparaffin of the reaction product is increased along with the continuous increase of the reaction temperature, so the optimum reaction temperature is 350 ℃.
The reaction pressure of the hydrodeoxygenation is that the reaction temperature is 350 ℃, and the liquid hourly space velocity is 1.0h-1Under the condition that the volume ratio of hydrogen to oil is 700, when the reaction pressure is 2-5 MPa, the influence of the reaction pressure on the conversion rate and the selectivity of the reaction is small, and the change of the generation amount of isoparaffin and heavy components is small, so that the optimal reaction pressure is 2 MPa.
The reaction airspeed of the hydrodeoxygenation is that under the conditions of reaction temperature of 350 ℃, reaction pressure of 2MPa and hydrogen-oil volume ratio of 700, when the airspeed is increased, the selectivity is gradually reduced, and the direct reason is the increase of the content of isoparaffin; when the space velocity is too low, the yield of industrial production is influenced, so that the optimum reaction space velocity is 1.0h-1。
The hydrogen-oil ratio of the hydrodeoxygenation is at the reaction temperature of 350 ℃, the reaction pressure of 2MPa and the liquid hourly space velocity of 1.0h-1When the volume ratio of hydrogen to oil is less than 700, the reduction of the hydrogen to oil ratio promotes the hydrolysis reaction of fatty acid and reduces the selectivity of straight-chain paraffin; when the hydrogen-oil volume ratio is more than 1000, the improvement is continued, and the reaction is not influenced, so that the optimal reaction hydrogen-oil volume ratio is 700.
The hydrodenitrification is the hydrodenitrification carried out on the hydrodeoxygenation product, if basic nitrides in petroleum products are removed, two process routes of strong acid adsorbent adsorption removal and acidic carrier loaded transition metal oxide catalyst hydrogenation removal are adopted, and for non-basic nitrides of pyrrole and tetrahydropyrrole in the bio-alkane products, the adsorption removal by the conventional strong acid adsorbent has no effect basically; if the acidic carrier is used for loading transition metal oxide for hydrogenation removal, cracking and isomerization reaction of straight-chain alkane can be caused, so that the yield of the target product is low, and the quality of the product is influenced. The invention utilizes the modification of a common hydrodenitrogenation catalyst, the volume ratio of hydrogen to oil in hydrodenitrogenation is 300, and the space velocity is 2.0h-1Under the conditions of reaction pressure of 2.0MPa and reaction temperature of 190 deg.C, the non-alkaline nitride of pyrrole and tetrahydropyrrole in the bio-alkane product can be basically and completely removed.
Further, 10-30% of rare earth cerium oxide metal elements are selectively added into the hydrodeoxygenation catalyst for modification, so that the alkane selectivity of the hydrodeoxygenation reaction is improved, the active ingredients comprise a cerium-nickel-molybdenum-cobalt combined diversified high-water-resistance supported composite catalyst, and 10-30% of nickel elements and cerium elements are added into a carrier selected from gamma-Al 2O3, so that the alkane conversion rate and the reaction rate of the hydrodeoxygenation reaction are improved.
Preferably, the modification of the hydrodeoxygenation catalyst is carried out, and the addition of 15% of rare earth for oxidation is selectedThe cerium metal element is modified, and the alkane selectivity of the hydrodeoxygenation reaction is improved. The active component comprises a diversified high-water-resistance supported composite catalyst of a cerium-nickel-molybdenum-cobalt combination. The carrier is selected from gamma-Al2O3And adding 25% of nickel element and 3% of cerium element, and improving the alkane conversion rate and the reaction rate of the hydrodeoxygenation reaction.
Further, rare earth zirconia is selectively added into the hydrodenitrogenation catalyst for modification, active ingredients comprise a zirconium-nickel-cobalt combined diversified supported adsorption center and a hydrogen dissociation active center catalyst, and a carrier is selected from gamma-Al 2O3 and 10-30% of zirconium element is added.
Preferably, 15% of rare earth zirconium oxide elements are added in the hydrodenitrogenation catalyst modification, and the active ingredients comprise zirconium-nickel-cobalt combined diversified supported adsorption centers and hydrogen dissociation active centers. The carrier is selected from gamma-Al2O3Adding 25% of zirconium element.
Has the advantages that:
the method can remove nitrogen and oxygen in the grease to ensure that unsaturated double bonds of long-chain aliphatic hydrocarbon chains of the grease are saturated at C = C chemical bonds in the hydrogenation reaction process, so that a high-purity biomass long-chain straight-chain alkane oil product which is generated by sulfur-free, benzene, nitrogen oxide, aromatization and isomerization and has more than 99% of C13-C22 content is obtained, the oil product is an important organic chemical raw material, has very wide application, plays a very important role in national economy, and the development of other basic organic chemical products drives the development of other basic organic chemical products. Other materials are also used for leather esterifying agents, high-grade detergents, cosmetics, chemical fertilizer additives, daily necessities diluents, solvents, pesticide emulsifiers, medicines and petroleum protein raw materials, and for liquid mosquito-repellent incense, aluminum rolling liquid, dibasic acid, plastic rubber solvents, textile auxiliary base oils, printing and dyeing ink solvents, electric discharge machining oil, base oils for special rust preventive oils, metal processing base oils, metal cleaning agents, liquid wax for lamps, high-grade perfumes, nylon plastics and the like. Wherein the long-chain straight-chain alkane of the biomass of C18-C22 is a natural raw material which is difficult to obtain for producing high-carbon poly alpha-olefin (lubricant is never replaced).
Detailed Description
The present invention is further illustrated by the following examples.
The specific embodiment is as follows:
aiming at the reaction property and characteristics of preparing the bio-alkane by hydrogenating the grease raw material, the invention adopts the hydrodeoxygenation modified catalyst with high straight-chain alkane selectivity and high water resistance and a relatively mild hydrogenation reaction process to remove nitrogen and oxygen in the bio-alkane by hydrogenation, and the product generates a nitrogen-free, oxygen-free, sulfur-free and high-content bio-alkane crude product. And (3) separating oil and water of the obtained crude bio-alkane to obtain a product which is high-purity long-chain straight-chain alkane with the purity of C13-C22.
Under the condition of the same operation severity, preferably, the hydrodeoxygenation catalyst is modified by adding 15% of rare earth cerium oxide metal element, so that the alkane selectivity and the conversion rate of the hydrodeoxygenation reaction are improved, and the carrier is selected from gamma-Al2O3Adding 25% of nickel element and 3% of cerium element, selecting a hydrogen-oil volume ratio of 700 under application conditions, and setting an airspeed of 1.0h-1The reaction pressure is 2.0Mpa, the reaction temperature is 350 ℃, the hydrogenation selectivity is 100%, and the conversion rate of the biological alkane is more than 99.6%.
The hydrodenitrogenation catalyst can adopt a common hydrogenation catalyst in the field, active components comprise nickel, molybdenum, cobalt and other compositions for modification, under the condition of the same operation severity, 15% of rare earth zirconia is preferably added in the hydrodenitrogenation catalyst for modification, and the active components comprise zirconium-nickel-cobalt combined diversified supported adsorption centers and hydrogen dissociation active centers. The carrier is selected from gamma-Al2O3Adding 25% of zirconium element, preferably selecting the hydrogen-oil volume ratio to be 300 under the application conditions, and setting the airspeed to be 2.0h-1The reaction pressure is 2.0Mpa, the reaction temperature is 190 ℃, and the residual quantity of organic nitride pyrrole and tetrahydropyrrole is less than 0.3 PPm.
The reaction product of the fatty acid ester hydrodeoxygenation and denitrification is separated to remove water impurities in the reaction product to obtain the biomass long-chain straight-chain alkane colorless transparent oil product, referred to as biological alkane oil product for short.
Example (b):
the first embodiment is as follows:
inputting the waste oil after oil-water separation into a fixed bed reactor device through a 100-mesh pipeline filter, and under the action of a common transition metal hydrodeoxygenation catalyst with r-AL2O3 as a carrier and Ni-Mo-Co as a component, when the volume ratio of hydrogen to oil is 700, the reaction temperature is 350 ℃, the reaction pressure is 2.0Mpa and the space velocity is 1.0h-1Under the optimal condition, the hydrogenation selectivity is 34%, the product conversion rate is 32%, the product is subjected to water flashing by a negative-pressure water flashing device to separate water impurities, and the biodiesel hydrocarbon mixture with the alkane content of about 31% is obtained. The biodiesel hydrocarbon mixture is fed into a fixed bed reactor for hydrodenitrogenation, and under the action of a common hydrodenitrogenation catalyst, when the volume ratio of hydrogen to oil is 200, the space velocity is 1.0h-1Under the optimal conditions that the reaction pressure is 2.0Mpa and the reaction temperature is 190 ℃, the orange biodiesel hydrocarbon mixture oil product is obtained.
Example two:
feeding the waste oil into a molecular distillation device, and distilling under reduced pressure by a molecular distillation method under the working pressure of-80 Pa and the temperature of 178 ℃ to remove water impurities and free acid in the oil, wherein the acid value of the oil is less than 0.5 (mgKOH/g). Feeding oil with acid value less than 0.5 (mgKOH/g) into a fixed bed reactor at alcohol-oil volume ratio of 1:3 and airspeed of 1.0h-1And replacing the glycerol in the oil under the conditions that the reaction pressure is 0.3Mpa and the reaction temperature is 68 ℃, so that the yield of the obtained fatty acid ester is 98%. Feeding the obtained fatty acid ester into a fixed bed reactor for hydrodeoxygenation, and under the action of a common transition metal hydrodeoxygenation catalyst with r-AL2O3 as a carrier and Ni-Mo-Co as a component, when the volume ratio of hydrogen to oil is 700, the reaction temperature is 350 ℃, the reaction pressure is 2.0Mpa and the space velocity is 1.0h-1Under the optimal condition, the hydrogenation selectivity is 54%, the product conversion rate is 54%, the product is subjected to water flashing by a negative pressure flashing device to separate water impurities, and the biodiesel hydrocarbon mixture with the content of about 53% is obtained. The biodiesel hydrocarbon mixture is fed into a fixed bed reactor device for hydrodenitrogenation, and is subjected to the action of a common hydrodenitrogenation catalystWhen the volume ratio of hydrogen to oil is 200, the space velocity is 1.0h-1Under the optimal conditions of the reaction pressure of 2.0Mpa and the reaction temperature of 190 ℃, the light yellow biodiesel oil mixture oil product mainly containing alkane is obtained.
Example three:
inputting the waste oil after oil-water separation into a fixed bed reactor device through a 100-mesh pipeline filter for direct hydrogenation, and under the action of a modified catalyst CeNiMoCo/r-AL 2O3+ Ni.Ce, when the volume ratio of hydrogen to oil is 700, the reaction temperature is 350 ℃, the reaction pressure is 2.0Mpa, and the airspeed is 1.0h-1Under the optimal condition, the hydrogenation selectivity is 100%, the product conversion rate is 100%, the product is subjected to water flashing and impurity separation by a negative pressure water flashing device, and the biomass high-purity long-chain straight-chain alkane oil product generated by non-isomerization and aromatization of C13-C22 with the yield of more than 98% and the content of more than 99% is obtained.
As can be seen from the above examples, the products obtained in examples one and two are biodiesel hydrocarbon mixtures. According to the invention, the waste oil is directly subjected to hydrodeoxygenation denitrification under the action of the modified catalyst, the hydrogenation selectivity is 100%, the product conversion rate is 100%, and the biomass high-purity long-chain straight-chain alkane oil product with the yield of more than 98% and the content of more than 99% and C13-C22 is obtained. The product has no toxic substances such as aromatic hydrocarbon, benzene, sulfur and the like, and has no formation, aromatization and the like.
Claims (7)
1. A method for preparing high-purity bio-alkane by using waste oil is characterized by comprising the following steps: removing water impurities from the waste oil, hydrodeoxygenation and denitrification modification under the action of a modification catalyst, wherein the hydrodenitrification is the hydrodenitrification of a hydrodeoxygenation product to obtain a crude bio-alkane product, and the obtained crude bio-alkane product is subjected to oil-water separation to obtain a product C13～C22And the content of the high-purity long-chain linear-chain biological alkane is more than 99%, the waste oil mainly comprises acidified oil and oil processing plant leftovers, 10-30% of rare earth cerium oxide is selectively added for modification of the hydrodeoxygenation catalyst, the alkane selectivity of the hydrodeoxygenation reaction is improved, and the active ingredient comprises cerium-nickel-molybdenum-cobalt combined multi-element alkaneThe high water resistance supported composite catalyst has carrier selected from gamma-Al 2O3Adding 10-30% of nickel element and cerium element to improve the alkane conversion rate and the reaction rate of the hydrodeoxygenation reaction; the hydrodenitrogenation catalyst is modified by selectively adding rare earth zirconia, the active components of the catalyst comprise zirconium-nickel-cobalt combined diversified supported adsorption centers and hydrogen dissociation active centers, and the carrier is selected from gamma-Al2O3And adding 10-30% of zirconium element.
2. The method for preparing high-purity bio-alkane by using waste oil and fat according to claim 1, wherein the step of removing water impurities in the waste oil and fat is to separate water in the waste oil and fat and then continuously filter the water by using a pipeline filter to remove mud and sand and metal debris impurities in the oil and fat.
3. The method for preparing high-purity bio-alkane by using waste oil and fat as claimed in claim 1, wherein the hydrodeoxygenation catalyst is modified by adding 15% of rare earth cerium oxide, the active component comprises a diversified high-water-resistance supported composite catalyst of a cerium-nickel-molybdenum-cobalt combination, and the carrier is selected from gamma-Al2O3Adding 25% of nickel element and 3% of cerium element, and improving the alkane conversion rate and the reaction rate of the hydrodeoxygenation reaction; adding 15% of rare earth zirconia into the hydrodenitrogenation catalyst for modification, wherein the active ingredients comprise a zirconium-nickel-cobalt combined diversified supported adsorption center and a catalyst of a hydrogen dissociation active center, and the carrier is selected from gamma-Al2O3Adding 25% of zirconium element.
4. The method for preparing high-purity bio-alkane by using waste oil and fat as claimed in claim 1, wherein the volume ratio of hydrogen to oil subjected to hydrodeoxygenation is 20-1000, and the space velocity is 1.0h-1The reaction pressure is 0.5-16Mpa, and the reaction temperature is 150-350 ℃.
5. The method for preparing high-purity bio-alkane by using waste oil and fat as claimed in claim 1, wherein the waste oil and fat is used as a raw materialThe volume ratio of hydrogen to oil for hydrodeoxygenation is 700, and the space velocity is 0.3-10h-1The reaction pressure is 2Mpa, and the reaction temperature is 350 ℃.
6. The method for preparing high-purity bio-alkane by using waste oil and fat as claimed in claim 1, wherein the volume ratio of hydrogen to oil for hydrodenitrogenation is 10-500, and the space velocity is 0.5-3h-1The reaction pressure is 0.5-5Mpa, and the reaction temperature is 150-300 ℃.
7. The method for preparing high-purity bio-alkane by using waste oil and fat as claimed in claim 1, wherein the volume ratio of hydrogen to oil for hydrodenitrogenation is 300, and the space velocity is 2.0h-1The reaction pressure is 2.0Mpa, and the reaction temperature is 190 ℃.
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