CN113429995A - Hydrogenation device and process for producing biodiesel with high cetane number and low condensation point by one-step method - Google Patents
Hydrogenation device and process for producing biodiesel with high cetane number and low condensation point by one-step method Download PDFInfo
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- CN113429995A CN113429995A CN202110729816.8A CN202110729816A CN113429995A CN 113429995 A CN113429995 A CN 113429995A CN 202110729816 A CN202110729816 A CN 202110729816A CN 113429995 A CN113429995 A CN 113429995A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/60—Controlling or regulating the processes
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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Abstract
The invention relates to the technical field of biodiesel production, in particular to a hydrogenation device and a process for producing biodiesel with high cetane number and low condensation point by one-step method. The first hydrogenation reactor, the second hydrogenation reactor and the third hydrogenation reactor are all connected with a hydrogenation unit pipeline, the first hydrogenation reactor is connected with a raw oil unit pipeline, the third hydrogenation reactor is connected with a hydrogenation product separation unit pipeline, and the hydrogenation product separation unit is connected with the hydrogenation unit pipeline. Compared with the prior art, the invention combines the hydroisomerization pour point depressing process and the hydrodeoxygenation process into the same device, creates conditions for optimizing and adjusting the cetane number and the freezing point, adopts one-step production, avoids repeated heating and cooling of materials, effectively utilizes heat, and has lower gas yield and naphtha yield and correspondingly higher biodiesel yield compared with a two-step method.
Description
Technical Field
The invention relates to the technical field of biodiesel production, in particular to a hydrogenation device and a hydrogenation process for producing biodiesel with high cetane number and low condensation point by a one-step method.
Background
At present, the development of world energy has entered a new strategic regulation period, developed countries and emerging countries make energy development strategies in a dispute by guiding energy technology roadmaps, and renewable energy is vigorously developed to reduce the emission of harmful substances and greenhouse gases so as to realize low-carbon and clean development.
The cultivated land resources in China are short, oil crops are not practical as raw materials of biodiesel, and the cost of the current raw materials of inedible oil plants such as jatropha curcas, pistacia chinensis, oil palm and the like is higher. At present, the biodiesel in China almost takes waste grease as a raw material, and the cost of the raw material is superior to that of rapeseed oil and American soybean oil used in Germany. However, the development of the biodiesel industry in China starts late, the esterification or ester exchange technology is adopted all the time, the product is mainly fatty acid methyl ester, the quality is poor, the heat value is low, the acid value is high, the corrosivity is strong, the production cost is high, the product can not be used independently, the mixing proportion is too small, and the product is difficult to accept in the market.
The technology for producing the second-generation biodiesel by catalytic hydrodeoxygenation is developed rapidly in recent years, a plurality of devices are put into production in China, and the product quality is greatly improved. Compared with fatty acid methyl ester, the second-generation biodiesel has no carboxyl and hydroxyl, so that the second-generation biodiesel has the same composition as petroleum diesel, and can be blended with the petroleum diesel in any proportion for use; compared with petroleum diesel, the diesel oil has the characteristics of low sulfur content, no aromatic hydrocarbon and high cetane number. However, the normal paraffin formed by hydrodeoxygenation and decarboxylation of the waste animal and vegetable oil has a high cetane number, but has a high freezing point reaching 16-18 ℃, and cannot be directly used at normal temperature.
In order to solve the problem of low-temperature flowing alkane of the second-generation biodiesel, a company in China is provided with a hydroisomerization pour point depressant taking noble metal as a catalyst active center behind a hydrodeoxygenation device, and normal alkane after hydrodeoxygenation is converted into isoparaffin. The condensation point of the second-generation biodiesel can be reduced to below 0 ℃, and the second-generation biodiesel has good fluidity, but the normal paraffin is converted into isoparaffin, and the cetane number is greatly reduced.
Because the two catalysts of hydrodeoxygenation and hydroisomerization need to be vulcanized and supplemented with sulfur, and sulfur is a poison for noble metals, only two sets of devices can be respectively built for hydrodeoxygenation and hydroisomerization so as to ensure respective circulating hydrogen systems. This brings about the following three problems: 1. the construction investment is greatly increased; 2. the operation cost is greatly increased; 3. in the process of isomerization reaction, along with cracking reaction, fuel gas and naphtha with low additional value are increased, and the yield of the target product, namely the second-generation biodiesel, is greatly reduced. Therefore, the development of a process device for producing biodiesel with high cetane number and low freezing point by using one-step method waste animal and vegetable oil through hydrodeoxygenation and isomerization is imperative.
Disclosure of Invention
Aiming at the defects of the background technology, the invention provides a hydrogenation device and a process for producing biodiesel with high cetane number and low condensation point by a one-step method.
The technical scheme adopted by the invention is as follows: the key point of the hydrogenation device for producing biodiesel with high cetane number and low condensation point by one-step method is that the hydrogenation device comprises a first hydrogenation reactor, a second hydrogenation reactor and a third hydrogenation reactor which are sequentially connected by pipelines, wherein the first hydrogenation reactor, the second hydrogenation reactor and the third hydrogenation reactor are all connected with a hydrogenation unit pipeline, the first hydrogenation reactor is connected with a waste oil unit pipeline, the third hydrogenation reactor is connected with a hydrogenation product separation unit pipeline, and the hydrogenation product separation unit is connected with the hydrogenation unit pipeline.
Preferably, the first hydrogenation reactor, the second hydrogenation reactor and the third hydrogenation reactor are two beds, the two beds of the first hydrogenation reactor (R1) are respectively filled with a catalyst for decalcification and a catalyst for saturation, the two beds of the second hydrogenation reactor (R2) are respectively filled with a catalyst for deferrization and a catalyst for deoxidation, and the two beds of the third hydrogenation reactor (R3) are respectively filled with a catalyst for isomerization and a catalyst for desulfurization.
Preferably, the hydrogenation unit comprises a hydrogen production PSA unit and a fresh hydrogen compressor connected by a pipeline, an outlet end of the fresh hydrogen compressor is connected by a pipeline to the first hydrogenation reactor, and an inlet end of the hydrogen production PSA unit is connected by a pipeline to the hydrogenation product separation unit.
Preferably, the gas outlet end of the fresh hydrogen compressor is communicated with the raw oil unit pipeline.
Preferably, the hydrogenation product separation unit comprises a first air cooler, a high-pressure separator, a low-pressure separator and a fractionating tower which are sequentially connected through pipelines, the first air cooler is connected with the bottom pipeline of the third hydrogenation reactor, the air outlet end of the high-pressure separator is connected with a second air cooler through a pipeline, the air outlet end of the second air cooler is respectively connected with the circulating hydrogen compressor and the desulfurizer, the air outlet end of the circulating hydrogen compressor is respectively connected with the second hydrogenation reactor and the third hydrogenation reactor through pipelines, and the desulfurizer is connected with the hydrogenation unit through a pipeline.
Preferably, the system further comprises a first heat exchanger and a second heat exchanger, wherein the first heat exchanger and the second heat exchanger are sequentially arranged on a pipeline between the raw oil unit and the first hydrogenation reactor, and the second heat exchanger and the first heat exchanger are sequentially arranged on a pipeline between the third hydrogenation reactor and the hydrogenation product separation unit.
The hydrogenation process for producing biodiesel with high cetane number and low condensation point by one-step method mainly comprises the following steps:
s1, mixing waste animal and vegetable oil of a raw oil unit with fresh hydrogen conveyed by a new hydrogen compressor, and then entering a first hydrogenation reactor for hydrogenation saturation reaction;
s2, heating the hydrogenation saturated product by a heating furnace, mixing the hydrogenation saturated product with circulating hydrogen conveyed by a circulating hydrogen compressor, and then feeding the mixture into a second hydrogenation reactor to perform hydrodeoxygenation reaction;
s3, mixing the hydrodeoxygenation product with the circulating hydrogen conveyed by a circulating hydrogen compressor, and then, allowing the mixture to enter a third hydrogenation reactor to perform a hydroisomerization reaction;
and S4, the hydroisomerization product enters a high-pressure separator after heat exchange and cooling, one part of the gas phase separated by the high-pressure separator enters a recycle hydrogen compressor for pressurization and then is recycled, the other part of the gas phase enters a hydrogen production PSA unit after desulfurization, the oil phase separated by the high-pressure separator enters a low-pressure separator, the oil phase separated by the low-pressure separator enters a rectifying tower, and the biodiesel with the cetane number and the low condensation point is obtained by separation.
Preferably, the hydrogen saturation reaction conditions in S1 are as follows: the first bed layer of the first hydrogenation reactor is filled with a large-aperture protective agent, the second bed layer is filled with a nickel-molybdenum catalyst with an acid center, and the mass ratio of the catalyst to oil is (800-: 1, the reaction pressure is 5-10MPa, the reaction temperature is 200-280 ℃, and the reaction volume space velocity is 0.5-1.5.
Preferably, the hydrodeoxygenation reaction conditions in S2 are as follows: the first bed layer of the second hydrogenation reactor is filled with a large-aperture protective agent, the second bed layer is filled with a nickel-molybdenum hydrodeoxygenation catalyst, the reaction temperature of the first bed layer is 310-360 ℃, and the reaction temperature of the second bed layer is 330-385 ℃.
Preferably, the hydroisomerization reaction conditions in S2 are: the first bed layer of the third hydrogenation reactor is filled with a nickel-molybdenum metal molecular sieve catalyst, the second bed layer is filled with a nickel-molybdenum hydrofining catalyst, and the reaction temperature is 360-380 ℃.
Compared with the prior art, the hydrogenation device and the process for producing the biodiesel with high cetane number and low condensation point by the one-step method have the following beneficial effects: ,
1. the hydroisomerization pour point depressing process and the hydrodeoxygenation process are combined into the same device, so that conditions are created for optimizing and adjusting the cetane number and the freezing point, biodiesel with high cetane number and low freezing point can be produced, and the construction cost is greatly reduced; the one-step method is adopted for production, so that repeated heating and cooling of materials are avoided, heat can be effectively utilized, and the operating cost is greatly reduced;
2. by adjusting the hydrodeoxygenation reaction depth of the second hydrogenation reactor, the hydrodeoxygenation reaction intensity is properly reduced, a proper amount of carboxyl is kept, and the existence of alpha carbon in the material entering the third hydrogenation reactor is ensured, so that a branched chain formed by alkyl transfer is in an ideal beta position in the hydroisomerization reaction process, the produced product is ensured to have a higher cetane number and a lower freezing point, and the added value of the product is improved;
3. by selective and hydrodeoxygenationThe third hydrogenation reactor is filled with the vulcanized non-noble metal catalyst and the bifunctional catalyst with the acidic active center, which are consistent in catalyst, so that the problem that the noble metal catalyst contains H is effectively solved2Sulfur poisoning in the circulating hydrogen of S and the matching of dehydrogenation and transalkylation in the hydroisomerization process are realized, so that the hydroisomerization and the hydrodeoxygenation are in the same circulating hydrogen system;
4. because the strength of the acid active center of the bifunctional catalyst is reduced, the selectivity of isomerization reaction is improved, and the cracking reaction is reduced. Compared with the two-step method, the distribution of the target product biodiesel is reduced, the gas yield and the naphtha yield are correspondingly improved, and the economic benefit is greatly improved.
Drawings
FIG. 1 is a schematic structural diagram of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Example 1
As shown in fig. 1, the hydrogenation apparatus for producing biodiesel with high cetane number and low condensation point by one-step process includes a first hydrogenation reactor R1, a second hydrogenation reactor R2, and a third hydrogenation reactor R3, which are connected by pipeline in sequence, wherein the first hydrogenation reactor R1, the second hydrogenation reactor R2, and the third hydrogenation reactor R3 are all connected by pipeline with a hydrogenation unit, the first hydrogenation reactor R1 is connected by pipeline with a raw oil unit, the third hydrogenation reactor R3 is connected by pipeline with a hydrogenation product separation unit, and the hydrogenation product separation unit is connected by pipeline with the hydrogenation unit.
Example 2
As shown in fig. 1, the hydrogenation apparatus for producing biodiesel with high cetane number and low condensation point by one-step process includes pipeline connection in sequence of a first hydrogenation reactor R1, a second hydrogenation reactor R2, and a third hydrogenation reactor R3, where the first hydrogenation reactor R1, the second hydrogenation reactor R2, and the third hydrogenation reactor R3 are both two beds, the six beds are respectively connected with hydrogenation unit pipeline, the first bed of the first hydrogenation reactor is filled with a large-aperture protective agent, the second bed is filled with a nickel-molybdenum catalyst with an acid center, the first bed of the second hydrogenation reactor is filled with a large-aperture protective agent, the second bed is filled with a nickel-molybdenum hydrodeoxygenation catalyst, the first bed of the third hydrogenation reactor is filled with a nickel-molybdenum metal molecular sieve catalyst, the second bed is filled with a nickel-molybdenum hydrorefining catalyst, the first hydrogenation reactor R1 is connected with a waste oil unit pipeline, the third hydrogenation reactor R3 is connected with a hydrogenation product separation unit pipeline, the hydrogenation product separation unit is in pipeline connection with the hydrogenation unit.
Example 3
As shown in fig. 1, the hydrogenation apparatus for producing biodiesel with high cetane number and low condensation point by one-step process comprises a first hydrogenation reactor R1, a second hydrogenation reactor R2 and a third hydrogenation reactor R3 which are connected by end-to-end pipelines in sequence, a heating furnace 14 is arranged on a pipeline connecting the first hydrogenation reactor R1 and the second hydrogenation reactor R2, the first hydrogenation reactor R1, the second hydrogenation reactor R2 and the third hydrogenation reactor R3 are two beds, the upper parts of the six beds are respectively connected with a hydrogenation unit pipeline, the first bed of the first hydrogenation reactor is filled with a nickel-molybdenum catalyst, the second bed is filled with a nickel-molybdenum molecular sieve catalyst, the first bed of the second hydrogenation reactor is filled with a nickel-molybdenum catalyst, the second bed is filled with a nickel-molybdenum hydrodeoxygenation catalyst, the first bed of the third hydrogenation reactor is filled with a nickel-molybdenum molecular sieve catalyst, the second bed is filled with a nickel-molybdenum hydrogenation catalyst, the first hydrogenation reactor R1 is connected with a waste oil unit pipeline, the third hydrogenation reactor R3 is connected with a hydrogenated product separation unit pipeline, and the hydrogenated product separation unit is connected with the hydrogenation unit pipeline;
the hydrogenated product separation unit comprises a first air cooler 3, a high-pressure separator 4, a low-pressure separator 5 and a fractionating tower 6 which are sequentially connected through pipelines, wherein a second heat exchanger 11 and a first heat exchanger 10 are sequentially connected to a pipeline connected with the bottoms of the first air cooler 3 and the third hydrogenation reactor R3, an air outlet end of the high-pressure separator 4 is connected with a second air cooler 7 through a pipeline, an air outlet end of the second air cooler 7 is respectively connected with the circulating hydrogen compressor 8 and the desulfurizer 9, and an air outlet end of the circulating hydrogen compressor 8 is respectively connected with two beds of the second hydrogenation reactor R2 and two beds of the third hydrogenation reactor R3 through pipelines; the hydrogenation unit comprises a hydrogen production PSA unit 1 and a new hydrogen compressor 2 which are connected by pipelines, the gas outlet end of the new hydrogen compressor 2 is connected with the two beds of the first hydrogenation reactor R1 and the raw oil unit by a pipeline communication pipeline, and the gas inlet end of the hydrogen production PSA unit 1 is connected with the desulfurizer 9 by a pipeline; the raw oil unit comprises an oil storage tank 12 and a raw material pump 13 which are connected through a pipeline, and the first heat exchanger 10 and the second heat exchanger 11 are sequentially arranged on a pipeline connected with the raw material pump 13 and the first hydrogenation reactor R1.
Example 4
The hydrogenation process for producing biodiesel with high cetane number and low condensation point by one-step method comprises the following steps:
s1, mixing waste animal and vegetable oil of a raw oil unit with fresh hydrogen conveyed by a fresh hydrogen compressor, and then feeding the mixture into a first hydrogenation reactor for hydrogenation saturation reaction, wherein the mass ratio of a catalyst to the oil is 800: 1, the reaction pressure is 5MPa, the reaction temperature is 200-240 ℃, and the space velocity of the reaction volume is 0.5;
s2, heating the hydrogenation saturated product in a heating furnace, mixing the hydrogenation saturated product with circulating hydrogen conveyed by a circulating hydrogen compressor, and then feeding the mixture into a second hydrogenation reactor to perform hydrodeoxygenation reaction, wherein the reaction temperature of a first bed layer is 310-330 ℃, and the reaction temperature of a second bed layer is 330-350 ℃;
s3, mixing the hydrodeoxygenation product with circulating hydrogen conveyed by a circulating hydrogen compressor, and then feeding the mixture into a third hydrogenation reactor for carrying out a hydroisomerization reaction at the reaction temperature of 360-385 ℃;
and S4, the hydroisomerization product enters a high-pressure separator after heat exchange and cooling, one part of the gas phase separated by the high-pressure separator enters a recycle hydrogen compressor for pressurization and then is recycled, the other part of the gas phase enters a hydrogen production PSA unit after desulfurization, the oil phase separated by the high-pressure separator enters a low-pressure separator, the oil phase separated by the low-pressure separator enters a rectifying tower, and the biodiesel with the cetane number and the low condensation point is obtained by separation.
And (3) detection results: the hydrogenation saturation rate of the material is 100 percent, the hydrogenation demetalization rate is 99.5 percent, the hydrogenation deoxidation rate is 99 percent, the cetane number of the product diesel oil is more than 85 percent, and the cold filter plugging point is-3 ℃.
Example 5
The hydrogenation process for producing biodiesel with high cetane number and low condensation point by one-step method comprises the following steps:
s1, mixing waste animal and vegetable oil of a raw oil unit with fresh hydrogen conveyed by a fresh hydrogen compressor, and then feeding the mixture into a first hydrogenation reactor for hydrogenation saturation reaction, wherein the mass ratio of a catalyst to the oil is 1000: 1, the reaction pressure is 6MPa, the reaction temperature is 250-280 ℃, and the space velocity of the reaction volume is 1.0;
s2, heating the hydrogenation saturated product by a heating furnace, mixing the hydrogenation saturated product with circulating hydrogen conveyed by a circulating hydrogen compressor, and then feeding the mixture into a second hydrogenation reactor to perform hydrodeoxygenation reaction, wherein the reaction temperature of a first bed layer is 350-360 ℃, and the reaction temperature of a second bed layer is 360-380 ℃;
s3, mixing the hydrodeoxygenation product with circulating hydrogen conveyed by a circulating hydrogen compressor, and then, allowing the mixture to enter a third hydrogenation reactor for a hydroisomerization reaction at the reaction temperature of 370-380 ℃;
and S4, the hydroisomerization product enters a high-pressure separator after heat exchange and cooling, one part of the gas phase separated by the high-pressure separator enters a recycle hydrogen compressor for pressurization and then is recycled, the other part of the gas phase enters a hydrogen production PSA unit after desulfurization, the oil phase separated by the high-pressure separator enters a low-pressure separator, the oil phase separated by the low-pressure separator enters a rectifying tower, and the biodiesel with the cetane number and the low condensation point is obtained by separation.
And (3) detection results: the hydrogenation saturation rate of the material is 100 percent, the hydrogenation demetalization rate is 99.5 percent, the hydrogenation deoxidation rate is 99 percent, the cetane number of the product diesel oil is more than 85 percent, and the cold filter plugging point is-3 ℃.
Example 6
The hydrogenation process for producing biodiesel with high cetane number and low condensation point by one-step method comprises the following steps:
s1, mixing waste animal and vegetable oil of a raw oil unit with fresh hydrogen conveyed by a fresh hydrogen compressor, then feeding the mixture into a first hydrogenation reactor, and carrying out hydrogenation saturation reaction, wherein the mass ratio of a catalyst to the oil is 850: 1, the reaction pressure is 6MPa, the reaction temperature is 220-270 ℃, and the space velocity of the reaction volume is 1.0;
s2, heating the hydrogenation saturated product in a heating furnace, mixing the hydrogenation saturated product with circulating hydrogen conveyed by a circulating hydrogen compressor, and then feeding the mixture into a second hydrogenation reactor for carrying out hydrodeoxygenation reaction, wherein the reaction temperature of a first bed layer is 320-350 ℃, and the reaction temperature of a second bed layer is 340-370 ℃;
s3, mixing the hydrodeoxygenation product with circulating hydrogen conveyed by a circulating hydrogen compressor, and then, allowing the mixture to enter a third hydrogenation reactor for a hydroisomerization reaction at the reaction temperature of 370-380 ℃;
and S4, the hydroisomerization product enters a high-pressure separator after heat exchange and cooling, one part of the gas phase separated by the high-pressure separator enters a recycle hydrogen compressor for pressurization and then is recycled, the other part of the gas phase enters a hydrogen production PSA unit after desulfurization, the oil phase separated by the high-pressure separator enters a low-pressure separator, the oil phase separated by the low-pressure separator enters a rectifying tower, and the biodiesel with the cetane number and the low condensation point is obtained by separation.
And (3) detection results: the hydrogenation saturation rate of the material is 100 percent, the hydrogenation demetalization rate is 99.5 percent, the hydrogenation deoxidation rate is 99 percent, the cetane number of the product diesel oil is more than 85 percent, and the cold filter plugging point is-3 ℃.
Finally, it should be noted that the above-mentioned description is only a preferred embodiment of the present invention, and those skilled in the art can make various similar representations without departing from the spirit and scope of the present invention.
Claims (10)
1. Hydrogenation equipment for producing biodiesel with high cetane number and low condensation point by one-step method is characterized in that: comprises a first hydrogenation reactor (R1), a second hydrogenation reactor (R2) and a third hydrogenation reactor (R3) which are connected in sequence by pipelines. The first hydrogenation reactor (R1), the second hydrogenation reactor (R2) and the third hydrogenation reactor (R3) are all connected with a hydrogenation unit pipeline, the first hydrogenation reactor (R1) is connected with a raw oil unit pipeline, the third hydrogenation reactor (R3) is connected with a hydrogenation product separation unit pipeline, and the hydrogenation product separation unit is connected with the hydrogenation unit pipeline.
2. The hydrogenation device for producing biodiesel with high cetane number and low condensation point according to the one-step method of claim 1, characterized in that: the device comprises a first hydrogenation reactor (R1), a second hydrogenation reactor (R2) and a third hydrogenation reactor (R3), wherein the first hydrogenation reactor (R1), the second hydrogenation reactor (R2) and the third hydrogenation reactor (R3) are both two beds, the two beds of the first hydrogenation reactor (R1) are respectively filled with a catalyst for decalcification and a catalyst for saturation, the two beds of the second hydrogenation reactor (R2) are respectively filled with a catalyst for deferrization and a catalyst for deoxidation, and the two beds of the third hydrogenation reactor (R3) are respectively filled with a catalyst for isomerization and a catalyst for desulfurization.
3. The hydrogenation device for producing biodiesel with high cetane number and low condensation point according to the one-step method of claim 1, characterized in that: the hydrogenation unit comprises a hydrogen production PSA unit (1) and a new hydrogen compressor (2) which are connected through pipelines, the gas outlet end of the new hydrogen compressor (2) is connected with the first hydrogenation reactor (R1) through a pipeline, and the gas inlet end of the hydrogen production PSA unit (1) is connected with the hydrogenation product separation unit through a pipeline.
4. The hydrogenation device for producing biodiesel with high cetane number and low condensation point according to the one-step method of claim 1, characterized in that: and the gas outlet end of the fresh hydrogen compressor (2) is communicated with the raw oil unit pipeline.
5. The hydrogenation device for producing biodiesel with high cetane number and low condensation point according to the one-step method of claim 4, characterized in that: hydrogenated product separation unit is including the first air cooler (3), high pressure separator (4), low pressure separator (5) and fractionating tower (6) of pipe connection in proper order, first air cooler (3) with the bottom pipe connection of third hydrogenation ware (R3), the mixed hydrogen pipe connection second air cooler (7) that high pressure separator (4) separated, the cold back mixed hydrogen of second air cooler (7) is connected circulating hydrogen compressor (8) and desulfurizer (9) respectively, the circulating gas of circulating hydrogen compressor (8) respectively with second hydrogenation ware (R2), third hydrogenation ware (R3) pipe connection, desulfurizer (9) with hydrogenation unit pipe connection.
6. The hydrogenation device for producing biodiesel with high cetane number and low condensation point according to the one-step method of claim 4, characterized in that: the hydrogenation equipment is characterized by further comprising a first heat exchanger (10) and a second heat exchanger (11), wherein the first heat exchanger (10) and the second heat exchanger (11) are sequentially arranged on a pipeline between the raw oil unit and the first hydrogenation reactor (R1), and the second heat exchanger (11) and the first heat exchanger (10) are sequentially arranged on a pipeline between the third hydrogenation reactor (R3) and the hydrogenation product separation unit.
7. The process for producing biodiesel by the hydrogenation unit for producing biodiesel with high cetane number and low condensation point according to the one-step method of claims 1 to 6, is characterized by comprising the following steps:
s1, mixing waste animal and vegetable oil of a raw oil unit with fresh hydrogen conveyed by a new hydrogen compressor, and then entering a first hydrogenation reactor for hydrogenation saturation reaction;
s2, heating the hydrogenation saturated product by a heating furnace, mixing the hydrogenation saturated product with circulating hydrogen conveyed by a circulating hydrogen compressor, and then feeding the mixture into a second hydrogenation reactor to perform hydrodeoxygenation reaction;
s3, mixing the hydrodeoxygenation product with the circulating hydrogen conveyed by a circulating hydrogen compressor, and then, allowing the mixture to enter a third hydrogenation reactor to perform a hydroisomerization reaction;
and S4, the hydroisomerization product enters a high-pressure separator after heat exchange and cooling, a gas phase separated by the high-pressure separator is air-cooled, one part of the gas phase enters a recycle hydrogen compressor for pressurization and then is recycled, the other part of the gas phase enters a hydrogen production PSA unit after desulfurization, an oil phase separated by the high-pressure separator enters a low-pressure separator, an oil phase separated by the low-pressure separator enters a rectifying tower, and the oil phase is separated to obtain the biodiesel with the cetane number and the low condensation point.
8. The one-step process for producing biodiesel with high cetane number and low condensation point according to claim 7, wherein the hydrogen saturation reaction conditions in S1 are as follows: the first bed layer of the first hydrogenation reactor is filled with a large-aperture protective agent, the second bed layer is filled with a nickel-molybdenum catalyst with an acid center, the mass ratio of the catalyst to oil is (800-.
9. The one-step process for producing biodiesel with high cetane number and low condensation point according to claim 7, wherein the hydrodeoxygenation reaction conditions in the S2 are as follows: the first bed layer of the second hydrogenation reactor is filled with a large-aperture protective agent, the second bed layer is filled with a nickel-molybdenum hydrodeoxygenation catalyst, the reaction temperature of the first bed layer is 310-360 ℃, and the reaction temperature of the second bed layer is 330-385 ℃.
10. The one-step process for producing biodiesel with high cetane number and low condensation point according to claim 7, wherein the hydroisomerization reaction conditions in S2 are as follows: the first bed layer of the third hydrogenation reactor is filled with a nickel-molybdenum metal molecular sieve catalyst, the second bed layer is filled with a nickel-molybdenum hydrofining catalyst, and the reaction temperature is 360-380 ℃.
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| CN115595171A (en) * | 2022-10-27 | 2023-01-13 | 江西尊创新能源有限公司（Cn） | Hydrogenation device and process for producing biodiesel with high cetane number and low condensation point by one-step method |
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| CN103102897A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrogenation method for production of low-condensation point motor fuel from biolipid |
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| CN103102897A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrogenation method for production of low-condensation point motor fuel from biolipid |
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| CN115595171A (en) * | 2022-10-27 | 2023-01-13 | 江西尊创新能源有限公司（Cn） | Hydrogenation device and process for producing biodiesel with high cetane number and low condensation point by one-step method |
| CN115595171B (en) * | 2022-10-27 | 2024-04-05 | 江西尊创新能源有限公司 | Hydrogenation device and process for producing biodiesel with high cetane number and low condensation point by one-step method |
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