CN108315050B - Method for producing liquid hydrocarbon by using biological material, liquid hydrocarbon and aviation fuel - Google Patents
Method for producing liquid hydrocarbon by using biological material, liquid hydrocarbon and aviation fuel Download PDFInfo
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- CN108315050B CN108315050B CN201710037268.6A CN201710037268A CN108315050B CN 108315050 B CN108315050 B CN 108315050B CN 201710037268 A CN201710037268 A CN 201710037268A CN 108315050 B CN108315050 B CN 108315050B
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- liquid hydrocarbon
- boiling point
- liquid
- oil
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 231
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- 238000000034 method Methods 0.000 claims abstract description 41
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 4
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 4
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- 230000000052 comparative effect Effects 0.000 description 4
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- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 3
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Images
Classifications
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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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- 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
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
- C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
- C10G2300/1007—Used oils
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
- C10G2300/1018—Biomass of animal origin
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2270/00—Specifically adapted fuels
- C10L2270/04—Specifically adapted fuels for turbines, planes, power generation
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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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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Abstract
A method of producing liquid hydrocarbons using a biological material, liquid hydrocarbons and aviation fuel, the method comprising: a reaction step, namely, carrying out hydrogenation saturation reaction, deoxidation reaction, alkane isomerization reaction and cracking reaction on feed and hydrogen on a catalyst in a reactor to generate a liquid hydrocarbon component, a gas component and water; a separation step of separating the liquid hydrocarbon component from the gas component and water; a distillation step of distilling the liquid hydrocarbon component from the separation step and collecting the liquid hydrocarbon component having a boiling point of 130-290 ℃; a recycling step of recycling the liquid hydrocarbon component from the separation step or the liquid hydrocarbon component having a boiling point higher than 290 ℃ from the distillation step and adding it to the fresh feed; wherein the catalyst is a supported catalyst of a ten-membered ring one-dimensional channel molecular sieve loaded with VIII group metals. The method of the invention reduces the reaction heat release and reduces the influence of the reaction heat effect on the catalyst by diluting the feeding material in the circulating step.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a method for producing liquid hydrocarbon by using biological materials, the liquid hydrocarbon and aviation fuel.
Background
Aviation fuel is a national strategic resource and material, and has extremely important social and economic utilization values in the civil and military fields. The aviation fuel mainly comprises aviation gasoline, aviation diesel oil, aviation kerosene and the like. The aviation kerosene is one of the main kerosene varieties of three major finished products, and currently accounts for about 95% of the kerosene output. Aviation kerosene is of many types and generally consists of hydrocarbon compounds with carbon chain lengths between 9 and 16, such as linear alkanes, aromatics and cycloalkanes, with boiling points between 130 ℃ and 290 ℃.
Currently, aviation fuels are produced mainly from petroleum, which is derived from straight run fractions of petroleum and products from hydrocracking and hydrofinishing. In addition, the synthesis gas prepared by coal gasification can be used as raw material to produce aviation kerosene. However, with the decrease in the amount of disposable energy such as petroleum and coal, the prices of crude oil and coal have increased in recent years, and the prices of aviation fuels have also increased. Meanwhile, because petroleum and coal both contain elements such as nitrogen and sulfur, toxic gases harmful to the environment are inevitably generated in the processes of conversion and use of products thereof. Based on this, some countries have developed relevant restrictive policies for the utilization of fossil energy products. The above factors have prompted researchers to seek new energy sources that can replace fossil energy sources. There are many renewable biomaterials containing carbon in nature. The grease substances contained in the biological materials can be converted into aviation fuels through reactions such as hydrogenation, deoxidation and the like. Carbon dioxide generated in the process can be consumed through photosynthesis of plants, and hardly influences the environment. From this point of view, the development of production technologies for producing aviation fuels using biomaterials is of great importance to protect the environment and to meet energy requirements.
In addition, the oil hydroconversion process belongs to a strong exothermic reaction. Taking soybean oil as an example, the results of thermodynamic analysis of the reactions involved in the process of producing isoparaffin from soybean oil show that the total enthalpy change of the process is as follows: 1562kJ/mol (hydrodeoxygenation mode), -1150kJ/mol (hydrodecarbonylation mode) and-1247 kJ/mol (hydrodedecarboxylation mode). If the heat can not be taken away in time in the reaction process, the active metal component of the catalyst can be sintered, and the service life of the catalyst is greatly reduced.
At present, the process for preparing aviation fuel by taking biological materials as raw materials is mainly realized by a two-step method, wherein the first step of the two-step method is hydrogenation saturation reaction and deoxidation reaction of the raw materials; the second step is that the separated and purified normal paraffin is subjected to isomerization reaction or cracking reaction to generate isoparaffin and short-chain branched paraffin.
For example, the fatty acid carbon chain of the animal and vegetable oil has about 12 to 24 carbon atoms (16 and 18 carbon chains are more), the normal paraffin, water and other byproducts can be generated through hydrogenation saturation reaction and deoxidation reaction, and the separated and purified long-chain normal paraffin can be further subjected to isomerization and cracking reaction to generate isoparaffin with 9 to 16 carbon atoms, and the isoparaffin can be used as aviation kerosene.
US2009229172a1 discloses a process for the final production of isoparaffins (diesel and aviation kerosene fractions) from fats and oils as feedstock by conversion in two separate reaction zones, hydrodeoxygenation and hydroisomerization, and by recycling a portion of the first and second reaction zone products to the two reaction zones, respectively;
CN103897718A discloses a method for producing diesel oil and aviation kerosene fraction by using oil as raw material, converting the oil through two separate reaction stages of hydrogenation-deoxidation and isomerization-cracking, and recycling the diesel oil product of the second reaction stage (isomerization-cracking) to the second reaction stage;
EP2141217a1 discloses a process for the final production of isoparaffins from fats and oils as feedstock, by conversion in two separate reaction stages, hydrodeoxygenation and hydroisomerization, by recycling the products of the second reaction stage (hydroisomerization) (fractions at temperatures greater than 200 ℃) to the second reaction stage;
US2009158637a1 discloses a process for converting fats and oils as feedstock through three separate reaction stages of hydro-deoxygenation, isomerisation and selective cracking, and by recycling the products of the first reaction stage (hydro-deoxygenation) to the first reaction stage, the final hydrocarbon product.
The processes disclosed in the above patents are both two-step hydrogenation processes, i.e., the hydrodeoxygenation of the oil and the hydroisomerization of the intermediate linear paraffin are carried out in two steps.
In the two-step hydrogenation method disclosed in the above patent, the first-step grease hydrodeoxygenation catalyst is generally an alumina or silica-supported cobalt, nickel, molybdenum, tungsten catalyst, and when in use, it needs to be pre-sulfurized, i.e., sulfur-containing substances such as hydrogen sulfide need to be introduced into the reaction system in the first step to convert cobalt, nickel, molybdenum, tungsten in oxidation state into cobalt, nickel, molybdenum, tungsten in vulcanization state. The presulfurized alumina or silica supported cobalt, nickel, molybdenum and tungsten catalyst has good hydrodeoxygenation performance, but because sulfide is introduced into the reaction system, the catalyst has a poisoning effect on the hydroisomerization catalyst (a noble metal catalyst supported by a molecular sieve) in the second step, so that the catalyst is quickly deactivated in the using process. Therefore, the two-step process must be conducted with multiple product separations to remove the sulfur-containing components from the first reaction step and two hydrogen systems to ensure that the second reaction step is performed stably. Because the two steps are respectively carried out on different reactors and/or different catalysts, the whole process needs a plurality of reactors and a plurality of operation procedures, the process is complex, the hydrogen consumption and the energy consumption are high, and the investment on production equipment is large.
Accordingly, there is a pressing need in the art to develop a process for producing aviation fuel that is efficient and environmentally friendly.
Disclosure of Invention
The invention aims to provide a method for producing liquid hydrocarbon by using biological materials, the liquid hydrocarbon and aviation fuel.
To achieve the above object, the present invention provides a method for producing liquid hydrocarbons using a biomaterial, comprising the steps of:
a reaction step, namely simultaneously carrying out hydrogenation saturation reaction, deoxidation reaction, alkane isomerization reaction and cracking reaction on a feed containing grease from a biological material and hydrogen on a catalyst in a reactor to generate a reaction product, wherein the reaction product contains a liquid hydrocarbon component mainly containing branched alkane, a gas component and water;
a separation step of separating the liquid hydrocarbon component from the gas component and water;
a distillation step of distilling at least a portion of the liquid hydrocarbon component from the separation step and collecting the liquid hydrocarbon component having a boiling point between 130 ℃ and 290 ℃; and
a recycling step of recycling at least a part of the liquid hydrocarbon components from the separation step or at least a part of the liquid hydrocarbon components from the distillation step having a boiling point above 290 ℃ and adding at least a part of the liquid hydrocarbon components from the separation step or at least a part of the liquid hydrocarbon components from the distillation step having a boiling point above 290 ℃ to a fresh feed for the reaction step;
wherein, the catalyst used in the reaction step is a supported catalyst of a ten-membered ring one-dimensional channel molecular sieve supported VIII group metal.
Further, the volume ratio of at least a portion of the liquid hydrocarbon components recycled from the separation step or at least a portion of the liquid hydrocarbon components recycled from the distillation step having a boiling point above 290 ℃ to fresh feed is from 1:2 to 10: 1.
Further, the volume ratio of at least a portion of the liquid hydrocarbon components recycled from the separation step or at least a portion of the liquid hydrocarbon components recycled from the distillation step having a boiling point above 290 ℃ to fresh feed is from 1:2 to 5: 1.
Further, the volume ratio of at least a portion of the liquid hydrocarbon components recycled from the separation step or at least a portion of the liquid hydrocarbon components recycled from the distillation step having a boiling point above 290 ℃ to fresh feed is from 2:1 to 5: 1.
Furthermore, the ten-membered ring one-dimensional pore channel molecular sieve in the catalyst is one or more of SAPO-11, SAPO-41, MeAPO-11, MeAPO-41, ZSM-22, ZSM-23 and ZSM-48.
Furthermore, the pore volume of the pores in the ten-membered ring one-dimensional channel molecular sieve is 0.1-0.6mL/g, and the acid amount is 1.5-2.5mmol (NH)3)/g。
Further, the VIII group metal is one or more of Pt, Pd, Ir, Ni and Co.
Further, the grease from the biological material comprises one or more of vegetable oil, animal fat and kitchen waste oil.
Further, the reaction temperature in the reaction step is 250-450 ℃, the reaction pressure is 1-10MPa, and the liquid space velocity is 0.1-5h-1The volume ratio between hydrogen and feed is from 300:1 to 5000:1 NL/NL.
Further, the distillation step collects liquid hydrocarbon components having boiling points between 130 ℃ and 290 ℃ in a yield of more than 50 wt%.
Further, the reactor is a fixed bed reactor.
In order to achieve the above object, the present invention also provides a liquid hydrocarbon prepared by the above method, wherein the isoparaffin selectivity in the liquid hydrocarbon is higher than 60 wt%, and the freezing point of the liquid hydrocarbon is not more than-40 ℃.
To achieve the above object, the present invention also provides an aviation fuel comprising the above liquid hydrocarbon.
The invention has the beneficial effects that:
1. a new method for preparing aviation fuel from grease is provided;
2. compared with the prior art, the method provided by the invention can realize oil hydrogenation saturation, hydrodeoxygenation and alkane hydroisomerization/cracking in one-step reaction, so that the device investment can be saved and the energy consumption can be reduced;
3. compared with the prior art, the method provided by the invention can relieve the heat release of grease hydrogenation, improve the stability of the catalyst and stably produce high-quality biological aviation kerosene.
Drawings
FIG. 1 is a flow chart of an apparatus for producing liquid hydrocarbons using a biomaterial according to the present invention.
FIG. 2 is a flow chart of another apparatus for producing liquid hydrocarbons using a biomaterial according to the present invention.
FIG. 3 is a flow chart of still another apparatus for producing liquid hydrocarbons using a biomaterial according to the present invention.
FIG. 4 is a gas chromatography-mass spectrum of aviation kerosene in example 2.
Wherein, the reference numbers:
a reactor
B separator
First distiller
D second distiller
E gas separator
Detailed Description
The following examples are given for the purpose of further illustrating the present invention, but the present invention is not limited to the examples.
From the analysis of the characteristics of the two-step reaction of grease hydrodeoxygenation and the hydroisomerization/cracking of the intermediate product straight-chain alkane to finally generate branched-chain alkane, the first-step reaction requires a catalyst with high hydrogenation activity, so that double bonds in grease are saturated, and oxygen in an ester group is removed; the second step reaction needs a catalyst with good hydrogenation-dehydrogenation activity and more acid sites, so that the straight-chain alkane can undergo dehydrogenation-protonation-carbocation transfer-isomerization/cracking-hydrogenation series reaction to generate the final product branched-chain alkane. According to the characteristics of the two-step reaction, the molecular sieve carrier with a specific framework acid site is developed to load metals such as platinum, palladium and the like, so that the electron-donating capability of the loaded metals can be changed, and the loaded metals have good hydrogenation-dehydrogenation activity; by a specific metal loading means, the metal loading capacity and the existing form of the metal loading capacity on the carrier are further adjusted, so that the hydrogenation performance and stability of the metal loading capacity can be further improved, and the grease is efficiently hydrodeoxygenated; meanwhile, the linear paraffin can be efficiently converted into branched paraffin by utilizing the framework acid position and the pore canal confinement effect of the molecular sieve, so that the catalyst can obtain one-step hydrogenation, isomerization and cracking performances. The grease hydrogenation process based on the catalyst can realize the one-step hydrogenation of grease to prepare branched alkane, thereby solving the problems of high energy consumption, large investment and the like of the existing two-step hydrogenation method.
A method for producing liquid hydrocarbons using biological material, comprising the steps of:
a reaction step, namely simultaneously carrying out hydrogenation saturation reaction, deoxidation reaction, alkane isomerization reaction and cracking reaction on a feed containing grease from a biological material and hydrogen on a catalyst in a reactor to generate a reaction product, wherein the reaction product contains a liquid hydrocarbon component mainly containing branched alkane, a gas component and water;
a separation step of separating the liquid hydrocarbon component from the gas component and water;
a distillation step of distilling at least a portion of the liquid hydrocarbon component from the separation step and collecting the liquid hydrocarbon component having a boiling point between 130 ℃ and 290 ℃; and
a recycling step of recycling at least a part of the liquid hydrocarbon components from the separation step or at least a part of the liquid hydrocarbon components from the distillation step having a boiling point above 290 ℃ and adding at least a part of the liquid hydrocarbon components from the separation step or at least a part of the liquid hydrocarbon components from the distillation step having a boiling point above 290 ℃ to a fresh feed for the reaction step;
wherein, the catalyst used in the reaction step is a supported catalyst of a ten-membered ring one-dimensional channel molecular sieve supported VIII group metal.
Further, the volume ratio of at least a portion of the liquid hydrocarbon components recycled from the separation step or at least a portion of the liquid hydrocarbon components recycled from the distillation step having a boiling point above 290 ℃ to fresh feed is from 1:2 to 10: 1.
Further, the volume ratio of at least a portion of the liquid hydrocarbon components recycled from the separation step or at least a portion of the liquid hydrocarbon components recycled from the distillation step having a boiling point above 290 ℃ to fresh feed is from 1:2 to 5: 1.
Further, the volume ratio of at least a portion of the liquid hydrocarbon components recycled from the separation step or at least a portion of the liquid hydrocarbon components recycled from the distillation step having a boiling point above 290 ℃ to fresh feed is from 2:1 to 5: 1.
Furthermore, the ten-membered ring one-dimensional pore channel molecular sieve in the catalyst is one or more of SAPO-11, SAPO-41, MeAPO-11, MeAPO-41, ZSM-22, ZSM-23 and ZSM-48.
Furthermore, the pore volume of the pores in the ten-membered ring one-dimensional channel molecular sieve is 0.1-0.6mL/g, and the acid amount is 1.5-2.5mmol (NH)3)/g。
Further, the VIII group metal is one or more of Pt, Pd, Ir, Ni and Co.
Further, the grease from the biological material comprises one or more of vegetable oil, animal fat and kitchen waste oil.
Further, the reaction temperature in the reaction step is 250-450 ℃, the reaction pressure is 1-10MPa, and the liquid space velocity is 0.1-5h-1The volume ratio between hydrogen and feed is from 300:1 to 5000:1 NL/NL.
Further, the distillation step collects liquid hydrocarbon components having boiling points between 130 ℃ and 290 ℃ in a yield of more than 50 wt%.
Further, the reactor is a fixed bed reactor.
The invention also provides a liquid hydrocarbon prepared by the method, wherein the selectivity of isoparaffin in the liquid hydrocarbon is higher than 60 wt%, and the freezing point of the liquid hydrocarbon is not more than-40 ℃.
The invention also provides an aviation fuel comprising the above liquid hydrocarbon.
The term "biological material" as used in the present invention includes any material derived from animals, plants or microorganisms or obtainable from animals, plants or microorganisms. Biological materials include, but are not limited to: i) plant products such as grasses, wood, crops, seeds (e.g., canola, peanut, soybean, corn, safflower seed, palm fruit, jatropha, castor, olive), and any material derived or obtainable from plant products; ii) animal products, such as pigs, cattle, sheep, chickens, fish, and any material derived or obtainable from animal products; iii) microbial products, such as bacteria, actinomycetes, fungi, viruses, protozoa, algae, and any material derived or obtainable from microbial products. The biomaterial may also include: i) biological waste products, including agricultural wastes (such as coconut shells, rice hulls, corn stalks, corn cobs and the like), or poultry derived wastes (such as animal wastes and the like), or byproducts obtained after industrial production and processing of biological materials, and the like; ii) food waste, including food processing waste water or restaurant waste, and the like.
The term "grease" as used herein is a generic term for oils and fats, including any oils and fatty substances. The grease may be solid or liquid at room temperature. In some embodiments, the fat from biological material comprises vegetable oil, animal fat, waste kitchen oil, and mixtures of any one or more of the foregoing. In some embodiments, the vegetable oil comprises canola oil, peanut oil, soybean oil, corn oil, rice bran oil, safflower oil, palm oil, jatropha oil, castor oil, coconut oil, olive oil, and mixtures of any one or more of the foregoing. In some embodiments, the animal fat includes lard, tallow, mutton fat, chicken fat, fish oil, whale oil, and mixtures of any one or more of the foregoing. In some embodiments, the oil from a biological material comprises by-product free fatty acids of vegetable oil refining.
The feed used in the process for producing liquid hydrocarbons according to the present invention may comprise fresh feed and/or recycled feed. The fresh feed is obtained by directly taking grease from biological materials as a feed, and simultaneously carrying out hydrogenation saturation reaction, deoxidation reaction, alkane isomerization reaction and cracking reaction on the grease and hydrogen in a reactor and on a catalyst to generate a reaction product, wherein the reaction product contains liquid hydrocarbon, gas, water and other components which mainly contain branched alkane.
The circulating feeding is to input at least a part of liquid hydrocarbon in the reaction product into a reaction system for use, mix the liquid hydrocarbon with grease from biological materials as a feeding material, and simultaneously perform hydrogenation saturation reaction, deoxidation reaction, alkane isomerization reaction and cracking reaction with hydrogen on a catalyst in a reactor to generate a reaction product, wherein the reaction product comprises components such as liquid hydrocarbon mainly containing branched alkane, gas and water. In some embodiments, at least a portion of the reused liquid hydrocarbon component is from the reaction products after gas-liquid separation. In some embodiments, at least a portion of the reused liquid hydrocarbon component is from the reaction product after the distillation step. In some embodiments, at least a portion of the liquid hydrocarbon component that is reused comes from the liquid hydrocarbon component produced in the distillation step that has a boiling point above 130 ℃. In some embodiments, at least a portion of the liquid hydrocarbon component that is reused comes from the liquid hydrocarbon component produced in the distillation step that has a boiling point between 130 ℃ and 290 ℃. In some embodiments, at least a portion of the reused liquid hydrocarbon component is from the liquid hydrocarbon component produced in the distillation step having a boiling point greater than 290 ℃.
The term "hydrocarbon" as used herein refers to organic compounds consisting essentially of hydrogen and carbon atoms, including, but not limited to, saturated alkanes, unsaturated alkanes (e.g., alkenes, alkynes), straight-chain hydrocarbons, branched hydrocarbons, cyclic alkanes, aromatic hydrocarbons, and mixtures thereof. In some embodiments, "hydrocarbons" as described herein may also include heteroatoms other than hydrogen and carbon atoms, such as oxygen, nitrogen, and phosphorus atoms. In some embodiments, the product contains less than 10%, or less than 8%, or less than 5%, or less than 3%, or less than 1% heteroatoms in mass ratio, in addition to hydrogen and carbon atoms. In some embodiments, the distillation step of the present invention collects liquid hydrocarbon components having boiling points between 130 ℃ and 290 ℃ that are entirely composed of hydrogen atoms and carbon atoms.
The term "liquid hydrocarbon" as used herein refers to hydrocarbons that are liquid under the reaction or separation conditions described herein. In some embodiments, the liquid hydrocarbons of the present invention comprise a mixture of one or more hydrocarbons having a number of carbon atoms in the range of from 4 to 70, such as a number of carbon atoms in the range of from 5 to 12, or 9 to 16, or 9 to 18, or 10 to 18, or 11 to 24, or 12 to 24, or 20 to 50, or 20 to 70. In some embodiments, the liquid hydrocarbon of the present invention has a boiling point between 40-600 ℃, for example, a boiling point between 40-205 ℃, or between 60-100 ℃, or between 130-290 ℃, or between 130-450 ℃, or between 150-290 ℃, or between 135-240 ℃, or between 150-280 ℃, or between 200-250 ℃, or between 290-450 ℃, or between 150-400 ℃, or between 150-450 ℃, or between 175-325 ℃, or between 250-350 ℃, or between 300-370 ℃, or between 370-600 ℃. In some embodiments, the boiling point of the liquid hydrocarbon of the present invention refers to the boiling point under atmospheric conditions.
In some embodiments, the gaseous components in the reaction product of the present invention include unreacted hydrogen and gaseous hydrocarbons having less than 5 carbon atoms.
In some embodiments, the liquid hydrocarbon component, the gas component, and the water in the reaction product of the present invention are separated into an oil phase, a gas phase, and an aqueous phase, wherein the liquid hydrocarbon component is contained in the oil phase, the gas component is contained in the gas phase, and the water is contained in the aqueous phase. The separation can be carried out using any suitable means known in the art. In some embodiments, the separation is performed using an oil-gas-water three-phase separator.
In some embodiments, at least a portion of the liquid hydrocarbon component obtained by the above separation of the present invention is further distilled to obtain a liquid hydrocarbon component having a boiling point within a certain range, such as a boiling point above 130 ℃, or a boiling point between 130-290 ℃, or a boiling point between 150-290 ℃, or a boiling point between 135-240 ℃, or a boiling point between 150-280 ℃, or a boiling point between 200-290 ℃, or a boiling point between 200-250 ℃, or a boiling point between 150-450 ℃, or a boiling point between 290-450 ℃. Suitable distillation conditions may be selected depending on the different boiling points and properties of the liquid hydrocarbon product desired. The distillation method used in the method of the present invention may include atmospheric distillation or vacuum distillation. In some embodiments, the distillation process is distillation under atmospheric conditions. In some embodiments, the distillation process is a reduced pressure distillation conducted at sub-atmospheric conditions, such as from 100Pa to 100kPa or from 1kPa to 10 kPa.
In some embodiments, the distillation step of the present invention may be carried out in two steps at different temperatures to obtain fractions of different boiling points. For example, a liquid hydrocarbon component boiling above 130 ℃ is separated from a liquid hydrocarbon component boiling below 130 ℃ in a first distillation step; in the second distillation step a liquid hydrocarbon component having a boiling point between 130-290 ℃ is obtained. In some embodiments, the distillation step of the present invention may further distill to obtain a liquid hydrocarbon component having a boiling point above 290 ℃.
In some embodiments, the distillation is performed using a cut-off distillation apparatus to separate components of different boiling points in the liquid hydrocarbon. In some embodiments, in the distillation step of the present invention, at least a portion of the liquid hydrocarbon component is distilled to collect the liquid hydrocarbon component having a boiling point of 130-290 ℃. In some embodiments, at least a portion of the liquid hydrocarbon components obtained by the above separation or at least a portion of the liquid hydrocarbon components obtained by the above distillation of the present invention are recycled to the reaction system and mixed with fresh feed to participate in the reaction as feed. In some embodiments, in the recycling step of the present invention, at least a portion of the liquid hydrocarbon component that is recycled is from the separating step. In some embodiments, in the recycling step of the present invention, at least a portion of the liquid hydrocarbon component that is recycled is from the distillation step. In some embodiments, in the recycling step of the present invention, at least a portion of the liquid hydrocarbon component that is recycled is from the liquid hydrocarbon component produced in the distillation step that has a boiling point above 130 ℃. In some embodiments, in the recycling step of the present invention, at least a portion of the liquid hydrocarbon component that is recycled is derived from the liquid hydrocarbon component produced in the distillation step that has a boiling point in the range of 130 ℃ to 290 ℃. In some embodiments, in the recycling step of the present invention, at least a portion of the liquid hydrocarbon component that is recycled is from the liquid hydrocarbon component produced in the distillation step that has a boiling point above 290 ℃. In some embodiments, in the recycling step of the present invention, the liquid hydrocarbon component that is recycled is derived in part from the separation step and in part from the distillation step.
In some embodiments, the volume ratio of the recycled liquid hydrocarbon component to the fresh feed of the present invention is from 1:2 to 10:1, or from 1:2 to 5:1, or from 2:1 to 5: 1. In some embodiments, the liquid hydrocarbon component is mixed and fed with fresh feed in real time (e.g., the recycled liquid hydrocarbon component flows into the reactor simultaneously with the fresh feed at a certain flow rate ratio) or at certain time intervals (e.g., the liquid hydrocarbon product is stored and mixed with fresh feed after a given interval and then fed; and so on).
In some embodiments, the reaction of the fresh feed, excluding any recycled material, with hydrogen is performed first, and the fresh feed is used after a given time interval to mix with the recycled liquid hydrocarbon component. In some embodiments, the circulation is initiated after the fresh fats and oils are reacted with hydrogen for 1 to 30 hours, or 1 to 25 hours, or 1 to 20 hours, or 1 to 16 hours, or 1 to 10 hours, or 1 to 5 hours, or 5 to 30 hours, or 5 to 25 hours, or 5 to 20 hours, or 5 to 16 hours, or 5 to 10 hours, or 10 to 30 hours, or 10 to 25 hours, or 10 to 20 hours, or 10 to 16 hours. In some embodiments, the reaction is carried out for every 1 to 30 hours, or 1 to 25 hours, or 1 to 20 hours, or 1 to 16 hours, or 1 to 10 hours, or 1 to 5 hours, or 5 to 30 hours, or 5 to 25 hours, or 5 to 20 hours, or 5 to 16 hours, or 5 to 10 hours, or 10 to 30 hours, or 10 to 25 hours, or 10 to 20 hours, or 10 to 16 hours, and the feeds are compounded again in proportion. In some embodiments, the ratio of the recycled material to the fresh feed is regulated by adjusting the flow ratio between the two. In some embodiments, the ratio of the recycled material to the fresh feed is regulated by adjusting the mixing volume ratio between the two.
In some embodiments, the reaction between the feed and the hydrogen comprises a hydrosaturation reaction, a deoxygenation reaction, a paraffin isomerization reaction, and a cracking reaction. The hydrogenation saturation reaction in the invention refers to an addition reaction of carbon-carbon unsaturated bonds in the feed and hydrogen. The deoxidation reaction referred to in the present invention means a reaction in which an oxygen atom is removed by reacting an oxygen-containing compound with hydrogen. In some embodiments, an exemplary reaction equation for the deoxygenation reaction of the present invention is as follows:
the alkane isomerization reaction in the invention refers to the reaction of isomerizing straight-chain alkane into branched-chain alkane. The cracking reaction in the present invention refers to a reaction of converting long-chain alkane into short-chain alkane by breaking.
The hydrosaturation reaction, the deoxidation reaction, the alkane isomerization reaction and the cracking reaction are carried out in the same reactor on one catalyst. In order for the catalyst to have this function, the catalyst in the present invention comprises a specific metal component and a specific support component. The metal component may be any metal species capable of catalyzing the aforementioned hydrosaturation, deoxygenation, alkane isomerization, and cracking reactions. In some embodiments, the metal component of the catalyst is selected from one or more of nickel (Ni), cobalt (Co), platinum (Pt), palladium (Pd), and iridium (Ir), which may be present in the form of metal ions, metal oxides, or other suitable forms. In some embodiments, the metal component of the catalyst comprises at least one noble metal. The noble metals include, but are not limited to, platinum (Pt), palladium (Pd), iridium (Ir).
The carrier component is ten-membered ring one-dimensional channel molecular sieve, including silicon-aluminum molecular sieve, silicon-aluminum phosphate molecular sieve and metal-aluminum phosphate molecular sieve with ten-membered ring one-dimensional channel. The silicoaluminophosphate molecular sieve with the ten-membered ring one-dimensional channel is selected from one or more of ZSM-22, ZSM-23 and ZSM-48; the silicoaluminophosphate molecular sieve with the ten-membered ring one-dimensional channel is selected from SAPO-11 and/or SAPO-41; the metalloaluminophosphate molecular sieve with the ten-membered ring one-dimensional channel is selected from MeAPO-11 and/or MeAPO-41.
In order to achieve the performance of simultaneously performing catalytic hydrogenation saturation reaction, deoxidation reaction, alkane isomerization reaction and cracking reaction, the carrier ten-membered ring one-dimensional channel molecular sieve also needs to have at least the following characteristics: the ten-membered ring one-dimensional channel molecular sieve has a pore volume of 0.1-0.6mL/g and an acid amount of 1.5-2.5mmol (NH)3)/g。
In some embodiments, a catalyst having one or more metal components is used to catalyze the reaction between the feed and hydrogen. In some embodiments, only a catalyst having a single metal component is used to catalyze the reaction between the feed and hydrogen. In some embodiments, a catalyst having a single metal component is used to catalyze the hydrosaturation reaction, deoxygenation reaction, alkane isomerization reaction, and cleavage reaction. In some embodiments, the catalyst of the present invention may catalyze the hydrosaturation reaction, the deoxygenation reaction, the paraffin isomerization reaction, and the cracking reaction simultaneously in the same reactor.
The reactor used in the process of the invention may comprise any reactor known to those skilled in the art to be suitable for the reaction of the invention. In some embodiments, the reactor of the present invention is a fixed bed reactor, which refers to a device in which a fluid is reacted through a bed of immobilized solid catalyst.
In some embodiments, the reaction of the invention is performed at a temperature of 250-450 ℃, or 250-400 ℃, or 400-450 ℃, or 300-400 ℃, or 300-350 ℃, or 350-380 ℃, or 380-400 ℃, or 350-365 ℃, or 365-400 ℃. In some embodiments, the reaction of the present invention is carried out under pressure conditions of 1 to 10MPa, or 2 to 8MPa, or 3 to 7MPa, or 4 to 6MPa, or 6 to 7MPa, or 5.5 to 6.5 MPa. In some embodiments, the reaction temperature and reaction pressure are maintained constant during the course of conducting the reaction between the feed and hydrogen.
In some embodiments, the feed is added during the reaction step of the present invention at a liquid space velocity (LHSV). The liquid space velocity (LHSV) described in the present invention can be calculated by the following formula:
in some embodiments, the liquid space velocity (LHSV) of the feed added during the reacting step is from 0.1 to 5 hours-1Or 0.2 to 2h-1Or 0.3 to 1h-1Or 1-2h-1Or 0.5-1.5h-1。
The term "NL" as used in the present invention is an indicator liter, i.e. the number of volumes in liters in the standard state (0 ℃, standard atmospheric pressure), which can be calculated by the following formula:
wherein
Vn — normal state volume (NL);
va — actual volume (L);
pn is 1.01325x10 in standard atmospheric pressure (Pa)5Pa；
Pa — actual pressure (Pa);
tn-standard state temperature (K) -273.15K;
ta — actual temperature (K);
in converting the volume to the standard state, the pressure should be absolute pressure and the temperature should be absolute temperature, i.e. 0 ℃ in the standard state should be calculated at 273.15K. In some embodiments of the invention, the volume ratio between the hydrogen gas and the feed (hydrogen-to-oil ratio) is a volume ratio of the two converted to liters at standard conditions. In some embodiments, in the reaction step of the invention, the volume ratio between the hydrogen and the feed is 300:1 to 5000:1NL/NL, or 300:1 to 3000:1NL/NL, or 400:1 to 4000:1NL/NL, or 500:1 to 5000:1NL/NL, or 3000:1 to 5000:1NL/NL, or 2700:1 to 3000:1 NL/NL.
The term distillation step as used in the present invention collects the yield (X) of liquid hydrocarbon component AA) And isoparaffin selectivity (S) in the liquid hydrocarbon component collected in the distillation stepM) And n-alkane selectivity (S)N) Can be calculated by the following formula:
in the above formula, "A" means the liquid hydrocarbon component collected in the distillation step, "M" means isoparaffin in the liquid hydrocarbon component A collected in the distillation step, and "N" means normal paraffin in the liquid hydrocarbon component A collected in the distillation step. The isoparaffin selectivity (S) in the liquid hydrocarbon component collected in the distillation step may be measured directly or calculated from measurements using any suitable means known in the artM) And n-alkane selectivity (S)N). In some embodiments, the isoparaffin selectivity in the liquid hydrocarbon component collected in the distillation step is calculated by gas chromatography-mass spectrometry (GS-MS) method measurements.
In some embodiments, the distillation step of the present invention collects a yield of liquid hydrocarbon components greater than 50 wt%, or greater than 55 wt%, or greater than 58 wt%, or greater than 60 wt%, or greater than 65 wt%, or greater than 70 wt%, or greater than 75 wt%. In some embodiments, the catalyst is left to react for at least 20 hours, or at least 100 hours, or at least 200 hours, or at least 400 hours before the liquid hydrocarbon components collected in the distillation step described herein still achieve a yield of greater than 50 wt%, or greater than 55 wt%, or greater than 58 wt%, or greater than 60 wt%, or greater than 65 wt%, or greater than 70 wt%, or greater than 75 wt%.
In some embodiments, the isoparaffin selectivity in the liquid hydrocarbon component collected in the distillation step of the present invention is greater than 55 wt%, or greater than 60 wt%, or greater than 65 wt%, or greater than 70 wt%, or greater than 75 wt%, or greater than 80 wt%, or greater than 85 wt%, or greater than 90 wt%. In some embodiments, the catalyst is allowed to react for at least 20 hours, or at least 100 hours, or at least 200 hours, or at least 400 hours before the liquid hydrocarbon components collected in the distillation step of the present invention still achieve isoparaffin selectivity greater than 55 wt%, or greater than 60 wt%, or greater than 65 wt%, or greater than 70 wt%, or greater than 75 wt%, or greater than 80 wt%, or greater than 85 wt%, or greater than 90 wt%.
The term "freezing point" as used herein refers to the lowest temperature at which liquid hydrocarbon is cooled to a temperature at which crystallization occurs and then warmed to remove the crystals that were formed under specified conditions. In some embodiments, the freezing point of the present invention refers to the freezing point at atmospheric pressure. In some embodiments, the freezing point of the liquid hydrocarbon component collected in the distillation step of the present invention is no more than or no more than-40 ℃, or no more than-42 ℃, or no more than-45 ℃, or no more than-47 ℃, or no more than-49 ℃, or no more than-55 ℃. In some embodiments, the freezing point of the liquid hydrocarbon component collected in the distillation step of the present invention ranges from-40 ℃ to-60 ℃, or from-55 ℃ to-60 ℃, or from-40 ℃ to-55 ℃, or from-40 ℃ to-42 ℃, or from-40 ℃ to-45 ℃, or from-40 ℃ to-47 ℃. In some embodiments, the catalyst is maintained at a temperature at which the freezing point of the liquid hydrocarbon component collected in the distillation step of the present invention does not exceed 0 ℃, or does not exceed-40 ℃, or does not exceed-42 ℃, or does not exceed-45 ℃, or does not exceed-47 ℃, or does not exceed-49 ℃, or does not exceed-55 ℃ after the reaction is continued for at least 20 hours, or at least 100 hours, or at least 200 hours, or at least 400 hours.
In some embodiments, the process of the present invention may further comprise the step of recovering hydrogen in the separated gas phase. In some embodiments, the recovered hydrogen may continue to participate as a feedstock in the reaction with the feed.
As shown in fig. 1, an exemplary set of equipment for carrying out the process of the present invention comprises five main operating units, reactor a, separator B, first distiller C, second distiller D and gas separator E, wherein each operating unit may consist of one or more equipment and is not limited to a single or single reactor a/separator B/first distiller C/second distiller D/gas separator E. In fig. 1, from left to right, as indicated by the arrows, the reaction mass, comprising feed (fresh feed or a mixture of fresh feed and recycled liquid hydrocarbons) and hydrogen (which may include hydrogen recycled from the reaction off-gas) is fed to reactor a. The reactor a may be a fixed bed reactor loaded with a catalyst. In the reactor A, the grease and hydrogen are subjected to hydrogenation saturation, deoxidation, alkane isomerization and cracking reaction under the action of a catalyst, and the generated reaction product mainly contains liquid hydrocarbon, water, gas and the like. The hydrosaturation, deoxygenation, paraffin isomerization and cracking reactions can be carried out in the same reactor a. Then, the reaction product flows from the reactor a to the separator B, where the gas, liquid hydrocarbon and water are separated into a water phase (at the lower part), an oil phase (at the middle part) and a gas phase (at the upper part), the water phase flowing out from the lower part of the separator B, the oil phase flowing out from the middle part of the separator B, and the gas phase flowing out from the upper part of the separator B. Part of the liquid hydrocarbons is taken from the separated oil phase and recycled back to the initial part of the reaction, mixed with fresh feed as feed to reactor a and the reaction continued. The remaining liquid hydrocarbon is transferred to a first distillation device C for distillation, the fraction with the boiling point of less than 130 ℃ is removed, the fraction with the boiling point of more than 130 ℃ is transferred to a second distillation device D for further distillation, and the liquid hydrocarbon component with the boiling point of 130-290 ℃ and the liquid hydrocarbon component with the boiling point of more than 290 ℃ are separated. In addition, the gas product separated in separator B may flow into gas separator E. In the gas separator E, hydrogen (including the remaining unreacted hydrogen) and gaseous lower hydrocarbons (hydrocarbons C1-C4) in the gas product are separated, and the separated hydrogen can be recycled back to the initial part of the reaction and added into the reactor A to participate in the reaction.
As illustrated in fig. 2, another set of exemplary apparatus for carrying out the process of the present invention comprises five main operating units, reactor a, separator B, first distiller C, second distiller D and gas separator E, wherein each operating unit may consist of one or more apparatus and is not limited to a single or single reactor a/separator B/first distiller C/second distiller D/gas separator E. In fig. 2, from left to right, as indicated by the arrows, the reaction mass, comprising feed (fresh feed or a mixture of fresh feed and recycled liquid hydrocarbons) and hydrogen (which may include hydrogen recycled from the reaction off-gas) is fed to reactor a. The reactor a may be a fixed bed reactor loaded with a catalyst. In the reactor A, the grease and hydrogen are subjected to hydrogenation saturation, deoxidation, alkane isomerization and cracking reaction under the action of a catalyst. The reaction product produced mainly contains liquid hydrocarbon, water, gas, etc. The hydrosaturation, deoxygenation, paraffin isomerization and cracking reactions can be carried out in the same reactor a. Then, the reaction product flows from the reactor a into a separator, where the gas, liquid hydrocarbon and water are separated into a water phase (at the lower part), an oil phase (at the middle part) and a gas phase (at the upper part) in the separator B, the water phase flows out from the lower part of the separator B, the oil phase flows out from the middle part of the separator B, and the gas phase flows out from the upper part of the separator B. And (3) moving the separated liquid hydrocarbon in the oil phase to a first distillation device C for distillation, removing a fraction with a boiling point of less than 130 ℃, and collecting the fraction with a boiling point of more than 130 ℃. Part of the liquid hydrocarbons is taken from the fraction boiling above 130 c and recycled back to the initial part of the reaction, mixed with fresh feed as feed to reactor a and the reaction continued. The rest liquid hydrocarbon with the boiling point of more than 130 ℃ is moved to a second distillation device D for further distillation to separate a liquid hydrocarbon component with the boiling point of 130-290 ℃ and a liquid hydrocarbon component with the boiling point of more than 290 ℃. In addition, the gas product separated by separator B may flow through separator B to gas separator E. In the gas separator E, hydrogen (including the remaining unreacted hydrogen) and gaseous lower hydrocarbons (hydrocarbons C1-4) in the gas product are separated, and the separated hydrogen can be recycled back to the initial part of the reaction and added into the reactor A to participate in the reaction.
As illustrated in fig. 3, another set of exemplary apparatus for carrying out the process of the present invention comprises five main operating units, reactor a, separator B, first distiller C, second distiller D and gas separator E, wherein each operating unit may consist of one or more apparatus and is not limited to a single or single reactor a/separator B/first distiller C/second distiller D/gas separator E. In fig. 3, from left to right, as indicated by the arrows, the reaction mass, comprising feed (fresh feed or a mixture of fresh feed and recycled liquid hydrocarbons) and hydrogen (which may include hydrogen recycled from the reaction off-gas) is fed to reactor a. The reactor a may be a fixed bed reactor loaded with a catalyst. In the reactor A, the grease and hydrogen are subjected to hydrogenation saturation, deoxidation, alkane isomerization and cracking reaction under the action of a catalyst. The reaction product produced mainly contains liquid hydrocarbon, water, gas, etc. The hydrosaturation, deoxygenation, paraffin isomerization, and cracking reactions may be accomplished in the same reactor. Then, the reaction product flows from the reactor a to the separator B, where the gas, liquid hydrocarbon and water are separated into a water phase (at the lower part), an oil phase (at the middle part) and a gas phase (at the upper part), the water phase flowing out from the lower part of the separator B, the oil phase flowing out from the middle part of the separator B, and the gas phase flowing out from the upper part of the separator B. The separated liquid hydrocarbon in the oil phase is moved to a first distillation device C for distillation, a fraction with the boiling point of less than 130 ℃ is removed, a fraction with the boiling point of more than 130 ℃ is moved to a second distillation device D for further distillation, and liquid hydrocarbon components with the boiling point of 130-290 ℃ and liquid hydrocarbon components with the boiling point of more than 290 ℃ are separated. Part or all of the liquid hydrocarbon with the boiling point of more than 290 ℃ is taken and recycled to the initial part of the reaction, and is mixed with fresh feed to enter the reactor A as feed to continue the reaction. In addition, the gas product separated by separator B may flow through separator B to gas separator E. In the gas separator E, hydrogen (including the remaining unreacted hydrogen) and gaseous lower hydrocarbons (hydrocarbons C1-4) in the gas product are separated, and the separated hydrogen can be recycled back to the initial part of the reaction and added into the reactor to participate in the reaction.
Examples
The invention is further described by the following non-limiting examples. It is to be noted that these examples are only for further illustrating the technical features of the present invention, and are not intended to be and should not be construed as limiting the present invention. The examples do not contain a detailed description of conventional methods (chemical synthesis techniques, etc.) well known to those of ordinary skill in the art. Unless otherwise specified, percentages refer to percent by mass, fractions refer to weight fractions, molecular weights refer to average molecular weights, temperatures are in degrees celsius, and pressures are at or near atmospheric.
Comparative example 1: the aviation kerosene is prepared by taking soybean oil as a raw material and respectively carrying out hydrogenation saturation and deoxidation reactions and alkane isomerization and cracking reactions in two reactors by using different catalysts
The first step is as follows: 78.5g of presulfided Ni-Mo/gamma-Al were weighed2O3The catalyst (100mL, particle size of 10-20 mesh), wherein the Ni and Mo loading is 5 wt% respectively, is loaded in a stainless steel fixed bed reactor with an inner diameter of 25mm and a tube length of 1.5m, and the two ends of the reactor are filled with 20-40 mesh quartz sand. Introducing hydrogen into the reactor, and taking soybean oil as a raw material for sample injection. The fatty acid composition of the fatty acid ester contained in the raw material soybean oil (produced by Zhongliang group Co., Ltd., third grade, meeting the national standard GB 1535-2003) is as follows: lauric acid (12:0, wherein 12 represents the number of carbon atoms, and 0 represents the number of carbon-carbon unsaturated double bonds in fatty acid) content of 0.1%, myristic acid (14:0) content of 0.1%, palmitic acid (16:0) content of 10.2%, stearic acid (18:0) content of 3.7%, oleic acid (18:1) content of 22.8%, linoleic acid (18:2) content of 53.7%, linolenic acid (18:3) content of 8.6%, and acid value of 0.2mg KOH.g-1(measured according to ASTM D974). The reaction conditions are as follows: 355 ℃, 4.0MPa, LHSV of 0.5h-1The hydrogen-oil ratio was 1800:1 NL/NL. A sample was taken 10 hours after the first reaction step, and the liquid product was analyzed by Gas Chromatography (GC), gas chromatography-mass spectrometry (GC-MS).
The reaction result is: the conversion rate of soybean oil is 100%, the proportion of water in the liquid-phase product is 13.5 wt%, the proportion of liquid hydrocarbon in the liquid-phase product is 86.5 wt%, the selectivity of isoparaffin in the liquid hydrocarbon is 1.5 wt%, and the selectivity of normal paraffin is 98.5 wt%.
Filtering the liquid phase product to remove residues possibly contained in the liquid phase product, then placing the filtered liquid phase product in a separating funnel, standing for 6 hours, discharging the lower layer product (water), and collecting the remaining upper layer product (liquid hydrocarbons) for later isomerization reaction.
The second step is that: 87.6g of Pt/SAPO-11 catalyst (100mL, particle size 10-20 mesh) was weighed, with a SAPO-11 molecular sieve having a mesopore volume of 0.08mL/g and an acid content of 0.90mmol (NH)3) The Pt supported amount is 0.5 wt%, the Pt supported amount is arranged in a stainless steel fixed bed reactor with the inner diameter of 25mm and the tube length of 1.5m, and both ends of the reactor are filled with 20-40 mesh quartz sand. Introducing hydrogen into the reactor, taking the product alkane in the first step as a raw material for sample injection, and the reaction conditions are as follows: 365 ℃, 4.0MPa and LHSV of 1h-1The hydrogen-oil ratio was 1300:1 NL/NL. After 10 hours of the second reaction, a sample was taken, and the liquid product was analyzed by GC and GC-MS. And separating naphtha (fraction less than 130 ℃), aviation kerosene (130-. And analyzing the freezing point of the aviation kerosene product by adopting an automatic freezing point analyzer.
The reaction result is: the selectivity of the isoparaffin in the product is 54.6 wt%, and the selectivity of the normal paraffin is 45.4 wt%. The yield of naphtha (fraction at less than 130 ℃) is 3.5 wt%, the yield of aviation kerosene (fraction at 130-290 ℃) is 12.5 wt%, and the yield of diesel oil (fraction at 290-450 ℃) is 65.2 wt%. The freezing point of the aviation kerosene is-15 ℃, and the aviation kerosene does not reach the standards of RP-3, RP-4, RP-5 and JetA-1 aviation kerosene. The reaction results are shown in Table 1.
Comparative example 2:
the aviation kerosene is prepared by using soybean oil as a raw material and performing one-step reaction of hydrogenation saturation, deoxidation, alkane isomerization and cracking by using the same catalyst in the same reactor without using a circulating material
89.2g of Pt/SAPO-11 catalyst (100mL, particle size 10-20 mesh) was weighed, with a SAPO-11 molecular sieve having a mesopore volume of 0.30mL/g and an acid amount of 1.80mmol (NH)3) The Pt supported amount is 1 wt%, the Pt supported amount is arranged in a stainless steel fixed bed reactor with the inner diameter of 25mm and the tube length of 1.5m, and two ends of the reactor are filled with 20-40 mesh quartz sand. Introducing hydrogen into the reactor, and adding soybean oil(produced by Zhongliang group Co., Ltd., third grade, which conforms to the GB1535-2003 national standard) as raw material sample introduction. The reaction conditions are as follows: 360 ℃, 4.0MPa and LHSV of 1h-1The hydrogen-oil ratio was 3000:1 NL/NL. Samples were taken after 20 hours, 100 hours and 200 hours of reaction. The liquid phase product was analyzed by GC, GC-MS. And analyzing the freezing point of the aviation kerosene product by adopting an automatic freezing point analyzer.
The reaction result is:
sample sampling at 20 hours: the conversion rate of soybean oil is 100%, the proportion of water in the liquid-phase product is 7.3 wt%, the proportion of liquid hydrocarbon in the liquid-phase product is 92.7 wt%, the selectivity of isoparaffin in the liquid hydrocarbon is 88.2 wt%, and the selectivity of normal paraffin is 11.8 wt%. The yield of naphtha (fraction at less than 130 ℃) is 8.1 wt%, the yield of aviation kerosene (fraction at 130-290 ℃) is 18.4 wt%, and the yield of diesel oil (fraction at 290-450 ℃) is 54.9 wt%. The freezing point of the aviation kerosene is-47 ℃, and reaches the standards of RP-3, RP-4, RP-5 and Jet A-1 aviation kerosene. The reaction results are shown in Table 1.
Sample sampling at 100 hours: the conversion rate of soybean oil is 100%, the proportion of water in the liquid-phase product is 7.5 wt%, the proportion of liquid hydrocarbon in the liquid-phase product is 92.5 wt%, the selectivity of isoparaffin in the liquid hydrocarbon is 73.1 wt%, and the selectivity of normal paraffin is 26.9 wt%. The yield of naphtha (fraction at a temperature of less than 130 ℃) is 7.1 wt%, the yield of aviation kerosene (fraction at a temperature of 130 ℃ and 290 ℃) is 13.5 wt%, and the yield of diesel oil (fraction at a temperature of 290 ℃ and 450 ℃) is 61.1 wt%. The freezing point of the aviation kerosene is-29 ℃, and the aviation kerosene does not reach various aviation kerosene standards. The reaction results are shown in Table 1.
Example 1:
using soybean oil as raw material, making the ratio of circulating material and fresh soybean oil be 5:1, utilizing the same catalyst to make hydrogenation saturation, deoxygenation, alkane isomerization and cracking reaction in the same reactor to prepare aviation kerosene
89.2g of Pt/SAPO-11 catalyst (100mL, particle size 10-20 mesh) was weighed, with a SAPO-11 molecular sieve having a mesopore volume of 0.30mL/g and an acid amount of 1.80mmol (NH)3) The Pt supported amount is 1 wt%, the Pt supported amount is arranged in a stainless steel fixed bed reactor with the inner diameter of 25mm and the tube length of 1.5m, and two ends of the reactor are filled with 20-40 mesh quartz sand. Introducing hydrogen into the reactor, and introducing soybean oil (C)Produced by Zhongliang group Limited, third grade, which conforms to GB1535-2003 national standard) as raw material. The reaction conditions are as follows: 360 ℃, 4.0MPa and LHSV of 1h-1The hydrogen-oil ratio was 3000:1 NL/NL. Samples were taken after 24 hours of reaction. And (3) separating the reaction product by oil, gas and water to obtain a liquid hydrocarbon product. Removing naphtha (fraction less than 130 ℃) in the liquid hydrocarbon product by atmospheric distillation, wherein the liquid hydrocarbon fraction with the boiling point higher than 130 ℃ is separated by further reduced pressure distillation (2kPa) to obtain aviation kerosene (fraction at 290 ℃ C.) and diesel oil (fraction at 450 ℃ C.). Wherein the diesel oil fraction and the soybean oil are mixed according to the volume ratio of 5:1 to prepare a feed, and then the reaction with the hydrogen is continued. The reaction conditions are as follows: 360 ℃, 4.0MPa and LHSV of 1h-1The hydrogen-oil ratio was 3000:1 NL/NL. Sampling after reacting for 16 hours, repeating the steps of separating the product, mixing and feeding materials and continuing to react with the hydrogen. After the reaction was continued for 400 hours, the liquid phase product was analyzed by GC, GC-MS. And analyzing the freezing point of the aviation kerosene product by adopting an automatic freezing point analyzer.
The reaction result is: the conversion rate of soybean oil is 100%, the proportion of water in the liquid-phase product is 7.4 wt%, the proportion of liquid hydrocarbon in the liquid-phase product is 92.6 wt%, the selectivity of isoparaffin in the liquid hydrocarbon is 89.3 wt%, and the selectivity of normal paraffin is 10.7 wt%. The yield of naphtha (fraction at less than 130 ℃) is 18.5 wt%, the yield of aviation kerosene (fraction at 130 ℃ and 290 ℃) is 58.2 wt%, and the yield of diesel oil (fraction at 290 ℃ and 450 ℃) is 3.8 wt%. The freezing point of the aviation kerosene is-49 ℃, and reaches the standards of RP-3, RP-4, RP-5 and Jet A-1 aviation kerosene. The reaction results are shown in Table 1.
Example 2:
using soybean oil as raw material, making the ratio of circulating material and fresh soybean oil be 4:1, utilizing the same catalyst to make hydrogenation saturation, deoxygenation, alkane isomerization and cracking reaction in the same reactor to prepare aviation kerosene
89.2g of Pd/SAPO-41 catalyst (100mL, particle size 10-20 mesh) was weighed, with the SAPO-41 molecular sieve having a mesopore volume of 0.26mL/g and an acid content of 1.90mmol (NH)3) The Pd loading amount is 1 wt%, the Pd loading amount is filled in a stainless steel fixed bed reactor with the inner diameter of 25mm and the tube length of 1.5m, and both ends of the reactor are filled with 20-40 mesh quartz sand.Introducing hydrogen into the reactor, and introducing the sample by using soybean oil (produced by Zhongliang group Co., Ltd., third grade, which meets GB1535-2003 national standard) as a raw material. The reaction conditions are as follows: 320 ℃, 6.0MPa and LHSV of 1h-1The hydrogen-oil ratio was 1500:1 NL/NL. Samples were taken after 24 hours of reaction. And after the reaction product is subjected to oil-gas-water three-phase separation, obtaining a liquid hydrocarbon product, and removing naphtha (fraction at a temperature of less than 130 ℃) in the liquid hydrocarbon product through atmospheric distillation, wherein the liquid hydrocarbon fraction with the boiling point higher than 130 ℃ is further subjected to distillation separation to obtain aviation kerosene (fraction at a temperature of 130-. Wherein the diesel oil fraction and the soybean oil are mixed according to the volume ratio of 4:1 to prepare a feed, and then the reaction with the hydrogen is continued. The reaction conditions are as follows: 320 ℃, 6.0MPa and LHSV of 1h-1The hydrogen-oil ratio was 1500:1 NL/NL. Sampling after reacting for 16 hours, repeating the steps of separating the product, mixing and feeding materials and continuing to react with the hydrogen. After the reaction was continued for 400 hours, the liquid phase product was analyzed by GC, GC-MS. And analyzing the freezing point of the aviation kerosene product by adopting an automatic freezing point analyzer. FIG. 4 is a gas chromatograph-mass spectrum of the aviation kerosene product of example 2. Wherein i and n represent respectively isomeric and normal alkanes, e.g. i-C15Represents the isomeric pentadecane.
The reaction result is: the conversion rate of soybean oil is 100%, the proportion of water in the liquid-phase product is 9.4 wt%, the proportion of liquid hydrocarbon in the liquid-phase product is 90.6 wt%, the selectivity of isoparaffin in the liquid hydrocarbon is 88.3 wt%, and the selectivity of normal paraffin is 11.7 wt%. The yield of naphtha (fraction at less than 130 ℃) is 13.4 wt%, the yield of aviation kerosene (fraction at 130-290 ℃) is 62.4 wt%, and the yield of diesel oil (fraction at 290-450 ℃) is 3.8 wt%. The freezing point of the aviation kerosene is-47 ℃, and reaches the standards of RP-3, RP-4, RP-5 and Jet A-1 aviation kerosene. The reaction results are shown in Table 1.
Example 3:
using soybean oil as raw material, making the ratio of circulating material and fresh soybean oil be 10:1, utilizing the same catalyst to make hydrogenation saturation, deoxygenation, alkane isomerization and cracking reaction in the same reactor to prepare aviation kerosene
89.2g of Pt/ZSM-22 catalyst (100mL, particle size 10-20 mesh) was weighed out, with a ZSM-22 molecular sieve having a mesopore volume of 0.32mL/g, acid amount 2.0mmol (NH)3) The Pt supported amount is 1 wt%, the Pt supported amount is arranged in a stainless steel fixed bed reactor with the inner diameter of 25mm and the tube length of 1.5m, and two ends of the reactor are filled with 20-40 mesh quartz sand. Introducing hydrogen into the reactor, and introducing the sample by using soybean oil (produced by Zhongliang group Co., Ltd., third grade, which meets GB1535-2003 national standard) as a raw material. The reaction conditions are as follows: 390 ℃, 8.0MPa and LHSV of 5h-1The hydrogen-oil ratio was 3000:1 NL/NL. Samples were taken after 24 hours of reaction. And (3) separating the reaction product by oil, gas and water to obtain a liquid hydrocarbon product. Removing naphtha (fraction less than 130 ℃) in the liquid hydrocarbon product by atmospheric distillation, wherein the liquid hydrocarbon fraction with the boiling point higher than 130 ℃ is separated by further reduced pressure distillation (2kPa) to obtain aviation kerosene (fraction at 290 ℃ C.) and diesel oil (fraction at 450 ℃ C.). Wherein the diesel oil fraction and the soybean oil are mixed according to the volume ratio of 10:1 to prepare a feed, and then the reaction with the hydrogen is continued. The reaction conditions are as follows: 390 ℃, 8.0MPa and LHSV of 5h-1The hydrogen-oil ratio was 3000:1 NL/NL. Sampling after reacting for 16 hours, repeating the steps of separating the product, mixing and feeding materials and continuing to react with the hydrogen. After the reaction was continued for 400 hours, the liquid phase product was analyzed by GC, GC-MS. And analyzing the freezing point of the aviation kerosene product by adopting an automatic freezing point analyzer.
The reaction result is: the conversion rate of soybean oil is 100%, the proportion of water in the liquid-phase product is 9.9 wt%, the proportion of liquid hydrocarbon in the liquid-phase product is 90.1 wt%, the selectivity of isoparaffin in the liquid hydrocarbon is 86.1 wt%, and the selectivity of normal paraffin is 13.9 wt%. The yield of naphtha (fraction at less than 130 ℃) was 9.7 wt%, the yield of aviation kerosene (fraction at 130-. The freezing point of the aviation kerosene is-45 ℃, and reaches the RP-4 aviation kerosene standard. The reaction results are shown in Table 1.
Example 4:
using soybean oil as raw material, making the ratio of circulating material and fresh soybean oil be 1:2, utilizing the same catalyst to make hydrogenation saturation, deoxygenation, alkane isomerization and cracking reaction in the same reactor to prepare aviation kerosene
89.2g of Pt/ZSM-48 catalyst (100mL, particle size 10-20 mesh) was weighed out, with the ZSM-48 molecular sieve centeredPore volume of 0.23mL/g and acid amount of 1.70mmol (NH)3) The Pt supported amount is 1 wt%, the Pt supported amount is arranged in a stainless steel fixed bed reactor with the inner diameter of 25mm and the tube length of 1.5m, and two ends of the reactor are filled with 20-40 mesh quartz sand. Introducing hydrogen into the reactor, and introducing the sample by using soybean oil (produced by Zhongliang group Co., Ltd., third grade, which meets GB1535-2003 national standard) as a raw material. The reaction conditions are as follows: 400 ℃, 10.0MPa and LHSV of 0.5h-1The hydrogen-oil ratio was 2700:1 NL/NL. Samples were taken after 24 hours of reaction. And (3) separating the reaction product by oil, gas and water to obtain a liquid hydrocarbon product. Removing naphtha (fraction less than 130 ℃) in the liquid hydrocarbon product by atmospheric distillation, wherein the liquid hydrocarbon fraction with the boiling point higher than 130 ℃ is separated by further reduced pressure distillation (2kPa) to obtain aviation kerosene (fraction at 290 ℃ C.) and diesel oil (fraction at 450 ℃ C.). Wherein the diesel oil fraction and the soybean oil are mixed according to the volume ratio of 1:2 to prepare a feed, and then the reaction with the hydrogen is continued. The reaction conditions are as follows: 400 ℃, 10.0MPa and LHSV of 0.5h-1The hydrogen-oil ratio was 2700:1 NL/NL. Sampling after reacting for 16 hours, repeating the steps of separating the product, mixing and feeding materials and continuing to react with the hydrogen. After the reaction was continued for 400 hours, the liquid phase product was analyzed by GC, GC-MS. And analyzing the freezing point of the aviation kerosene product by adopting an automatic freezing point analyzer.
The reaction result is: the conversion rate of soybean oil is 100%, the proportion of water in the liquid-phase product is 10.8 wt%, the proportion of liquid hydrocarbon in the liquid-phase product is 89.2 wt%, the selectivity of isoparaffin in the liquid hydrocarbon is 80.4 wt%, and the selectivity of normal paraffin is 19.6 wt%. The yield of naphtha (fraction at less than 130 ℃) is 4.8 wt%, the yield of aviation kerosene (fraction at 130-290 ℃) is 54.5 wt%, and the yield of diesel oil (fraction at 290-450 ℃) is 20.4 wt%. The freezing point of the aviation kerosene is-42 ℃, and reaches the RP-4 aviation kerosene standard. The reaction results are shown in Table 1.
Example 5:
coconut oil is used as a raw material, the ratio of the circulating material to the fresh coconut oil is 4:1, and the aviation kerosene is prepared by performing hydrogenation saturation, deoxidation, alkane isomerization and cracking reactions by using the same catalyst in the same reactor
89.2g of Ir/SAPO-11 catalyst (100mL, particle size 10-20 mesh) was weighed outThe medium pore volume of the SAPO-11 molecular sieve is 0.48mL/g, and the acid amount is 2.20mmol (NH)3) The Ir supporting amount is 1 wt%, the Ir supporting amount is arranged in a stainless steel fixed bed reactor with the inner diameter of 25mm and the tube length of 1.5m, and both ends of the reactor are filled with 20-40 mesh quartz sand. Introducing hydrogen into the reactor, and introducing a sample by using coconut oil (produced by south sea grease industry (Chiwan) Co., Ltd., according with NY/T230-2006 national standard) as a raw material. The fatty acid component of the fatty acid ester contained in the raw coconut oil is as follows: lauric acid (12:0, wherein 12 represents the number of carbon atoms, and 0 represents the number of carbon-carbon unsaturated double bonds in fatty acid) content of 46.5%, myristic acid (14:0) content of 19.2%, palmitic acid (16:0) content of 9.8%, stearic acid (18:0) content of 3.0%, oleic acid (18:1) content of 6.9%, linoleic acid (18:2) content of 2.2%, and acid value of 0.1mgKOH. g-1. The reaction conditions are as follows: 350 ℃, 1.0MPa and LHSV of 1h-1The hydrogen-oil ratio was 5000:1 NL/NL. Samples were taken after 24 hours of reaction. And (3) separating the reaction product by oil, gas and water to obtain a liquid hydrocarbon product. Removing naphtha (fraction less than 130 ℃) in the liquid hydrocarbon product by atmospheric distillation, wherein the liquid hydrocarbon fraction with the boiling point higher than 130 ℃ is separated by further reduced pressure distillation (2kPa) to obtain aviation kerosene (fraction at 290 ℃ C.) and diesel oil (fraction at 450 ℃ C.). Wherein the diesel fraction and the coconut oil are mixed according to the volume ratio of 4:1 to prepare a feed, and then the reaction with hydrogen is continued. The reaction conditions are as follows: 350 ℃, 1.0MPa and LHSV of 1h-1The hydrogen-oil ratio was 5000:1 NL/NL. Sampling after reacting for 16 hours, repeating the steps of separating the product, mixing and feeding materials and continuing to react with the hydrogen. After the reaction was continued for 400 hours, the liquid phase product was analyzed by GC, GC-MS. And analyzing the freezing point of the aviation kerosene product by adopting an automatic freezing point analyzer.
The reaction result is: the conversion rate of coconut oil is 100%, the proportion of water in the liquid-phase product is 9.5 wt%, the proportion of liquid hydrocarbon in the liquid-phase product is 90.5 wt%, the selectivity of isoparaffin in the liquid hydrocarbon is 90.9 wt%, and the selectivity of normal paraffin is 9.1 wt%. The yield of naphtha (fraction at less than 130 ℃) is 5.4 wt%, the yield of aviation kerosene (fraction at 130-290 ℃) is 72.8 wt%, and the yield of diesel oil (fraction at 290-450 ℃) is 2.1 wt%. The freezing point of the aviation kerosene is-51 ℃, and reaches the standards of RP-2, RP-3, RP-4, RP-5 and Jet A-1 aviation kerosene. The reaction results are shown in Table 1.
Example 6:
taking rice bran oil as a raw material, performing hydrogenation saturation, deoxidation, alkane isomerization reaction and cracking on a circulating material and fresh rice bran oil in a ratio of 4:1 in the same reactor by using the same catalyst to prepare the aviation kerosene
89.2g of Pt/MgAPO-11 catalyst (100mL, particle size 10-20 mesh) was weighed, wherein the mesopore volume of the MgAPO-11 molecular sieve was 0.10mL/g and the acid amount was 1.50mmol (NH)3) The Pt supported amount is 1 wt%, the Pt supported amount is arranged in a stainless steel fixed bed reactor with the inner diameter of 25mm and the tube length of 1.5m, and two ends of the reactor are filled with 20-40 mesh quartz sand. Introducing hydrogen into the reactor, and introducing sample by using rice bran oil (produced by Nanhai grease industry (Chiwan) Co., Ltd., which meets the national standard of GB 19112-2003) as a raw material. The fatty acid ester contained in the raw material rice bran oil comprises the following fatty acid components: palmitic acid (16:0, wherein 16 represents the number of carbon atoms, and 0 represents the number of carbon-carbon unsaturated double bonds in a fatty acid) 12.5%, stearic acid (18:0) 2.2%, oleic acid (18:1) 45.3%, linoleic acid (18:2) 31.9%, linolenic acid (18:3) 1.2%, and an acid value of 21mgKOH. g-1. The reaction conditions are as follows: 410 ℃, 3.0MPa and LHSV of 2h-1The hydrogen-oil ratio was 2000:1 NL/NL. Samples were taken after 24 hours of reaction. And (3) separating the reaction product by oil, gas and water to obtain a liquid hydrocarbon product. Removing naphtha (fraction less than 130 ℃) in the liquid hydrocarbon product by atmospheric distillation, wherein the liquid hydrocarbon fraction with the boiling point higher than 130 ℃ is separated by further reduced pressure distillation (2kPa) to obtain aviation kerosene (fraction at 290 ℃ C.) and diesel oil (fraction at 450 ℃ C.). Wherein the diesel fraction and the rice bran oil are mixed according to the volume ratio of 4:1 to prepare a feed, and then the reaction with hydrogen is continued. The reaction conditions are as follows: 410 ℃, 3.0MPa and LHSV of 2h-1The hydrogen-oil ratio was 2000:1 NL/NL. Sampling after reacting for 16 hours, repeating the steps of separating the product, mixing and feeding materials and continuing to react with the hydrogen. After the reaction was continued for 400 hours, the liquid phase product was analyzed by GC, GC-MS. And analyzing the freezing point of the aviation kerosene product by adopting an automatic freezing point analyzer.
The reaction result is: the rice bran oil conversion rate is 100%, the water proportion in the liquid phase product is 9.3 wt%, the liquid hydrocarbon proportion in the liquid phase product is 90.7 wt%, the isoparaffin selectivity in the liquid hydrocarbon is 87.8 wt%, and the normal paraffin selectivity is 12.2 wt%. The yield of naphtha (fraction at less than 130 ℃) is 13.6 wt%, the yield of aviation kerosene (fraction at 130-290 ℃) is 62.3 wt%, and the yield of diesel oil (fraction at 290-450 ℃) is 3.7 wt%. The freezing point of the aviation kerosene is-46 ℃, and reaches the standards of RP-3, RP-4 and RP-5 aviation kerosene. The reaction results are shown in Table 1.
Example 7:
the waste cooking oil is used as raw material, the ratio of the circulating material to the fresh waste cooking oil is 4:1, and the same catalyst is used for carrying out hydrogenation saturation, deoxidation, alkane isomerization and cracking reaction in the same reactor to prepare the aviation kerosene
89.2g of Ni/ZSM-23 catalyst (100mL, particle size 10-20 mesh) was weighed with a ZSM-23 molecular sieve having a mesopore volume of 0.60mL/g and an acid content of 2.50mmol (NH)3) The Ni load is 5 wt%, the reactor is arranged in a stainless steel fixed bed reactor with the inner diameter of 25mm and the tube length of 1.5m, and both ends of the reactor are filled with 20-40 mesh quartz sand. Waste cooking oil is used as a raw material, and solid matters in the waste cooking oil are filtered before use. The filtered pure waste cooking oil contains fatty acid ester with the fatty acid composition as follows: lauric acid (12:0, wherein 12 represents the number of carbon atoms, and 0 represents the number of carbon-carbon unsaturated double bonds in fatty acid) content of 0.1%, myristic acid (14:0) content of 0.1%, palmitic acid (16:0) content of 19.2%, stearic acid (18:0) content of 18.7%, oleic acid (18:1) content of 41.5%, linoleic acid (18:2) content of 11.2%, linolenic acid (18:3) content of 1.4%, arachidic acid (20:0) content of 1.3%, behenic acid (22:0) content of 2.5%, ligninic acid (24:0) content of 1.2%, and acid value of 0.8mgKOH.g-1. Introducing hydrogen into the reactor, wherein the reaction conditions are as follows: 290 ℃, 4.0MPa and LHSV of 1.5h-1The hydrogen-oil ratio was 4000:1 NL/NL. Samples were taken after 24 hours of reaction. And (3) separating the reaction product by oil, gas and water to obtain a liquid hydrocarbon product. Removing naphtha (fraction less than 130 ℃) in the liquid hydrocarbon product by atmospheric distillation, wherein the liquid hydrocarbon fraction with the boiling point higher than 130 ℃ is separated by further reduced pressure distillation (2kPa) to obtain aviation kerosene (fraction at 290 ℃ of 130 ℃) and diesel oil (fraction at 450 ℃ of 290-Minute). Wherein the diesel fraction and the restaurant waste oil are mixed according to the volume ratio of 4:1 to prepare a feed material, and then the reaction with hydrogen is continued. The reaction conditions are as follows: 290 ℃, 4.0MPa and LHSV of 1.5h-1The hydrogen-oil ratio was 4000:1 NL/NL. Sampling after reacting for 16 hours, repeating the steps of separating the product, mixing and feeding materials and continuing to react with the hydrogen. After the reaction was continued for 400 hours, the liquid phase product was analyzed by GC, GC-MS. And analyzing the freezing point of the aviation kerosene product by adopting an automatic freezing point analyzer.
The reaction result is: the conversion rate of waste cooking oil is 100%, the proportion of water in the liquid-phase product is 10.7 wt%, the proportion of liquid hydrocarbon in the liquid-phase product is 89.3 wt%, the selectivity of isoparaffin in the liquid hydrocarbon is 88.4 wt%, and the selectivity of normal paraffin is 11.6 wt%. The yield of naphtha (fraction at less than 130 ℃) is 13.1 wt%, the yield of aviation kerosene (fraction at 130-290 ℃) is 62.1 wt%, and the yield of diesel oil (fraction at 290-450 ℃) is 5.0 wt%. The freezing point of the aviation kerosene is-47 ℃, and reaches the standards of RP-3, RP-4, RP-5 and Jet A-1 aviation kerosene. The reaction results are shown in Table 1.
Example 8:
taking rice bran oil as a raw material, performing hydrogenation saturation, deoxidation, alkane isomerization reaction and cracking on a circulating material and fresh rice bran oil in a ratio of 4:1 in the same reactor by using the same catalyst to prepare the aviation kerosene
89.2g of Pt-Co/MgAPO-41 catalyst (100mL, particle size of 10-20 mesh) is weighed, wherein the mesopore volume of the MgAPO-41 molecular sieve is 0.4mL/g, and the acid content is 2.0mmol (NH)3) And/g, the Pt loading amount is 1 wt%, the Co loading amount is 2 wt%, the reactor is arranged in a stainless steel fixed bed reactor with the inner diameter of 25mm and the tube length of 1.5m, and two ends of the reactor are filled with 20-40 mesh quartz sand. Introducing hydrogen into the reactor, and introducing sample by using rice bran oil (produced by Nanhai grease industry (Chiwan) Co., Ltd., which meets the national standard of GB 19112-2003) as a raw material. The fatty acid ester contained in the raw material rice bran oil comprises the following fatty acid components: palmitic acid (16:0, wherein 16 represents the number of carbon atoms, and 0 represents the number of carbon-carbon unsaturated double bonds in the fatty acid) 12.5%, stearic acid (18:0) 2.2%, oleic acid (18:1) 45.3%, linoleic acid (18:2) 31.9%, linolenic acid (18:3) 1.2%, and an acid value of 21mgKOH.g-1. The reaction conditions are as follows: 430 ℃, 7.0MPa and LHSV of 2.5h-1The hydrogen-oil ratio is 300:1 NL/NL. Samples were taken after 24 hours of reaction. And (3) separating the reaction product by oil, gas and water to obtain a liquid hydrocarbon product. Removing naphtha (fraction less than 130 ℃) in the liquid hydrocarbon product by atmospheric distillation, wherein the liquid hydrocarbon fraction with the boiling point higher than 130 ℃ is separated by further reduced pressure distillation (2kPa) to obtain aviation kerosene (fraction at 290 ℃ C.) and diesel oil (fraction at 450 ℃ C.). Wherein the diesel fraction and the rice bran oil are mixed according to the volume ratio of 4:1 to prepare a feed, and then the reaction with hydrogen is continued. The reaction conditions are as follows: 430 ℃, 7.0MPa and LHSV of 2.5h-1The hydrogen-oil ratio is 300:1 NL/NL. Sampling after reacting for 16 hours, repeating the steps of separating the product, mixing and feeding materials and continuing to react with the hydrogen. After the reaction was continued for 400 hours, the liquid phase product was analyzed by GC, GC-MS. And analyzing the freezing point of the aviation kerosene product by adopting an automatic freezing point analyzer.
The reaction result is: the rice bran oil conversion rate is 100%, the water proportion in the liquid phase product is 9.5 wt%, the liquid hydrocarbon proportion in the liquid phase product is 90.5 wt%, the isoparaffin selectivity in the liquid hydrocarbon is 89.9 wt%, and the normal paraffin selectivity is 10.1 wt%. The yield of naphtha (fraction at less than 130 ℃) is 14.2 wt%, the yield of aviation kerosene (fraction at 130 ℃ and 290 ℃) is 62.5 wt%, and the yield of diesel oil (fraction at 290 ℃ and 450 ℃) is 3.4 wt%. The freezing point of the aviation kerosene is-49 ℃, and reaches the standards of RP-3, RP-4 and RP-5 aviation kerosene. The reaction results are shown in Table 1.
TABLE 1 results of the reactions in the examples
The examples in the present invention describe the preparation of aviation kerosene with all-hydrocarbon composition from oils and fats derived from biomaterials. The aviation kerosene product described in the above example is a hydrocarbon with a distillation range of between 130-290 ℃ and mainly comprises isoparaffin. In the comparative example 1, the process of generating the target product by the grease through catalytic hydrogenation, deoxidation reaction, hydroisomerization and cracking is realized in two steps of reaction, but the product performance is poor; in comparative example 2 and examples 1 to 8, the process of producing the target product by catalytic hydrogenation, deoxidation, hydroisomerization and cracking of the oil was carried out in one step. In addition, in examples 1 to 8, the diesel oil product with the boiling point of more than 290 ℃ is used as the circulating material to dilute the oil feed, so that the heat release of the oil hydrogenation reaction is relieved, the influence of the reaction heat effect on the catalyst is reduced, the aviation kerosene can be stably produced, and the catalyst still keeps activity after the reaction is carried out for 400 hours. The aviation kerosene produced by the methods described in examples 1-8 has high energy density, high stability, low freezing point, low aromatics, and low sulfur.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (11)
1. A method for producing liquid hydrocarbons using biological material, comprising the steps of:
a reaction step, namely simultaneously carrying out hydrogenation saturation reaction, deoxidation reaction, alkane isomerization reaction and cracking reaction on a feed containing grease from a biological material and hydrogen on a catalyst in a reactor to generate a reaction product, wherein the reaction product contains a liquid hydrocarbon component mainly containing branched alkane, a gas component and water;
a separation step of separating the liquid hydrocarbon component from the gas component and water;
a distillation step of distilling at least a portion of the liquid hydrocarbon component from the separation step and collecting the liquid hydrocarbon component having a boiling point between 130 ℃ and 290 ℃; and
a recycling step of recycling at least a part of the liquid hydrocarbon components from the separation step or at least a part of the liquid hydrocarbon components from the distillation step having a boiling point above 290 ℃ and adding at least a part of the liquid hydrocarbon components from the separation step or at least a part of the liquid hydrocarbon components from the distillation step having a boiling point above 290 ℃ to a fresh feed for the reaction step;
wherein, the catalyst used in the reaction step is a supported catalyst of a ten-membered ring one-dimensional channel molecular sieve supported VIII group metal; the ten-membered ring one-dimensional channel molecular sieve has a pore volume of 0.1-0.6mL/g and an acid amount of 1.5-2.5mmol (NH)3)/g。
2. The method for producing liquid hydrocarbons using biological materials according to claim 1, wherein the volume ratio of the liquid hydrocarbon component with boiling point higher than 290 ℃ from the distillation step to the fresh feed is 1:2 to 10: 1.
3. The method for producing liquid hydrocarbons using biological materials according to claim 1, wherein the volume ratio of the liquid hydrocarbon component with boiling point higher than 290 ℃ from the distillation step to the fresh feed is 1:2 to 5: 1.
4. The method for producing liquid hydrocarbons using biological materials according to claim 1, wherein the volume ratio of the liquid hydrocarbon component with boiling point higher than 290 ℃ from the distillation step to the fresh feed is 2:1 to 5:1 for at least a part of the liquid hydrocarbon component recycled from the separation step or at least a part of the liquid hydrocarbon component recycled from the distillation step.
5. The method for producing liquid hydrocarbons using biomaterials of claim 1, wherein the ten-membered ring one-dimensional channel molecular sieve in the catalyst is one or more of SAPO-11, SAPO-41, MeAPO-11, MeAPO-41, ZSM-22, ZSM-23 and ZSM-48.
6. The method for producing liquid hydrocarbons using biomaterials of claim 1, wherein the group VIII metal is one or more of Pt, Pd, Ir, Ni, and Co.
7. The method for producing liquid hydrocarbons using biological materials according to claim 1, wherein the fats and oils derived from biological materials include one or more of vegetable oil, animal fat, and waste kitchen oil.
8. The method for producing liquid hydrocarbons using biomaterials as claimed in any one of claims 1-7, wherein the reaction temperature in the reaction step is 250-450 ℃, the reaction pressure is 1-10MPa, and the liquid space velocity is 0.1-5h-1The volume ratio between hydrogen and feed is from 300:1 to 5000:1 NL/NL.
9. The method for producing liquid hydrocarbons using biomaterials of any one of claims 1-7, wherein the distillation step collects a yield of liquid hydrocarbon components with boiling points between 130-290 ℃ higher than 50 wt%.
10. The liquid hydrocarbon having a boiling point between 130-290 ℃ prepared by the method as claimed in any one of claims 1-7, wherein the isoparaffin selectivity in the liquid hydrocarbon having a boiling point between 130-290 ℃ is higher than 60 wt%, and the freezing point of the liquid hydrocarbon having a boiling point between 130-290 ℃ is not more than-40 ℃.
11. An aviation fuel comprising the liquid hydrocarbon of claim 10 having a boiling point between 130 and 290 ℃.
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| CN103897718A (en) * | 2012-12-27 | 2014-07-02 | 中国石油天然气股份有限公司 | Method for producing diesel oil fraction and aviation fuel fraction from animal and vegetable oil |
| CN106281401A (en) * | 2015-05-21 | 2017-01-04 | 中国石化工程建设有限公司 | A kind of method utilizing waste animal and plant fat to produce aviation bio-fuel |
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| CN103897718A (en) * | 2012-12-27 | 2014-07-02 | 中国石油天然气股份有限公司 | Method for producing diesel oil fraction and aviation fuel fraction from animal and vegetable oil |
| CN106281401A (en) * | 2015-05-21 | 2017-01-04 | 中国石化工程建设有限公司 | A kind of method utilizing waste animal and plant fat to produce aviation bio-fuel |
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