CN105921160A - Preparation method of catalyst used in bio-oil hydrodeoxygenation - Google Patents
Preparation method of catalyst used in bio-oil hydrodeoxygenation Download PDFInfo
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- CN105921160A CN105921160A CN201610283402.6A CN201610283402A CN105921160A CN 105921160 A CN105921160 A CN 105921160A CN 201610283402 A CN201610283402 A CN 201610283402A CN 105921160 A CN105921160 A CN 105921160A
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- catalyst
- acid
- oxygen
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- 235000010981 methylcellulose Nutrition 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 description 1
- 229910001630 radium chloride Inorganic materials 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000012306 spectroscopic technique Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/049—Sulfides with chromium, molybdenum, tungsten or polonium with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
- C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
- C11C3/123—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on nickel or derivates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
- C11C3/126—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on other metals or derivates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a preparation method of a catalyst used in bio-oil hydrodeoxygenation. The preparation method comprises the following steps: during a process of roasting a catalyst carrier impregnated with an active component, the catalyst carrier impregnated with the active component contacts an oxygen-containing organic matter, such that an oxidation-state catalyst is obtained when the roasting process is finished; the oxidation-state catalyst absorbs inorganic acid, and is subjected to a high-temperature drying treatment; and a vulcanization treatment is carried out, such that a product is obtained. The active component is mainly composed of one or more selected from Group VIB metals and one or more selected from Group VIII metals. According to the invention, the catalyst is pretreated with the oxygen-containing organic matter and inorganic acid, such that the selectivity of a hydrogenation decarboxylation and decarbonylation reaction is enhanced, and catalyst sulfur fixation performance and thermal stability are improved.
Description
Technical field
The present invention relates to modifying oil product technical field, especially relate to the preparation method of a kind of catalyst for biological oil hydrodeoxygenation.
Background technology
Along with increasingly sharpening of crude oil heaviness and environmental pollution, liquefied coal coil, Fischer-Tropsch synthesis oil and bio oil (various vegetable and animals oils) enjoy the concern of researcher as preferable fungible energy source, especially bio oil, because it has pollutant emission is few, cycle period is short feature and becomes the focus of research.Compared with crude oil, in bio oil, the content of oxygenatedchemicals is higher, and main oxygenatedchemicals type includes phenols, furans, esters and ketone etc..Existence due to a large amount of oxygenatedchemicalss, the oxygen content of biological oil product is sometime up to more than 50 weight %, thus cause bio oil to have combustion heat value is low, unstable chemcial property, heating are easily polymerized, acid compared with strong, to unfavorable features such as the corrosivity of equipment are big, seriously hinder it directly to use as vehicle fuel, it is therefore desirable to by hydrogenation deoxidation, bio oil is carried out upgrading.
Animals and plants main body of oil is triglyceride, and fatty acid chain length is generally C14～C22, wherein C16And C18Account for the 90% of all fatty acids.The diesel component that vegetable and animals oils hydrogenation deoxidation is prepared is mainly by C12～C22Linear paraffin composition, its Cetane number, up to 90～100, can be in harmonious proportion with petroleum diesel in any proportion, and without sulfur, without aromatic hydrocarbons, the most oxygen-containing, NOx emission is few, environmental friendliness, and storage stability is good, can use as high cetane number diesel oil addO-on therapy.Therefore, vegetable and animals oils hydrogenation deoxidation prepares biodiesel technology, acts on a kind of novel renewable automobile-used supplementing and is favored by people with alternative fuel.
Vegetable and animals oils Hydrogenation for containing multiple chemical reaction during diesel component, mainly have that the hydrogenation of unsaturated fatty acid in vegetable and animals oils is saturated, hydrogenation deoxidation, hydrogenation decarboxylation, hydrogenation de-carbonyl reaction, the most also hydroisomerization reaction etc..At present, the reaction of vegetable and animals oils hydrogenation deoxidation is main uses sulphided state CoMo/Al2O3Or NiMo/Al2O3Catalyst, this kind of catalyst has higher hydrodesulfurization and hydrogenation deoxidation activity, the most also has higher hydrogenation deoxidation initial activity, but shortcoming is poor catalyst stability, it is easy to inactivation.
Such as, CN101831315A discloses the method that a kind of use catalyst based on nickel and molybdenum will come from the raw material hydrogenation deoxidation of renewable source with restricted decarboxylation conversion ratio.This invention finds that described activity uses the atomic ratio of one or more metals selected from VIII and one or more metals selected from group vib mutually, especially with suitable Ni/Mo atomic ratio, can control and strengthen the selectivity of hydrogenation deoxidation reaction, thus limit decarboxylation/decarbonylation reaction, and therefore limit by the disadvantage caused by being formed of oxycarbide.But the shortcomings such as this poor, easy in inactivation of catalyst existence and stability.
CN102427880A discloses a kind of catalyst comprising metal phosphide, and it is used for preparing biodiesel, also discloses one and utilizes described catalyst that vegetable oil carries out hydrotreating, thus the method preparing biodiesel.The advantage of this catalyst is: when comprising the biodiesel of metal phosphide described in use, the preparation activity of the biodiesel of hydrotreating is high, even without vulcanizing agent without interruption, and hydrotreating and isomerization reaction are carried out simultaneously, it is possible to obtain the high-quality hydrotreating biodiesel that pour point is low.Equally, it is poor that this catalyst there is also hydrothermal stability, and active phase easily assembles the shortcomings such as inactivation.
Therefore, the hydrogenation deoxidation catalyst for preparing biodiesel of a kind of high stability of exploitation is needed at present badly.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of catalyst for biological oil hydrodeoxygenation, described preparation method utilizes oxygen-bearing organic matter that catalyst is carried out pretreatment, add the selectivity of hydrogenation decarboxylation decarbonylation reaction, improve sulfur fixation performance and the heat stability of catalyst.
Another object of the present invention is to provide a kind of catalyst for biological oil hydrodeoxygenation, described catalyst has hydrogenation decarboxylation decarbonylation selectivity height, sulfur fixation performance and heat stability high.
The preparation method of a kind of catalyst for biological oil hydrodeoxygenation, comprises the following steps:
During roasting is impregnated with the catalyst carrier of active component, make described in be impregnated with the catalyst carrier of active component and contact with oxygen-bearing organic matter, complete described roasting and obtain oxidized catalyst, carry out vulcanizing treatment afterwards, obtain product；Wherein, described active component is mainly made up of with one or more in group VIII metal one or more in group vib metal.
As a rule, the main cause of vegetable and animals oils hydrogenation deoxidation catalyst inactivation has the exchange of carbon deposit, oxygen sulfur and carrier to be hydrated the carrier specific surface area reduction caused and activity gathering mutually etc..Therefore the specific surface area that the hydration of suppression carrier causes reduces and the gathering of activity phase, and the raising for hydrogenation deoxidation catalyst stability has important function.But prior art is generally not capable of taking into account suppression carrier hydration and high two effects of reaction selectivity.As a example by existing alumina support, the aluminium oxide that hydrogenation deoxidation catalyst is used is spinel-like type structure, the a large amount of cation in its surface and anion vacancy play pivotal role for alumina hydration, therefore widespread practice is all to pass through support modification, add auxiliary agent atom and occupy alumina carrier surface room, thus suppress carrier to be hydrated；But, the shortcoming of this way is to reduce active metal and carrier Interaction Force, thus impact vulcanizes the active facies type of rear catalyst to a certain extent, and and then reduces hydrogenation deoxidation and the selectivity of decarboxylation.
And the preparation method of the present invention is by being passed through oxygen-bearing organic matter and selecting two measures of suitable active metal component in roasting process, oxygen-bearing organic matter can not only be utilized to occupy carrier surface room to suppress the hydration of carrier, play increase acidity of catalyst and active phase dispersion, and and then increase the decarboxylation decarbonylation reaction selectivity to dehydration, but also improve the sulfur fixation performance of catalyst, the sulfur in catalyst is made to not easily run off in course of reaction, even if without vulcanizing agent, its sulphidity remains above catalyst prepared by conventional method.
Catalyst of the present invention is preferentially used for the hydrogenation deoxidation modification of vegetable and animals oils, naturally it is also possible to for the modification of other oil products such as gasoline, oil, coal tar, even more technical field.
The above-mentioned preparation method of the present invention can also be improved, such as further:
Oxygen-bearing organic matter of the present invention refers to arbitrarily contain the Organic substance of oxygen atom, is selected from one or more in Organic Alcohol, organic acid, organic ketone, phenols, preferably Organic Alcohol and/or organic acid.
Under normal circumstances, after Organic Alcohol, organic acid process, the selectivity to hydrogenation decarboxylation decarbonylation reaction is higher.
Described Organic Alcohol can be selected from one or more in one or more in ethylene glycol, glycerol, Polyethylene Glycol, diethylene glycol and butanediol, preferably ethylene glycol, glycerol and Polyethylene Glycol；The number-average molecular weight of described Polyethylene Glycol is preferably 200-1500.
Described organic acid can be selected from acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2-CDTA, citric acid, tartaric acid, malic acid, 1, one or more in one or more in 2-1,2-diaminocyclohexane tetraacetic acid, glycine, nitrilotriacetic acid(NTA) and ethylenediaminetetraacetic acid, preferably acetic acid, citric acid and ethylenediaminetetraacetic acid.
Described phenolic compound can be selected from one or more in phenol, Benzodiazepines, benzenetriol, cresol, amino phenols, nitrophenols, chlorophenol, preferably phenol and/or Benzodiazepines.
Above-mentioned oxygen-bearing organic matter contacts when contacting with catalyst carrier the most as a solution, the mode of contact also has a variety of, can be the most all mixing, can also be that the solution of oxygen-bearing organic matter is continuously injected in catalyst carrier, can be fully contacted and be attached together both ensureing.Carrying out roasting while contact, the temperature of described roasting is preferably 400-600 DEG C, more preferably 420-500 DEG C；The time of described roasting is preferably 2-8h, more preferably 3-6h.The selectivity of the hydrogenation decarboxylation decarbonylation of catalyst, and heat stability can be improved by above preferably roasting condition, extend the cycle of operation of oil product processing unit (plant).
Preferably adding oxygen-bearing organic matter in the way of being continuously injected into, described oxygen-bearing organic matter is preferably with 0.1-20h-1Air speed contact with the described catalyst carrier being impregnated with active component, more preferably 1-10h-1.The problem selecting the strength reduction that suitable air speed can avoid catalyst efflorescence to cause.
Consumption about oxygen-bearing organic matter, it is preferable that be impregnated with the catalyst carrier of active component described in making when contacting with oxygen-bearing organic matter, described oxygen-bearing organic matter is 0-10% with the mass ratio of described catalyst carrier, it is preferably 5-8%, preferably 0.1-5%, preferably 0.05-4%.
In addition to using oxygen-bearing organic matter and catalyst processed, it is also possible to carry out vulcanizing front pretreatment with oxygen-containing inorganic acid the most again, specifically, make described oxidized catalyst adsorb oxygen-containing inorganic acid；Oxygen-containing inorganic acid mainly occupies carrier surface room to suppress the hydration of carrier.
Oxygen-containing inorganic acid of the present invention refers to any oxygen containing mineral acid, one or more in the oxygen-containing inorganic acid of preferably VA race, preferably phosphoric acid, arsenic acid, metaantimmonic acid etc., preferably phosphoric acid.The stability of these mineral acids is high, it is possible to increase the heat stability of catalyst.
About the consumption of oxygen-containing inorganic acid, such as, on the basis of described catalyst carrier, the consumption of described VA race oxygen-containing inorganic acid can be 0.1-10wt%, preferably 0.2-5wt%, more preferably 0.2-3wt%.Described VA race oxygen-containing inorganic acid can use in pure form, it is also possible to uses with the form of its aqueous solution, preferably the latter.Additionally, when described VA race oxygen-containing inorganic acid uses with the form of its aqueous solution, in VA race oxygen-containing inorganic acid aqueous solution, described VA race oxygen-containing inorganic acid can be 1:1-80, preferably 1:2-10 with the weight ratio of water.Now, described oxygen-containing inorganic acid does not include the consumption of water relative to the above-mentioned consumption of hydrogenation catalyst.
The present invention is not particularly limited by the mode that described hydrogenation catalyst contacts with VA race oxygen-containing inorganic acid, for example, it is possible to mixed with VA race oxygen-containing inorganic acid by hydrogenation catalyst, it is also possible to constantly sprayed on hydrogenation catalyst by the aqueous solution containing organic additive.Preferably, the method of described absorption mineral acid is: contacted with described oxidized catalyst under 100-140 DEG C (more preferably 120 DEG C) by the solution of mineral acid, and is additionally included under 200-250 DEG C (more preferably 230 DEG C) dry after described absorption and before described vulcanizing treatment.The front carrying out being adsorbed with beneficially catalyst in a heated condition is modified.
Preferably, by the mode that described hydrogenation catalyst contacts with VA race oxygen-containing inorganic acid it is: described VA race oxygen-containing inorganic acid aqueous solution is continuously injected in the fixed bed reactors being filled with described hydrogenation catalyst, so enable to pretreated hydrogenation catalyst directly apply to, in biological oil hydrodeoxygenation reactor, simplify technique.Further: make described oxidized catalyst and described mineral acid react in fixed bed reactors, and to keep the temperature in reactor be 100-140 DEG C (more preferably 120 DEG C), partial pressure is 1.5-4MPa (more preferably 3MPa), and gas flow is 50-70L/h (more preferably 60L/h).Under the conditions of process above, the mechanical strength of catalyst will not be had a negative impact by preprocessing process.(in the present invention, pressure refers both to gauge pressure)
Catalyst carrier of the present invention can use any conventional can type, such as the mixture of at least one in alumina support, or aluminium oxide and silicon oxide, titanium oxide and zirconium oxide；Wherein, described aluminium oxide can be such as at least one in gama-alumina, η-aluminium oxide, θ-aluminium oxide, δ-aluminium oxide and χ-aluminium oxide.Additionally, described carrier can be cloverleaf pattern, butterfly, cylinder, hollow cylindrical, quatrefoil, five shapes such as leaf, spherical.Above-mentioned carrier can be commercially available, it is also possible to according to well known to a person skilled in the art that various method prepares.Such as, alumina support can be by by aluminium oxide precursor roasting so that it is be converted at least one in gama-alumina, η-aluminium oxide, θ-aluminium oxide, δ-aluminium oxide and χ-aluminium oxide.Optionally, before firing and/or afterwards, the shape (such as spherical, lamellar, bar shaped etc.) required for practical operation can be suitable for first by aluminium oxide precursor molding with preparation.Described molding can be carried out, such as rolling ball method, pressed disc method and extrusion method etc. according to the method that this area is conventional.In forming process, such as during extruded moulding, in order to ensure being smoothed out of molding, water, extrusion aid and/or peptizer can be added in described aluminium oxide precursor, and be optionally added expanding agent, then extrusion molding, it is dried afterwards and roasting.The kind of described extrusion aid, peptizer and expanding agent and consumption can use the process of routine, such as, common extrusion aid can be selected from least one in sesbania powder, methylcellulose, starch, polyvinyl alcohol and PVOH, described peptizer can be Organic Alcohol and/or organic acid, and described expanding agent can be at least one in starch, synthetic cellulose, polymeric alcohol and surfactant.Wherein, at least one during described synthetic cellulose is preferably hydroxymethyl cellulose, methylcellulose, ethyl cellulose and hydroxyl fiber fat alcohol polyethylene ether.Described polymeric alcohol is preferably at least one in Polyethylene Glycol, poly-propanol and polyvinyl alcohol.Described surfactant preferably fat alcohol polyethylene ether, fatty alkanol amide and derivant thereof, molecular weight are at least one in the propenyl copolymer of 200-10000 and maleic acid copolymer.The condition that extrusion bar is dried is generally included: baking temperature can be 40-350 DEG C, preferably 100-200 DEG C；Drying time can be 1-24 hour, preferably 2-12 hour.The condition of dried extrusion bar roasting is generally included: sintering temperature can be 350-1000 DEG C, preferably 600-950 DEG C；Roasting time can be 1-10 hour, preferably 2-6 hour.Described aluminium oxide precursor can be selected from least one in Alumina hydrate, monohydrate alumina, amorphous hydroted alumina etc..
Group vib of the present invention and group VIII metal component add the most in the form of the oxide, it is of course possible to use the chemical form that other is feasible, such as nitrate, carbonate, sulfate, meta-acid salt, ammonium salt etc..Wherein, group vib metal component includes but not limited to: Cr (can be selected from least one in chromium oxide, chromic nitrate and chromic sulfate), Mo (can be selected from least one in molybdenum oxide, molybdate and paramolybdate) and W (can be selected from least one in tungstates, metatungstate and ethyl metatungstate).Described group VIII metal component includes but not limited to: Fe (can be selected from ferric nitrate, iron acetate, iron chloride, one or more in ferrous sulfate and ferrum oxide), Co (can be selected from cobalt nitrate, cobaltous acetate, at least one in basic cobaltous carbonate and cobaltous chloride), Ni (can be selected from nickel nitrate, nickel acetate, at least one in basic nickel carbonate and Nickel dichloride .), Ru (can be selected from ruthenium trichloride, at least one in ruthenic oxide and nitric acid ruthenium), Rh (can be selected from rhodium nitrate, at least one in radium chloride and rhodium oxide) and Pd (Palladium monoxide can be selected from, at least one in palladium dydroxide Palladous nitrate. and Palladous chloride .).Preferably, described group vib metal component is Mo and/or W, and described group VIII metal component is Co and/or Ni；Described active component is preferably molybdenum and nickel.
Preferably, on the basis of described catalyst carrier, the content of group vib metal is 0-30wt%, preferably 3-20wt%；The content of group VIII metal is 0-30wt%, preferably 1-10wt%.
In catalyst carrier, the method for impregnating metal active component has a variety of, such as infusion process, spraying.Preferably, by carrier impregnation in the impregnation liquid of the compound of metallic components, then it is dried.Wherein, the solvent in impregnation liquid can be the various inertia liquids that can dissolve described group vib metallic compound and group VIII metal compound, for example, it is possible at least one in water, alcohol, ether, aldehyde and ketone.
It addition, finally the vulcanizing treatment to catalyst can use dry pre-sulfiding or wet method sulfuration.Specifically, for dry pre-sulfiding, the curing medium of employing can be H2And H2H in the mixture of S, and described curing medium2The volumetric concentration of S can be 0.1-5v%, preferably 1-2v%.For vulcanizing for wet method, it generally uses and faces hydrogen sulfuration, and the curing medium of employing can be that in diesel oil and disulphide and/or the mixture of mercaptan, and described curing medium, the volumetric concentration of sulphur-containing substance can be 0.1-10v%, it is preferably 0.1-3.5v%, more preferably 0.4-2v%.Wherein, described disulphide can be CS2、CH3-S-S-CH3And CH3-S-S-C2H5In at least one.Described mercaptan can be C4H9SH、C2H5SH and CH3At least one in SH.
The most dry pre-sulfiding method is: with the speed of 25-35 DEG C/h, from 20-40 DEG C, the temperature of vulcanizing system is risen to 160-180 DEG C, and starts into H2S；With the speed of 10-20 DEG C/h, the temperature of vulcanizing system is risen to 220-240 DEG C again, and maintain gas phase H in vulcanizing system at such a temperature2S concentration is constant and constant temperature vulcanizes 2-6h；With the speed of 5-15 DEG C/h, the temperature of vulcanizing system is risen to 270-290 DEG C and constant temperature sulfuration 2-6h again；With the speed of 5-15 DEG C/h, the temperature of vulcanizing system is risen to 300-370 DEG C the most again, and maintain gas phase H in vulcanizing system at such a temperature2S concentration is constant and constant temperature vulcanizes 2-6h.
It addition, the content of active component is preferably in catalyst: on the basis of described catalyst carrier, the content of group vib metal is 0-30wt%, preferably 3-20wt%；The content of group VIII metal is 0-30wt%, preferably 1-10wt%.
The catalyst prepared by above technical scheme all shows hydrogenation decarboxylation decarbonylation selectivity more higher than existing catalyst, and the feature such as higher sulfur fixation performance and heat stability.
Compared with prior art, invention achieves techniques below effect:
(1) with group vib metal and group VIII metal as active component, in conjunction with oxygen-bearing organic matter and the pretreatment of oxygen-containing inorganic acid, improve the sulfur fixation performance of catalyst, heat stability is, and the selectivity of hydrogenation decarboxylation decarbonylation reaction；
(2) can be used for vegetable and animals oils and prepare diesel oil；
(3) specific area and the sulphidity of catalyst of the present invention are higher.
Detailed description of the invention
Below in conjunction with detailed description of the invention, technical scheme is clearly and completely described, but it will be understood to those of skill in the art that, following described embodiment is a part of embodiment of the present invention, rather than whole embodiments, it is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art are obtained under not making creative work premise, broadly fall into the scope of protection of the invention.Unreceipted actual conditions person in embodiment, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or instrument unreceipted production firm person, being can be by the commercially available conventional products bought and obtain.
Air speed of the present invention refers both to " volume space velocity "
Embodiment 1
(1) the dry bar of catalyst is prepared:
Weigh 1000 grams of dry glue powders and 30 grams of sesbania powder mix homogeneously, add 900 milliliters of nitre aqueous acids Han 28g afterwards, plunger type bar extruder is extruded into the wet bar of cylinder of external diameter φ 1.4mm.Then being dried 4 hours in 120 DEG C by cylindrical wet bar, then at 600 DEG C of roastings 3 hours, obtain carrier Z, its pore volume is 0.7mL/g, and specific surface area is 280m2/g。
100g ammonium heptamolybdate, 30g nickel nitrate and 1000g ammonia are added in 400mL aqueous solution, heats and stir to after being completely dissolved, obtaining impregnation liquid 500mL.Take 400g above-mentioned carrier Z, above-mentioned impregnation liquid is the most uniformly sprayed on carrier Z, then half dry catalyst obtained put in baking oven and dry 4 hours in 120 DEG C, obtaining being impregnated with the catalyst dry bar G1 of active component.
(2) oxygen-bearing organic matter processes:
G1 is placed in ventable vertical tubular furnace, 400 DEG C of constant temperature calcinings 3 hours, roasting process needs by the aqueous solution that pre-configured acetic acid content is 5 weight %, according to air speed 2h-1, persistently squeeze in catalyst roasting bed with plunger displacement pump, finally give oxidized catalyst C1.Wherein, relative to the dry bar of the catalyst of 100 weight portions, the quality being passed through aqueous solution amounts to 0.01.
(3) pretreatment before sulfuration:
VA race oxygen-containing inorganic acid selects phosphoric acid, and total injection rate is 100g.Specifically, 200g phosphoric acid and 300g water are mixed the phosphate aqueous solution of phosphoric acid 40 weight %.In a nitrogen atmosphere, injecting in above-mentioned hydrogenation deoxidation reactor by phosphate aqueous solution with the speed of 100g/h, maintaining reaction bed temperature during this period is 120 DEG C, and nitrogen partial pressure is 3.0MPa, and nitrogen flow is 60L/h.
After phosphate aqueous solution all injects, reaction bed temperature is risen to 230 DEG C, in a nitrogen atmosphere catalyst is carried out high temperature drying process, controlling reactor inlet temperature during this period is 230 DEG C, reactor outlet temperature is 230 DEG C, nitrogen partial pressure is 2.0MPa, and nitrogen flow is 60L/h, and drying time is 6 hours.It is dried after terminating and reaction bed temperature is down to 145 DEG C, then introduce hydrogen.
(4) sulfuration:
With the speed of 30 DEG C/h, the temperature of vulcanizing system is risen to 180 DEG C from 30 DEG C, and start into H2S；With the speed of 10 DEG C/h, the temperature of vulcanizing system is risen to 240 DEG C again, and maintain gas phase H in vulcanizing system at such a temperature2S concentration is constant and constant temperature vulcanizes 4h；With the speed of 15 DEG C/h, the temperature of vulcanizing system is risen to 290 DEG C and constant temperature sulfuration 6h again；With the speed of 15 DEG C/h, the temperature of vulcanizing system is risen to 320 DEG C the most again, and maintain gas phase H in vulcanizing system at such a temperature2S concentration is constant and constant temperature vulcanizes 5h.
Embodiment 2
(1) the dry bar of catalyst is prepared: same as in Example 1.
(2) oxygen-bearing organic matter processes:
G1 is placed in ventable vertical tubular furnace, 400 DEG C of constant temperature calcinings 3 hours, roasting process needs by the aqueous solution that pre-configured phenol content is 7 weight %, according to air speed 5h-1, persistently squeeze in catalyst roasting bed with plunger displacement pump, finally give oxidized catalyst C2.Wherein, relative to the dry bar of the catalyst of 100 weight portions, the quality being passed through aqueous solution amounts to 0.2.
(3) pretreatment before sulfuration
VA race oxygen-containing inorganic acid selects phosphoric acid, and total injection rate is 100g.Specifically, 100g phosphoric acid and 900g water are mixed the phosphate aqueous solution of 10 weight %.In a nitrogen atmosphere, injecting in above-mentioned hydrogenation deoxidation reactor by phosphate aqueous solution with the speed of 100g/h, maintaining reaction bed temperature during this period is 120 DEG C, and nitrogen partial pressure is 3.0MPa, and nitrogen flow is 60L/h.
After phosphate aqueous solution all injects, reaction bed temperature is risen to 230 DEG C, in a nitrogen atmosphere catalyst is carried out high temperature drying process, controlling reactor inlet temperature during this period is 230 DEG C, reactor outlet temperature is 230 DEG C, nitrogen partial pressure is 2.0MPa, and nitrogen flow is 60L/h, and drying time is 6 hours.It is dried after terminating and reaction bed temperature is down to 150 DEG C, then introduce hydrogen.
(4) sulfuration:
Same as in Example 1.
Embodiment 3-7
Embodiment 3 to 7 and embodiment 1 to differ only in metal active constituent different, the molal quantity of its group vib metallic element, group VIII metal element molal quantity all identical with embodiment, the compound of active component is respectively as follows:
MoO3/CoCl2、WO3/CoCl2、WO3/Ni(NO3)2、Cr2O3+MoO3(both equimolar mixing)/CoCl2、Cr2O3+MoO3(both equimolar mixing)/CoCl2+FeO。
Embodiment 8-13
Embodiment 8-13 is different from the active component consumption differing only in dipping of embodiment 1, and consumption is respectively as follows: 30g ammonium heptamolybdate/30g nickel nitrate, 200g ammonium heptamolybdate/30g nickel nitrate, 300g ammonium heptamolybdate/30g nickel nitrate, 100g ammonium heptamolybdate/10g nickel nitrate, 100g ammonium heptamolybdate/100g nickel nitrate, 100g ammonium heptamolybdate/300g nickel nitrate.
Embodiment 14-20
Embodiment 14-20 is different from the consumption differing only in acetic acid used during oxygen-bearing organic matter processes of embodiment 1, but consumption identical (percentage by weight), oxygen-bearing organic matter is respectively as follows:
Ethylene glycol, glycerol, Polyethylene Glycol (molecular weight 200), Polyethylene Glycol (molecular weight 1500), ethylenediaminetetraacetic acid, citric acid, Benzodiazepines.
Embodiment 21-26
Embodiment 21-26 is different from the consumption differing only in acetic acid used during oxygen-bearing organic matter processes of embodiment 1, and on the basis of the quality of Z, consumption is respectively as follows: 0.05%, 0.1%, 4%, 5%, 8%, 10%.
Embodiment 27-28
Embodiment 27-28 and embodiment 1 to differ only in oxygen-containing inorganic acid kind used in pretreatment before sulfuration different, but consumption identical (percentage by weight), oxygen-containing inorganic acid is respectively as follows: arsenic acid, metaantimmonic acid.
Embodiment 29-33
Embodiment 29-33 is different from the consumption differing only in phosphoric acid used in the front pretreatment of sulfuration of embodiment 1, and on the basis of the quality of Z, consumption is respectively as follows: 0.1%, 0.2%, 3%, 5%, 10%.
Embodiment 34-36
Embodiment 34-36 and embodiment 1 to differ only in sintering temperature when oxygen-bearing organic matter processes different, be respectively as follows: 420 DEG C, 500 DEG C, 600 DEG C.
Embodiment 37-39
Embodiment 37-39 and embodiment 1 to differ only in roasting time when oxygen-bearing organic matter processes different, be respectively as follows: 2h, 6h, 8h.
Embodiment 40-43
Embodiment 40-43 and embodiment 1 to differ only in air speed when oxygen-bearing organic matter processes different, be respectively as follows: 0.1h-1、1h-1、10h-1、20h-1。
Embodiment 44-45
Embodiment 44-45 is different from the reaction temperature differing only in the front pretreatment of sulfuration of embodiment 1, is respectively as follows: 100 DEG C, 140 DEG C.
Embodiment 46-47
Embodiment 46-47 is different from the baking temperature differing only in the front pretreatment of sulfuration of embodiment 1, is respectively as follows: 200 DEG C, 250 DEG C.
Embodiment 48-49
Gaseous environment when differing only in pretreatment reaction before sulfuration of embodiment 48-49 and embodiment 1 is different, is respectively as follows: 1.5MPa+50L/h, 4MPa+70L/h.
Embodiment 50
Embodiment 50 eliminates the front pretreatment of step (3) sulfuration with differing only in of embodiment 1.
Comparative example 1
(1) the dry bar of catalyst is prepared: same as in Example 1.
(2) by G1 directly in 400 DEG C of roastings 3 hours, obtaining reference oxidized catalyst, do not carry out vulcanizing front pretreatment, be directly entered sulfurating stage, vulcanization process is with embodiment 1.
Comparative example 2
(1) the dry bar of catalyst is prepared: same as in Example 1.
(2) by G1 directly in 400 DEG C of roastings 3 hours, obtaining reference oxidized catalyst, process according still further to " pre-treatment step before sulfuration " same as in Example 2, enter sulfurating stage afterwards, vulcanization process is with embodiment 1.
The quality evaluation of catalyst:
Reaction pressure be 5.0MPa, temperature 340 DEG C, liquid hourly space velocity (LHSV) 1.5h-1, under the conditions of hydrogen to oil volume ratio is 800, soybean oil (character is as shown in table 1) is carried out hydrogenation deoxidation modification, evaluates each catalyst performance.Result shows, all embodiments all show following characteristics: the catalyst of all embodiments of the present invention is after running 100h, hydrogenation decarboxylation and hydrogenation decarbonylation selectivity are between 25-35%, on unloading rear catalyst, unloading rear catalyst (is characterized more than 70% by Mo sulphidity with x-ray photoelectron spectroscopic technique, and account for the ratio of total Mo atom to represent Mo sulphidity with+4 valency molybdenum atoms on catalyst), the specific surface area of unloading rear catalyst is at 270m2/ more than g, and the diesel oil distillate obtained can be in harmonious proportion in any proportion with petroleum diesel, and without sulfur, without aromatic hydrocarbons, the most oxygen-containing, NOx emission is few, environmental friendliness, and storage stability is good, can use as high cetane number diesel oil addO-on therapy.
The concrete outcome of section Example is listed below, and as shown in table 2 and table 3, table 2 is the result after running 24 hours, and table 3 is the result after running 100h.
Table 1
| Project | Numerical value |
| 20 DEG C of density/(g/cm3) | 0.9116 |
| 40 DEG C of viscosity/(mm2/s) | 40.84 |
| Freezing point/DEG C | 10 |
| C content/% | 76.66 |
| H content/% | 11.95 |
| O content/% | 11.39 |
| D-2887 boiling range/DEG C | |
| 0.5% | 438 |
| 30% | 534 |
| 50% | 542 |
| 70% | 552 |
| 90% | 567 |
| 95% | 571 |
Table 2
Table 3
From table 2 with the result of table 3 it can be seen that compared with two comparative examples, the catalyst of the present invention, when preparing biodiesel, has higher stability and hydrogenation decarboxylation selectivity, and hydrothermal energy is good, sulphidity is high.
Last it is noted that various embodiments above is only in order to illustrate technical scheme, it is not intended to limit；Although the present invention being described in detail with reference to foregoing embodiments, it will be understood by those within the art that: the technical scheme described in foregoing embodiments still can be modified by it, or the most some or all of technical characteristic is carried out equivalent；And these amendments or replacement, do not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme.
Claims (10)
1. the preparation method for the catalyst of biological oil hydrodeoxygenation, it is characterised in that include
Following steps:
During roasting is impregnated with the catalyst carrier of active component, make described in be impregnated with activity group
The catalyst carrier divided contacts with oxygen-bearing organic matter, completes described roasting and obtains oxidized catalyst, it
After carry out vulcanizing treatment, obtain product；
Wherein, described active component is mainly by one or more in group vib metal, and VIII
One or more compositions in metal.
The preparation method of the catalyst for biological oil hydrodeoxygenation the most according to claim 1,
It is characterized in that, described oxygen-bearing organic matter is selected from Organic Alcohol, organic acid, organic ketone, phenols extremely
Few one, preferably Organic Alcohol and/or organic acid；
Described Organic Alcohol is in ethylene glycol, glycerol, Polyethylene Glycol, diethylene glycol and butanediol
Plant or multiple, preferably at least one in ethylene glycol, glycerol and Polyethylene Glycol；Described poly-second two
The number-average molecular weight of alcohol is preferably 200-1500；
Described organic acid is acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2-cyclohexane diamine four
Acetic acid, citric acid, tartaric acid, malic acid, 1,2-1,2-diaminocyclohexane tetraacetic acid, glycine, secondary nitrogen
At least one in base triacetic acid and ethylenediaminetetraacetic acid, preferably acetic acid, citric acid and ethylenediamine tetraacetic
At least one in acetic acid；
Described phenolic compound selected from phenol, Benzodiazepines, benzenetriol, cresol, amino phenols, nitrophenols,
At least one in chlorophenol, preferably phenol and/or Benzodiazepines.
The preparation method of the catalyst for biological oil hydrodeoxygenation the most according to claim 1,
It is characterized in that, and also include before described sulfuration after described roasting: make described oxidation state be catalyzed
Agent absorption oxygen-containing inorganic acid；
Preferably, described oxygen-containing inorganic acid is the oxygen-containing inorganic acid of VA race, preferably phosphoric acid, arsenic acid,
At least one in metaantimmonic acid etc., preferably phosphoric acid.
The preparation method of the catalyst for biological oil hydrodeoxygenation the most according to claim 1,
It is characterized in that, described catalyst carrier is alumina support；Described group vib metal be preferably Mo and
/ or W, described group VIII metal is preferably Co and/or Ni；Described active component is preferably molybdenum and nickel；
Preferably, on the basis of described catalyst carrier, the content of group vib metallic compound is
0-30wt%, preferably 3-20wt%；The content of group VIII metal compound is 0-30wt%, is preferably
1-10wt%.
The preparation method of the catalyst for biological oil hydrodeoxygenation the most according to claim 1,
It is characterized in that, the temperature of described roasting is 400-600 DEG C, preferably 420-500 DEG C；Preferably,
The time of described roasting is 2-8h, preferably 3-6h.
The preparation side of the catalyst for biological oil hydrodeoxygenation the most according to claim 1 and 2
Method, it is characterised in that the described method that contacts with oxygen-bearing organic matter is: described oxygen-bearing organic matter with
0.1-20h-1Air speed contact with the described catalyst carrier being impregnated with active component, preferably 1-10h-1。
The preparation method of the catalyst for biological oil hydrodeoxygenation the most according to claim 3,
It is characterized in that, the method for described absorption oxygen-containing inorganic acid is: existed by the solution of oxygen-containing inorganic acid
Contact with described oxidized catalyst at 100-140 DEG C, and after described absorption and at described sulfuration
It is dried at being additionally included in 200-250 DEG C before reason；
Preferably, the method for described absorption oxygen-containing inorganic acid is: make described oxidized catalyst and described
Oxygen-containing inorganic acid reacts in fixed bed reactors, and keeps the temperature in reactor to be 100-140 DEG C,
Partial pressure is 1.5-4MPa, and gas flow is 50-70L/h.
The preparation side of the catalyst for biological oil hydrodeoxygenation the most according to claim 1 and 2
Method, it is characterised in that the catalyst carrier being impregnated with active component described in making contacts with oxygen-bearing organic matter
Time, described oxygen-bearing organic matter is 0-10%, preferably 5-8% with the mass ratio of described catalyst carrier,
It is preferably 0.1-5%, preferably 0.05-4%.
The preparation method of the catalyst for biological oil hydrodeoxygenation the most according to claim 3,
It is characterized in that, when carrying out described absorption, on the basis of described catalyst carrier, described oxygen-containing inorganic
The consumption of acid is: 0.1-10wt%, preferably 0.2-5wt%, more preferably 0.2-3wt%.
The preparation method of the catalyst for biological oil hydrodeoxygenation the most according to claim 1,
It is characterized in that, described in be impregnated with the catalyst carrier of active component possibly together with extrusion aid, peptizer and
One or more in expanding agent.
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