CN105903475A - Hydrodeoxygenation method of bio-oil as well as catalyst and preparation method used thereby - Google Patents
Hydrodeoxygenation method of bio-oil as well as catalyst and preparation method used thereby Download PDFInfo
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- CN105903475A CN105903475A CN201610284615.0A CN201610284615A CN105903475A CN 105903475 A CN105903475 A CN 105903475A CN 201610284615 A CN201610284615 A CN 201610284615A CN 105903475 A CN105903475 A CN 105903475A
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- catalyst
- acid
- preparation
- oxygen
- organic matter
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
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- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-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
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8877—Vanadium, tantalum, niobium or polonium
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
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- 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
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
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- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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Abstract
The invention provides a hydrodeoxygenation method of bio-oil as well as a catalyst and a preparation method used thereby. The preparation method comprises: contacting a catalyst carrier dipped with active components with an oxygen-containing organic matter during the process of roasting the catalyst carrier dipped with the active components, completing the roasting to obtain an oxidized catalyst; vulcanizing the oxidized catalyst to obtain the product, wherein the active components comprise at least one or more of VIB group metals, one or more of VIII group metals, and one or more of VB group metals. By preprocessing the catalyst with the oxygen-containing organic matter, the selectivity of hydrogenated decarboxylation and decarbonylation reaction is increased; the sulfur fixation performance and thermal stability of the catalyst are improved.
Description
Technical field
The present invention relates to modifying oil product technical field, especially relate to the method for biological oil hydrodeoxygenation and catalyst used thereof and preparation method thereof.
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 catalyst that the reaction of vegetable and animals oils hydrogenation deoxidation is used 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, CN1946831A and US7608558 discloses a kind of carbon monoxide-olefin polymeric, it contains selected from the group vib metal component of molybdenum, tungsten and mixture thereof and selected from vanadium, niobium and the V race metal component of tantalum and mixture thereof with selected from nickel, cobalt, ferrum and the group VIII metal component of mixture thereof, these metal components (calculating with oxide) are constituted at least 50 weight % of catalyst, and wherein the mol ratio between metal component meets following formula: (group vib+V race): (VIII)=(0.35-2): 1.Research shows, this carbon monoxide-olefin polymeric shows high activity and good aromatic compounds removal capacity in terms of removal of sulphur.But, this catalyst easy in inactivation, hydrothermal stability in hydrogenation deoxidation reacts is poor.
Therefore, the hydrogenation deoxidation catalyst preparation method for preparing biodiesel of a kind of high activity and 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 third object of the present invention is a kind of method providing biological oil hydrodeoxygenation, described method can the cycle of operation of extension fixture, improve production efficiency.
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；
Described oxidized catalyst is carried out vulcanizing treatment, obtains product；
Wherein, described active component at least contains one or more in group vib metal, one or more compositions in group VIII metal, and one or more in VB race 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 oxygen-bearing organic matter pretreatment, and select group vib, VIII, VB race three metalloid component, not only inhibit 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, make the sulfur in catalyst 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 mainly used in the hydrogenation deoxidation modification of vegetable and animals oils, naturally it is also possible to for other modifying oil product, 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.More than 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).
When the described herein above way of contact 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%.
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..Described carrier can be cloverleaf pattern, butterfly, cylinder, hollow cylindrical, quatrefoil, five shapes such as leaf, spherical.
Group vib of the present invention, VB race metal 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, the example of described group vib metal component includes but not limited to: chromium oxide (Cr2O3), molybdenum oxide (MoO3) and tungsten oxide (WO3).The example of described VB race metal component includes but not limited to: vanadium oxide (V2O5), niobium oxide (Nb2O5) and tantalum oxide (Ta2O5).The example of described group VIII metal component includes but not limited to: ferrum oxide (FeO), cobalt oxide (CoO), nickel oxide (NiO), ruthenium-oxide (AuO2), rhodium oxide (Rh2O3) and Palladium monoxide (PdO).On the other hand, if for merely with metallic element, described group vib metal is preferably at least one in Cr, Mo, W, and described group VIII metal is preferably at least one in Fe, Co, Ni；Described VB race metal is preferably at least one in vanadium, niobium, tantalum.
In described hydrogenation catalyst, preferably, described group vib metal component is MoO3Or WO3, described VB race metal component is V2O5, described group VIII metal component is CoO or NiO.More excellent, described active component is preferably vanadium, molybdenum and nickel.
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, VB race 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, in order to improve deoxidation effectiveness and specific surface area, in catalyst, the content of active component is preferably: on the basis of described catalyst carrier, on the basis of described catalyst carrier, the content of group vib metallic compound is 0.01-9.5wt%；Preferably, the content of group VIII metal compound is 0.01-0.5wt%；Preferably, the content of VB race metallic compound is 0.01-11.5wt%；Preferably, on the basis of the described group vib metallic element total mole number with VB race metallic element, the content of VB race metallic element is 2-10%.
Compared with prior art, invention achieves techniques below effect:
(1) with group vib metal, VB race metal, group VIII metal as active component, in conjunction with the pretreatment of oxygen-bearing organic matter, improve the sulfur fixation performance of catalyst, heat stability, 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 more stable.
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 0.62mL/g, and specific surface area is 280m2/g。
50g ammonium metavanadate, 50g ammonium heptamolybdate, 10g nickel nitrate and 1000g citric acid 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) 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:
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 0.62mL/g, and specific surface area is 280m2/g。
28g ammonium metavanadate, 18g ammonium heptamolybdate, 1g nickel nitrate are added in 350mL aqueous solution, after heating and stirring and be completely dissolved to ammonium metavanadate and citric acid, obtains 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 G2 of active component.
(2) oxygen-bearing organic matter processes:
G2 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) sulfuration:
Same as in Example 1.
Embodiment 3
(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 0.62mL/g, and specific surface area is 280m2/g。
60g ammonium metavanadate, 70g ammonium heptamolybdate, 10g nickel nitrate are added in 350mL aqueous solution, after heating and stirring and be completely dissolved to ammonium metavanadate and citric acid, obtains 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 G2 of active component.
(2) oxygen-bearing organic matter processes:
G2 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 8 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 0.5.
(3) sulfuration:
Same as in Example 1.
Embodiment 4-6
Embodiment 4-6 and embodiment 1 to differ only in metal active constituent different, the molal quantity of its VI B race metallic element, the molal quantity of group vib metallic element, group VIII metal element the molal quantity of metal of all corresponding with the embodiment race of molal quantity identical, the compound of active component is respectively as follows:
V2O5/WO3/ NiO, V2O5/MoO3/ CoO, V2O5/MoO3+WO3(both mix with equimolar)/CoO+NiO (both mix with equimolar).
Embodiment 7-8
Embodiment 7-8 is different from the active component consumption differing only in dipping of embodiment 1, and consumption is respectively as follows: 0.1 ammonium metavanadate/95g ammonium heptamolybdate/5g nickel nitrate, 115 ammonium metavanadates/0.1g ammonium heptamolybdate/0.1g nickel nitrate.
Embodiment 9-15
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 16
Different from the consumption differing only in acetic acid used during oxygen-bearing organic matter processes of embodiment 1, on the basis of the quality of Z, consumption is: 1%.
Embodiment 17-19
Embodiment 17-19 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 20-22
Embodiment 20-22 and embodiment 1 to differ only in roasting time when oxygen-bearing organic matter processes different, be respectively as follows: 2h, 6h, 8h.
Embodiment 23-26
Embodiment 23-26 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。
Comparative example 1
Take the carrier Z of 400g embodiment 1 preparation, with 500 milliliters containing 90 grams per liter MoO3Filtering after impregnating 1 hour with the ammonium heptamolybdate of 32 grams per liter NiO and nickel nitrate mixed solution, then dry 4 hours in 120 DEG C, then at 400 DEG C of roastings 2 hours, obtain reference oxidized catalyst, be directly entered sulfurating stage, vulcanization process is with embodiment 1.
Comparative example 2
The dry bar G1 that in Example 1 prepared by step (1), loads in horizontal pipe stove, is only passed through air, directly in 400 DEG C of roastings 2 hours, obtains reference oxidized catalyst, enter sulfurating stage afterwards, and vulcanization process is with embodiment 1.
The quality evaluation of catalyst:
Reaction pressure be 5.0MPa, temperature 360 DEG C, liquid hourly space velocity (LHSV) 2h-1, under the conditions of hydrogen to oil volume ratio is 1000, rapeseed oil 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 more than 25%, on unloading rear catalyst, unloading rear catalyst (is characterized more than 75% 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 250m2/ 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 1 and Table 2, table 1 is the result after running 24 hours, and table 2 is the result after running 100h.
Table 1
Table 2
From the result of Tables 1 and 2 it can be seen that compared with three 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；
Described oxidized catalyst is carried out vulcanizing treatment, obtains product；
Wherein, described active component at least contains one or more in group vib metal, VIII gold
One or more compositions in genus, and one or more in VB race 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
Plant or multiple, 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 one or more in ethylene glycol, glycerol and Polyethylene Glycol；Described poly-second
The number-average molecular weight of glycol 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
One or more in base triacetic acid and ethylenediaminetetraacetic acid, preferably acetic acid, citric acid and ethylenediamine
One or more in tetraacethyl；
Described phenolic compound selected from phenol, Benzodiazepines, benzenetriol, cresol, amino phenols, nitrophenols,
One or more 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, described catalyst carrier is alumina support；Described group vib metal be preferably Cr,
At least one in Mo, W, described group VIII metal is preferably at least one in Fe, Co, Ni；
Described VB race metal is preferably at least one in vanadium, niobium, tantalum；
Described active component is preferably vanadium, molybdenum and nickel.
4. according to the preparation side of the catalyst for biological oil hydrodeoxygenation described in claim 1 or 3
Method, it is characterised in that preferably, on the basis of described catalyst carrier, group vib metallic compound
Content is 0.01-9.5wt%；
Preferably, the content of group VIII metal compound is 0.01-0.5wt%；
Preferably, the content of VB race metallic compound is 0.01-11.5wt%；
Preferably, on the basis of the described group vib metallic element total mole number with VB race metallic element,
The consumption of VB race metallic element is 2-10%.
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 is with 0.1-20h-1Air speed carry with the described catalyst being impregnated with active component
Body contacts, preferably 1-10h-1。
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 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.
9. the catalyst for biological oil hydrodeoxygenation, it is characterised in that use claim 1-8
Preparation method described in any one prepares.
10. the method for biological oil hydrodeoxygenation, it is characterised in that use the catalysis described in claim 9
Agent carries out hydrogenation deoxidation modification to bio oil.
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Cited By (3)
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| CN110871082A (en) * | 2019-12-03 | 2020-03-10 | 中国科学院青岛生物能源与过程研究所 | Biodiesel hydrodeoxygenation catalyst and preparation method thereof |
| CN110871084A (en) * | 2019-12-03 | 2020-03-10 | 中国科学院青岛生物能源与过程研究所 | Non-supported hydrodeoxygenation catalyst and preparation method thereof |
| CN112844464A (en) * | 2021-01-22 | 2021-05-28 | 华南农业大学 | Hydrodeoxygenation catalyst and preparation method and application thereof |
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| CN112844464B (en) * | 2021-01-22 | 2022-07-12 | 华南农业大学 | Hydrodeoxygenation catalyst and preparation method and application thereof |
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