CN105903475B - The method of biological oil hydrodeoxygenation and its catalyst and preparation method thereof used - Google Patents
The method of biological oil hydrodeoxygenation and its catalyst and preparation method thereof used Download PDFInfo
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- CN105903475B CN105903475B CN201610284615.0A CN201610284615A CN105903475B CN 105903475 B CN105903475 B CN 105903475B CN 201610284615 A CN201610284615 A CN 201610284615A CN 105903475 B CN105903475 B CN 105903475B
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- catalyst
- preparation
- biological oil
- oil hydrodeoxygenation
- oxygen
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- 239000003054 catalyst Substances 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 37
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 37
- 239000001301 oxygen Substances 0.000 claims abstract description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000005416 organic matter Substances 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 47
- 239000003921 oil Substances 0.000 claims description 45
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 43
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 19
- 238000005984 hydrogenation reaction Methods 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 150000007524 organic acids Chemical class 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000012075 bio-oil Substances 0.000 claims description 6
- 235000015165 citric acid Nutrition 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 229910000765 intermetallic Inorganic materials 0.000 claims description 6
- 150000002989 phenols Chemical class 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229960001484 edetic acid Drugs 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 150000002736 metal compounds Chemical class 0.000 claims description 3
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- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 150000001896 cresols Chemical class 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 15
- 239000001257 hydrogen Substances 0.000 abstract description 14
- 238000006114 decarboxylation reaction Methods 0.000 abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 10
- 150000002431 hydrogen Chemical class 0.000 abstract description 10
- 238000006606 decarbonylation reaction Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 5
- 235000019198 oils Nutrition 0.000 description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 9
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 9
- 238000004073 vulcanization Methods 0.000 description 9
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- 238000001035 drying Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 229910000480 nickel oxide Inorganic materials 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical class [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
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- 239000002283 diesel fuel Substances 0.000 description 5
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- 238000006703 hydration reaction Methods 0.000 description 5
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- 239000000126 substance Substances 0.000 description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- 235000005979 Citrus limon Nutrition 0.000 description 2
- 244000131522 Citrus pyriformis Species 0.000 description 2
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- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
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- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
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- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- AFTJNIKGLUJJPI-UHFFFAOYSA-N acetic acid;cyclohexane-1,2-diamine Chemical class CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NC1CCCCC1N AFTJNIKGLUJJPI-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
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- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
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- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 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
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- XBBXDTCPEWHXKL-UHFFFAOYSA-N rhodium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Rh+3].[Rh+3] XBBXDTCPEWHXKL-UHFFFAOYSA-N 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
Abstract
The present invention provides the method for biological oil hydrodeoxygenation and its catalyst and preparation method thereof used.Preparation method is：During roasting is impregnated with the catalyst carrier of active component, the catalyst carrier for being impregnated with active component is made to be contacted with oxygen-bearing organic matter, completes the roasting and obtain oxidized catalyst；Vulcanizing treatment is carried out to get product to the oxidized catalyst；Wherein, the active component is one or more in the one or more compositions and VB races metal in group VIII metal at least containing one or more in group vib metal.The present invention pre-processes catalyst using oxygen-bearing organic matter, increases the selectivity for adding hydrogen decarboxylation decarbonylation reaction, improves the sulfur fixation performance and thermal stability of catalyst.
Description
Technical field
The present invention relates to modifying oil product technical fields, method more particularly, to biological oil hydrodeoxygenation and its used urge
Agent and preparation method thereof.
Background technology
With increasingly sharpening for crude oil heaviness and environmental pollution, liquefied coal coil, Fischer-Tropsch synthesis oil and bio oil are (various dynamic
Vegetable oil) concern of researcher, especially bio oil are received as ideal fungible energy source, because it is with pollutant emission
Less, the short feature of cycle period and as research focus.Compared with crude oil, the content of oxygenatedchemicals is higher in bio oil,
Main oxygenatedchemicals type includes phenols, furans, esters and ketone etc..It is raw due to the presence of a large amount of oxygenatedchemicals
The oxygen content of object oil product is sometime up to 50 weight % or more, and to cause bio oil to have, combustion heat value is low, chemical property is unstable
It is straight as vehicle fuel seriously to hinder it compared with the unfavorable feature such as strong, big to the corrosivity of equipment for fixed, heating easily polymerization, acidity
Connect use, it is therefore desirable to which upgrading is carried out to bio oil by hydrogenation deoxidation.
The main component of vegetable and animals oils is triglyceride, and fatty acid chain length is generally C14~C22, wherein C16With
C18Account for about the 90% of all fatty acids.The diesel component that vegetable and animals oils hydrogenation deoxidation is prepared is mainly by C12~C22Straight chain alkane
Hydrocarbon forms, and Cetane number can in any proportion reconcile up to 90~100 with petroleum diesel, and no sulphur, no aromatic hydrocarbons is not oxygen-containing,
NOx emission is few, environmental-friendly, and storage stability is good, can be used as high cetane number diesel oil addO-on therapy.Therefore, it moves and plants
Object oil hydrogenation deoxidation prepares biodiesel technology, and a kind of novel renewable automobile-used supplement of effect is with alternative fuel by the blueness of people
It looks at.
Vegetable and animals oils Hydrogenation mainly has insatiable hunger in vegetable and animals oils for a variety of chemical reactions are contained during diesel component
With aliphatic acid plus hydrogen saturation, hydrogenation deoxidation plus hydrogen decarboxylation, add hydrogen de-carbonyl reaction, other also hydroisomerization reaction
Deng.Currently, catalyst used by the reaction of vegetable and animals oils hydrogenation deoxidation has higher hydrodesulfurization and hydrogenation deoxidation activity, together
When also there is higher hydrogenation deoxidation initial activity, but the disadvantage is that poor catalyst stability, it is easy to inactivate.
For example, CN1946831A and US7608558 disclose a kind of carbon monoxide-olefin polymeric, contain selected from molybdenum, tungsten and its
The group vib metal component of mixture and V races metal component selected from vanadium, niobium and tantalum and its mixture and selected from nickel, cobalt, iron and
The group VIII metal component of its mixture, these metal components (being calculated with oxide) are constituted at least 50 weight % of catalyst,
Molar ratio wherein between metal component meets following formula：(group vib+V races):(VIII group)=(0.35-2):1.Studies have shown that should
Carbon monoxide-olefin polymeric shows high activity and good aromatic compounds removal capacity in terms of removal of sulphur.However, the catalysis
Agent easy in inactivation, hydrothermal stability in hydrogenation deoxidation reaction is poor.
Therefore, there is an urgent need for develop a kind of hydrogenation deoxidation catalyst for being used to prepare biodiesel of high activity and stability at present
Preparation method.
Invention content
The purpose of the present invention is to provide a kind of preparation method of the catalyst for biological oil hydrodeoxygenation, the systems
Preparation Method pre-processes catalyst using oxygen-bearing organic matter, increases the selectivity for adding hydrogen decarboxylation decarbonylation reaction, improves
The sulfur fixation performance and thermal stability of catalyst.
Another object of the present invention is to provide a kind of catalyst for biological oil hydrodeoxygenation, catalyst tools
There is the features such as adding hydrogen decarboxylation decarbonylation high selectivity, sulfur fixation performance and thermal stability are high.
The third object of the present invention is to provide a kind of method of biological oil hydrodeoxygenation, and the method can extend dress
The cycle of operation set improves production efficiency.
A kind of preparation method of catalyst for biological oil hydrodeoxygenation, includes the following steps：
During roasting is impregnated with the catalyst carrier of active component, make the catalyst for being impregnated with active component
Carrier is contacted with oxygen-bearing organic matter, is completed the roasting and is obtained oxidized catalyst；
Vulcanizing treatment is carried out to get product to the oxidized catalyst；
Wherein, the active component is at least containing one or more in group vib metal, one kind in group VIII metal or
It is one or more in a variety of compositions and VB races metal.
Usually, the main reason for vegetable and animals oils hydrogenation deoxidation catalyst inactivates has carbon deposit, the exchange of oxygen sulphur and carrier
Carrier specific surface area caused by hydration reduces and activity mutually aggregation etc..Therefore inhibit carrier hydration caused by specific surface area reduce with
And the aggregation of active phase, play an important roll for the raising of hydrogenation deoxidation catalyst stability.However the prior art is usually not
It can take into account and inhibit carrier hydration and high two effects of reaction selectivity.By taking existing alumina support as an example, hydrogenation deoxidation catalysis
Aluminium oxide used by agent is spinel-like type structure, and a large amount of cations in surface and anion vacancy play alumina hydration
Key effect, therefore widespread practice is all that auxiliary agent atom is added and occupies alumina carrier surface vacancy by support modification,
To inhibit carrier to be hydrated；However, the shortcomings that way, is to reduce active metal and carrier Interaction Force, to one
Determine the active facies type of influence vulcanization rear catalyst in degree, and reduces the selectivity of hydrogenation deoxidation and decarboxylation in turn.
And the preparation method of the present invention is pre-processed by oxygen-bearing organic matter, and select group vib, VIII group, VB races three classes
Metal component not only inhibits the aquation of carrier, plays and increases acidity of catalyst and active phase dispersion, and increases in turn
Decarboxylation decarbonylation reaction also improves the sulfur fixation performance of catalyst to the selectivity of dehydration, and the sulphur in catalyst is made to exist
It is not easily runed off in reaction process, even if not adding vulcanizing agent, sulphidity remains above the catalyst of conventional method preparation.
Catalyst of the present invention is mainly used for the hydrogenation deoxidation modification of vegetable and animals oils, naturally it is also possible to be used for other oil
Product modify, even more technical fields.
The above-mentioned preparation method of the present invention can also be further improved, such as：
Oxygen-bearing organic matter of the present invention refers to the arbitrarily organic matter containing oxygen atom, for example, selected from Organic Alcohol, organic acid,
It is one or more in organic ketone, phenols, preferably Organic Alcohol and/or organic acid.
Under normal conditions, higher to the selectivity for adding hydrogen decarboxylation decarbonylation reaction after Organic Alcohol, organic acid processing.
The Organic Alcohol can be selected from one kind in ethylene glycol, glycerine, polyethylene glycol, diethylene glycol and butanediol or more
Kind, it is preferably one or more in ethylene glycol, glycerine and polyethylene glycol；The number-average molecular weight of the polyethylene glycol is preferably
200-1500。
The organic acid can be selected from acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2- cyclohexanediamine tetraacetic acids, lemon
In lemon acid, tartaric acid, malic acid, 1,2- 1,2-diaminocyclohexane tetraacetic acids, amion acetic acid, nitrilotriacetic acid and ethylenediamine tetra-acetic acid
It is one or more, it is preferably one or more in acetic acid, citric acid and ethylenediamine tetra-acetic acid.
The phenolic compound can be in phenol, benzenediol, benzenetriol, cresols, amino phenols, nitrophenols, chlorophenol
It is one or more, preferably phenol and/or benzenediol.
It is mainly contacted as a solution when above-mentioned oxygen-bearing organic matter is contacted with catalyst carrier, the mode of contact also has very
It is a variety of, it can be direct all mixing, can also be that the solution of oxygen-bearing organic matter is continuously injected into catalyst carrier
On, it can come into full contact with and be attached together with both guarantees.It is roasted while the above contact, the temperature of the roasting is excellent
It is selected as 400-600 DEG C, more preferably 420-500 DEG C；The time of the roasting is preferably 2-8h, more preferably 3-6h.By with
Upper preferred roasting condition can improve catalyst plus hydrogen decarboxylation decarbonylation selectivity and thermal stability, extend oil product and add
The cycle of operation that tooling is set.
When the way of contact being continuously injected into described herein above, the oxygen-bearing organic matter is preferably with 0.1-20h-1Air speed
It is contacted with the catalyst carrier for being impregnated with active component, more preferably 1-10h-1.Select suitable air speed can be to avoid urging
Caused by agent dusting the problem of remitted its fury.
Dosage about oxygen-bearing organic matter, it is preferable that the catalyst carrier for being impregnated with active component is made to have with oxygen-containing
When machine object contacts, the mass ratio of the oxygen-bearing organic matter and the catalyst carrier is 0-10%, preferably 5-8%, preferably
0.1-5%, preferably 0.05-4%.
The available type of any conventional, such as alumina support or oxygen may be used in catalyst carrier of the present invention
Change the mixture of at least one of aluminium and silica, titanium oxide and zirconium oxide；Wherein, the aluminium oxide for example can be γ-oxygen
Change at least one of aluminium, η-aluminium oxide, θ-aluminium oxide, δ-aluminium oxide and χ-aluminium oxide.In addition, the carrier can be three leaves
Careless shape, butterfly, cylinder, hollow cylindrical, quatrefoil, five shapes such as leaf, spherical.Above-mentioned carrier can be obtained by commercially available
It arrives, it can also be according to well known to a person skilled in the art various methods to be prepared.For example, alumina support can be by by oxygen
Change the roasting of aluminium precursor, it is made to be converted into gama-alumina, η-aluminium oxide, θ-aluminium oxide, δ-aluminium oxide and χ-aluminium oxide extremely
Few one kind.Optionally, before firing and/or later, first aluminium oxide precursor can be molded, to prepare suitable practical operation
Required shape (such as spherical shape, sheet, bar shaped).The molding can be carried out according to the method for this field routine, such as spin
Method, pressed disc method and extrusion method etc..In forming process, such as during extruded moulding, in order to ensure it is molding be smoothed out,
Water, extrusion aid and/or peptizing agent can be added into the aluminium oxide precursor, and be optionally added expanding agent, be then extruded into
Type is dried and roasts later.Conventional place may be used in the extrusion aid, the type of peptizing agent and expanding agent and dosage
Reason, for example, common extrusion aid can be in sesbania powder, methylcellulose, starch, polyvinyl alcohol and polyethanol at least one
Kind, the peptizing agent can be Organic Alcohol and/or organic acid, the expanding agent can be starch, synthetic cellulose, polymeric alcohol and
At least one of surfactant.Wherein, the synthetic cellulose is preferably hydroxymethyl cellulose, methylcellulose, ethyl
At least one of cellulose and hydroxyl fiber fat alcohol polyethylene ether.The polymeric alcohol be preferably polyethylene glycol, poly- propyl alcohol and
At least one of polyvinyl alcohol.The surfactant be preferably fat alcohol polyethylene ether, fatty alkanol amide and its derivative,
Molecular weight is at least one of propylene alcohol copolymer and maleic acid copolymer of 200-10000.The item of item drying will be squeezed out
Part generally includes：Drying temperature can be 40-350 DEG C, preferably 100-200 DEG C；Drying time can be 1-24 hours, preferably
It is 2-12 hours.The condition of extrusion item roasting after drying is generally included：Calcination temperature can be 350-1000 DEG C, preferably
600-950℃；Roasting time can be 1-10 hours, preferably 2-6 hours.The aluminium oxide precursor can be selected from three hydrations
At least one of aluminium oxide, monohydrate alumina, amorphous hydroted alumina etc..The carrier can be cloverleaf pattern, butterfly,
Cylinder, hollow cylindrical, quatrefoil, five shapes such as leaf, spherical.
Group vib, VB races metal and group VIII metal component of the present invention are usually added in the form of the oxide, certainly
Other feasible chemical forms, such as nitrate, carbonate, sulfate, meta-acid salt, ammonium salt etc. may be used.Wherein, described
The example of group vib metal component includes but not limited to：Chromium oxide (Cr2O3), molybdenum oxide (MoO3) and tungsten oxide (WO3).The VB
The example of race's metal component includes but not limited to：Vanadium oxide (V2O5), niobium oxide (Nb2O5) and tantalum oxide (Ta2O5).The VIII
The example of race's metal component includes but not limited to：Iron oxide (FeO), cobalt oxide (CoO), nickel oxide (NiO), ruthenium-oxide
(AuO2), rhodium oxide (Rh2O3) and palladium oxide (PdO).On the other hand, if merely with metallic element for, the group vib metal
Preferably at least one of Cr, Mo, W, the group VIII metal are preferably at least one of Fe, Co, Ni；The VB races gold
Belong to is preferably at least one of vanadium, niobium, tantalum.
In the hydrogenation catalyst, preferably, the group vib metal component is MoO3Or WO3, VB races metal
Group is divided into V2O5, the group VIII metal group is divided into CoO or NiO.More preferably, the active component is preferably vanadium, molybdenum and nickel.
In catalyst carrier there are many kinds of the methods of impregnating metal active component, such as infusion process, spraying.Preferably,
By carrier impregnation in the maceration extract of the compound of metallic components, then it is dried.Wherein, the solvent in maceration extract can be with
For the various inert liquids that can dissolve the group vib metallic compound, VB races metallic compound and group VIII metal compound
State substance, for example, at least one of water, alcohol, ether, aldehyde and ketone can be selected from.
Vulcanize in addition, dry pre-sulfiding or wet method finally may be used to the vulcanizing treatment of catalyst.Specifically, for dry method
For vulcanization, the curing medium used can be H2And H2The mixture of S, and H in the curing medium2The volumetric concentration of S can be with
For 0.1-5v%, preferably 1-2v%.For wet method vulcanization, generally use faces hydrogen vulcanization, and the curing medium of use can
Think diesel oil and disulphide and/or the mixture of mercaptan, and the volumetric concentration of sulphur-containing substance can be in the curing medium
0.1-10v%, preferably 0.1-3.5v%, more preferably 0.4-2v%.Wherein, the disulphide can be CS2、CH3-S-
S-CH3And CH3-S-S-C2H5At least one of.The mercaptan can be C4H9SH、C2H5SH and CH3At least one of SH.
Preferably dry pre-sulfiding method is：The temperature of vulcanizing system is risen to from 20-40 DEG C with the rate of 25-35 DEG C/h
160-180 DEG C, and start into H2S；The temperature of vulcanizing system is risen to 220-240 DEG C with the rate of 10-20 DEG C/h again, and at this
At a temperature of maintain vulcanizing system in gas phase H2S concentration is constant and constant temperature vulcanizes 2-6h；Body will be vulcanized with the rate of 5-15 DEG C/h again
The temperature of system rises to 270-290 DEG C and constant temperature vulcanization 2-6h；Then again with the rate of 5-15 DEG C/h by the temperature liter of vulcanizing system
To 300-370 DEG C, and gas phase H in vulcanizing system is maintained at such a temperature2S concentration is constant and constant temperature vulcanizes 2-6h.
In addition, in order to improve deoxidation effectiveness and specific surface area, the content of active component is preferably in catalyst：It is urged with described
On the basis of agent carrier, on the basis of the catalyst carrier, the content of group vib metallic compound is 0.01-9.5wt%；It is excellent
The content of selection of land, group VIII metal compound is 0.01-0.5wt%；Preferably, the content of VB races metallic compound is 0.01-
11.5wt%；Preferably, on the basis of the total mole number of the group vib metallic element and VB races metallic element, VB races metal member
The content of element is 2-10%.
Compared with prior art, invention achieves following technique effects：
(1) using group vib metal, VB races metal, group VIII metal as active component, in conjunction with the pretreatment of oxygen-bearing organic matter,
The sulfur fixation performance of catalyst, thermal stability are improved, and adds the selectivity of hydrogen decarboxylation decarbonylation reaction；
(2) it can be used for vegetable and animals oils and prepare diesel oil；
(3) specific area of catalyst of the present invention and sulphidity are more stable.
Specific implementation mode
Technical scheme of the present invention is clearly and completely described below in conjunction with specific implementation mode, but ability
Field technique personnel will be understood that following described embodiments are some of the embodiments of the present invention, instead of all the embodiments,
It is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, the common skill in this field
The every other embodiment that art personnel are obtained without making creative work belongs to the model that the present invention protects
It encloses.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same or instrument
Production firm person is not specified, is the conventional products that can be obtained by commercially available purchase.
Air speed of the present invention refers both to " volume space velocity ".
Embodiment 1
(1) the dry item of catalyst is prepared：
It weighs 1000 grams of dry glue powders and 30 grams of sesbania powders and is uniformly mixed, 900 milliliters of nitric acid containing 28g of addition is water-soluble later
Liquid is extruded into the cylindrical wet bar of outer diameter φ 1.4mm on plunger type bar extruder.Then cylindrical wet bar is small in 120 DEG C of dryings 4
When, it is roasted 3 hours then at 600 DEG C, obtains carrier Z, Kong Rongwei 0.62mL/g, specific surface area 280m2/g。
50g ammonium metavanadates, 50g ammonium heptamolybdates, 10g nickel nitrates and 1000g citric acids are added in 400mL aqueous solutions,
It heats and stirs to after being completely dissolved, obtain maceration extract 500mL.The above-mentioned carrier Z of 400g are taken, all uniformly sprays by above-mentioned maceration extract
It is sprinkled upon on carrier Z, then half obtained dry catalyst is put into baking oven and is dried 4 hours in 120 DEG C, obtain impregnating active
The catalyst of component does a G1.
(2) oxygen-bearing organic matter is handled：
G1 is placed in ventable vertical tubular furnace, 400 DEG C of constant temperature calcinings 3 hours need in advance to match in roasting process
The acetic acid content set is the aqueous solution of 5 weight %, according to air speed 2h-1, it is persistently squeezed into plunger pump in catalyst roasting bed,
Finally obtain oxidized catalyst C1.Wherein, relative to the dry item of catalyst of 100 parts by weight, the quality for being passed through aqueous solution is total
It is 0.01.
(3) vulcanize：
The temperature of vulcanizing system is risen to 180 DEG C from 30 DEG C with the rate of 30 DEG C/h, and is started into H2S；Again with 10 DEG C/h
Rate the temperature of vulcanizing system is risen to 240 DEG C, and maintain gas phase H in vulcanizing system at such a temperature2S concentration is constant and permanent
Temperature vulcanization 4h；The temperature of vulcanizing system is risen to 290 DEG C with the rate of 15 DEG C/h again and constant temperature vulcanizes 6h；Then again with 15 DEG C/h
Rate the temperature of vulcanizing system is risen to 320 DEG C, and maintain gas phase H in vulcanizing system at such a temperature2S concentration is constant and permanent
Temperature vulcanization 5h.
Embodiment 2
(1) the dry item of catalyst is prepared：
It weighs 1000 grams of dry glue powders and 30 grams of sesbania powders and is uniformly mixed, 900 milliliters of nitric acid containing 28g of addition is water-soluble later
Liquid is extruded into the cylindrical wet bar of outer diameter φ 1.4mm on plunger type bar extruder.Then cylindrical wet bar is small in 120 DEG C of dryings 4
When, it is roasted 3 hours then at 600 DEG C, obtains carrier Z, Kong Rongwei 0.62mL/g, specific surface area 280m2/g。
28g ammonium metavanadates, 18g ammonium heptamolybdates, 1g nickel nitrates are added in 350mL aqueous solutions, heats and stirs to inclined vanadium
After sour ammonium and citric acid are completely dissolved, maceration extract 500mL is obtained.The above-mentioned carrier Z of 400g are taken, all uniformly sprays by above-mentioned maceration extract
It is sprinkled upon on carrier Z, then half obtained dry catalyst is put into baking oven and is dried 4 hours in 120 DEG C, obtain impregnating active
The catalyst of component does a G2.
(2) oxygen-bearing organic matter is handled：
G2 is placed in ventable vertical tubular furnace, 400 DEG C of constant temperature calcinings 3 hours need in advance to match in roasting process
The phenol content set is the aqueous solution of 7 weight %, according to air speed 5h-1, it is persistently squeezed into plunger pump in catalyst roasting bed,
Finally obtain oxidized catalyst C2.Wherein, relative to the dry item of catalyst of 100 parts by weight, the quality for being passed through aqueous solution is total
It is 0.2.
(3) vulcanize：
It is same as Example 1.
Embodiment 3
(1) the dry item of catalyst is prepared：
It weighs 1000 grams of dry glue powders and 30 grams of sesbania powders and is uniformly mixed, 900 milliliters of nitric acid containing 28g of addition is water-soluble later
Liquid is extruded into the cylindrical wet bar of outer diameter φ 1.4mm on plunger type bar extruder.Then cylindrical wet bar is small in 120 DEG C of dryings 4
When, it is roasted 3 hours then at 600 DEG C, obtains carrier Z, Kong Rongwei 0.62mL/g, specific surface area 280m2/g。
60g ammonium metavanadates, 70g ammonium heptamolybdates, 10g nickel nitrates are added in 350mL aqueous solutions, heats and stirs to inclined vanadium
After sour ammonium and citric acid are completely dissolved, maceration extract 500mL is obtained.The above-mentioned carrier Z of 400g are taken, all uniformly sprays by above-mentioned maceration extract
It is sprinkled upon on carrier Z, then half obtained dry catalyst is put into baking oven and is dried 4 hours in 120 DEG C, obtain impregnating active
The catalyst of component does a G2.
(2) oxygen-bearing organic matter is handled：
G2 is placed in ventable vertical tubular furnace, 400 DEG C of constant temperature calcinings 3 hours need in advance to match in roasting process
The phenol content set is the aqueous solution of 8 weight %, according to air speed 5h-1, it is persistently squeezed into plunger pump in catalyst roasting bed,
Finally obtain oxidized catalyst C2.Wherein, relative to the dry item of catalyst of 100 parts by weight, the quality for being passed through aqueous solution is total
It is 0.5.
(3) vulcanize：
It is same as Example 1.
Embodiment 4-6
Embodiment 4-6 and embodiment 1 differ only in that metal active constituent is different, mole of group vib metallic element
The molal quantity of the metal of the molal quantity race corresponding to embodiment of number, the molal quantity of group vib metallic element, group VIII metal element
Identical, the compound of active component is respectively：
V2O5/WO3/ NiO, V2O5/MoO3/ CoO, V2O5/MoO3+WO3(the two is mixed with equimolar)/CoO+NiO (the two
It is mixed with equimolar).
Embodiment 7-8
Embodiment 7-8 and embodiment 1 differ only in that the active component dosage of dipping is different, and dosage is respectively：0.1 partially
Ammonium vanadate/95g ammonium heptamolybdates/5g nickel nitrates, 115 ammonium metavanadates/0.1g ammonium heptamolybdates/0.1g nickel nitrates.
Embodiment 9-15
Embodiment 14-20 and embodiment 1 to differ only in the dosage of acetic acid used in oxygen-bearing organic matter processing different,
But dosage is identical (weight percent), and oxygen-bearing organic matter is respectively：
Ethylene glycol, glycerine, polyethylene glycol (molecular weight 200), polyethylene glycol (molecular weight 1500), ethylenediamine tetra-acetic acid,
Citric acid, benzenediol.
Embodiment 16
From embodiment 1 differ only in oxygen-bearing organic matter processing used in the dosage of acetic acid it is different, be with the quality of Z
Benchmark, dosage are：1%.
Embodiment 17-19
Embodiment 17-19 is different from the calcination temperature of embodiment 1 differed only in when oxygen-bearing organic matter is handled, respectively
For：420℃、500℃、600℃.
Embodiment 20-22
Embodiment 20-22 is different from the roasting time of embodiment 1 differed only in when oxygen-bearing organic matter is handled, respectively
For：2h、6h、8h.
Embodiment 23-26
Embodiment 23-26 is different from the air speed of embodiment 1 differed only in when oxygen-bearing organic matter is handled, respectively
For：0.1h-1、1h-1、10h-1、20h-1。
Comparative example 1
The carrier Z for taking 400g embodiments 1 to prepare contains 90 grams per liter MoO with 500 milliliters3With the ammonium heptamolybdate of 32 grams per liter NiO
It filters after being impregnated 1 hour with nickel nitrate mixed solution, is then dried 4 hours in 120 DEG C, roast 2 hours, obtain then at 400 DEG C
Reference oxidized catalyst is directly entered sulfurating stage, and vulcanization process is the same as embodiment 1.
Comparative example 2
The dry G1 that in Example 1 prepared by step (1), is fitted into horizontal pipe stove, air is only passed through, directly in 400
DEG C roasting 2 hours, obtain reference oxidized catalyst, later enter sulfurating stage, vulcanization process is the same as embodiment 1.
The quality evaluation of catalyst：
It is 5.0MPa, 360 DEG C of temperature, liquid hourly space velocity (LHSV) 2h in reaction pressure-1, under the conditions of hydrogen to oil volume ratio is 1000, to oil
Rapeseed oil carries out hydrogenation deoxidation modification, evaluates each catalyst performance.The results show that all embodiments show following spy
Point：The catalyst of all embodiments of the present invention after run 100h, add hydrogen decarboxylation and plus hydrogen decarbonylation selectively 25% or more,
On unloading rear catalyst Mo sulphidities 75% or more (unloading rear catalyst is characterized with x-ray photoelectron spectroscopy technology,
And the ratio of total Mo atoms is accounted for represent Mo sulphidities with+4 valence molybdenum atoms on catalyst), unload the specific surface area of rear catalyst
In 250m2/ g or more, and the diesel oil distillate obtained can in any proportion reconcile with petroleum diesel, and no sulphur, no aromatic hydrocarbons is free of
Oxygen, NOx emission is few, environmental-friendly, and storage stability is good, can be used as high cetane number diesel oil addO-on therapy.
The concrete outcome of section Example is listed below, as shown in Table 1 and Table 2, table 1 is the knot after running 24 hours
Fruit, table 2 are the result run after 100h.
Table 1
Table 2
It can be seen that compared with three comparative examples from the result of Tables 1 and 2, catalyst of the invention is preparing biological bavin
When oily, there is higher stability and add hydrogen decarboxylation selectivity, and hydrothermal energy is good, sulphidity is high.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (23)
1. a kind of preparation method of catalyst for biological oil hydrodeoxygenation, which is characterized in that include the following steps：
During roasting is impregnated with the catalyst carrier of active component, make the catalyst carrier for being impregnated with active component
It is contacted with oxygen-bearing organic matter, completes the roasting and obtain oxidized catalyst；
Vulcanizing treatment is carried out to get product to the oxidized catalyst；
Wherein, the active component is one or more in group VIII metal at least containing one or more in group vib metal
It is one or more in composition and VB races metal；
The temperature of the roasting is 400-600 DEG C；
The oxygen-bearing organic matter is one or more in Organic Alcohol, organic acid, organic ketone, phenols.
2. the preparation method of the catalyst according to claim 1 for biological oil hydrodeoxygenation, which is characterized in that described
Organic Alcohol is one or more in ethylene glycol, glycerine, polyethylene glycol, diethylene glycol and butanediol；
The organic acid is acetic acid, maleic acid, oxalic acid, aminotriacetic acid, citric acid, tartaric acid, malic acid, 1,2- cyclohexanediamine
It is one or more in tetraacethyl, amion acetic acid, nitrilotriacetic acid and ethylenediamine tetra-acetic acid；
The phenols is one or more in phenol, benzenediol, benzenetriol, cresols, amino phenols, nitrophenols, chlorophenol.
3. the preparation method of the catalyst according to claim 2 for biological oil hydrodeoxygenation, which is characterized in that described
Oxygen-bearing organic matter is Organic Alcohol and/or organic acid.
4. the preparation method of the catalyst according to claim 2 for biological oil hydrodeoxygenation, which is characterized in that described
Organic Alcohol is one or more in ethylene glycol, glycerine and polyethylene glycol.
5. the preparation method of the catalyst according to claim 4 for biological oil hydrodeoxygenation, which is characterized in that described
The number-average molecular weight of polyethylene glycol is 200-1500.
6. the preparation method of the catalyst according to claim 2 for biological oil hydrodeoxygenation, which is characterized in that described
Organic acid is one or more in acetic acid, citric acid and ethylenediamine tetra-acetic acid.
7. the preparation method of the catalyst according to claim 2 for biological oil hydrodeoxygenation, which is characterized in that described
Phenols is phenol and/or benzenediol.
8. the preparation method of the catalyst according to claim 1 for biological oil hydrodeoxygenation, which is characterized in that described
Catalyst carrier is alumina support.
9. the preparation method of the catalyst according to claim 8 for biological oil hydrodeoxygenation, which is characterized in that described
Group vib metal is at least one of Cr, Mo, W, and the group VIII metal is at least one of Fe, Co, Ni；The VB races
Metal is at least one of vanadium, niobium, tantalum.
10. the preparation method of the catalyst according to claim 9 for biological oil hydrodeoxygenation, which is characterized in that institute
It is vanadium, molybdenum and nickel to state active component.
11. the preparation method according to claim 1 or 8-10 any one of them for the catalyst of biological oil hydrodeoxygenation,
It is characterized in that, on the basis of the catalyst carrier, the content of group vib metallic compound is 0.01-9.5wt%.
12. the preparation method of the catalyst according to claim 11 for biological oil hydrodeoxygenation, which is characterized in that with
On the basis of the catalyst carrier, the content of group VIII metal compound is 0.01-0.5wt%.
13. the preparation method of the catalyst according to claim 11 for biological oil hydrodeoxygenation, which is characterized in that with
On the basis of the catalyst carrier, the content of VB races metallic compound is 0.01-11.5wt%.
14. the preparation method of the catalyst according to claim 11 for biological oil hydrodeoxygenation, which is characterized in that with
For the group vib metallic element on the basis of the total mole number of VB races metallic element, the dosage of VB races metallic element is 2-10%.
15. the preparation method of the catalyst according to claim 1 for biological oil hydrodeoxygenation, which is characterized in that institute
The temperature for stating roasting is 420-500 DEG C.
16. the preparation method of the catalyst according to claim 15 for biological oil hydrodeoxygenation, which is characterized in that institute
The time for stating roasting is 2-8h.
17. the preparation method of the catalyst according to claim 16 for biological oil hydrodeoxygenation, which is characterized in that institute
The time for stating roasting is 3-6h.
18. the preparation method according to claim 1-7 any one of them for the catalyst of biological oil hydrodeoxygenation, feature
It is, the method contacted with oxygen-bearing organic matter is：
The oxygen-bearing organic matter is with 0.1-20h-1Volume space velocity contacted with the catalyst carrier for being impregnated with active component.
19. the preparation method of the catalyst according to claim 18 for biological oil hydrodeoxygenation, which is characterized in that institute
Stating the method contacted with oxygen-bearing organic matter is：The oxygen-bearing organic matter is with 1-10h-1Volume space velocity with described be impregnated with activearm
The catalyst carrier contact divided.
20. the preparation method according to claim 1-7 any one of them for the catalyst of biological oil hydrodeoxygenation, feature
Be, make it is described be impregnated with the catalyst carrier of active component and when oxygen-bearing organic matter contacts, the oxygen-bearing organic matter with it is described
The mass ratio of catalyst carrier is 0.05-4%.
21. the preparation method of the catalyst according to claim 1 for biological oil hydrodeoxygenation, which is characterized in that institute
The catalyst carrier for being impregnated with active component is stated also containing one or more in extrusion aid, peptizing agent and expanding agent.
22. a kind of catalyst for biological oil hydrodeoxygenation, which is characterized in that use claim 1-21 any one of them
Preparation method is made.
23. the method for biological oil hydrodeoxygenation, which is characterized in that carried out to bio oil using the catalyst described in claim 22
Hydrogenation deoxidation modifies.
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| 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 |
| 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 |
| 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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| CN1769376A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Hydrotreatment catalyst and its preparation method |
| CN1946831A (en) * | 2004-04-22 | 2007-04-11 | 阿尔伯麦尔荷兰有限公司 | Hydrotreating catalyst containing a group V metal |
| CN101279289A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN105478129A (en) * | 2014-09-17 | 2016-04-13 | 中国石油化工股份有限公司 | Hydrotreatment catalyst and application thereof |
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| CN1946831A (en) * | 2004-04-22 | 2007-04-11 | 阿尔伯麦尔荷兰有限公司 | Hydrotreating catalyst containing a group V metal |
| CN1769376A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Hydrotreatment catalyst and its preparation method |
| CN101279289A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN105478129A (en) * | 2014-09-17 | 2016-04-13 | 中国石油化工股份有限公司 | Hydrotreatment catalyst and application thereof |
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