CN105861038B - The method of biological oil hydrodeoxygenation - Google Patents
The method of biological oil hydrodeoxygenation Download PDFInfo
- Publication number
- CN105861038B CN105861038B CN201610286336.8A CN201610286336A CN105861038B CN 105861038 B CN105861038 B CN 105861038B CN 201610286336 A CN201610286336 A CN 201610286336A CN 105861038 B CN105861038 B CN 105861038B
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- oxygen
- catalyst
- biological oil
- acid
- oil hydrodeoxygenation
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- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 description 1
- 229910001630 radium chloride Inorganic materials 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012306 spectroscopic technique Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
-
- 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
- B01J23/882—Molybdenum and cobalt
-
- 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
- B01J23/883—Molybdenum and nickel
-
- 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
- B01J23/8878—Chromium
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention provides a kind of method of biological oil hydrodeoxygenation.Method is：Using hydrogenation deoxidation catalyst as catalysts, hydrogenation deoxidation processing is carried out to bio oil；The preparation method of the hydrogenation deoxidation catalyst is：During roasting is impregnated with the catalyst carrier of active component, the catalyst carrier for being impregnated with active component is contacted with oxygen-bearing organic matter, complete the roasting and obtain oxidized catalyst；Make the oxidized catalyst absorption inorganic acid, carry out vulcanizing treatment afterwards, produce product；Wherein, the active component is mainly made up of the one or more in group vib metal with the one or more in group VIII metal.The present invention is pre-processed using oxygen-bearing organic matter and inorganic acid to catalyst, adds the selectivity of hydrogenation decarboxylation decarbonylation reaction, the sulfur fixation performance and heat endurance of catalyst is improved, so as to extend the cycle of operation of device.
Description
Technical field
The present invention relates to modifying oil product technical field, more particularly, to a kind of method of biological oil hydrodeoxygenation.
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 enjoyed as preferable fungible energy source, because it has pollutant emission
Less, the characteristics of cycle period is short 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 thing oil product is sometime up to more than 50 weight %, and so as to cause bio oil to have, combustion heat value is low, chemical property is unstable
Fixed, heating easily polymerization, acid compared with the unfavorable feature such as strong, big to the corrosivity of equipment, it is straight as vehicle fuel seriously to hinder it
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 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 its Cetane number can reconcile up to 90~100 in any proportion with petroleum diesel, and no sulphur, no aromatic hydrocarbons is not oxygen-containing,
NOx emission is few, environment-friendly, and storage stability is good, can be used as high cetane number diesel oil addO-on therapy.Therefore, move and plant
Thing oil hydrogenation deoxidation prepares biodiesel technology, a kind of green grass or young crops of the new renewable automobile-used supplement of effect with alternative fuel by people
Look 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
Hydrogenation saturation, hydrogenation deoxidation with aliphatic acid, hydrogenation decarboxylation, hydrogenation de-carbonyl reaction, in addition also hydroisomerization reaction
Deng.At present, vegetable and animals oils hydrogenation deoxidation reaction mainly uses sulphided state CoMo/Al2O3Or NiMo/Al2O3Catalyst, it is this kind of to urge
Agent has higher hydrodesulfurization and hydrogenation deoxidation activity, while also has higher hydrogenation deoxidation initial activity, but shortcoming is
Poor catalyst stability, it is easy to inactivate, cause the hydrogenation deoxidation plant running cycle short, it is necessary to frequent clean or replacing catalysis
Agent.
For example, CN101831315A discloses a kind of catalyst of use based on nickel and molybdenum with restricted decarboxylation conversion ratio
The method that the raw material hydrogenation deoxidation of renewable source will be come from.The invention finds the activity mutually using one kind selected from VIII
Or the atomic ratio of various metals and one or more metals selected from group vib, can especially with suitable Ni/Mo atomic ratios
To control and strengthen the selectivity of hydrogenation deoxidation reaction, so as to limit decarboxylation/decarbonylation reaction, and therefore limit by oxycarbide
Form caused disadvantage.But the shortcomings of catalyst existence and stability is poor, easy in inactivation.
CN102427880A discloses a kind of catalyst for including metal phosphide, and it is used to prepare biodiesel, also public affairs
Opened it is a kind of using the catalyst to vegetable oil carry out hydrotreating, so as to prepare the method for biodiesel.The catalyst
Advantage is：During using the biodiesel comprising metal phosphide, the preparation of the biodiesel of hydrotreating
It is active high, in this embodiment it is not even necessary to vulcanizing agent without interruption, and hydrotreating is carried out simultaneously with isomerization reaction, thus, it is possible to obtain
The low high-quality hydrotreating biodiesel of pour point.Equally, the catalyst is poor there is also hydrothermal stability, catalyst activity phase
The shortcomings of easily aggregation inactivates.
Therefore, a kind of hydrogenation deoxidation catalyst for being used to prepare biodiesel of high stability of exploitation is needed badly at present.
The content of the invention
It is an object of the invention to provide a kind of method of biological oil hydrodeoxygenation, described method utilizes special catalysis
Agent, the catalyst has the characteristics that to be hydrogenated with the selective high, sulfur fixation performance of decarboxylation decarbonylation and heat endurance is high, can extend hydrogenation
The cycle of operation of device for deoxidizing, so as to improve the efficiency of biological oil hydrodeoxygenation.
A kind of method of biological oil hydrodeoxygenation, using hydrogenation deoxidation catalyst as catalysts, adds to bio oil
Hydrogen deoxidation treatment；The preparation method of the hydrogenation deoxidation catalyst comprises the following steps：
During roasting is impregnated with the catalyst carrier of active component, make the catalyst for being impregnated with active component
Carrier contacts with oxygen-bearing organic matter, completes the roasting and obtains oxidized catalyst, carries out vulcanizing treatment afterwards, produce product；
Wherein, the active component mainly by group vib metal one or more with group VIII metal in one kind or
A variety of compositions.
As a rule, the main reason for hydrogenation deoxidation plant running cycle is short is catalyst easy in inactivation, and vegetable and animals oils add
Hydrogen dehydrogenation catalyst inactivate the main reason for have carbon deposit, oxygen sulphur exchange and carrier hydration caused by carrier specific surface area reduce and
Active mutually aggregation etc..Therefore specific surface area caused by suppressing carrier hydration reduces and the aggregation of active phase, for hydrogenation deoxidation
The raising of catalyst stability plays an important roll.But prior art generally can not be taken into account and suppress carrier hydration and selecting response
High two effects of property.By taking existing alumina support as an example, aluminum oxide is spinel-like type used by hydrogenation deoxidation catalyst
Structure, a large amount of cations in its surface and anion vacancy play key effect for alumina hydration, therefore widespread practice is all
It is by support modification, adds auxiliary agent atom and occupy alumina carrier surface room, so as to suppresses carrier hydration；However, this does
The shortcomings that method, is to reduce active metal and carrier Interaction Force, so as to influence vulcanization rear catalyst to a certain extent
Active facies type, and and then reduction hydrogenation deoxidation and the selectivity of decarboxylation.
And the method for the present invention employs special catalyst, the catalyst is oxygen-containing organic by being passed through in roasting process
Thing and select suitable two measures of active metal component, can not only be occupied using oxygen-bearing organic matter carrier surface room come
Suppress the aquation of carrier, play increase acidity of catalyst and active phase dispersion, and and then increase decarboxylation decarbonylation reaction pair
The selectivity of dehydration, and the sulfur fixation performance of catalyst is also improved, the sulphur in catalyst is not easy during the course of the reaction
It is lost in, even if not adding vulcanizing agent, its sulphidity remains above the catalyst of conventional method preparation.
The above-mentioned method of the present invention can also be improved further, such as：
Oxygen-bearing organic matter of the present invention refers to the arbitrarily organic matter containing oxygen atom, be selected from Organic Alcohol, organic acid,
One or more in organic ketone, phenols, preferably Organic Alcohol and/or organic acid.
Under normal circumstances, it is higher to being hydrogenated with the selectivity of decarboxylation decarbonylation reaction after Organic Alcohol, organic acid treatment.
The Organic Alcohol can be selected from one kind in ethylene glycol, glycerine, polyethylene glycol, diethylene glycol and butanediol or more
Kind, the 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, NTA and ethylenediamine tetra-acetic acid
One or more in one or more, preferably acetic acid, citric acid and ethylenediamine tetra-acetic acid.
The phenolic compound can be in phenol, benzenediol, benzenetriol, cresols, amino phenols, nitrophenols, chlorophenol
One or more, preferably phenol and/or benzenediol.
Mainly contacted as a solution when above-mentioned oxygen-bearing organic matter contacts with catalyst carrier, the mode of contact also has very
It is a variety of, can directly all mix or the solution of oxygen-bearing organic matter is continuously injected into catalyst carrier
On, to ensure that both fully can contact and be attached together.It is calcined while contact, the temperature of the roasting is preferred
For 400-600 DEG C, more preferably 420-500 DEG C；The time of the roasting is preferably 2-8h, more preferably 3-6h.Pass through the above
Preferable roasting condition can improve the selectivity of the hydrogenation decarboxylation decarbonylation of catalyst, and heat endurance, extend oil product processing
The cycle of operation of device.
It is preferred that adding oxygen-bearing organic matter in a manner of being continuously injected into, the oxygen-bearing organic matter is preferably with 0.1-20h-1Air speed
Contacted with the catalyst carrier for being impregnated with active component, more preferably 1-10h-1.It can avoid urging from suitable air speed
Caused by agent efflorescence the problem of remitted its fury.
Dosage on oxygen-bearing organic matter, it is preferable that make the catalyst carrier for being impregnated with active component have with oxygen-containing
When machine thing contacts, the mass ratio of the oxygen-bearing organic matter and the catalyst carrier is 0-10%, preferably 5-8%, is preferably
0.1-5%, preferably 0.05-4%.
In addition to being handled using oxygen-bearing organic matter catalyst, it can also be entered again with oxygen-containing inorganic acid on this basis
Pre-processed before row vulcanization, specifically, make the oxidized catalyst absorption oxygen-containing inorganic acid；Oxygen-containing inorganic acid mainly occupies load
Body surface vacancy suppresses the aquation of carrier.
Oxygen-containing inorganic acid of the present invention refers to the oxygen-containing inorganic acid of any oxygen containing inorganic acid, preferably VA races, preferably
For the one or more in phosphoric acid, arsenic acid, metaantimmonic acid etc., preferably phosphoric acid.The stability of these inorganic acids is high, it is possible to increase catalysis
The heat endurance of agent.
On the dosage of oxygen-containing inorganic acid, for example, on the basis of the catalyst carrier, VA races oxygen-containing inorganic acid
Dosage can be 0.1-10wt%, preferably 0.2-5wt%, more preferably 0.2-3wt%.VA races oxygen-containing inorganic acid can be with
Use, can also be used in the form of its aqueous solution, preferably the latter in pure form.In addition, when the VA races are oxygen-containing inorganic
Acid is in the form of its aqueous solution in use, in the VA races oxygen-containing inorganic acid aqueous solution, the weight of VA races oxygen-containing inorganic acid and water
It can be 1 to measure ratio：1-80, preferably 1：2-10.Now, the oxygen-containing inorganic acid relative to hydrogenation catalyst above-mentioned dosage not
Dosage including water.
The present invention is not particularly limited to the mode for contacting the hydrogenation catalyst with VA races oxygen-containing inorganic acids, example
Such as, hydrogenation catalyst can be mixed with VA races oxygen-containing inorganic acids, the aqueous solution containing organic additive can also be constantly sprayed
On hydrogenation catalyst.Preferably, the method for the absorption inorganic acid is：By the solution of inorganic acid at 100-140 DEG C (more preferably
120 DEG C) under contacted with the oxidized catalyst, and be additionally included in after the absorption and before the vulcanizing treatment
Dried under 200-250 DEG C (more preferably 230 DEG C).The front being adsorbed with a heated condition beneficial to catalyst is modified.
Preferably, it is by the mode that the hydrogenation catalyst contacts with VA races oxygen-containing inorganic acids：By the oxygen-containing nothing of VA races
Machine aqueous acid, which is continuously injected into, to be filled with the fixed bed reactors of the hydrogenation catalyst, is so enabled to pretreated
Hydrogenation catalyst is directly applied in biological oil hydrodeoxygenation reactor, simplifies technique.Further：Urge the oxidation state
Agent and the inorganic acid react in fixed bed reactors, and keep temperature in reactor for 100-140 DEG C (more preferably
120 DEG C), partial pressure is 1.5-4MPa (more preferably 3MPa), and gas flow is 50-70L/h (more preferably 60L/h).Above work
Under the conditions of skill, preprocessing process will not have a negative impact to the mechanical strength of catalyst.(in the present invention, pressure refers both to table
Pressure)
Catalyst carrier of the present invention can use the available type of any conventional, such as alumina support, or oxygen
Change the mixture of at least one of aluminium and silica, titanium oxide and zirconium oxide；Wherein, the aluminum oxide for example can be γ-oxygen
Change at least one of aluminium, η-aluminum oxide, θ-aluminum oxide, δ-aluminum oxide and χ-aluminum 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
Arrive, can also be prepared according to well known to a person skilled in the art various methods.For example, alumina support can be by by oxygen
Change the roasting of aluminium precursor, it is converted into gama-alumina, η-aluminum oxide, θ-aluminum oxide, δ-aluminum oxide and χ-aluminum oxide extremely
Few one kind.Optionally, before firing and/or afterwards, first aluminum oxide precursor can be molded, to prepare suitable practical operation
Required shape (such as spherical, sheet, bar shaped).The shaping can be carried out according to the conventional method in this area, such as spin
Method, pressed disc method and extrusion method etc..In forming process, such as during extruded moulding, in order to ensure being smoothed out for shaping,
Water, extrusion aid and/or peptizing agent can be added into the aluminum oxide precursor, and is optionally added expanding agent, is then extruded into
Type, it is dried and is calcined afterwards.The extrusion aid, the species of peptizing agent and expanding agent and dosage can use conventional place
Reason, for example, common extrusion aid can be in sesbania powder, methylcellulose, starch, polyvinyl alcohol and PVOH at least one
Kind, the peptizing agent can be Organic Alcohol and/or organic acid, the expanding agent can for 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 200-10000 propylene alcohol copolymer and maleic acid copolymer.The bar of bar drying will be extruded
Part generally includes：Drying temperature can be 40-350 DEG C, preferably 100-200 DEG C；Drying time can be 1-24 hours, preferably
For 2-12 hours.The condition of dried extrusion bar roasting is generally included：Sintering temperature can be 350-1000 DEG C, be preferably
600-950℃；Roasting time can be 1-10 hours, preferably 2-6 hours.The aluminum oxide precursor can be selected from three hydrations
At least one of aluminum oxide, monohydrate alumina, amorphous hydroted alumina etc..
Group vib of the present invention and group VIII metal component generally add in the form of the oxide, it is of course possible to use
Other feasible chemical forms, such as nitrate, carbonate, sulfate, meta-acid salt, ammonium salt etc..Wherein, group vib metal component
Including but not limited to：Cr at least one of (can be selected from chromium oxide, chromic nitrate and chromium sulfate), Mo (can be selected from molybdenum oxide,
At least one of molybdate and paramolybdate) and W (can be in tungstates, metatungstate and ethyl metatungstate extremely
Few one kind).The group VIII metal component includes but is not limited to：Fe (it is sub- can be selected from ferric nitrate, ferric acetate, iron chloride, sulfuric acid
One or more in iron and iron oxide), Co (can be in cobalt nitrate, cobalt acetate, basic cobaltous carbonate and cobalt chloride at least
It is a kind of), Ni (at least one of nickel nitrate, nickel acetate, basic nickel carbonate and nickel chloride can be selected from), Ru (three can be selected from
At least one of ruthenic chloride, ruthenic oxide and nitric acid ruthenium), Rh (can be in rhodium nitrate, radium chloride and rhodium oxide at least
It is a kind of) and Pd (at least one of palladium oxide, palladium dydroxide palladium nitrate and palladium bichloride can be selected from).Preferably, the VIB
Race's metal component is Mo and/or W, and the group VIII metal component is Co and/or Ni；The active component is preferably molybdenum and nickel.
Preferably, on the basis of the catalyst carrier, the content of group vib metal is 0-30wt%, preferably 3-
20wt%；The content of group VIII metal is 0-30wt%, preferably 1-10wt%.
The method of impregnating metal active component has many kinds, such as infusion process, spraying in catalyst carrier.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
The group vib metallic compound and the inertia liquid of group VIII metal compound can be dissolved to be various, for example, can be with
Selected from least one of water, alcohol, ether, aldehyde and ketone.
In addition, finally dry pre-sulfiding or wet method can be used to vulcanize the vulcanizing treatment of catalyst.Specifically, for dry method
For vulcanization, the curing medium used can be H2And H2S mixture, and H in the curing medium2S volumetric concentration can be with
For 0.1-5v%, preferably 1-2v%.For wet method vulcanization, its 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 25-35 DEG C/h speed
160-180 DEG C, and start into H2S；The temperature of vulcanizing system is risen to 220-240 DEG C with 10-20 DEG C/h speed 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 5-15 DEG C/h speed again
The temperature of system rises to 270-290 DEG C and constant temperature vulcanization 2-6h；Then again with 5-15 DEG C/h speed 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, the content of active component is preferably in catalyst：On the basis of the catalyst carrier, group vib metal
Content is 0-30wt%, preferably 3-20wt%；The content of group VIII metal is 0-30wt%, preferably 1-10wt%.
During using above-mentioned catalyst to biological oil hydrodeoxygenation, reaction condition used can use commonly used in the prior art
Condition, it is preferable that 280-400 DEG C of reaction bed temperature, hydrogen partial pressure 2-8MPa, liquid hourly space velocity (LHSV) 0.5-2.0h-1, hydrogen oil
Volume ratio is 300-1000.At this point in the reaction, the premium properties of catalyst can be given full play to, improves final cut matter
Amount, and can improve reaction efficiency.
After hydrogenation deoxidation reaction terminates, the products of different fractions can be obtained, can according to being actually needed categorised collection, or
Reprocessed.
In addition, bio oil of the present invention can be the oil product of any biological source, both can be waste reclamation,
Such as gutter oil or pure vegetable and animals oils, such as soybean oil, castor oil, lard, sheep oil etc..Can also be by bio oil
With other oil product hybrid process, it is preferable that by least one of bio oil and kerosene, straight-run diesel oil with 1:1-1:5 quality
Than mixing, more preferably with 1:3-1:5 mass ratio mixing or 1:1-1:3 mass ratio mixing.
The hydrogenation decarboxylation decarbonylation higher than existing catalyst is shown by catalyst made from above technical scheme
Selectivity, and the features such as higher sulfur fixation performance and heat endurance, therefore the device used in corresponding hydrodeoxygenation process
The cycle of operation is grown, and production efficiency is high.
Compared with prior art, invention achieves following technique effect：
(1) using group vib metal and group VIII metal as active component, with reference to the pre- place of oxygen-bearing organic matter and oxygen-containing inorganic acid
Reason, improve the sulfur fixation performance of catalyst, heat endurance, and the selectivity of hydrogenation decarboxylation decarbonylation reaction, catalyst of the present invention
Specific area and sulphidity it is more stable；
(2) cycle of operation of hydrogenation deoxidation device can be extended；
(3) production efficiency of biological oil hydrodeoxygenation can be improved；
(4) cut quality can be improved.
Embodiment
Technical scheme is clearly and completely described below in conjunction with embodiment, but ability
Field technique personnel will be understood that following described embodiment is part of the embodiment of the present invention, rather than whole embodiments,
The present invention is merely to illustrate, and is not construed as limiting the scope of the present invention.Based on the embodiment in the present invention, the common skill in this area
The every other embodiment that art personnel are obtained under the premise of creative work is not made, belong to the model that the present invention protects
Enclose.Unreceipted actual conditions person in embodiment, the condition suggested according to normal condition or manufacturer are carried out.Agents useful for same or instrument
Unreceipted production firm person, it 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 bar of catalyst is prepared：
Weigh 1000 grams of dry glue powders and 30 grams of sesbania powders and be well mixed, 900 milliliters of nitric acid containing 28g of addition is water-soluble afterwards
Liquid, external diameter φ 1.4mm cylindrical wet bar is extruded on plunger type bar extruder.Then it is small the wet bar of cylinder to be dried 4 in 120 DEG C
When, it is calcined 3 hours then at 600 DEG C, obtains carrier Z, its pore volume is 0.7mL/g, specific surface area 280m2/g。
100g ammonium heptamolybdates, 30g nickel nitrates and 1000g ammoniacal liquor are added in the 400mL aqueous solution, heats and stirs to complete
After fully dissolved, maceration extract 500mL is obtained.The above-mentioned carrier Z of 400g are taken, above-mentioned maceration extract are all uniformly sprayed on carrier Z, so
Half obtained dry catalyst is put into baking oven afterwards and dried 4 hours in 120 DEG C, the catalyst for obtaining being impregnated with active component is done
Bar 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, needs in advance to match somebody with somebody in roasting process
The acetic acid content put is the 5 weight % aqueous solution, according to air speed 2h-1, persistently squeezed into plunger pump in catalyst roasting bed,
Finally give oxidized catalyst C1.Wherein, relative to the dry bar of catalyst of 100 parts by weight, the quality for being passed through the aqueous solution amounts to
For 0.01.
(3) pre-processed before vulcanization：
VA races oxygen-containing inorganic acid selects phosphoric acid, total injection rate 100g.Specifically, 200g phosphoric acid is mixed into system with 300g water
Into the weight % of phosphoric acid 40 phosphate aqueous solution.In a nitrogen atmosphere, it is phosphate aqueous solution is above-mentioned with 100g/h speed injection
In hydrogenation deoxidation reactor, it is 120 DEG C, nitrogen partial pressure 3.0MPa to maintain reaction bed temperature during this period, nitrogen flow
For 60L/h.
After phosphate aqueous solution all injection, reaction bed temperature is risen to 230 DEG C, in a nitrogen atmosphere to catalyst
High temperature drying processing is carried out, it is 230 DEG C to control reactor inlet temperature during this period, and reactor outlet temperature is 230 DEG C, nitrogen
Partial pressure is 2.0MPa, and nitrogen flow 60L/h, drying time is 6 hours.Dry and be down to reaction bed temperature after terminating
145 DEG C, then introduce hydrogen.
(4) vulcanize：
The temperature of vulcanizing system is risen to 180 DEG C from 30 DEG C with 30 DEG C/h speed, and started into H2S；Again with 10 DEG C/h
Speed 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 15 DEG C/h speed again and constant temperature vulcanizes 6h；Then again with 15 DEG C/h
Speed 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.
(5) hydrogenation deoxidation reacts：
The catalyst that step (4) obtains is fitted into hydrogenation deoxidation reactor, passes through soybean oil and hydrogen, the property of soybean oil
Matter is as shown in table 1, and reaction condition is：5.0MPa, 340 DEG C of temperature, liquid hourly space velocity (LHSV) 1.5h-1, hydrogen to oil volume ratio 800.
Embodiment 2
(1) the dry bar of catalyst is prepared：It is same as Example 1.
(2) oxygen-bearing organic matter is handled：
G1 is placed in ventable vertical tubular furnace, 400 DEG C of constant temperature calcinings 3 hours, needs in advance to match somebody with somebody in roasting process
The phenol content put is the 7 weight % aqueous solution, according to air speed 5h-1, persistently squeezed into plunger pump in catalyst roasting bed,
Finally give oxidized catalyst C2.Wherein, relative to the dry bar of catalyst of 100 parts by weight, the quality for being passed through the aqueous solution amounts to
For 0.2.
(3) pre-processed before vulcanization
VA races oxygen-containing inorganic acid selects phosphoric acid, total injection rate 100g.Specifically, 100g phosphoric acid is mixed into system with 900g water
Into 10 weight % phosphate aqueous solution.In a nitrogen atmosphere, phosphate aqueous solution is injected into above-mentioned hydrogenation with 100g/h speed to take off
In oxygen reactor, it is 120 DEG C, nitrogen partial pressure 3.0MPa, nitrogen flow 60L/ to maintain reaction bed temperature during this period
h。
After phosphate aqueous solution all injection, reaction bed temperature is risen to 230 DEG C, in a nitrogen atmosphere to catalyst
High temperature drying processing is carried out, it is 230 DEG C to control reactor inlet temperature during this period, and reactor outlet temperature is 230 DEG C, nitrogen
Partial pressure is 2.0MPa, and nitrogen flow 60L/h, drying time is 6 hours.Dry and be down to reaction bed temperature after terminating
150 DEG C, then introduce hydrogen.
(4) vulcanize：
It is same as Example 1.
(5) hydrogenation deoxidation reacts：It is same as Example 1.
Embodiment 3-7
Embodiment 3 to 7 and embodiment 1 differ only in that metal active constituent is different, mole of its group vib metallic element
Number, the molal quantity of group VIII metal element are identical with embodiment, and the compound of active component is respectively：
MoO3/CoCl2、WO3/CoCl2、WO3/Ni(NO3)2、Cr2O3+MoO3(both are mixed with equimolar)/CoCl2、
Cr2O3+MoO3(both are mixed with equimolar)/CoCl2+FeO。
Embodiment 8-13
Embodiment 8-13 is different from the active component dosage for differing only in dipping of embodiment 1, and dosage is respectively：30g
Ammonium heptamolybdate/30g nickel nitrates, 200g ammonium heptamolybdates/30g nickel nitrates, 300g ammonium heptamolybdates/30g nickel nitrates, the molybdic acids of 100g seven
Ammonium/10g nickel nitrates, 100g ammonium heptamolybdates/100g nickel nitrates, 100g ammonium heptamolybdates/300g nickel nitrates.
Embodiment 14-20
Embodiment 14-20 is different from the dosage for differing only in acetic acid used in oxygen-bearing organic matter processing of embodiment 1,
But dosage is identical (percentage by weight), 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 21-26
Embodiment 21-26 is different from the dosage for differing only in acetic acid used in oxygen-bearing organic matter processing of embodiment 1,
On the basis of Z quality, dosage is respectively：0.05%th, 0.1%, 4%, 5%, 8%, 10%.
Embodiment 27-28
Embodiment 27-28 differs only in oxygen-containing inorganic acid species used in the preceding pretreatment of vulcanization not with embodiment 1
Together, but dosage is identical (percentage by weight), and oxygen-containing inorganic acid is respectively：Arsenic acid, metaantimmonic acid.
Embodiment 29-33
Embodiment 29-33 is different from the dosage for differing only in phosphoric acid used in the preceding pretreatment of vulcanization of embodiment 1, with
On the basis of Z quality, dosage is respectively：0.1%th, 0.2%, 3%, 5%, 10%.
Embodiment 34-36
Embodiment 34-36 is different from the sintering temperature differed only in when oxygen-bearing organic matter is handled of embodiment 1, respectively
For：420℃、500℃、600℃.
Embodiment 37-39
Embodiment 37-39 is different from the roasting time differed only in when oxygen-bearing organic matter is handled of embodiment 1, respectively
For：2h、6h、8h.
Embodiment 40-43
Embodiment 40-43 is different from the air speed differed only in when oxygen-bearing organic matter is handled of embodiment 1, respectively
For：0.1h-1、1h-1、10h-1、20h-1。
Embodiment 44-45
Embodiment 44-45 is different from the reaction temperature for differing only in the preceding pretreatment of vulcanization of embodiment 1, is respectively：100
℃、140℃。
Embodiment 46-47
Embodiment 46-47 is different from the drying temperature for differing only in the preceding pretreatment of vulcanization of embodiment 1, is respectively：200
℃、250℃。
Embodiment 48-49
Gaseous environment when differing only in pretreatment reaction before vulcanization of embodiment 48-49 and embodiment 1 is different, distinguishes
For：1.5MPa+50L/h、4MPa+70L/h.
Embodiment 50-51
Embodiment 50-51 is different from the temperature for differing only in hydrogenation deoxidation reaction of embodiment 1, is respectively：280℃、
400℃。
Embodiment 52-53
Embodiment 52-53 is different from the pressure for differing only in hydrogenation deoxidation reaction of embodiment 1, is respectively：2MPa、
8MPa。
Embodiment 54-55
Embodiment 54-55 is different from the liquid hourly space velocity (LHSV) for differing only in hydrogenation deoxidation reaction of embodiment 1, is respectively
0.5h-1、2.0h-1。
Embodiment 56-57
Embodiment 56-57 is different from the hydrogen to oil volume ratio for differing only in hydrogenation deoxidation reaction of embodiment 1, is respectively
300、1000。
Embodiment 58-60
The soybean oil that differs only in of embodiment 58-60 and embodiment 1 is mixed with kerosene, and three embodiments mixing
Mass ratio is respectively 1:1、1:3、1:5.
Embodiment 61
Embodiment 61 eliminates step (3) with differing only in for embodiment 1 --- pre-processed before vulcanization.
Comparative example 1
(1) the dry bar of catalyst is prepared：It is same as Example 1.
(2) G1 is directly calcined 3 hours in 400 DEG C, obtains reference oxidized catalyst, without being pre-processed before vulcanization,
Sulfurating stage is directly entered, vulcanization process is the same as embodiment 1.Afterwards by the catalyst be used for soybean oil hydrogenation deoxidation, method with
Embodiment 1 is identical.
Comparative example 2
(1) the dry bar of catalyst is prepared：It is same as Example 1.
(2) G1 is directly calcined 3 hours in 400 DEG C, reference oxidized catalyst is obtained, according still further to same as Example 2
" pre-treatment step before vulcanization " handled, afterwards into sulfurating stage, vulcanization process is the same as embodiment 1.This is catalyzed afterwards
Agent is used for the hydrogenation deoxidation of soybean oil, and method is same as Example 1.
Evaluation of result：
As a result show, all embodiments show following characteristics：The catalyst of all embodiments of the present invention is being transported
After row 100h, be hydrogenated with decarboxylation and hydrogenation decarbonylation selectivity between 25-35%, unload rear catalyst on Mo sulphidities 70% with
It is upper (unloading rear catalyst to be characterized with x-ray photoelectron spectroscopic technique, and total Mo originals are accounted for+4 valency molybdenum atoms on catalyst
The ratio of son represents Mo sulphidities), unload the specific surface area of rear catalyst in 270m2/ more than g, and the diesel oil obtained evaporates
Divide and can be reconciled in any proportion with petroleum diesel, no sulphur, no aromatic hydrocarbons, not oxygen-containing, NOx emission is few, environment-friendly, stable storing
Property 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 2 and table 3, table 2 is the knot after running 24 hours
Fruit, table 3 are the result after operation 100h.
Table 1
Table 2
Table 3
It is can be seen that from the result of table 2 and table 3 compared with two comparative examples, catalyst of the invention is preparing biological bavin
When oily, there is higher stability and hydrogenation decarboxylation selectivity, and hydrothermal energy is good, sulphidity is high.
Finally it should be noted that：Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；To the greatest extent
The present invention is described in detail with reference to foregoing embodiments for pipe, it will be understood by those within the art that：Its according to
The technical scheme described in foregoing embodiments can so be modified, either which part or all technical characteristic are entered
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme.
Claims (29)
- A kind of 1. method of biological oil hydrodeoxygenation, it is characterised in that using hydrogenation deoxidation catalyst as catalysts, to biology Oil carries out hydrogenation deoxidation processing；The preparation method of the hydrogenation deoxidation catalyst comprises the following steps：During roasting is impregnated with the catalyst carrier of active component, make the catalyst carrier for being impregnated with active component Contacted with oxygen-bearing organic matter, complete the roasting and obtain oxidized catalyst, carry out vulcanizing treatment afterwards, produce product；Wherein, the active component is mainly by the one or more in group vib metal and the one or more in group VIII metal Composition；One or more of the oxygen-bearing organic matter in Organic Alcohol, organic acid, organic ketone, phenols；Wherein, the Organic Alcohol is the one or more in ethylene glycol, glycerine, polyethylene glycol, diethylene glycol and butanediol；Institute Organic acid is stated as acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2- cyclohexanediamine tetraacetic acids, citric acid, tartaric acid, apple One or more in acid, 1,2- 1,2-diaminocyclohexane tetraacetic acids, amion acetic acid, NTA and ethylenediamine tetra-acetic acid；It is described One or more of the phenolic compound in phenol, benzenediol, benzenetriol, cresols, amino phenols, nitrophenols, chlorophenol；When the catalyst carrier for being impregnated with active component contacts with oxygen-bearing organic matter, the quality of the oxygen-bearing organic matter is institute The 0-10% of catalyst carrier quality is stated, and does not include 0%；The temperature of the roasting is 400-600 DEG C, and the time of roasting is 2-8h.
- 2. the method for biological oil hydrodeoxygenation according to claim 1, it is characterised in that the oxygen-bearing organic matter is organic Alcohol and/or organic acid.
- 3. the method for biological oil hydrodeoxygenation according to claim 1 or 2, it is characterised in that the Organic Alcohol is second two One or more in alcohol, glycerine and polyethylene glycol.
- 4. the method for biological oil hydrodeoxygenation according to claim 3, it is characterised in that the molecular weight polyethylene glycol is 200-1500。
- 5. the method for biological oil hydrodeoxygenation according to claim 1 or 2, it is characterised in that the organic acid be acetic acid, One or more in citric acid and ethylenediamine tetra-acetic acid.
- 6. the method for biological oil hydrodeoxygenation according to claim 1, it is characterised in that the phenolic compound is phenol And/or benzenediol.
- 7. the method for biological oil hydrodeoxygenation according to claim 1, it is characterised in that after the roasting and described Also include before vulcanization：Make the oxidized catalyst absorption oxygen-containing inorganic acid.
- 8. the method for biological oil hydrodeoxygenation according to claim 7, it is characterised in that the oxidized catalyst absorption Oxygen-containing inorganic acid be VA races oxygen-containing inorganic acid.
- 9. the method for biological oil hydrodeoxygenation according to claim 8, it is characterised in that the oxygen-containing inorganic acid of the VA races For the one or more in phosphoric acid, arsenic acid, metaantimmonic acid etc..
- 10. the method for biological oil hydrodeoxygenation according to claim 9, it is characterised in that the VA races it is oxygen-containing inorganic Acid is phosphoric acid.
- 11. the method for biological oil hydrodeoxygenation according to claim 1, it is characterised in that the catalyst carrier is oxygen Change alumina supporter.
- 12. the method for biological oil hydrodeoxygenation according to claim 1, it is characterised in that the group vib metal is Mo And/or W.
- 13. the method for biological oil hydrodeoxygenation according to claim 1, it is characterised in that the group VIII metal is Co And/or Ni.
- 14. the method for biological oil hydrodeoxygenation according to claim 1, it is characterised in that the active component be molybdenum and Nickel.
- 15. the method for biological oil hydrodeoxygenation according to claim 1, it is characterised in that using the catalyst carrier as Benchmark, the content of group vib metallic compound is 0-30wt%.
- 16. the method for biological oil hydrodeoxygenation according to claim 15, it is characterised in that using the catalyst carrier as Benchmark, the content of group vib metallic compound is 3-20wt%.
- 17. the method for biological oil hydrodeoxygenation according to claim 1, it is characterised in that using the catalyst carrier as Benchmark, the content of group VIII metal compound is 0-30wt%.
- 18. the method for biological oil hydrodeoxygenation according to claim 17, it is characterised in that using the catalyst carrier as Benchmark, the content of group VIII metal compound is 1-10wt%.
- 19. the method for biological oil hydrodeoxygenation according to claim 1, it is characterised in that the temperature of the roasting is 420-500℃。
- 20. the method for biological oil hydrodeoxygenation according to claim 1, it is characterised in that the time of the roasting is 3- 6h。
- 21. the method for biological oil hydrodeoxygenation according to claim 1, it is characterised in that described to be connect with oxygen-bearing organic matter Tactile method is：The oxygen-bearing organic matter is with 0.1-20h-1Air speed connect with the catalyst carrier for being impregnated with active component Touch.
- 22. the method for biological oil hydrodeoxygenation according to claim 21, it is characterised in that described to be connect with oxygen-bearing organic matter Tactile method is：The oxygen-bearing organic matter is with 1-10h-1Air speed contacted with the catalyst carrier for being impregnated with active component.
- 23. the method for biological oil hydrodeoxygenation according to claim 7, it is characterised in that the absorption oxygen-containing inorganic acid Method be：The solution of oxygen-containing inorganic acid is contacted at 100-140 DEG C with the oxidized catalyst, and in the absorption It is additionally included at 200-250 DEG C and dries before with the vulcanizing treatment afterwards.
- 24. the method for biological oil hydrodeoxygenation according to claim 23, it is characterised in that the absorption oxygen-containing inorganic acid Method be：The oxidized catalyst and the oxygen-containing inorganic acid is reacted in fixed bed reactors, and keep reactor In temperature be 100-140 DEG C, partial pressure 1.5-4MPa, gas flow 50-70L/h.
- 25. the method for biological oil hydrodeoxygenation according to claim 1, it is characterised in that be impregnated with activearm described in making When the catalyst carrier divided contacts with oxygen-bearing organic matter, the quality of the oxygen-bearing organic matter is the 5- of the catalyst carrier quality 8%.
- 26. the method for biological oil hydrodeoxygenation according to claim 7, it is characterised in that when carrying out the absorption, with institute On the basis of stating catalyst carrier, the dosage of the oxygen-containing inorganic acid is 0.1-10wt%.
- 27. the method for biological oil hydrodeoxygenation according to claim 26, it is characterised in that when carrying out the absorption, with On the basis of the catalyst carrier, the dosage of the oxygen-containing inorganic acid is 0.2-5wt%.
- 28. the method for biological oil hydrodeoxygenation according to claim 27, it is characterised in that when carrying out the absorption, with On the basis of the catalyst carrier, the dosage of the oxygen-containing inorganic acid is 0.2-3wt%.
- 29. the method for biological oil hydrodeoxygenation according to claim 1, it is characterised in that the hydrogenation deoxidation processing Reaction condition is：280-400 DEG C of reaction bed temperature, hydrogen partial pressure 2-8MPa, liquid hourly space velocity (LHSV) 0.5-2.0h-1, hydrogen oil Volume ratio is 300-1000.
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