CN103638938B - A kind of preparation method of the catalyst for biological oil hydrodeoxygenation - Google Patents

A kind of preparation method of the catalyst for biological oil hydrodeoxygenation Download PDF

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CN103638938B
CN103638938B CN201310747963.3A CN201310747963A CN103638938B CN 103638938 B CN103638938 B CN 103638938B CN 201310747963 A CN201310747963 A CN 201310747963A CN 103638938 B CN103638938 B CN 103638938B
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catalyst
preparation
solution
nickel
reducing agent
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CN103638938A (en
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王威燕
杨运泉
张锟
刘文英
乔志强
仵奎
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Xiangtan University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Abstract

The invention discloses a kind of preparation method being applicable to the amorphous catalyst of the catalytic hydrodeoxygenation reaction of phenols in bio oil, aldehydes, alcohols and ketone oxygenatedchemicals.The main active of this catalyst is Ni, W and B, and its preparation method is: with the nickel salt of solubility and tungstates for raw material, with NaBH 4or KBH 4for reducing agent, with ammoniacal liquor or ethylenediamine for complexing agent, adopt induction-chemical deposition method preparation.Feature of the present invention is to improve reducing agent NaBH 4or KBH 4utilization rate, reduce boron oxide compound to the covering at catalyst surface active center, increase the number of active center of catalyst surface; Whole preparation process technique is simple, and preparation condition is gentle, does not need to use protective gas; Institute's controlling catalyst has very high catalytic activity, the catalytic hydrodeoxygenation of oxygenatedchemicals can be made to react and carry out under lower reaction temperature, and significantly can reduce the content of benzene and aromatic hydrocarbons in product.

Description

A kind of preparation method of the catalyst for biological oil hydrodeoxygenation
Technical field
The invention belongs to oil refinery technical field, be specifically related to a kind of preparation method of the catalyst for biological oil hydrodeoxygenation.
Background technology
Along with the continuous exhaustion of fossil energy reserves, the mankind are faced with energy crisis, therefore cause sharp rising of the sharp fight of petroleum resources and oil price.Bio oil, as a kind of regenerative resource, has been acknowledged as at present the substitute of the most potential and optimal fossil energy in the world.But contain a large amount of oxygenatedchemicals in bio oil as phenols, aldehydes, alcohols and ketone etc., oxygen content is wherein up to more than 40%, cause bio oil fuel value low, poor chemical stability, has the shortcomings such as corrosivity to equipment, have a strong impact on bio oil widely using as hydrocarbon fuel.Therefore, catalytic hydrodeoxygenation (Hydrodeoxygenation is called for short HDO) must be carried out to the oxygenatedchemicals in bio oil to refine to improve oil quality.
At present, the catalyst for the catalytic hydrodeoxygenation of oxygenatedchemicals in bio oil has multiple.For these HDO catalyst, although the deoxy activity of sulfide catalyst is better, but carry out in the process of HDO reaction utilizing it, because the sulfur content in bio oil is very low, oxygen wherein can destroy the vulcanizable construction of sulfide, thus causes catalyst activity reduction, therefore, must maintain the catalytic activity of sulfide by adding a small amount of vulcanizing agent, the bio oil after this just inevitably gives hydrogenation has brought new sulphur pollution source into.Meanwhile, because the hydrogenation activity of sulfide catalyst is not good enough, cause benzene and arene content in the bio oil product after deoxidation all higher; The HDO reaction of phosphide catalysis phenolic compound is also mainly undertaken by the path of direct deoxidation, and product does not reach the standard of clean fuel oil; Then there is cost compared with high, easy in inactivation, the deficiency such as specific area is little, aperture is little or deoxy activity is not good enough in noble metal and nitride negative supported catalyst, seriously hinders its commercial Application.For HDO reaction, the phenolic compound HDO reaction temperature of current bibliographical information is substantially more than 300 DEG C, and some is up to 450 DEG C.High-temperature energy consumption of reaction is large, and easily coking phenomenon on catalyst occurs and reduce its activity; And under low temperature (≤250 DEG C) condition, the activity of this kind of catalyst is lower again, cause it lower to the DNA vaccine of raw material.
Amorphous catalyst, due to the structure of its uniqueness, makes it in HDO reaction, have excellent catalytic activity, anti-poisoning, decay resistance and eco-friendly feature.At Catalysis Communications, 2011,12 (14): 1275-1279 and Industrial & Engineering Chemistry Research, 2011, in 50 (19): 10936-10942, report and adopted chemical reduction method with NaBH 4for the method for Ni – W – B amorphous catalyst prepared by reducing agent.But because of this preparation process NaBH 4the rate of addition of solution slowly and easily makes it that oxidation Decomposition fast occurs, boron oxide compound is caused to be accumulated in a large number at catalyst surface, partially catalyzed activated centre is capped, cause thus the metal state nickel of catalyst surface and tungstic acid content very low, thus significantly reduce the activity of Ni – W – B amorphous catalyst, and make to produce a certain amount of benzene or aromatic product in the reaction of catalyst aromatic ring class oxygenatedchemicals in catalysis biological oil, the bio oil after deoxidation still can not meet the quality standard of clean fuel oil.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the catalyst for biological oil hydrodeoxygenation, catalyst has the advantages such as amorphous structure, low preparation cost, superior catalytic activity.
Technical scheme of the present invention:
For a preparation method for the catalyst of biological oil hydrodeoxygenation, body is made up of nickel, tungsten, boron and oxygen, adopts following processing step:
1. obtain solution A, by water-soluble for the nickel salt of solubility, adds complexing agent, makes NH in solution 4 +/ Ni 2+mol ratio is 5 ~ 30, then adds a certain proportion of tungsten salt, makes W/Ni atomic molar ratio in solution be 0.1 ~ 10; By NaBH 4or KBH 4reducing agent wiring solution-forming B, wherein reductant concentration is 0.2 ~ 10 mol/mL;
At ② – 10 DEG C ~ 80 DEG C, by solution A and B solution mixing, vigorous stirring, add the derivant of 0.001 ~ 2 mol//mL, immediate response, obtain black precipitate after reaction terminates after washing, alcohol wash, dry under vacuum, baking temperature is 40 ~ 120 DEG C, and vacuum is 0.05 ~ 0.1Mpa, and gained catalyst is kept away oxygen and preserved;
The nickel salt of described solubility is nickelous sulfate or nickel nitrate or nickel chloride or nickel acetate, preferred nickel nitrate or nickel acetate;
Described complexing agent is ammoniacal liquor or organic amine, preferred ammoniacal liquor or ethylenediamine, and consumption is NH 4 +/ Ni 2+mol ratio is 5 ~ 30, preferably 10 ~ 20;
Described tungsten salt is tungsten hexachloride or ammonium metatungstate or sodium tungstate, preferred metatungstic acid sodium;
Described derivant is Pb 2+or Ag +solution;
Described reducing agent is NaBH 4or KBH, concentration is 0.2 ~ 10 mol/mL, preferably 0.5 ~ 2 mol/mL;
The molar ratio of described reducing agent and nickel salt and tungsten salt is 0.01 ~ 10, preferably 0.3 ~ 5, by the ratio of the integral molar quantity of all metals in the mole of boron element in reducing agent and solution;
Described catalyst preparing reaction temperature Shi – 10 ~ 80 DEG C, You Xuan – 5 ~ 30 DEG C.
Ni – W – B amorphous state hydrogenation deoxidation catalyst prepared by the induced chemical plating method adopted in the present invention solves a difficult problem of the prior art.This method can improve reducing agent NaBH 4or KBH 4utilization rate, reduce boron oxide compound to the covering at catalyst surface active center; Whole preparation process technique is simple, and preparation condition is gentle, without the need to using protective gas; Prepared catalyst activity is high, can reduce the catalytic hydrodeoxygenation reaction temperature of oxygenatedchemicals in bio oil, realize low temperature (≤225 DEG C) deoxidation, is conducive to saving energy consumption; Catalyst significantly can reduce benzene or arene content in the bio oil product after deoxidation, realizes high-quality deoxidation and highly effective hydrogenation, improves the quality of refining artifact oil product.
Ni – W – B amorphous catalyst prepared by the present invention has excellent catalytic activity, may be used for the catalytic hydrodeoxygenation reaction of phenols oxygenatedchemicals.Catalytic activity is better than traditional sulphurized catalyst and phosphatization catalyst greatly, with noble metal catalyst active quite but its cost significantly lower than noble metal catalyst, and the hydrogenation deoxidation reaction temperature of phenolic compound can be reduced greatly, be the refining new catalyst of a kind of efficient, eco-friendly bio oil catalytic hydrodeoxygenation.
Accompanying drawing explanation
Fig. 1 is the X-ray powder diffraction figure of Ni – W – B amorphous catalyst prepared by the present invention.
Fig. 2 is the transmission electron microscope picture of Ni – W – B-S amorphous catalyst prepared by the present invention.
Fig. 3 is the transmission electron microscope picture of Ni – W – B-C amorphous catalyst prepared by the present invention.
Detailed description of the invention
The present invention is described in detail by following examples.
It is pure that reagent used in embodiment is analysis, and water is ultra-pure water.
Ni – W – B amorphous catalyst prepared by the present invention is characterized by following means: adopt Rigaku D/max2550 18 KW to turn the amorphous structure that target X-ray diffractometer measures catalyst; Utilize pattern and the particle size of the JSM – 6360LV scanning electronic microscope observation catalyst of company of NEC; The NOVA – 2100e specific surface area analysis instrument adopting Quantachrome company of the U.S. to produce measures the specific area of catalyst.In the X – x ray diffration pattern x of described Ni – W – B amorphous catalyst 2 θ=20 ~ 80 ° scope in the only ° diffraction maximum that place's appearance one is wide in 2 θ=45 ± 1, in catalyst, active component Ni, W and B all exist with amorphous form.
Embodiment 1
By 1.31 g NiSO 46H 2o is dissolved in 25 mL water, and adding 2.5 g mass fractions is the NH of 25% 3h 2o, then add 1.65 g Na 2wO 42H 2o, moves to 250 mL there-necked flasks after stirring and dissolving, then adds the NaBH of 25 mL 1.0 mol/mL 4solution, under 30 DEG C and intense agitation, adds the Ag of 1 mL 0.001 mol//mL +solution, reaction occurs immediately, obtains black precipitate after reaction terminates, and after washing, alcohol wash, is placed in vacuum drying chamber 40 DEG C of dryings 5 hours.
The catalyst of 88.24 g n-dodecanes, 11.76 g phenol and the above-mentioned preparation of 0.20 g is added in autoclave, install device, get rid of air in still, then 225 DEG C are risen to the speed of 10 DEG C/min from room temperature, adjustment rotating speed is 900 r/min, Hydrogen Vapor Pressure is 4.0 MPa, sustained response 3 h, and product is analyzed through Agilent 6890/5973N gas chromatograph-mass spectrometer.The conversion ratio of phenol reaches 100%, and cyclohexane is selective reaches 79.6%.
Embodiment 2
By 1.18 g NiCl 26H 2o is dissolved in 25 mL water, and adding 2.5 g mass fractions is the NH of 25% 3h 2o, then add 1.65 g Na 2wO 42H 2o, moves to 250 mL there-necked flasks after stirring and dissolving, then adds the NaBH of 25 mL 1.0 mol/mL 4solution, under 30 DEG C and intense agitation, adds the Ag of 1 mL 0.001 mol//mL +solution, reaction occurs immediately, obtains black precipitate after reaction terminates, and after washing, alcohol wash, is placed in vacuum drying chamber 40 DEG C of dryings 5 hours.
The catalyst of 88.24g n-dodecane, 11.76 g phenol and the above-mentioned preparation of 0.20 g is added in autoclave, install device, get rid of air in still, then 225 DEG C are risen to the speed of 10 DEG C/min from room temperature, adjustment rotating speed is 900 r/min, Hydrogen Vapor Pressure is 4.0 MPa, sustained response 3h, and product is analyzed through Agilent 6890/5973N gas chromatograph-mass spectrometer.The conversion ratio of phenol reaches 100%, and cyclohexane is selective reaches 71.8%.
Embodiment 3
By 0.59 g NiCl 26H 2o is dissolved in 25 mL water, and adding 2.5 g mass fractions is the NH of 25% 3h 2o, then add 1.65 g Na 2wO 42H 2o, moves to 250 mL there-necked flasks after stirring and dissolving, then adds the NaBH of 25 mL 1.0 mol/mL 4solution, under 30 DEG C and intense agitation, adds the Ag of 1 mL 0.001 mol//mL +solution, reaction occurs immediately, obtains black precipitate after reaction terminates, and after washing, alcohol wash, is placed in vacuum drying chamber 40 DEG C of dryings 5 hours.
The catalyst of 88.24 g n-dodecanes, 11.76 g phenol and the above-mentioned preparation of 0.20 g is added in autoclave, install device, get rid of air in still, then 225 DEG C are risen to the speed of 10 DEG C/min from room temperature, adjustment rotating speed is 900 r/min, Hydrogen Vapor Pressure is 4.0 MPa, sustained response 3h, and product is analyzed through Agilent 6890/5973N gas chromatograph-mass spectrometer.The conversion ratio of phenol reaches 100%, and cyclohexane is selective reaches 86.0%.
Embodiment 4
By 0.40 g NiCl 26H 2o is dissolved in 25 mL water, and adding 2.5 g mass fractions is the NH of 25% 3h 2o, then add 1.65 g Na 2wO 42H 2o, moves to 250 mL there-necked flasks after stirring and dissolving, then adds the NaBH of 25 mL 1.0 mol/mL 4solution, under 30 DEG C and intense agitation, adds the Ag of 1 mL 0.001 mol//mL +solution, reaction occurs immediately, obtains black precipitate after reaction terminates, and after washing, alcohol wash, is placed in vacuum drying chamber 40 DEG C of dryings 5 hours.
The catalyst of 88.24 g n-dodecanes, 11.76 g phenol and the above-mentioned preparation of 0.20 g is added in autoclave, install device, get rid of air in still, then 225 DEG C are risen to the speed of 10 DEG C/min from room temperature, adjustment rotating speed is 900r/min, Hydrogen Vapor Pressure is 4.0MPa, sustained response 3h, and product is analyzed through Agilent 6890/5973N gas chromatograph-mass spectrometer.The conversion ratio of phenol reaches 100%, and cyclohexane is selective reaches 96.2%.
Embodiment 5
By 0.24 g NiCl 26H 2o is dissolved in 25 mL water, and adding 2.5 g mass fractions is the NH of 25% 3h 2o, then add 1.65 g Na 2wO 42H 2o, moves to 250 mL there-necked flasks after stirring and dissolving, then adds the NaBH of 25 mL 1.0 mol/mL 4solution, under 30 DEG C and intense agitation, adds the Ag of 1 mL 0.001 mol//mL +solution, reaction occurs immediately, obtains black precipitate after reaction terminates, and after washing, alcohol wash, is placed in vacuum drying chamber 40 DEG C of dryings 5 hours.
The catalyst of 88.24 g n-dodecanes, 11.76 g phenol and the above-mentioned preparation of 0.20 g is added in autoclave, install device, get rid of air in still, then 225 DEG C are risen to the speed of 10 DEG C/min from room temperature, adjustment rotating speed is 900 r/min, Hydrogen Vapor Pressure is 4.0 MPa, sustained response 3h, and product is analyzed through Agilent 6890/5973N gas chromatograph-mass spectrometer.The conversion ratio of phenol reaches 100%, and cyclohexane is selective reaches 99.0%.
Embodiment 6
The catalyst of 86.75 g n-dodecanes, 13.25 g benzaldehydes and 0.20 g embodiment 4 preparation is added in autoclave, install device, get rid of air in still, then rise to 225 DEG C with the speed of 10 DEG C/min from room temperature, adjustment rotating speed is 900 r/min, and Hydrogen Vapor Pressure is 4.0 MPa, sustained response 4 h, product is analyzed through Agilent 6890/5973N gas chromatograph-mass spectrometer, and the conversion ratio of benzaldehyde reaches 100 %, and the selective of hexahydrotoluene reaches 98.7%.
Embodiment 7
The catalyst of 85 g n-dodecanes, 15 g acetophenones and 0.10 g embodiment 4 preparation is added in autoclave, install device, get rid of air in still, then rise to 225 DEG C with the speed of 10 DEG C/min from room temperature, adjustment rotating speed is 900 r/min, and Hydrogen Vapor Pressure is 4.0 MPa, sustained response 4 h, product is analyzed through Agilent 6890/5973N gas chromatograph-mass spectrometer, and the conversion ratio of acetophenone reaches 100 %, and the selective of hexahydrotoluene reaches 95.4%.
Embodiment 8
By 0.26 g NiSO 46H 2o is dissolved in 25 mL water, and adding 2.5 g mass fractions is the NH of 25% 3h 2o, then add 1.65 g Na 2wO 42H 2o, moves to 250 mL there-necked flasks after stirring and dissolving, then adds the NaBH of 25 mL 1.0 mol/mL 4solution, under 30 DEG C and intense agitation, adds the Ag of 1 mL 0.001 mol//mL +solution, reaction occurs immediately, obtains black precipitate after reaction terminates, and after washing, alcohol wash, is placed in vacuum drying chamber 40 DEG C of dryings 5 hours.
The catalyst of 84.49 g n-dodecanes, 15.51 g p methoxy phenols and the above-mentioned preparation of 0.20 g is added in autoclave, install device, get rid of air in still, then rise to 225 DEG C with the speed of 10 DEG C/min from room temperature, adjustment rotating speed is 900 r/min, and Hydrogen Vapor Pressure is 4.0 MPa, sustained response 4h, product is analyzed through Agilent 6890/5973N gas chromatograph-mass spectrometer, and the conversion ratio of p methoxy phenol reaches 100%, and the selective of cyclohexane reaches 99.0%.
Embodiment 9
The catalyst of 86.34 g n-dodecanes, 13.76 g hydroquinones and 0.20 g embodiment 8 preparation is added in autoclave, install device, get rid of air in still, then rise to 225 DEG C with the speed of 10 DEG C/min from room temperature, adjustment rotating speed is 900 r/min, and Hydrogen Vapor Pressure is 4.0 MPa, sustained response 4h, product is analyzed through Agilent 6890/5973N gas chromatograph-mass spectrometer, and the conversion ratio of hydroquinones reaches 100%, and the selective of cyclohexane reaches 99.8%.
Embodiment 10
The catalyst of 87.49 g n-dodecanes, 12.51 g cyclohexanol and 0.20 g embodiment 8 preparation is added in autoclave, install device, get rid of air in still, then rise to 275 DEG C with the speed of 10 DEG C/min from room temperature, adjustment rotating speed is 900 r/min, and Hydrogen Vapor Pressure is 4.0 MPa, sustained response 4h, product is analyzed through Agilent 6890/5973N gas chromatograph-mass spectrometer, and the conversion ratio of cyclohexanol reaches 100%, and the selective of cyclohexane reaches 100%.

Claims (7)

1. for a preparation method for the catalyst of biological oil hydrodeoxygenation, body is made up of nickel, tungsten, boron and oxygen, it is characterized in that adopting following processing step:
(1) obtain solution A, by water-soluble for the nickel salt of solubility, adds complexing agent, makes NH in solution 4 +/ Ni 2+mol ratio is 5 ~ 30, then adds a certain proportion of tungsten salt, makes W/Ni atomic molar ratio in solution be 0.1 ~ 10; By NaBH 4or KBH 4reducing agent wiring solution-forming B, wherein reductant concentration is 0.2 ~ 10 mol/ml;
(2) at-10 DEG C ~ 30 DEG C, by solution A and B solution mixing, vigorous stirring, add the derivant of 0.001 ~ 2 mol/ml, immediate response, obtain black precipitate after reaction terminates after washing, alcohol wash, dry under vacuum, baking temperature is 40 ~ 120 DEG C, and vacuum is 0.05 ~ 0.1Mpa, and gained catalyst is kept away oxygen and preserved;
The nickel salt of described solubility is nickelous sulfate or nickel nitrate or nickel chloride or nickel acetate;
Described complexing agent is ammoniacal liquor or ethylenediamine;
Described tungsten salt is tungsten hexachloride or ammonium metatungstate or sodium tungstate;
Described derivant is Pb 2+or Ag +solution;
The molar ratio of described reducing agent and nickel salt and tungsten salt is 0.01 ~ 10, by the ratio of the integral molar quantity of all metals in the mole of boron element in reducing agent and solution.
2. the preparation method of a kind of catalyst for biological oil hydrodeoxygenation according to claim 1, is characterized in that: the preferred nickel nitrate of nickel salt of described solubility or nickel acetate.
3. the preparation method of a kind of catalyst for biological oil hydrodeoxygenation according to claim 1, is characterized in that: described amount of complex is NH 4 +/ Ni 2+mol ratio preferably 10 ~ 20.
4. the preparation method of a kind of catalyst for biological oil hydrodeoxygenation according to claim 1, is characterized in that: the preferred metatungstic acid sodium of described tungsten salt.
5. the preparation method of a kind of catalyst for biological oil hydrodeoxygenation according to claim 1, is characterized in that: described reducing agent is NaBH 4or KBH 4, concentration is preferably 0.5 ~ 2 mol/ml.
6. the preparation method of a kind of catalyst for biological oil hydrodeoxygenation according to claim 1, it is characterized in that: the molar ratio of described reducing agent and nickel salt and tungsten salt is preferably 0.3 ~ 5, by the ratio of the integral molar quantity of all metals in the mole of boron element in reducing agent and solution.
7. the preparation method of a kind of catalyst for biological oil hydrodeoxygenation according to claim 1, is characterized in that: described catalyst preparing reaction temperature is preferably-5 ~ 30 DEG C.
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