CN104785274A - Method for preparing bulk Ni-Mo hydrodeoxygenation catalyst with large aperture - Google Patents
Method for preparing bulk Ni-Mo hydrodeoxygenation catalyst with large aperture Download PDFInfo
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Abstract
The invention discloses a method for preparing a bulk Ni-Mo hydrodeoxygenation catalyst with a large aperture. The method comprises the following steps: (1) respectively dissolving a soluble nickel salt, a soluble molybdenum salt, and an organic acid into an ethanol-water solution; in addition, taking a pore-expanding agent solution; then, mixing the above solutions to obtain a uniform liquid mixture, and adjusting the pH value of the liquid mixture with ammonia water; conducting magnetic stirring on the liquid mixture till collosol is formed; ultrasonically vibrating; drying to obtain xerogel after 1 to 4 hours' ageing at room temperature; (2) roasting the xerogel for 1 to 4 hours under nitrogen atmosphere at 180 to 300 DEG C, and then roasting for 2 to 5 hours at 400 to 700 DEG C to obtain Ni-Mo composite oxide powder; mixing the Ni-Mo composite oxide powder, an adhesive, and powder of sesbaria cannabina to be uniform; dripping nitric acid, of which the mass concentration is 3%, for extrusion; roasting to obtain the bulk Ni-Mo composite oxide catalyst with the large aperture. The activation of the bulk Ni-Mo hydrodeoxygenation catalyst provided by the invention is superior to that of a bulk catalyst prepared for without adding of a pore-enlarging additive, and significantly higher than that of the conventional supported-type hydrodeoxygenation catalyst.
Description
Technical field
The present invention relates to the preparation method of a kind of large aperture this build Ni-Mo hydrogenation deoxidation catalyst.
Background technology
Petroleum resources day by day reduce and improving constantly of environmental requirement makes to pay close attention to widely for raw material is obtained by the research that hydrogenation deoxidation prepares alternative fossil fuel and eco-friendly second generation biodiesel with reproducible animal and plant fat.Hydrogenation deoxidation catalyst common mostly at present is transition metal loaded catalyst, but this type of catalyst is subject to the restriction of carrier specific area because of activity component load quantity, be difficult to improve its activity further by improving load capacity, thus reaction condition is comparatively harsh.Compare with conventional load type hydrogenation deoxidation catalyst, this build catalyst is not owing to using carrier, whole component all has catalytic activity, so just makes active component content contained by unit mass or volume of catalyst reach maximum, thus has stronger hydrogenation deoxidation ability.
The fatty acid chain length of vegetable oil is generally C14 ~ C22, its molecular weight is about 800 ~ 900, hydrogenation deoxidation for large molecular biosciences grease reacts, if make the aperture of catalyst comparatively large and have relatively many mesoporous, then can reduce the resistance that reactant molecule enters catalyst, and then improve its catalytic activity.Adopt physics or chemical enlargement agent process supported catalyst agent carrier or this build catalyst, can effectively increase its aperture size, or mesoporous quantity, or improve the connectivity in its duct, and then the catalytic activity of catalyst can be improved.
Wang Xin etc. adopt thermal precipitator method to prepare nanoscale (particle diameter is at 15 ~ 30nm) Ni (Co)-Mo-Al
2o
3this build catalyst, and the hydrogenation deoxidation reactivity worth having investigated its catalysis acetic acid in continuous fixed bed reactor.Result shows, at reaction conditions, adding of Ni, Co active component can make monometallic Mo-Al
2o
3the activity of catalyst significantly improves, Ni-Mo-Al
2o
3the hydrogenation deoxidation of catalyst is active in Co-Mo-Al
2o
3the activity of catalyst (Wang Xin, Zhang Shunguang, Hou Kaihu. unsupported Ni (Co)-Mo-Al
2o
3the preparation of nanocatalyst and bio oil model compound hydrogenation deoxidation performance study [J] thereof. Journal of Molecular Catalysis, 2010,24 (2): 153-157).The people such as Zhang Le adopt a kind of novel synthetic method to prepare non-loading type Ni-W-Mo hydrogenation catalyst, and are that raw material is evaluated the hydrogenation activity of catalyst on medium-sized hydrogenation plant with diesel oil.Result shows, the hydrodesulfurization activity of unsupported catalyst about can reach 7 times of the agent of industrial load type reference, hydrodenitrogenationactivity activity is about 3 times of (Zhang Le of support type reference agent, Long Xiangyun, Chen Ruolei, Deng. the research [J] of high activity non-supported hydrogenation catalyst. petroleum refining and chemical industry, 2008,39 (8): 30-35).Chinese patent CN102989526A discloses a kind of method that microwave method prepares distillate oil deep hydrofinishing body catalyst, by active metal component and pore former mixing, be placed in ball mill to mix after abundant ball milling, again mixture is positioned in microwave reactor and heats certain hour, obtain a kind of catalyst particles self with nano pore and high specific surface area, after shaping of catalyst, under microwave, carry out calcination process.Patent CN103506165A discloses a kind of preparation method of large-aperture fat hydrogenation catalyst, using nickel as active component, alkaline-earth metal is as auxiliary agent, and titanium aluminum oxide is as complex carrier, add amine oxide in preparation process as expanding agent, specific surface area of catalyst is 200 ~ 400m
2/ g, pore volume is 0.5 ~ 2.0m
3/ g, average pore size is 9 ~ 20nm.
Advantage of the present invention prepares in the process of this build catalyst at sol-gal process to add expanding agent, and obtained have compared with bigger serface and have this build of high activity Ni-Mo hydrogenation deoxidation catalyst of larger aperture simultaneously.
Summary of the invention
The present invention is based on the excellent catalytic activity of this build catalyst and the demand of large molecular biosciences oil hydrogenation deoxygenation, sol-gal process is adopted to prepare this build Ni-Mo composite oxide catalysts, in preparation process, add expanding agent, thus obtain having compared with bigger serface and there is this build of high activity Ni-Mo hydrogenation deoxidation catalyst of larger aperture simultaneously.
Technical scheme of the present invention is:
A preparation method for large aperture this build Ni-Mo hydrogenation deoxidation catalyst, comprises the following steps:
(1), soluble nickel salt, soluble molybdenum salt, organic acid are dissolved in ethanol water respectively, separately get expanding agent solution, above solution is mixed and regulates the pH of mixed solution to be 1 ~ 5 with ammoniacal liquor, mixed liquor is placed in 60-90 DEG C of water-bath magnetic agitation until form colloidal sol, sonic oscillation 10-30min, after aged at room temperature 1 ~ 4h at 120 DEG C dry xerogel;
Wherein, described expanding agent is one or more in starch, gelatin, sucrose, and addition is 10 ~ 50g/ (Mo+Ni) mol;
Material proportion is: described nickel salt, molybdenum salt, organic acid ratio are mol ratio Mo:Ni=0.2 ~ 1.0:1, (Mo+Ni): organic acid=0.5 ~ 2.0:1; In mixed solution, ethanol water amount is 500 ~ 900mL/ (Ni+Mo) mol;
(2), by xerogel first 180 ~ 300 DEG C of roasting 1 ~ 4h under nitrogen atmosphere in tube furnace, in Muffle furnace, 400 ~ 700 DEG C of roasting 2 ~ 5h obtain Ni-Mo composite oxide powder again, Ni-Mo composite oxide powder, binder and sesbania powder are mixed, drip the dust technology extruded moulding of 3%, in Muffle furnace, namely roasting obtains this build Ni-Mo composite oxide catalysts;
Wherein, the amount of 3% described dust technology is that every gram of Ni-Mo powder drips 0.5-1.5mL dust technology;
Mass ratio Ni-Mo composite oxide powder: binder: sesbania powder=5 ~ 8:2 ~ 5:0.3;
Described soluble nickel salt is Ni (NO
3)
26H
2o, NiSO
46H
2o, NiCl
26H
2o, C
4h
6o
4ni4H
2one or more in O;
Described soluble molybdenum salt is (NH
4)
6mo
7o
244H
2o, Mo (NO
3)
35H
2o, H
2moO
4h
2one or more in O;
Described organic acid is one or more in citric acid, oxalic acid, glycolic, malic acid.
The concentration of described ethanol water is volume fraction 50%.
Described binder is one or both in aluminum hydroxide solid elastomer, boehmite.
Beneficial effect of the present invention is:
The specific area of this build catalyst that the present invention obtains is 60 ~ 80m
2/ g, pore volume is 0.10 ~ 0.30cm
3/ g, average pore size is 10 ~ 15nm, and the XRD of catalyst characterizes spectrogram and sees Fig. 1, and Fig. 2 is shown in by the SEM photo of Ni-Mo composite oxide powder.And the specific area of not adding catalyst prepared by expanding agent is 36.4m
2/ g, pore volume is 0.06cm
3/ g, average pore size is 6.9nm.Reaction temperature 330 and 310 DEG C, pressure 2.0MPa, air speed 2 ~ 8h
-1, under hydrogen to oil volume ratio 200 condition, with the hydrogenation deoxidation performance that the normal octane solution containing 20% Jatropha curcas oil is raw material evaluate catalysts on continuous flow fixed bed reactor, result shows the activity that the activity adding this build catalyst prepared by expanding agent is better than not adding this build catalyst prepared by expanding agent, and is significantly higher than the activity of traditional load hydrogenation dehydrogenation catalyst.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates of this build Ni-Mo composite oxide catalysts prepared by the embodiment of the present invention 2 and embodiment 3;
Fig. 2 is ESEM (SEM) figure of this build Ni-Mo composite oxide catalysts prepared by the embodiment of the present invention 2;
Fig. 3 is ESEM (SEM) figure of this build Ni-Mo composite oxide catalysts prepared by the embodiment of the present invention 3.
Detailed description of the invention:
Embodiment 1
Take a certain amount of NiSO in proportion
46H
2o, (NH
4)
6mo
7o
244H
2o, citric acid, mol ratio is Mo:Ni=0.3, mol ratio (Mo+Ni): citric acid=1.5 (wherein, the implication of " (Mo+Ni) mol " is the molal quantity sum of molybdenum element and nickel element), be dissolved in the ethanol water of a certain amount of 50% (volume fraction) respectively, the total amount of ethanol water is made to be 500mL/ (Ni+Mo) mol after mixing, again according to the proportioning of 20g expanding agent/(Mo+Ni) mol by expanding agent starch dissolution in distilled water (water yield for can dissolve expanding agent completely), above solution is mixed and use mass percent be 27% ammoniacal liquor regulate mixed solution pH value to be 5.Mixed liquor is placed in 70 DEG C of water-bath magnetic agitation until form colloidal sol, sonic oscillation 30min, aged at room temperature 4h, dry xerogel at 120 DEG C.Xerogel 260 DEG C of roasting 3h under nitrogen atmosphere in tube furnace, in Muffle furnace air atmosphere, 500 DEG C of roasting 5h, obtain Ni-Mo composite oxide powder.By Ni-Mo powder, binder (aluminum hydroxide solid elastomer), sesbania powder in mass ratio 5:5:0.3 mix, drip dust technology (0.7mL/gNi-Mo powder) extruded moulding (the diameter 2mm that mass percent is 3%, be about 2-3mm), 500 DEG C of roasting 3h in Muffle furnace air atmosphere, obtained this build Ni-Mo composite oxide catalysts A.The BET characterization result of catalyst A is specific area 60.6m
2/ g, pore volume 0.20cm
3/ g, average pore size 13.7nm
With containing volume fraction be the normal octane solution of 20% Jatropha curcas oil for raw material, the hydrogenation deoxidation that continuous fixed bed is investigated catalyst is active.The catalyst first reduction activation 3h under temperature 400 DEG C, pressure 0.1MPa, hydrogen flow rate 30mL/min condition of oxidation state.Temperature 330,310 DEG C, pressure 2MPa, air speed 2h
-1, 5h
-1and 8h
-1, under hydrogen to oil volume ratio 200 condition, the evaluation result of catalyst A is in table 1.
Embodiment 2
Take a certain amount of Ni (NO in proportion
3)
26H
2o, (NH
4)
6mo
7o
244H
2o, oxalic acid, mol ratio is Mo:Ni=0.4, mol ratio (Mo+Ni): oxalic acid=1 (wherein, the implication of " (Mo+Ni) mol " is the molal quantity sum of molybdenum element and nickel element), be dissolved in the ethanol water of a certain amount of 50% (volume fraction) respectively, the total amount of ethanol water is made to be 600mL/ (Ni+Mo) mol after mixing, again according to the proportioning of 40g expanding agent/(Mo+Ni) mol by expanding agent starch dissolution in distilled water (water yield for can dissolve expanding agent completely), above solution is mixed and use mass percent be 27% adjustment mixed solution pH value be 3.5.Mixed liquor is placed in 80 DEG C of water-bath magnetic agitation until form colloidal sol, sonic oscillation 15min, aged at room temperature 1h, dry xerogel at 120 DEG C.Xerogel 300 DEG C of roasting 3h under nitrogen atmosphere in tube furnace, in Muffle furnace air atmosphere, 550 DEG C of roasting 4h, obtain Ni-Mo composite oxide powder.By Ni-Mo powder, binder (boehmite), sesbania powder in mass ratio 8:2:0.3 mix, drip dust technology (0.5mL/gNi-Mo powder) extruded moulding (the diameter 2mm that mass percent is 3%, be about 2-3mm), 600 DEG C of roasting 2h in Muffle furnace air atmosphere, obtained this build Ni-Mo composite oxide catalysts B.The BET characterization result of catalyst B is specific area 65.0m
2/ g, pore volume 0.22cm
3/ g, average pore size 14.2nm.
The reducing condition of catalyst B, evaluate raw material and the same catalyst A of appreciation condition, its evaluation result is in table 1.
Embodiment 3
Take a certain amount of C in proportion
4h
6o
4ni4H
2o, Mo (NO
3)
35H
2o, glycolic, mol ratio is Mo:Ni=0.5, mol ratio (Mo+Ni): glycolic=0.6 (wherein, the implication of " (Mo+Ni) mol " is the molal quantity sum of molybdenum element and nickel element), be dissolved in the ethanol water of a certain amount of 50% (volume fraction) respectively, make the total amount of ethanol water be 700mL/ (Ni+Mo) mol after mixing, then according to the proportioning of 30g expanding agent/(Mo+Ni) mol by expanding agent sucrose dissolved in distilled water (water yield for can dissolve expanding agent completely).Above solution is mixed and use mass percent be 27% adjustment mixed solution pH value be 2.Mixed liquor is placed in 90 DEG C of water-bath magnetic agitation until form colloidal sol, sonic oscillation 20min, aged at room temperature 3h, dry xerogel at 120 DEG C.Xerogel 200 DEG C of roasting 4h under nitrogen atmosphere in tube furnace, in Muffle furnace air atmosphere, 600 DEG C of roasting 2h, obtain Ni-Mo composite oxide powder.By Ni-Mo powder, binder (aluminum hydroxide solid elastomer), sesbania powder in mass ratio 7:3:0.3 mix, drip dust technology (1.0mL/gNi-Mo powder) extruded moulding (the diameter 2mm that mass percent is 3%, be about 2-3mm), 600 DEG C of roasting 3h in Muffle furnace air atmosphere, obtained this build Ni-Mo composite oxide catalysts C.The BET characterization result of catalyst C is specific area 66.0m
2/ g, pore volume 0.21cm
3/ g, average pore size 14.3nm.
The reducing condition of catalyst C, evaluate raw material and the same catalyst A of appreciation condition, its evaluation result is in table 1.
Embodiment 4
Take a certain amount of NiCl in proportion
26H
2o, H
2moO
4h
2o, malic acid, mol ratio is Mo:Ni=0.8, mol ratio (Mo+Ni): malic acid=0.6 (wherein, the implication of " (Mo+Ni) mol " is the molal quantity sum of molybdenum element and nickel element), be dissolved in the ethanol water of a certain amount of 50% (volume fraction) respectively, make the total amount of ethanol water be 800mL/ (Ni+Mo) mol after mixing, then according to the proportioning of 50g expanding agent/(Mo+Ni) mol by expanding agent Gelatin in distilled water (water yield for can dissolve expanding agent completely).Above solution is mixed and use mass percent be 27% adjustment mixed solution pH value be 1.Mixed liquor is placed in 60 DEG C of water-bath magnetic agitation until form colloidal sol, sonic oscillation 10min, aged at room temperature 2h, dry xerogel at 120 DEG C.Xerogel 300 DEG C of roasting 2h under nitrogen atmosphere in tube furnace, in Muffle furnace air atmosphere, 500 DEG C of roasting 3h, obtain Ni-Mo composite oxide powder.By Ni-Mo powder, binder (boehmite), sesbania powder in mass ratio 6:4:0.3 mix, drip dust technology (1.3mL/gNi-Mo powder) extruded moulding (the diameter 2mm that mass percent is 3%, be about 2-3mm), 550 DEG C of roasting 4h in Muffle furnace air atmosphere, obtained this build Ni-Mo composite oxide catalysts D.The BET characterization result of catalyst D is specific area 70.1m
2/ g, pore volume 0.25cm
3/ g, average pore size 14.7nm.
The reducing condition of catalyst D, evaluate raw material and the same catalyst A of appreciation condition, its evaluation result is also in table 1.
Comparative example
For comparison purpose, do not add expanding agent by condition described in embodiment 1 and prepared this build Ni-Mo composite oxide catalysts, be designated as catalyst E.The BET characterization result of catalyst E is specific area 36.4m
2/ g, pore volume 0.06cm
3/ g, average pore size 6.9nm.
The reducing condition of catalyst E, evaluate raw material and the same catalyst A of appreciation condition, its evaluation result is also in table 1.
The structural parameters of table 1 catalyst and hydrogenation deoxidation evaluation result
From data in table, add the specific area of this build Ni-Mo hydrogenation deoxidation catalyst of preparing of expanding agent, aperture, pore volume and hydrogenation deoxidation activity all higher than this build catalyst not adding expanding agent and prepare, and loaded catalyst Ni-Mo/ γ-Al
2o
3at 4MPa, 360 DEG C, air speed 1.00h
-1condition under, the DNA vaccine of catalysis cottonseed oil hydrogenation deoxidation is 99.2% (Dong Guangda, Wang Yujun, Zhang Weidong, Deng. cottonseed oil hydrogenation deoxidation prepares second generation biodiesel [J]. petrochemical industry, 2013,42 (7): 737-742.) activity of this build catalyst therefore, prepared in the present invention will apparently higher than conventional load type hydrogenation deoxidation catalyst.
Obviously, above-described embodiment is only for clearly demonstrating done citing, the restriction not to embodiment.Here without the need to also cannot being illustrated to all embodiments, and thus the apparent change of extending out or variation be still among the protection domain of the invention.
Unaccomplished matter of the present invention is known technology.
Claims (3)
1. a preparation method for this build of large aperture Ni-Mo hydrogenation deoxidation catalyst, is characterized by and comprise the following steps:
(1), soluble nickel salt, soluble molybdenum salt, organic acid are dissolved in ethanol water respectively, separately get expanding agent solution, above solution is mixed and regulates the pH of mixed solution to be 1 ~ 5 with ammoniacal liquor, mixed liquor is placed in 60-90 DEG C of water-bath magnetic agitation until form colloidal sol, sonic oscillation 10-30min, after aged at room temperature 1 ~ 4h at 120 DEG C dry xerogel;
Wherein, described expanding agent is one or more in starch, gelatin, sucrose, and addition is 10 ~ 50g/ (Mo+Ni) mol;
Material proportion is: described nickel salt, molybdenum salt, organic acid ratio are mol ratio Mo:Ni=0.2 ~ 1.0:1, (Mo+ Ni): organic acid=0.5 ~ 2.0:1; In mixed solution, ethanol water amount is 500 ~ 900mL/ (Ni+Mo) mol;
(2), by xerogel first 180 ~ 300 DEG C of roasting 1 ~ 4h under nitrogen atmosphere in tube furnace, in Muffle furnace, 400 ~ 700 DEG C of roasting 2 ~ 5 h obtain Ni-Mo composite oxide powder again, Ni-Mo composite oxide powder, binder and sesbania powder are mixed, drip the dust technology extruded moulding of 3%, in Muffle furnace, namely roasting obtains this build Ni-Mo composite oxide catalysts;
Wherein, the amount of 3% described dust technology is that every gram of Ni-Mo powder drips 0.5-1.5mL dust technology;
Mass ratio Ni-Mo composite oxide powder: binder: sesbania powder=5 ~ 8:2 ~ 5:0.3;
Described soluble nickel salt is Ni (NO
3)
26H
2o, NiSO
46H
2o, NiCl
26H
2o, C
4h
6o
4ni4H
2one or more in O;
Described soluble molybdenum salt is (NH
4)
6mo
7o
244H
2o, Mo (NO
3)
35H
2o, H
2moO
4h
2one or more in O;
Described organic acid is one or more in citric acid, oxalic acid, glycolic, malic acid.
2. the preparation method of large aperture as claimed in claim 1 this build Ni-Mo hydrogenation deoxidation catalyst, the concentration that it is characterized by described ethanol water is volume fraction 50%.
3. the preparation method of large aperture as claimed in claim 1 this build Ni-Mo hydrogenation deoxidation catalyst, it is characterized by described binder is one or both in aluminum hydroxide solid elastomer, boehmite.
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| CN106076359A (en) * | 2016-07-14 | 2016-11-09 | 安徽海德石油化工有限公司 | A kind of oil hydrogenation deoxidation nickel-base catalyst |
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| CN106916921A (en) * | 2015-12-28 | 2017-07-04 | 正大能源材料(大连)有限公司 | A kind of method that utilization waste oil fat hydrogenation catalyst prepares deoxidier |
| US10953389B2 (en) | 2016-02-01 | 2021-03-23 | Albemarle Europe Sprl | Nickel containing mixed metal-oxide/carbon bulk hydroprocessing catalysts and their applications |
| CN106076359A (en) * | 2016-07-14 | 2016-11-09 | 安徽海德石油化工有限公司 | A kind of oil hydrogenation deoxidation nickel-base catalyst |
| CN109745993A (en) * | 2017-11-01 | 2019-05-14 | 中国石油天然气股份有限公司 | A kind of preparation method of mesoporous figure Mo-Ni hydrogenation deoxidation catalyst |
| CN110756196A (en) * | 2018-07-26 | 2020-02-07 | 中国石油天然气股份有限公司 | Preparation method of vegetable oil hydrodeoxygenation catalyst |
| CN110756196B (en) * | 2018-07-26 | 2022-10-04 | 中国石油天然气股份有限公司 | Preparation method of vegetable oil hydrodeoxygenation catalyst |
| CN109603839A (en) * | 2019-01-09 | 2019-04-12 | 泰州学院 | A kind of preparation method of figure cobalt molybdenum Hydrobon catalyst |
| CN109603839B (en) * | 2019-01-09 | 2022-02-15 | 泰州学院 | Preparation method of bulk cobalt-molybdenum hydrodesulfurization catalyst |
| CN115770580A (en) * | 2022-11-30 | 2023-03-10 | 中国石油大学(华东) | Multifunctional hydrogenation catalyst for preparing aviation kerosene component by one-step hydrogenation of grease and preparation method thereof |
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