CN101612584B - Preparation method of nickel phosphide catalyst carried by composite carrier - Google Patents
Preparation method of nickel phosphide catalyst carried by composite carrier Download PDFInfo
- Publication number
- CN101612584B CN101612584B CN2009100233941A CN200910023394A CN101612584B CN 101612584 B CN101612584 B CN 101612584B CN 2009100233941 A CN2009100233941 A CN 2009100233941A CN 200910023394 A CN200910023394 A CN 200910023394A CN 101612584 B CN101612584 B CN 101612584B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- nickel
- tio
- butyl titanate
- carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention relates to a preparation method of a nickel phosphide catalyst carried by a composite carrier. The method is characterized by comprising the following steps: firstly, using activated alumina and relative enzymes and alcohols as raw materials to prepare a composite carrier of TiO2-Al2O3 by adopting an improved sol-gel method; further, selecting suitable nickel salt and phosphate and carrying out ultrasound dipping and drying in microwaves to obtain a catalyst precursor; and finally, increasing a temperature by a program and reducing to obtain the composite support. The composite carrier of TiO2-Al2O3 prepared by the invention not only can effectively overcome the defect that nickel phosphide is apt to react with gamma-Al2O3 to generate AlP4 to lose the activity, but also overcomes the defect that a specific surface area of single TiO2 is relatively small, effectively exerts the strong metal-support interaction (SMSI) of the TiO2, thereby obtaining a hydrodesulfurization catalyst with remarkable activity efficacy.
Description
Technical field
The present invention relates to a kind of preparation of oil hydrogenation desulphurization catalyst, particularly a kind ofly change the preparation method that active component supports the catalyst of phosphatizing nickel of used carrier
Background technology
As everyone knows, catalytic desulfurhydrogenation (HDS) technology is still the main path that reduces the petrol and diesel oil sulfur content, and the activity of traditional Hydrobon catalyst has not reached the standard of the low sulfur content of new appearance, therefore presses for and seeks Hydrobon catalyst efficiently.
Studies show that, transition metal phosphide catalyst, especially nickel phosphide, owing to its excellent hydrodesulfurization activity receives much concern, but non-loading type Ni
2The specific area of P catalyst is very little (less than 1m
2g
-1), in order to improve its active surface area, need Ni
2P loads on the carrier of high specific surface area.So preparation high dispersive, highly active load type metal nickel phosphide will be the striving directions of development fuel oil Hydrobon catalyst of new generation.And the research in this field, mainly concentrating on the loading method and the exploration that improve active component at present can better two aspect of carrier.
The loading method of previously disclosed relevant nickel phosphide active component comprises: (1) one step or multistep immersion process for preparing catalyst precursor prepares catalyst by the temperature programmed reduction precursor then; (2) amorphous state low temperature prepares catalyst.
It is undesirable that traditional temperature programmed reduction method prepares the active component dispersion effect of support type nickel phosphide, thereby the gathering that causes the carrier surface active component causes the specific area of catalyst to reduce greatly, metal phosphorizing nickel related activity center number is less in the unit mass catalyst, thereby reduces activity of such catalysts.Though prepare Ni by amorphous state Ni-P low temperature
2The P catalyst can prepare the catalyst of high dispersive under low relatively temperature, but needs to use the gaseous mixture of hydrogen phosphide and hydrogen, and is not easy to operate.
The carrier of previously disclosed relevant support type catalyst of phosphatizing nickel comprises: Al
2O
3, SiO
2, MCM-41, HZSM-5, KUSY, SBA-15, active carbon, TiO
2And SiO
2-Al
2O
3Deng, but the different carriers and the performance and the structure thereof of the interaction partners catalyst between the active component have very big influence.
Macropore γ-Al
2O
3Be industrial traditional catalyst for desulphurization of oil products carrier, because macropore γ-Al
2O
3Have bigger specific area, suitable pore structure, stronger mechanical strength and good excellent properties such as heat endurance.If catalyst of phosphatizing nickel is with γ-Al
2O
3Be carrier, phosphate is easy to and γ-Al in preparation process
2O
3The Al of surface four-coordination
3+The strong interaction taken place and generated AlPO in ion
4Thereby, cause the loss of active component even the destruction of catalyst surface institutional framework, make catalyst activity reduction, thereby limited macropore γ-Al
2O
3The application of load catalyst of phosphatizing nickel in hydrogenation industry.
Mesopore molecular sieves such as MCM-41 also are used as the carrier of Hydrobon catalyst.This class mesopore molecular sieve has high-specific surface area, mesoporous aperture that homogeneous is adjustable and stable skeleton structure, but its duct easily stops up, and sometimes activity of such catalysts is produced negative effect.
SiO
2Be considered to load nickel phosphide carrier preferably, but SiO
2Thereby the more weak dispersion that is unfavorable for active component at carrier surface of the interaction between carrier and metal component also can reduce the activity of hydrodesulfurization.
TiO
2Not only play the effect of conventional carrier as hydrodesulfurization catalyst support, but also play the effect of electronics promoter.TiO
2Can have strong interaction with the intermetallic of institute load as carrier, this effect is actually because the TiO that part is reduced
2(as Ti
3+) in action, be electronic effect in essence, based on this effect, can impel the activated centre component, thereby improve the surface texture of metallic catalyst with Thermodynamically stable state high degree of dispersion.TiO in addition
2Carrier will have influence on the absorption property of catalyst, thereby improves activity of such catalysts and selectivity greatly owing to the reducibility of itself.But TiO
2Also there are some weakness as catalyst carrier, less relatively as its specific area, generally be not more than 100m
2G
-1, active Detitanium-ore-type is at high temperature stable inadequately, easily is converted into the rutile structure of inertia, bad mechanical strength and acidity a little less than, make it be difficult in industrial being widely used.
Summary of the invention
The object of the invention is to overcome the deficiency of the carrier of desulphurization catalyst described in the background technology, provides a kind of based on the NEW TYPE OF COMPOSITE carrier, and the preparation method of the catalyst of phosphatizing nickel of the loading mode of improvement catalyst activity component, thereby obtains desulfurized effect preferably.
For reaching above purpose, the present invention takes following technical scheme to be achieved:
The preparation method of the catalyst of phosphatizing nickel that a kind of complex carrier supports is characterized in that, comprises the steps:
A. butyl titanate is dissolved in the mixed solution that makes its formation butyl titanate in ethanol and the glacial acetic acid, wherein the volume ratio of butyl titanate, ethanol and glacial acetic acid is: 1: 1: 0.1-0.3; Quality with butyl titanate is a radix then, adds the γ-Al of 40-60% quality
2O
3Place the mixed solution of butyl titanate, in the ultrasonic 20min that disperses at least down, ageing half a day then is promptly at γ-Al with above-mentioned mixed solution
2O
3The surface coats one deck TiO
2Gains after centrifugal filtration are used absolute ethyl alcohol and washed with de-ionized water respectively, drying, and calcining 3-5h makes complex carrier TiO under 300～500 ℃
2-Al
2O
3
B. nickel nitrate, DAP, water are pressed 1: the mass ratio of 0.6-0.9: 2.5-3 mixes, and makes nickel nitrate and DAP soluble in water fully, and the pH that drips the nitric acid regulator solution is 2-4, gets the green transparent dipping solution; This dipping solution is joined the complex carrier TiO of this solution quality 20-25%
2-Al
2O
3In, ultrasonic immersing 30～40min, quick then evaporating water is warming up to 400-600 ℃ of roasting 3-6h in air, make the catalyst of phosphatizing nickel presoma of oxidation state;
C. last, adopt temperature programmed reduction technology, obtain complex carrier TiO
2-Al
2O
3The catalyst of phosphatizing nickel that supports.
In the such scheme, the temperature programmed reduction technology of described step c comprises the steps:
The catalyst of phosphatizing nickel presoma for preparing is purged 30-60min with the flow velocity of 40-100ml/min to the catalyst of phosphatizing nickel presoma with nitrogen at 100-300 ℃, switch hydrogen then and the catalyst of phosphatizing nickel presoma is carried out heating reduction with the flow velocity of 40-100mL/min, speed with 3-5 ℃/min is warming up to 600 ℃～700 ℃, be incubated 2～4 hours, in N2, reduce to room temperature at last, and at N
2Middle passivation 1h.
The present invention compared with prior art, TiO
2-Al
2O
3Complex carrier had both had both Al simultaneously
2O
3The carrier specific area is big, pore structure is suitable, the excellent properties of mechanical strength and good thermal stability, has brought into play TiO again
2Effect as the electronics promoter of hydrodesulfurization catalyst support has weakened phosphorus and Al
2O
3The loss of activity that interaction caused.Adopt improved Prepared by Sol Gel Method complex carrier and ultrasonic wave facture to replace traditional immersion process for preparing catalyst precursor, can improve the dispersion effect of catalyst activity component significantly, avoid the minimizing at catalyst of phosphatizing nickel related activity center, and then improve activity of such catalysts.
Description of drawings
Fig. 1 is complex carrier TiO of the present invention
2-Al
2O
3XRD spectra before and after the catalyst of phosphatizing nickel I reaction that supports.Wherein (1) is the XRD spectra of reaction procatalyst I; (2) be the XRD spectra of post catalyst reaction I.
Fig. 2 is the catalyst activity histogram relatively of catalyst I-IV of the present invention.Transverse axis is represented different catalyst, and the longitudinal axis is represented the conversion ratio % of dibenzothiophenes.Reaction condition is: 340 ℃ of temperature, pressure 2MPa, charging mass space velocity 2h during liquid
-1, hydrogen to oil volume ratio is 400.
The specific embodiment
The present invention is described in further detail below in conjunction with specific embodiment.
Embodiment 1
A. the butyl titanate with 13ml is dissolved in 13ml ethanol and the 1.3ml glacial acetic acid, makes it form the mixed solution of butyl titanate, takes by weighing 7.8g γ-Al
2O
3Place the mixed solution of butyl titanate, above-mentioned mixed liquor is disperseed 30min, ultrasonic power 500W under ultrasonic.Ageing half a day, can be at γ-Al
2O
3Carrier surface coats one deck TiO
2After the centrifugal filtration, use absolute ethyl alcohol and washed with de-ionized water three times respectively, put into 120 ℃ of dry 12h of drying box.Dried powder is placed muffle furnace, and calcining 5h is cooled to room temperature under 300 ℃, can make TiO
2-Al
2O
3Complex carrier.
B. take by weighing the carrier 8.25g of method for preparing, adding has in the there-necked flask of funnel.Take by weighing 7.5g nitric acid nickel (NO respectively
3)
26H
2O and 6.5g DAP (NH
4)
2HPO
4Be dissolved in the 20g deionized water, obtain yellow mercury oxide, dripping nitric acid adjusting pH is 3, the precipitation dissolving becomes the solution of green transparent, maceration extract added fill in the carrier there-necked flask, by behind the ultrasonic wave dipping 30min (ultrasonic power 700W), in micro-wave oven under the power of 700W dry about 10min, roasting 3 hours in air under 500 ℃ then makes the catalyst of phosphatizing nickel presoma of oxidation state.
C. with the catalyst of phosphatizing nickel presoma for preparing, add the temperature control district of quartz ampoule, the two ends of quartz ampoule are supported with silica wool.With the flow velocity of 60mL/min the catalyst of phosphatizing nickel presoma is purged 30min with nitrogen at 200 ℃, switch hydrogen then and catalyst is carried out temperature programmed reduction, be warming up to 700 ℃ and under this temperature, keep 2h with the speed of 3 ℃/min with the flow velocity of 60/min.Reduce to room temperature then, and at N
2Middle passivation 1h obtains Ni
2P/TiO
2-Al
2O
3Catalyst is designated as catalyst I.
The flat-temperature zone that the support type catalyst of phosphatizing nickel I for preparing is added fixed bed reactors, the two ends of bed are supported with silica wool, before the heating, purge with nitrogen, and then begin to be heated to 450 ℃, feeding hydrogen activates catalyst I with the flow velocity of 40-100mL/min, be cooled to 340 ℃ of hydrodesulfurization reaction temperature at last, squeeze into the n-heptane solution (wherein sulfur content is 1000ppm) that contains dibenzothiophenes with high-pressure metering pump in reactor, and keep constant temperature, air speed is controlled at 5hr
-1, the beginning hydrodesulfurization reaction.Gathered a sample every one hour, and form with gas-chromatography (FPD) check and analysis product.When 340 ℃ of reactions, the desulfurization degree of dibenzothiophenes surpasses 99%.
Embodiment 2
A. the butyl titanate with 13ml is dissolved in 13ml ethanol and the 3.9ml glacial acetic acid, makes it form the mixed solution of butyl titanate, takes by weighing 5.2g γ-Al
2O
3Place the mixed solution of butyl titanate, above-mentioned mixed liquor is disperseed 20min, ultrasonic power 700W under ultrasonic.Ageing half a day, can be at γ-Al
2O
3Carrier surface coats one deck TiO
2After the centrifugal filtration, use absolute ethyl alcohol and washed with de-ionized water three times respectively, put into 120 ℃ of dry 12h of drying box.Dried powder is placed muffle furnace, and calcining 3h is cooled to room temperature under 500 ℃, can make TiO
2-Al
2O
3Complex carrier.
B. take by weighing the carrier 8.5g of method for preparing, adding has in the there-necked flask of funnel.Take by weighing 7.5g nitric acid nickel (NO respectively
3)
26H
2O and 4.5g DAP (NH
4)
2HPO
4Be dissolved in the 22g deionized water, obtain yellow mercury oxide, dripping nitric acid adjusting pH is 4, the precipitation dissolving becomes the solution of green transparent, maceration extract added fill in the carrier there-necked flask, by behind the ultrasonic wave dipping 40min (ultrasonic power 500W), in micro-wave oven under the power of 700W the about 10min of drying and roasting, roasting 6 hours in air under 400 ℃ then makes the catalyst of phosphatizing nickel presoma of oxidation state.
C. with the catalyst of phosphatizing nickel presoma for preparing, add the temperature control district of quartz ampoule, the two ends of quartz ampoule are supported with silica wool.With the flow velocity of 60mL/min the catalyst of phosphatizing nickel presoma is purged 60min with nitrogen at 200 ℃, switch hydrogen then and catalyst is carried out temperature programmed reduction, be warming up to 600 ℃ and under this temperature, keep 4h with the speed of 5 ℃/min with the flow velocity of 40/min.Reduce to room temperature then, and at N
2Middle passivation 1h obtains Ni
2P/TiO
2-Al
2O
3Catalyst is designated as catalyst I '.This activity of such catalysts evaluation is carried out according to the method for embodiment 1.When 340 ℃ of reactions, the desulfurization degree of dibenzothiophenes is about 98%.
Embodiment 3
This routine step a complex carrier TiO
2-Al
2O
3Preparation process in, adopt traditional mechanical agitation to replace ultrasonic dispersion; In the step b oxidation state catalyst of phosphatizing nickel preparation process of precursor, replace ultrasonic immersing with traditional mechanical agitation equally, the drying under the power of 700W in the dry replacement micro-wave oven in 120 ℃ of drying boxes, other operating procedure obtains Ni according to embodiment 1
2P/TiO
2-Al
2O
3Catalyst is designated as catalyst I I.This activity of such catalysts evaluation is carried out according to the method for embodiment 1.When 340 ℃ of reactions, the desulfurization degree of dibenzothiophenes is about 95%.
Comparative example 1
With the carrier of titanium dioxide, adopt step b of the present invention to prepare Ni to step c as the load nickel phosphide
2P/TiO
2Catalyst is designated as catalyst I II.According to embodiment 1 method it is estimated.When 340 ℃ of reactions, the desulfurization degree of dibenzothiophenes is about 90%.
Comparative example 2
With the carrier of active alundum (Al, adopt step b of the present invention to prepare Ni to step c as the load nickel phosphide
2P/Al
2O
3Catalyst is designated as catalyst I V.According to embodiment 1 method it is estimated.When 340 ℃ of reactions, the desulfurization degree of dibenzothiophenes is about 75%.
As shown in Figure 1, show the crystalline structure of the catalyst of phosphatizing nickel I of the embodiment of the invention 1 and standard N i with the standard diagram check analysis
2The P collection of illustrative plates meets, and Ni do not occur
12P
5Wait other crystal formations, and the crystalline structure of post catalyst reaction is not damaged.As shown in Figure 2, the specific activity from several catalyst of phosphatizing nickel is the highest than the activity of the catalyst of phosphatizing nickel I that can intuitively demonstrate the embodiment of the invention 1.
The infrared analysis characterization result shows, at γ-Al
2O
3Carrier surface is introduced TiO
2Can obviously reduce γ-Al
2O
3The Al of surface four-coordination
3+Ion, thus Ni weakened
2P/TiO
2-Al
2O
3Ni in the catalyst
2P and γ-Al
2O
3The strong interaction of carrier surface; The BET measurement result shows, TiO
2-Al
2O
3Complex carrier still can keep γ-Al
2O
3Carrier suit pore structure, bigger specific area, Ni
2P/TiO
2-Al
2O
3The fall of the specific area of catalyst is little; The XRD characterization result shows that the main thing of catalyst is Ni mutually
2P; Transmission electron microscope (TEM) characterization result shows Ni
2The P active component well is distributed on the complex carrier, Ni
2The average grain diameter of P is approximately about 20nm.The activity rating result confirms that above-mentioned composite catalyst can be reduced to sulfur content in the oil product below the 10ppm from 2000ppm, thereby satisfies the preparation needs of cleaning oil product.
Claims (2)
1. the preparation method of the catalyst of phosphatizing nickel that supports of a complex carrier is characterized in that, comprises the steps:
A. butyl titanate is dissolved in the mixed solution that makes its formation butyl titanate in ethanol and the glacial acetic acid, wherein the volume ratio of butyl titanate, ethanol and glacial acetic acid is: 1: 1: 0.1-0.3; Quality with butyl titanate is a radix then, adds the γ-Al of 40-60% quality
2O
3Place the mixed solution of butyl titanate, in the ultrasonic 20min that disperses at least down, ageing half a day then is promptly at γ-Al with above-mentioned mixed solution
2O
3The surface coats one deck TiO
2The gains of solution after the ageing after centrifugal filtration are used absolute ethyl alcohol and washed with de-ionized water respectively, drying, and calcining 3-5h makes complex carrier TiO under 300～500 ℃
2-Al
2O
3
B. nickel nitrate, diammonium hydrogen phosphate, water are pressed 1: the mass ratio of 0.6-0.9: 2.5-3 mixes, and makes nickel nitrate and diammonium hydrogen phosphate soluble in water fully, and the pH that drips the nitric acid regulator solution is 2-4, gets the green transparent dipping solution; Dipping solution is joined complex carrier TiO by the 20-25% of this dipping solution quality
2-Al
2O
3In, ultrasonic immersing 30～40min, quick then evaporating water is warming up to 400-600 ℃ of roasting 3-6h in air, make the catalyst of phosphatizing nickel presoma of oxidation state;
C. last, adopt temperature programmed reduction technology, obtain complex carrier TiO
2-Al
2O
3The catalyst of phosphatizing nickel that supports.
2. the preparation method of the catalyst of phosphatizing nickel that complex carrier as claimed in claim 1 supports is characterized in that, the temperature programmed reduction technology of described step c comprises the steps:
1) the catalyst of phosphatizing nickel presoma for preparing is purged 30-60min with the flow velocity of 40-100mL/min to the catalyst of phosphatizing nickel presoma with nitrogen at 100-300 ℃;
2) switch hydrogen then and with the flow velocity of 40-100mL/min the catalyst of phosphatizing nickel presoma is carried out heating reduction: the speed with 3-5 ℃/min is warming up to 600 ℃～700 ℃, is incubated 2～4 hours, at last at N
2In reduce to room temperature, and at N
2Middle passivation 1h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100233941A CN101612584B (en) | 2009-07-21 | 2009-07-21 | Preparation method of nickel phosphide catalyst carried by composite carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100233941A CN101612584B (en) | 2009-07-21 | 2009-07-21 | Preparation method of nickel phosphide catalyst carried by composite carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101612584A CN101612584A (en) | 2009-12-30 |
| CN101612584B true CN101612584B (en) | 2010-11-10 |
Family
ID=41492570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100233941A Expired - Fee Related CN101612584B (en) | 2009-07-21 | 2009-07-21 | Preparation method of nickel phosphide catalyst carried by composite carrier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101612584B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108906098A (en) * | 2018-05-29 | 2018-11-30 | 东北石油大学 | A kind of mesoporous TiO 2 cladding catalyst of phosphatizing nickel constitutes the preparation method of core-shell structure catalyst |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102773112B (en) * | 2012-08-10 | 2014-06-04 | 西安交通大学 | Method for preparing ternary complex carrier supported nickel phosphide catalyst |
| CN104437578B (en) * | 2013-09-16 | 2017-04-26 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst, preparation method and applications thereof |
| CN104437571B (en) * | 2013-09-16 | 2017-06-06 | 中国石油化工股份有限公司 | A kind of Hydrobon catalyst, preparation method and applications |
| CN104923196B (en) * | 2015-05-12 | 2017-05-24 | 东北石油大学 | Preparation method for preparing core-shell structure carrier of hydrodeoxygenation catalyst |
| CN105195208A (en) * | 2015-09-24 | 2015-12-30 | 神华集团有限责任公司 | Monolithic catalyst, preparation method thereof and desulphurization method utilizing monolithic catalyst |
| CN107955643A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | A kind of deactivating process for the treatment of of nickel system aromatic hydrocarbon hydrogenation catalyst |
| CN108246341B (en) * | 2016-12-28 | 2020-11-10 | 南开大学 | Preparation method and use method of hydrogenation dearomatization catalyst |
| CN108721949A (en) * | 2018-05-25 | 2018-11-02 | 高阳 | A kind of organic silicon defoamer and preparation method thereof |
| CN113828336B (en) * | 2020-06-23 | 2024-02-13 | 中国石油化工股份有限公司 | Catalyst and preparation method and application thereof |
| CN112412430B (en) * | 2020-09-18 | 2022-02-01 | 西安交通大学 | System and method for underground in-situ pyrolysis of coal |
| CN112717946A (en) * | 2020-12-31 | 2021-04-30 | 西北化工研究院有限公司 | Spent lubricating oil hydrogenation regeneration catalyst and preparation method thereof |
| CN112844398B (en) * | 2021-02-10 | 2023-05-30 | 中国海洋石油集团有限公司 | Catalyst for hydrogenation of carbon four-superimposed product and preparation method thereof |
| CN113042057B (en) * | 2021-02-10 | 2023-06-23 | 中国海洋石油集团有限公司 | Catalyst for hydrogenation of carbon four-superimposed product and preparation method thereof |
| CN116273049A (en) * | 2022-12-28 | 2023-06-23 | 惠生工程（中国）有限公司 | Preparation method and activation method of catalyst for synthesizing methyl glycolate |
-
2009
- 2009-07-21 CN CN2009100233941A patent/CN101612584B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| Sun Fuxia,et al..A Novel Highly Active Hydrodesulfurization Catalyst: Nickel Phosphide Supported on Silica.《催化学报》.2004,第25卷(第9期),685-687. * |
| 胡见波等.负载型纳米TiO2复合载体催化剂及其HDS 活性研究.《南开大学学报(自然科学)》.2002,第35卷(第3期),1-5. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108906098A (en) * | 2018-05-29 | 2018-11-30 | 东北石油大学 | A kind of mesoporous TiO 2 cladding catalyst of phosphatizing nickel constitutes the preparation method of core-shell structure catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101612584A (en) | 2009-12-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101612584B (en) | Preparation method of nickel phosphide catalyst carried by composite carrier | |
| CN106669786B (en) | A kind of catalytic diesel oil hydrocracking catalyst and preparation method thereof | |
| CN105817259A (en) | Productive naphtha type hydrocracking catalyst and preparation method thereof | |
| CN109364905A (en) | A kind of aluminium oxide containing auxiliary agent, preparation method and the catalyst containing the aluminium oxide | |
| WO2021027018A1 (en) | Highly dispersible hydrogenation catalyst, preparation method thereof, and use thereof in producing biofuels from palm oil and other oils and fats | |
| CN107304375B (en) | A kind of catalytic diesel oil conversion process catalyst grade matches process | |
| CN110075907A (en) | A kind of ammoxidation catalyst and preparation method thereof for diesel car tail gas refining | |
| CN101574659A (en) | Catalyst for using coal tar to prepare clean fuel oil by catalytic hydrogenation, preparation method and applications | |
| CN104549411A (en) | Preparation method of nickel-based catalyst based on SBA-15 and application of nickel-based catalyst in SNG preparation | |
| CN107442166A (en) | Hydrogenation catalyst suitable for producing biodiesel and its preparation method and application | |
| CN104437578B (en) | Hydrodesulfurization catalyst, preparation method and applications thereof | |
| CN110876933B (en) | Composite oxide carrier, cobalt-based Fischer-Tropsch synthesis catalyst and preparation method thereof | |
| CN104941639B (en) | A kind of selective hydrogenation catalyst and its preparation method and application | |
| CN108465484B (en) | Preparation method of FCC gasoline desulfurization and hydrogenation modified catalyst | |
| CN109908946A (en) | The catalyst and preparation method thereof of biological Aviation Fuel component is prepared by jatropha oil | |
| CN101327453B (en) | Aluminum-silicon-titanium composite oxide carrier and load type catalytic hydro-dearomatization catalyst | |
| CN108554441A (en) | A kind of high-activity hydrocracking pretreatment catalyst, preparation method and applications | |
| CN104741125A (en) | Catalyst as well as preparation method and application thereof | |
| CN107362825A (en) | Exempt to be calcined hydrogenation catalyst and its preparation method and application | |
| CN106140255A (en) | A kind of Modified Zeolite Y and preparation thereof and application | |
| CN107224992A (en) | Suitable for efficiently hydrogenation catalyst of production biodiesel and its preparation method and application | |
| CN106994351A (en) | A kind of distillate hydrogenation dearsenic catalyst and preparation method | |
| CN106179388B (en) | A kind of preparation method of hydrotreating catalyst | |
| CN108404976B (en) | FCC gasoline desulfurization and hydrogenation modification method | |
| CN100569366C (en) | The preparation method of full microwave radiation sulfur-tolerant type molybdenum base catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101110 Termination date: 20130721 |