CN101439289B - Preparation of hydrogenation catalyst - Google Patents
Preparation of hydrogenation catalyst Download PDFInfo
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- CN101439289B CN101439289B CN2008102400291A CN200810240029A CN101439289B CN 101439289 B CN101439289 B CN 101439289B CN 2008102400291 A CN2008102400291 A CN 2008102400291A CN 200810240029 A CN200810240029 A CN 200810240029A CN 101439289 B CN101439289 B CN 101439289B
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Abstract
The invention discloses a preparation method for a hydrogenation catalyst. The metal components of the catalyst comprise one or two metals from Co and Ni as well as one or two metals from Mo and W; carbamide or ammonia is used as a reaction addition agent; a method of reaction in-situ in the hole of a carrier is adopted to lead the metal active components to generate nickel molybdate (cobalt) or nickel tungstate (cobalt) compounds, thereby being capable of avoiding the reaction between the metals and the carrier, simultaneously leading the metal active components to be easier to be sulfurized and being capable of improving the activity of the hydrogenation catalyst.
Description
Technical field
The present invention relates to a kind of hydrogenization catalyst preparation method, this technology belongs to the improvement of Preparation of catalysts method in the technical field of chemistry and chemical engineering.This technology mainly is that this catalyst is a metal active constituent with Ni, Mo, Co, W, with urea or ammonia is reaction promoter, with the aluminium oxide is carrier, and the method for reaction in-situ makes metal active constituent generate nickel molybdate (cobalt) or wolframic acid nickel (cobalt) compounds in the use carrier hole, thereby can avoid the reaction of metal and carrier, make simultaneously that metal active constituent is easier to cure, can improve the activity of hydrogenation catalyst.
Background technology
The most common hydrogenation catalyst is catalyst such as load type Co-Mo, Ni-Mo, Ni-W, Ni-Mo-W, Co-Mo-W, Co-Ni-Mo, Co-Ni-W and Co-Ni-Mo-W at present, and typical carrier material generally has Al
2O
3, silica etc.And preparing of traditional hydrogenation catalyst adopted dipping or mixed the method for pinching, and obtains through super-dry, roasting then.But, because in preparation process, reactive metal Co, Mo, Ni, W and Al
2O
3Can both form very strong M-O-Al key, promptly so-called " carrier effect " causes the catalyst activity component to form spinelle and loses activity, and perhaps causes active component sulfuration difficulty and reduces catalyst activity.Present studies confirm that, can not be at the molybdenum that with the aluminium oxide is the last branch of Co-Mo catalyst of carrier by complete cure, and the CoAl that a part of simultaneously Co and aluminium oxide have formed non-activity
2O
4Phase.Ni also can form a kind of phase of non-activity on the alumina catalyst support surface.
Summary of the invention
Purpose of the present invention has proposed a kind of hydrogenization catalyst preparation method with regard to being to avoid above-mentioned the deficiencies in the prior art part.This technology mainly is to be metal active constituent with Ni, Mo, Co, W, with urea or ammonia is reaction promoter, with the aluminium oxide is carrier, and the method for reaction in-situ makes metal active constituent generate nickel molybdate (cobalt) or wolframic acid nickel (cobalt) compounds in the use carrier hole, thereby can avoid the reaction of metal and carrier, make simultaneously that metal active constituent is easier to cure, can improve the activity of hydrogenation catalyst.Its main preparation process is as follows:
1. the preparation of carrier
The preferred alumina support of the present invention, according to the forming method of conventional carrier, with alumina powder extruded moulding (strip or granular), dry, roasting can be added some cracking component such as molecular sieve, silica etc. in the carrier.
2. impregnating metal active component and reaction promoter
At first metal active constituent is dissolved in the deionized water, its metal component is made of one or both metal ingredients among one or both and Mo, the W that comprise among Co, the Ni, wherein the molar ratio of metal promoter Ni, Co and host Mo, W is 1: 1, with reaction promoter urea or ammoniacal liquor in metal molar than 1～4: 1 ratio adds in the solution, stirring makes its dissolving, adopt the method for incipient impregnation to flood, making its metal oxide content is 10～35wt%.When the metal active constituent presoma that is added simultaneously during water-soluble solution, can adopt the method for step impregnation, after having flooded, it is dried or dry naturally with infrared lamp.
3. reaction in-situ in the hole
The catalyst of above-mentioned steps preparation is put into airtight crystallizing kettle, put into baking oven, then the lid of crystallizing kettle is opened, continued in baking oven 100～120 degree dry 4～20 hours in the reaction 4～48 hours down of 100～180 degree.
4. the roasting of catalyst
The catalyst that has reacted oven dry is carried out roasting under air or nitrogen atmosphere, initial temperature 200 degree, with 10 degree/minute speed heat up, 250～400 ℃ of roasting temperatures 1～10 hour, promptly get hydrogenation catalyst.
Description of drawings
Accompanying drawing is the XRD spectra of comparative catalyst and catalyst of the present invention, wherein:
(1)--comparative catalyst (2)----catalyst of the present invention
The specific embodiment
Below in conjunction with embodiment in detail technical characterstic of the present invention is described in detail.
Embodiment one (comparative catalyst I): take by weighing the 6.9g ammonium paramolybdate and be dissolved in the 10mL water, add the 11.4g nickel nitrate again, make its dissolving, it is standby to be made into maceration extract; Prepare 20g alumina support (the about 30ml of volume), flood according to the method for incipient impregnation.The catalyst that dipping is good is dried under infrared lamp, is placed in the 120 degree baking ovens oven dry 24 hours, and then roasting 4 hours under 500 degree, promptly gets comparative catalyst I, NiO and MoO
3Load capacity be about 30wt%.
Embodiment two (comparative catalyst II): take by weighing the 2.9g ammonium paramolybdate, the 4.4g ammonium metatungstate is dissolved in the 10mL water, adds the 9.5g nickel nitrate again, makes its dissolving, it is standby to be made into maceration extract; Prepare 20g alumina support (the about 30ml of volume), flood according to the method for incipient impregnation.The catalyst that dipping is good is dried under infrared lamp, is placed in the 120 degree baking ovens oven dry 24 hours, and then roasting 4 hours under 500 degree, promptly gets comparative catalyst II, NiO, MoO
3And WO
3Load capacity be about 30wt%.
Embodiment three: take by weighing the 6.9g ammonium paramolybdate and be dissolved in the 10mL water, add the 11.4g nickel nitrate again, make its dissolving, add 2.0g urea then, it is standby to be made into maceration extract; Prepare 20g alumina support (the about 30ml of volume), flood according to the method for incipient impregnation.The catalyst that dipping is good is dried under infrared lamp, pack in the airtight crystallizing kettle, putting into baking oven reacted 24 hours down in 120 degree, then the lid of crystallizing kettle is opened, continuation dry 20 hours of 120 degree in baking oven, the catalyst that reacted in roasting 4 hours under 400 degree under the air atmosphere, is promptly got catalyst of the present invention, NiO and MoO
3Load capacity be about 30wt%.
Embodiment four: take by weighing the 6.9g ammonium paramolybdate and be dissolved in the 10mL water, add the 11.4g nickel nitrate again, make its dissolving, add 2.0g urea then, it is standby to be made into maceration extract; Prepare 20g alumina support (the about 30ml of volume), flood according to the method for incipient impregnation.The catalyst that dipping is good is dried under infrared lamp, pack in the airtight crystallizing kettle, putting into baking oven reacted 24 hours down in 150 degree, then the lid of crystallizing kettle is opened, continuation dry 20 hours of 120 degree in baking oven, the catalyst that reacted in roasting 4 hours under 400 degree under the air atmosphere, is promptly got catalyst of the present invention, NiO and MoO
3Load capacity be about 30wt%.
Embodiment five: take by weighing the 2.9g ammonium paramolybdate, the 4.4g ammonium metatungstate is dissolved in the 10mL water, adds the 9.5g nickel nitrate again, makes its dissolving, adds 2.0g urea then, it is standby to be made into maceration extract; Prepare 20g alumina support (the about 30ml of volume), flood according to the method for incipient impregnation.The catalyst that dipping is good is dried under infrared lamp, pack in the airtight crystallizing kettle, putting into baking oven reacted 24 hours down in 150 degree, then the lid of crystallizing kettle is opened, continuation dry 20 hours of 120 degree in baking oven, the catalyst that reacted in roasting 4 hours under 400 degree under the air atmosphere, is promptly got catalyst of the present invention, Ni, MoO
3And WO
3Load capacity be about 30wt%.
The invention effect
Utilize the hydrogenation catalyst of method preparation of the present invention, its metal oxide supported amount is at 10-35wt%, suitable with conventional hydrogenation catalyst, form under the effect of ammonia at ammoniacal liquor or urea decomposition, these metal component reactions form the sour nickel of molybdenum (tungsten) (cobalt) compound. Fig. 1 has provided the inventive method prepared catalyst and comparative catalyst's XRD spectra, therefrom can find, has new material to produce in the inventive method prepared catalyst, has namely formed the sour nickel of molybdenum (tungsten) (cobalt) compound. Because formed molybdenum (tungsten) sour nickel (cobalt) compound and carrier function are few, and cure easily, can form the active phase of more " II " class, thereby has a higher hydrogenation activity, can be used for comprising that the oil product of high, medium and low cut wet goods surpasses Deep Hydrotreating, and other suitable hydrotreatment occasions. The outstanding advantage of catalyst of the present invention is exactly to have higher hydrodesulfurization and hydrodenitrogenationactivity activity, such as the sulfur content of diesel oil from the heavy catalytic cracking being reduced to 30ppm from 4000ppm with catalyst of the present invention, nitrogen content is reduced to 10ppm from 2000ppm, and the catalyst that adopts conventional method to prepare only is reduced to respectively 200ppm and 50ppm under the similarity condition.
Claims (1)
1. hydrogenization catalyst preparation method, this catalyst is to be metal active constituent with Ni, Mo, Co, W, is reaction promoter with urea or ammonia, is carrier with the aluminium oxide, and the method for reaction in-situ makes in the use carrier hole, it is characterized in that Preparation of catalysts is to carry out as follows:
1.. the preparation of carrier
Choosing aluminium oxide is carrier, according to the forming method of conventional carrier, with the alumina powder extruded moulding, carries out drying, roasting then;
2.. impregnating metal active component and reaction promoter
At first metal active constituent is dissolved in the deionized water, metal component is by Co, among the Ni one or both and Mo, one or both metal ingredients among the W constitute, Ni wherein, Co is a metal promoter, Mo, W is a metal host, both molar ratios are 1: 1, then with reaction promoter in metal molar than 1～4: 1 ratio adds in the solution, stirring makes its dissolving, adopt the method for incipient impregnation to flood, making its metal oxide content is 10～35wt%, when the metal active constituent presoma that is added simultaneously during water-soluble solution, adopts the method for step impregnation, after having flooded, it is dried or dry naturally with infrared lamp;
3.. reaction in-situ in the hole
The catalyst of above-mentioned steps preparation is put into airtight crystallizing kettle, puts into baking oven, then the lid of crystallizing kettle is opened in 100～180 ℃ of reactions 4～48 hours down, continue in baking oven 100～120 ℃ dry 4-20 hour;
4.. the roasting of catalyst
The catalyst that has reacted oven dry is carried out roasting under air atmosphere, 200 ℃ of initial temperatures heat up with 10 ℃/minute speed, at 250-400 ℃ of roasting temperature 1-10 hour, promptly get purpose hydrogenation of net product catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102400291A CN101439289B (en) | 2008-12-17 | 2008-12-17 | Preparation of hydrogenation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102400291A CN101439289B (en) | 2008-12-17 | 2008-12-17 | Preparation of hydrogenation catalyst |
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| CN101439289A CN101439289A (en) | 2009-05-27 |
| CN101439289B true CN101439289B (en) | 2011-02-09 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103191772B (en) * | 2012-01-06 | 2014-09-17 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst |
| WO2015007230A1 (en) | 2013-07-18 | 2015-01-22 | 中国石油大学(北京) | Iron-based hydrogenation catalyst and applications thereof |
| CN104549328B (en) * | 2013-10-22 | 2016-11-16 | 中国石油化工股份有限公司 | A kind of preparation method of residuum hydrogenating and metal-eliminating catalyst |
| CN104549333B (en) * | 2013-10-23 | 2017-02-22 | 中国石油化工股份有限公司 | Preparation method for residual oil hydrogenation and demetalization catalyst |
| CN104275191B (en) * | 2014-07-24 | 2016-08-17 | 中国石油大学(华东) | A kind of catalyst being hydrogenated with in advance for FCC gasoline and preparation method thereof |
| CN105582946B (en) * | 2014-10-22 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of preparation method of residuum hydrogenating and metal-eliminating catalyst |
| CN105618070B (en) * | 2014-11-03 | 2017-12-15 | 中国石油化工股份有限公司 | A kind of preparation method of high activity desulfurization catalyst of flue gas |
| CN105709800B (en) * | 2014-12-04 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of low NOxThe hydrocracking catalyst preparation method of discharge |
| CN105727980B (en) * | 2014-12-06 | 2018-02-09 | 中国石油化工股份有限公司 | A kind of preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane |
| CN107790162B (en) * | 2016-08-29 | 2020-04-14 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN108654630B (en) * | 2017-03-30 | 2021-02-26 | 神华集团有限责任公司 | Sulfur-tolerant shift catalyst and preparation method thereof |
| CN109894125A (en) * | 2019-03-20 | 2019-06-18 | 中国矿业大学 | A kind of preparation method and application of supported sulfided state Co-Mo/ γ-Al2O3 bimetallic catalyst |
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