CN101733114A - Superfine powder composite metallic oxide catalyst and application thereof - Google Patents
Superfine powder composite metallic oxide catalyst and application thereof Download PDFInfo
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- CN101733114A CN101733114A CN 200810226924 CN200810226924A CN101733114A CN 101733114 A CN101733114 A CN 101733114A CN 200810226924 CN200810226924 CN 200810226924 CN 200810226924 A CN200810226924 A CN 200810226924A CN 101733114 A CN101733114 A CN 101733114A
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Abstract
The invention relates to superfine powder composite metallic oxide catalyst and application thereof. The catalyst is a composite metallic oxide containing metal Mo and metal Fe, wherein the molar ratio of the Mo to the Fe is (1-6):(1-10), and the average particle diameter of the catalyst is 20-100nm. The catalyst of the invention is a nano-scale solid powder catalyst which has strong hydrogenation performance and good dispersibility, can be better suitable for the hydrogenation process of a heavy oil suspension bed and can be used for machining poor-quality heavy oil containing high impurity content of metals, sulfur, nitrogen, asphaltene and the like. The obtained residual oil has high conversion ratio, and the obtained distillate oil has high yield. Because the consumption of the catalyst is low, the invention has higher economic applicability.
Description
Technical field
The present invention relates to catalyst of a kind of superfine powder composite metallic oxide and uses thereof, more particularly, is the superfines catalyst of the composite metal oxide of a kind of Fe of comprising metal and Mo metal, and it is applied in the suspension bed heavy oil hydrogenation process.
Background technology
Along with the heaviness day by day of crude oil and poor qualityization, and to the increase of light-end products demand, the efficient technique of rainwater utilization of heavy oil, residual oil is subjected to researcher's attention.Residue Hydrotreating Technology is one of important research direction, can obtain fluid product as much as possible and remove impurity such as metal, asphalitine.Existing reactor types comprises fixed bed, moving bed, ebullated bed and suspension bed.Wherein floating bed hydrogenation has adaptability preferably to high poor residuums of impurity content such as metal, sulphur, nitrogen, asphalitines, and at present that is that all right is ripe for industrial applications.Exploitation is applicable to that the catalyst of the efficient cheapness of hydrogenation of residual oil suspended bed is very important.
The big carbon residue height of residual oil viscosity, impurity content height such as metal, asphalitine, so the reactivity worth of catalyst and dispersibility are the main difficult points of development.The catalyst of prior art has heterogeneous pressed powder type catalyst, has adopted the powder behind the coal combustion as catalyst as US 4299685, but cheap, addition is big, but its bad dispersibility a little less than the hydrogenation, contains solid particle and is difficult to handle in the tail oil.
For improving catalyst dispersive property and catalytic activity, also have the water-soluble catalyst and the oil-soluble catalyst of homogeneous phase in the prior art.As having proposed to adopt the compounded catalyst aqueous solution of slaine preparations such as Fe, Ni, Mo among the CN 1133725C, has higher strong cracking activity.The deficiency of such catalyst is: aqueous catalyst solution and heavy oil intermiscibility are poor, and dispersion effect is not good.CN 1445339A proposes a kind of high dispersive type catalyst, contains one or more of metallic compounds such as Cu, Ag, Au, Zn, Hg in the catalyst, is distributed to then in alcohols or the alcohol/water mixed solution, reaches aim of even dispersion in oil.Use alcohols or alcohol/water mixed solution can improve the dispersion of slaine in heavy oil, but before processing of heavy oil is handled, need to remove moisture, to reduce the reaction stagnation pressure or to reduce the corrosion of water reaction unit.
Directly adopt oil-soluble catalyst to have better dispersibility and catalytic activity, CN1644658A proposes halogen compounds to be used for the auxiliary agent of heavy-oil hydrogenation cracking, its major catalyst is MoDTC (molybdenum dithiocarbamate), adds acid compound auxiliary agent and improves gasoline, diesel yield.CN 1133727C discloses the organo-metallic catalyst of a kind of Mo, W metal and phenylhydroxylamine and derivatives reaction gained thereof, and this catalyst good dispersion in mink cell focus can effectively improve yield of light oil.The advantage of organo-metallic compound is good with the intermiscibility of heavy oil, heavy oil transformation rate height.But the shortcoming of above-mentioned catalyst is: the organo-metallic compound molecular weight is big, and tenor is low, and use amount is big when measuring with tenor, the cost costliness.
Summary of the invention
The objective of the invention is on the basis of existing technology, a kind of catalyst of superfine powder composite metallic oxide is provided, and the application process of this catalyst in the suspension bed heavy oil hydrogenation process.
Catalyst provided by the present invention is: described catalyst is the composite metal oxide that comprises Mo metal and Fe metal, and wherein the mol ratio of Mo and Fe is (1～6): (1～10), the average grain diameter of this catalyst are 20-100nm.
The mol ratio that also contains any metal M, wherein Mo: Fe: M in the described catalyst is (1～6): (1～10): (0.1～3), described metal M are selected from the group VIII metal of having got rid of the Fe metal, or are selected from the group vib metal of having got rid of the Mo metal.
Described catalyst is the binary O composite metallic oxide catalyst, and its expression formula is MoO
x-FeO
y, wherein x is 2～3, y is 1～3.
Described catalyst is a ternary composite metal oxide catalyst, and its expression formula is MoO
x-FeO
y-MO
z, wherein M is selected from Co, Ni, the W metallic element any, and x is 2～3, and y is 1～3, and z is 0.8～3.
Described superfine powder composite metallic oxide catalyst is by coprecipitation or sol-gel process preparation.This composite metal oxide does not comprise the mixed metal oxide powders that adopts mechanical lapping and mixing.
Coprecipitation is meant in containing multiple cationic soluble-salt solution, add precipitating reagent after, all cations precipitate and fully with original anion flush away, obtain the method for oxide through pyrolytic or dehydration.The composite oxide power purity height that coprecipitation is produced, component is even.
Sol-gel process (Sol-Gel method, be called for short S-G method) is meant that inorganic matter or metal alkoxide solidify through solution, colloidal sol, gel, again the oxide that forms through heat treatment or the method for other compound solid.The utilization sol-gel process is mixed with mixed solution with the predecessor of required composition, after gelation, heat treatment, generally can both the obtained performance index powder preferably.This is owing to contain a large amount of liquid phases or pore in the gel, makes to be difficult for making powder particle to produce serious the reunion in heat treatment process that this method is easily controlled powder particle size in preparation process simultaneously.Sol-gel process is compared than other conventional method, and synthesis temperature is low, particle is little (in the nanoscale scope), narrow diameter distribution, homogeneity is good, specific area is big.
Application of Catalyst method provided by the invention is: described superfine powder composite metallic oxide catalyst is applied in the suspension bed heavy oil hydrogenation process, with the heavy oil feedstock is benchmark, Mass Calculation with reactive metal oxides, the addition of described catalyst is 50～1000ppm, reaction temperature is 380～450 ℃, reaction pressure is 6～20MPa, and hydrogen/oil mol ratio is 2～10.
With the heavy oil feedstock is benchmark, and with the Mass Calculation of reactive metal oxides, the addition of preferred described catalyst is 100～500ppm.
Preferred described reaction temperature is 395～415 ℃, and reaction pressure is 8～18MPa, and hydrogen/oil mol ratio is 5～8.
Described heavy oil contains optional coal dust, and described heavy oil is selected from one or more in reduced crude, decompression residuum, oil sands bitumen, shale oil, the coal direct liquefaction oil.
Described catalyst carries out presulfurization before carrying out hydrogenation reaction, curing temperature is 300～350 ℃, and the sulfuration initial pressure is 1～6MPa, and cure time is 1～60min.
Advantage of the present invention is:
(1) catalyst of the present invention is different from solid powder th-1 catalyst, water-soluble liquid catalyst and the oil soluble liquid catalyst that uses in the prior art, catalyst of the present invention is the composite metal oxide body catalyst, comprise strong IVB of hydrogenation performance and/or group VIII metallic element, the employing chemical method is prepared into the ultra-fine grain less than 100nm, good dispersion in residual oil.And, has higher economic serviceability because the catalyst use amount is little.
(2) catalyst of the present invention is that the hydrogenation performance is strong, the nanoscale solids fine catalyst of good dispersion, can be applicable to preferably in the heavy oil floating bed hydrogenation technology.Can processing metal, the high inferior heavy oil of impurity content such as sulphur, nitrogen, asphalitine, the bottoms conversion height of gained, distillate yield height.
The specific embodiment
The following examples will give further instruction to method of the present invention, but therefore not limit method of the present invention.
Embodiment 1
Prepare catalyst A according to sol-gel process: take by weighing the ammonium molybdate and the ferric nitrate of amount of calculation according to the amount of producing the 15g catalyst, add deionized water dissolving respectively, stir ammonium molybdate solution under the room temperature and drip iron nitrate solution, generate yellow mercury oxide.Add citric acid, addition be molybdenum molal quantity 0.5.Fully stir into the clarification yellow solution, use ammoniacal liquor adjust pH 3.0～13.0 then.105 ℃ of dried overnight obtain gel, last 500 ℃ of roastings 4 hours, obtain catalyst A, and this catalyst is compound Mo-Fe oxide superfines, and wherein the mol ratio of Mo and Fe is 3: 2, and the average grain diameter of catalyst A is 20-100nm.
Embodiment 2
Prepare catalyst B according to sol-gel process: the ammonium molybdate, ferric nitrate and the cobalt nitrate that take by weighing amount of calculation according to the amount of producing the 15g catalyst, add deionized water dissolving respectively, behind mixed nitrate iron and the cobalt nitrate aqueous solution, stir ammonium molybdate solution under the room temperature and drip ferric nitrate and the mixed solution of cobalt nitrate, generate the yellowish red color precipitation.Add citric acid, addition be molybdenum molal quantity 0.5.Fully stir into clarification yellowish red color solution, use ammoniacal liquor adjust pH 3.0～13.0 then.105 ℃ of dried overnight obtain gel, last 500 ℃ of roastings 4 hours, obtain catalyst B, and this catalyst is compound Mo-Fe-Co oxide superfines, and wherein the mol ratio of Mo, Fe and Co is 2: 2: 1, and the average grain diameter of catalyst B is 20-100nm.
Embodiment 3
Prepare catalyst C according to coprecipitation: take by weighing the ammonium molybdate and the ferric nitrate of amount of calculation according to the amount of producing the 15g catalyst, add deionized water dissolving respectively, stir ammonium molybdate solution under the room temperature and drip iron nitrate solution, generate yellow mercury oxide.Make precipitation more complete with the ammoniacal liquor adjust pH then.105 ℃ of dried overnight, last 500 ℃ of roastings 4 hours obtain catalyst C, and this catalyst is compound Mo-Fe oxide superfines, and wherein the mol ratio of Mo and Fe is 3: 1, and the average grain diameter of catalyst C is 20-100nm.
Embodiment 4
Prepare catalyst D according to coprecipitation: the ammonium molybdate, ferric nitrate and the nickel nitrate that take by weighing amount of calculation according to the amount of producing the 15g catalyst, add deionized water dissolving respectively, stir ammonium molybdate solution under the room temperature and drip iron nitrate solution, generate precipitation, continue to stir and be added dropwise to nickel nitrate solution.Make precipitation more complete with the ammoniacal liquor adjust pH then.105 ℃ of dried overnight, last 500 ℃ of roastings 4 hours obtain catalyst D, and this catalyst is compound Mo-Fe-Ni oxide superfines, and wherein the mol ratio of Mo, Fe and Ni is 2: 1: 0.5, and the average grain diameter of catalyst D is 20-100nm.
Embodiment 5
Prepare catalyst E according to coprecipitation: the ammonium molybdate, ferric nitrate and the ammonium tungstate that take by weighing amount of calculation according to the amount of producing the 15g catalyst, add deionized water dissolving respectively, stir ammonium molybdate solution under the room temperature and drip iron nitrate solution, generate yellow mercury oxide, continue the agitation and dropping ammonium tungstate aqueous solution.Precipitation is more complete during then with the ammoniacal liquor adjust pH.105 ℃ of dried overnight, last 500 ℃ of roastings 4 hours obtain catalyst E, and this catalyst is compound Mo-Fe-W oxide superfines, and wherein the mol ratio of Mo, Fe and W is 2: 1: 2, and the average grain diameter of catalyst E is 20-100nm.
Embodiment 6～7
Embodiment 6 and embodiment 7 are respectively catalyst A and the application of catalyst B in heavy oil floating bed hydrogenation technology.Calculate bottoms conversion and distillate yield according to following formula, as the evaluation index of reaction effect:
Liquid yield=all liq product quality/feedstock oil quality * 100%
Constituent mass (containing gas)/feedstock oil quality * 100% below bottoms conversion=524 ℃
Liquid component quality/feedstock oil quality * 100% below distillate yield=524 ℃
The quality of coking yield=toluene insolubles/feedstock oil quality * 100%
Heavy oil feedstock is a kind of asphalitine and the higher reduced crude of tenor, and character is as shown in table 1.Reactor is 0.5 liter a high pressure agitating device.Catalyst A and catalyst B are carried out online sulfuration in reaction in the temperature-rise period, promptly add sublimed sulfur or carbon disulfide as vulcanizing agent in reaction system, and curing temperature is 300～350 ℃.
Reaction condition: 410～420 ℃ of reaction temperatures, initial hydrogen partial pressure 5.25～5.40MPa, reaction pressure 9.5～13.0MPa, the heavy oil feedstock addition is 90g, the catalyst addition is 0.030g, sublimed sulfur 0.030g, mixing speed 420r/min, reaction time 60min, its reaction result is listed table 2 in.
As can be seen from Table 2, the conversion ratio of residual oil is respectively 83.3 heavy % and 84.2 heavy %, and the distillate yield is respectively 75.5 heavy % and 73.6 heavy %.
Embodiment 8～10
Embodiment 8, embodiment 9 and embodiment 10 are respectively catalyst C, catalyst D and the application of catalyst E in heavy oil floating bed hydrogenation technology.
Heavy oil feedstock is a kind of asphalitine and the higher reduced crude of tenor, and character is as shown in table 1.Reactor is 0.5 liter a high pressure agitating device.Catalyst C, catalyst D and catalyst E carry out online sulfuration in reaction in the temperature-rise period, promptly add sublimed sulfur or carbon disulfide as vulcanizing agent in reaction system, and curing temperature is 300～350 ℃.
Reaction condition: 410～420 ℃ of reaction temperatures, initial hydrogen partial pressure 5.20～5.30MPa, reaction pressure 9.5～13.0MPa, the heavy oil feedstock addition is 90g, the catalyst addition is 0.030g, sublimed sulfur 0.030g, mixing speed 420r/min, reaction time 60min, its reaction result is listed table 3 in.
As can be seen from Table 3, the conversion ratio of residual oil is respectively 84.3 heavy %, 82.9 heavy % and 81.7 heavy %, is respectively 73.2 heavy %, 72.1 heavy % and 70.6 heavy % less than 524 ℃ distillate yields.
Table 1
| Density (20 ℃)/g/cm 3 | ??0.9914 |
| Carbon residue, heavy % | ??16.6 |
| Saturated hydrocarbons, % | ??30.8 |
| Aromatic hydrocarbons, % | ??36.2 |
| Colloid, heavy % | ??22.1 |
| Asphalitine, heavy % | ??10.9 |
| S, heavy % | ??2.11 |
| N, heavy % | ??0.50 |
| ??Ni，μg.g -1 | ??35.9 |
| ??V，μg.g -1 | ??201 |
| ??Fe，μg.g -1 | ??15.0 |
Table 2
| Embodiment 6 | Embodiment 7 | |
| Catalyst | Catalyst A | Catalyst B |
| Reactive metal | ??Mo-Fe | ??Mo-Co-Fe |
| Liquid yield, heavy % | ??87.8 | ??83.2 |
| Coking yield, heavy % | ??4.4 | ??6.2 |
| Bottoms conversion, heavy % | ??83.3 | ??84.2 |
| ＜524 ℃ of distillate yields, heavy % | ??75.5 | ??73.6 |
Table 3
| Embodiment 8 | Embodiment 9 | Embodiment 10 | |
| Catalyst | Catalyst C | Catalyst D | Catalyst E |
| Reactive metal | ??Mo-Fe | ??Mo-Fe-Ni | ??Mo-Fe-W |
| Liquid yield, heavy % | ??82.3 | ??81.0 | ??80.4 |
| Coking yield, heavy % | ??6.6 | ??8.2 | ??8.5 |
| Bottoms conversion, heavy % | ??84.3 | ??82.9 | ??81.7 |
| ＜524 ℃ of distillate yields, heavy % | ??73.2 | ??72.1 | ??70.6 |
Claims (10)
1. superfine powder composite metallic oxide catalyst, it is characterized in that, described catalyst is the composite metal oxide that comprises Mo metal and Fe metal, and wherein the mol ratio of Mo and Fe is (1～6): (1～10), the average grain diameter of this catalyst are 20-100nm.
2. according to the described catalyst of claim 1, it is characterized in that also containing in the described catalyst any metal M, wherein the mol ratio of Mo: Fe: M is (1～6): (1～10): (0.1～3), described metal M is selected from the group VIII metal of having got rid of the Fe metal, or is selected from the group vib metal of having got rid of the Mo metal.
3. according to the described catalyst of claim 1, it is characterized in that described catalyst is the binary O composite metallic oxide catalyst, its expression formula is MoO
x-FeO
y, wherein x is 2～3, y is 1～3.
4. according to the described catalyst of claim 2, it is characterized in that described catalyst is a ternary composite metal oxide catalyst, its expression formula is MoO
x-FeO
y-MO
z, wherein M is selected from Co, Ni, the W metallic element any, and x is 2～3, and y is 1～3, and z is 0.8～3.
5. according to the described catalyst of claim 1, it is characterized in that described superfine powder composite metallic oxide catalyst is by coprecipitation or sol-gel process preparation.
6. any Application of Catalyst method of claim 1～5, it is characterized in that, described superfine powder composite metallic oxide catalyst is applied in the suspension bed heavy oil hydrogenation process, with the heavy oil feedstock is benchmark, with the Mass Calculation of reactive metal oxides, the addition of described catalyst is 50～1000ppm, and reaction temperature is 380～450 ℃, reaction pressure is 6～20MPa, and hydrogen/oil mol ratio is 2～10.
7. in accordance with the method for claim 6, it is characterized in that, is benchmark with the heavy oil feedstock, and with the Mass Calculation of reactive metal oxides, the addition of described catalyst is 100～500ppm.
8. in accordance with the method for claim 6, it is characterized in that described reaction temperature is 395～415 ℃, reaction pressure is 8～18MPa, and hydrogen/oil mol ratio is 5～8.
9. in accordance with the method for claim 6, it is characterized in that described heavy oil contains optional coal dust, described heavy oil is selected from one or more in reduced crude, decompression residuum, oil sands bitumen, shale oil, the coal direct liquefaction oil.
10. in accordance with the method for claim 6, it is characterized in that described catalyst carries out presulfurization before carrying out hydrogenation reaction, curing temperature is 300～350 ℃, and the sulfuration initial pressure is 1～6MPa, and cure time is 1～60min.
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Cited By (5)
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| CN102309948A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for charging boiling bed catalyst on line |
| CN102309947A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | On-line filling method for boiling bed catalyst |
| CN103285928A (en) * | 2012-02-22 | 2013-09-11 | 中国石油化工股份有限公司 | Iron-oxide-ore-containing heavy oil hydrogenation catalyst, and preparation and application thereof |
| CN107952448A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | A kind of O composite metallic oxide catalyst and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1133725C (en) * | 2001-03-05 | 2004-01-07 | 石油大学(华东) | Residual suspension bed hydrocracking catalyst compounded by several kinds of metal salts |
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2008
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| CN102309948A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for charging boiling bed catalyst on line |
| CN102309947A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | On-line filling method for boiling bed catalyst |
| CN103285928A (en) * | 2012-02-22 | 2013-09-11 | 中国石油化工股份有限公司 | Iron-oxide-ore-containing heavy oil hydrogenation catalyst, and preparation and application thereof |
| CN103285928B (en) * | 2012-02-22 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of heavy-oil hydrogenation catalyst containing ferric oxide ore and Synthesis and applications thereof |
| CN107952448A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | A kind of O composite metallic oxide catalyst and its preparation method and application |
| CN107952448B (en) * | 2016-10-14 | 2020-10-27 | 中国石油化工股份有限公司 | Composite metal oxide catalyst and preparation method and application thereof |
| CN109926057A (en) * | 2019-03-14 | 2019-06-25 | 李大鹏 | A kind of Fe (III) base catalyst and its preparation method and application |
| CN109926057B (en) * | 2019-03-14 | 2021-11-02 | 李大鹏 | Fe (III) -based catalyst and preparation method and application thereof |
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