CN100515565C - Method for preparing highly dispersed, amorphous, high-efficiency desulfurization catalyst - Google Patents
Method for preparing highly dispersed, amorphous, high-efficiency desulfurization catalyst Download PDFInfo
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- CN100515565C CN100515565C CNB2005100830376A CN200510083037A CN100515565C CN 100515565 C CN100515565 C CN 100515565C CN B2005100830376 A CNB2005100830376 A CN B2005100830376A CN 200510083037 A CN200510083037 A CN 200510083037A CN 100515565 C CN100515565 C CN 100515565C
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Abstract
本发明创建了一种新型的真空浸渍法制备高分散、非晶态、高脱硫活性催化剂的新工艺新方法。本发明特征在于：1、该催化剂采用真空浸渍法制备；2、该浸渍液中加入了表面活性剂，以阻止活性组分Mo、Co、W等金属元素在干燥和煅烧的过程中团聚及颗粒长大；3、该催化剂的载体是经过其它元素调变的γ-Al2O3；4、该催化剂活性物质的负载采用各活性组分分步浸渍并分步煅烧法；5、对于粗苯精制，柴油、汽油深度脱硫具有较高的脱硫性能，能使噻吩含量从2000～3000mg/L下降到0.5mg/L。The invention creates a new process and a new method for preparing a catalyst with high dispersion, amorphous state and high desulfurization activity by a novel vacuum impregnation method. The present invention is characterized in that: 1. The catalyst is prepared by a vacuum impregnation method; 2. A surfactant is added to the impregnation solution to prevent the active components such as Mo, Co, W from agglomerating and granulating during the drying and calcination process. 3. The carrier of the catalyst is γ-Al 2 O 3 modulated by other elements; 4. The loading of the active material of the catalyst adopts step-by-step impregnation and step-by-step calcination of each active component; 5. For crude benzene Refined, deep desulfurization of diesel and gasoline has high desulfurization performance, and can reduce the thiophene content from 2000-3000mg/L to 0.5mg/L.
Description
Technical field:
The object of the invention provide a kind of prepare high dispersive, amorphous have high catalytic activity and excellent stability can be used for crude benzol, diesel oil, gasoline, etc. the method for deep desulfurization catalyst of oils.The catalyst that the present invention is prepared, active component on carrier, has good desulfurization performance with amorphous form high degree of dispersion.The prepared catalyst of method provided by the invention can make the content of organic sulfur in the oils such as crude benzol, diesel oil, gasoline drop to less than 0.5ppm from 2900ppm, even is 0ppm.
Background technology:
Be new opportunity and new challenge in the face of the new century Clean Fuel Production, the catalysis technique of various production clean fuels is unexpectedly mutually among the exploitation, especially produces low-sulfur, super-low sulfur even do not have the fuel technology of sulphur.Day by day strict in addition environmental regulation has proposed more and more harsher restriction to the content of sulphur in the oil product: in December, 2000, U.S. EPA (EnvironmentalProtection Agency Environmental Protection Administration) has been delivered the low sulfuration regulation of diesel oil, require in September, 2006 U.S.'s diesel oil sulfur content of 80% to be reduced to from present 500ppm below the 15ppm, will all reach this qualification target in 2010.Europe also will come into effect " zero sulphur " diesel oil standard below the 10ppm on January 1st, 2005 when the 350ppm that requires diesel oil sulfur content in 2005 from 2000 drops to 50ppm.The world fuel committee in the up-to-date clean fuel for vehicle standard of promulgation, sulfur content is required very tight, in III, IV class, restriction diesel oil sulfur content must be respectively less than 30ppm be " zero " (＜5～10ppm).To later no sulfur diesel, total development trend is more and more stricter to the requirement of deep desulfuration from low-sulfur diesel-oil, ultra-low-sulphur diesel.
At present, the hydrodesulfurization technology is to reduce the main means of sulfur content in the oil product, and wherein technical merit depends on the hydrodesulfurization performance of catalyst system therefor more to a great extent.Therefore, although the Hydrobon catalyst of existing various kinds on the market, people expect to develop the more excellent catalyst of performance.
Typical Hydrobon catalyst is to be carrier with the aluminium oxide, and group vib and VIII family metal component constitute, and the most frequently used group vib element is chromium, molybdenum, tungsten, and VIII family element is iron, cobalt, nickel.Because existing Preparation of catalysts technology causes the active component can not high degree of dispersion on carrier, thereby influences its catalytic activity.
Carrying out the dipping of active component and add surfactant under vacuum condition in maceration extract is the important channel of improving catalyst performance.
The object of the present invention is to provide a kind of preparation method of Hydrobon catalyst.Problem at the prior art existence, adopted the method that in maceration extract, adds surfactant, carrier is carried out modification and adopts vacuum impregnation, step calcination, and selected more stable maceration extract for use, prepared the active component high degree of dispersion, catalyst color is even, desulphurizing activated higher catalyst.
Catalyst of the present invention is by γ-Al
2O
3And the γ-Al of other element modified mistake of adding
2O
3, 1～8% (quality) VIII family metal oxide and 5～25% (quality) group vib metal oxide form, and added active component in the 3rd simultaneously.Wherein group vib and VIII family metal component are formed with the aqueous slkali that is added with surfactant of molybdate and the aqueous solution that is added with surfactant of cobalt salt respectively.Adopt the graded impregnation method to support, and adopt the distribution calcining method to calcine.Catalyst pore volume of the present invention is 0.6ml/g～0.8ml/g, and specific area is at 300m
2/ g～320m
2Between/the g.This high-efficiency desulfurization Preparation of catalysts method that contains molybdenum, cobalt and tungsten metallic element is characterized in that: the carrier of (1) this catalyst is the γ-Al through lanthanum, boron, silicon, gallium, indium, titanium, germanium or tin element modification
2O
3(2) this catalyst adopts the vacuum impregnation technology preparation; (3) load of this catalyst activity material adopts each active component to flood respectively and the step calcination method; (4) having added non-ionic surface active agent in this maceration extract stops active component Mo and Co and W metallic element to reunite in the process of dry and calcining and particle is grown up;
The concrete preparation process of catalyst of the present invention is as follows:
1, will be through the γ-Al of modification
2O
3105 ℃ of degassing dehydrations 3 hours, to transfer in the vacuum extractor then and vacuumize, vacuum kept two hours at the 710mm mercury column.
2, take by weighing a certain amount of molybdenum salt and be dissolved in an amount of ammoniacal liquor, add surfactant, stir and it was fully dissolved in 1.5 hours.
3, the solution of preparation of last step is joined in the carrier that vacuumizes slowly, it is fully contacted with carrier, transfer to then in the beaker, drying is 48 hours on 35 ℃ water-bath oscillator.
4, dried sample of last step is placed in the Muffle furnace calcines, adopt the method for the calcination that progressively heats up, is calcining 2 hours under 500 ℃ of conditions until temperature.
5, the semi-finished product catalyst after the last step calcining is re-applied in the vacuum extractor vacuumizes, vacuum kept two hours at the 710mm mercury column.
6, take by weighing in the water-soluble solution of a certain amount of cobalt salt, add surfactant, stir and it was fully dissolved in 1.5 hours.
7, repeat top the 3rd, 4 steps, prepare the catalyst of active component high dispersive, high desulfurization performance.
Used molybdenum salt is ammonium molybdate in the catalyst preparation process of the present invention, and molecular formula is: (NH
4)
6Mo
7O
244H
2O, its standard is pure for analyzing.Used ammonia concn is 3mol/L, and its use amount is a standard with few amount greater than the covering carrier.
Used cobalt salt is a cobalt nitrate in the catalyst preparation process of the present invention, and its molecular formula is: Co (NO
3)
26H
2O, its standard is pure for analyzing.Institute's water is the deionization pure water, and its use amount is a standard with few amount greater than the covering carrier.
Used surfactant is a nonionic surface active agent in the catalyst preparation process of the present invention.
The concentration of maceration extract is formulated according to constituent content size in the catalyst preparation process among the present invention.
Catalyst of the present invention has hydrodesulfurization effect preferably to clumsy, diesel oil, gasoline etc. under the hydrodesulfurizationconditions conditions of routine.
By following embodiments of the invention and comparative example, the characteristics of Preparation of Catalyst of the present invention as can be seen are by estimating the hydrodesulfurization activity of the embodiment of the invention and comparative example catalyst, the hydrodesulfurization effect of catalyst of the present invention as can be seen.
Activity rating uses the crude benzol raw material, is model with the thiophene of the most difficult desulfurization, and other benzene,toluene,xylene loss is as the catalyst performance criterion, and its each constituent content sees the following form 1:
Table 1: each constituent content of crude benzol raw material (gas chromatography determination)
| Form | Benzene | Thiophene | Toluene | Dimethylbenzene | Other |
| Content wt% | 60.1656 | 0.2850 | 21.3457 | 10.1196 | 8.0841 |
The evaluation process conditions are: hydrogen partial pressure: 3MPa, and reaction temperature: 315 ℃, liquid air speed: 2.0h
-1, hydrogen to oil volume ratio: 669, evaluating apparatus: press microreactor in the self-control: the desulphurizing activated account form of catalyst:
The hydrogenation loss late computing formula of other non-sulfur material:
Embodiment 1:
1, with the γ-Al of 10 grams through this property of lanthanum
2O
3Degassing dehydration is 3 hours under 105 ℃ of conditions, changes over to then in the vacuum extractor that vacuum is 710mmHg to keep 2 hours.
2, get 2.3421 gram ammonium molybdates and be dissolved in the 3mol/L ammoniacal liquor of 8ml, add 2 in surfactant, stir and it was fully dissolved in 1.5 hours.
3, above-mentioned solution is slowly added in the carrier that vacuumizes, be transferred to then in the beaker, drying is 48 hours on 35 ℃ water-bath oscillator.Being placed on the method for taking in the Muffle furnace progressively to heat up at last kept 2 hours when 500 ℃ of calcinings.
4, the above-mentioned carrier that flooded molybdenum is placed in the vacuum extractor once more kept the 710mm mercury column 2 hours.
5, get 2.9995 gram cobalt nitrates and be dissolved in the deionized water solution of 8ml, add 2 of surface-actives, stir and it was fully dissolved in 1.5 hours.
6, repeated for the 3rd step, make finished catalyst at last.
Embodiment 2:
This routine catalyst preparation process is similar to Example 1, just uses without the common infusion process that vacuumizes in the dipping process.
Embodiment 3:
This routine catalyst preparation process is similar to Example 1, does not just add surfactant in the maceration extract.
Embodiment 4:
This routine catalyst preparation process is similar to Example 1, and just carrier is the γ-Al through the gallium modification
2O
3
Embodiment 5:
This routine catalyst preparation process is similar to Example 4, just in the dipping process carrier without the common infusion process that vacuumizes.
Embodiment 6:
This routine catalyst preparation process is similar to Example 4, does not just add surfactant in the maceration extract.
Embodiment 7:
This routine catalyst preparation process is similar to Example 1, and just carrier is the γ-Al through the indium modification
2O
3
Embodiment 8:
This routine catalyst preparation process is similar to Example 7, and just dipping process adopts without the common infusion process that vacuumizes.
Embodiment 9:
This routine catalyst preparation process is similar to Example 7, does not just add surfactant in the maceration extract.
Embodiment 10:
This routine catalyst preparation process is similar to Example 1, and just carrier is the common γ-Al that adopts non-modified
2O
3
It the results are shown in following table 2:
Claims (1)
1, a kind of high-efficiency desulfurization Preparation of catalysts method that contains molybdenum, cobalt and tungsten metallic element is characterized in that: the carrier of (1) this catalyst is the γ-Al through lanthanum, boron, silicon, gallium, indium, titanium, germanium or tin element modification
2O
3(2) this catalyst adopts the vacuum impregnation technology preparation; (3) load of this catalyst activity material adopts each active component to flood respectively and the step calcination method; (4) having added non-ionic surface active agent in this maceration extract stops active component Mo and Co and W metallic element to reunite in the process of dry and calcining and particle is grown up.
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| CNB2005100830376A CN100515565C (en) | 2005-07-13 | 2005-07-13 | Method for preparing highly dispersed, amorphous, high-efficiency desulfurization catalyst |
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| CNB2005100830376A CN100515565C (en) | 2005-07-13 | 2005-07-13 | Method for preparing highly dispersed, amorphous, high-efficiency desulfurization catalyst |
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|---|---|
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| CN100515565C true CN100515565C (en) | 2009-07-22 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049179B (en) * | 2009-10-30 | 2015-06-10 | 北京三聚环保新材料股份有限公司 | Method for preparing supported iron oxide series desulfurizing agent |
| WO2013137286A1 (en) * | 2012-03-13 | 2013-09-19 | 株式会社ダイキアクシス | Solid acid catalyst, method for manufacturing same, and method for manufacturing a fatty acid alkyl ester using same |
| CN103785393B (en) * | 2012-10-31 | 2016-12-07 | 湖南长岭石化科技开发有限公司 | Aromatic hydrogenation desulphurization catalyst and its preparation method and application and the method for aromatic hydrogenation desulfurization |
| CN103055918B (en) * | 2013-01-22 | 2015-04-08 | 天津市达利嘉化工科技有限公司 | Preparation method for supported solid-acid catalyst for synthesising 2-isonaphthol via one-step hydroxylation of naphthalene |
| CN103120943B (en) * | 2013-01-29 | 2014-12-17 | 沈阳三聚凯特催化剂有限公司 | Application of Mo-Ni catalyst in hydrogenation of mixture of crude benzene and absorber oil |
| CN103263922A (en) * | 2013-05-15 | 2013-08-28 | 武汉工程大学 | Preparation method of high-dispersibility m-dinitrobenzene hydrogenation structuring catalyst |
| CN104971773B (en) * | 2014-04-09 | 2017-12-22 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and its application |
| CN104492247B (en) * | 2014-12-15 | 2016-06-08 | 沈阳三聚凯特催化剂有限公司 | A kind of preparation method of porcelain ball desulfurizing agent |
-
2005
- 2005-07-13 CN CNB2005100830376A patent/CN100515565C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| CO2/CH4重整镍基催化剂制备与性能的关系. 李基涛等.分子催化，第13卷第3期. 1999 * |
| 加氢处理催化剂的制备和表征I.MoNiP/Al2O3催化剂的制备及助剂的作用. 曹光伟等.催化学报，第22卷第2期. 2001 * |
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