CN1451717A - Hydrogenation Ti-Si composite oxide catalyst and method for preparing same - Google Patents
Hydrogenation Ti-Si composite oxide catalyst and method for preparing same Download PDFInfo
- Publication number
- CN1451717A CN1451717A CN 02116851 CN02116851A CN1451717A CN 1451717 A CN1451717 A CN 1451717A CN 02116851 CN02116851 CN 02116851 CN 02116851 A CN02116851 A CN 02116851A CN 1451717 A CN1451717 A CN 1451717A
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- hours
- tungsten
- carrier
- hydrogenation
- 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.)
- Granted
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
A hydrocatalyst is prepared from the composite nano oxide TiO2-SiO2 as carrier and Ni-W as active component through preparing the solution of W and Ni compounds, impregnating said carrier in it, drying and calcining. Its advantages are high desulfurizing activity, mild hydrogenating condition, and high stability.
Description
Technical field:
The present invention relates to a kind of is the Catalysts and its preparation method of carrier with the novel nano composite oxides, and particularly relating to a kind of is petroleum fractions hydrogenation catalyst of carrier and preparation method thereof with titanium dioxide and silicon-dioxide compound nano-powder.
Background technology:
Domestic and international employed petroleum fractions hydrogenation catalyst major part is to be carrier with the aluminum oxide at present, is active ingredient with cobalt, molybdenum, nickel, tungsten.In recent years in order to improve the performance of hydrogenation catalyst, carried out a few thing at aspects such as the employing of support modification, novel material and preparation methods.As:
CN1210759A discloses a kind of with TiO
2-SiO
2Composite oxides are that carrier, nickel are the hydrogenation catalyst of active ingredient, employing be sol-gel process for preparing.This catalyzer has catalytic activity and selectivity preferably to benzene hydrogenation, and has good heat-resistant.But this catalyzer can not be applicable to the petroleum fractions hydrogenation process of higher reaction and regeneration temperature.
CN1289636A discloses a kind of preparation method and purposes of Ti-contained aluminium hydroxide, is the surperficial homodisperse titanium oxide layer at aluminum oxide, and avoids stopping up the micropore of aluminum oxide.Think that the hydrogenation catalyst that this titanium-contained aluminum oxide makes has good use properties.With the aluminum oxide of titanium modification is that the performance of the hydrogenation catalyst of carrier can obtain certain improvement, but the contradiction that the raising of metal loading and pore volume descend is difficult to solve, thereby the performance difficulty of catalyzer is improved largely.
CN1040610A discloses to contain the γ-Al of titanium oxide
2O
3Be the Hydrodevulcanizing catalyst for hydro-carbons of carrier, active ingredient is a cobalt molybdenum nickel.γ-Al
2O
3The content of middle titanium oxide is 5～30wt%, and this catalyzer is lower because of its specific surface, and the charge capacity of metal active constituent is still bigger, thereby makes cost higher; The surface acidity of carrier does not significantly improve simultaneously, and denitrification effect is also not obvious.
It is the hydro-dearsenic catalyst of carrier and carrier and preparation method thereof with titanium dioxide blending aluminum oxide that WO96/14152 and CN1212992A disclose a kind of, this catalyzer low temperature dearsenification is active high, active component content is low, can satisfy the needs of China's cracking of ethylene stock oil dearsenification, but because its carrier compound poor heat stability brought of machinery and higher Lewis acid and lower Br nsted acid can not be used for the hydrogenation than heavy petroleum fractions oil.
In sum, of the prior art is that the hydrogenation catalyst of carrier has the low and high shortcoming of metal component content of low temperature active with the aluminum oxide.Though and improve to some extent as the titanium dioxide of new class catalystic material, as catalyst carrier for hydrgenating, still have poor stability, acid weak shortcoming, be not suitable for hydrofining, thereby need the new petroleum fractions catalyzer of exploitation one class than heavy distillate.
Summary of the invention:
The object of the present invention is to provide a kind of new titanium-silicone composite oxides hydrogenation catalyst and preparation method thereof, the hydrogenation catalyst low temperature active is high and metal component content is low, and carrier good stability, acid strong characteristics are suitable for the hydrofining than heavy distillate.
The invention provides a kind of novel petroleum fractions hydrogenation catalyst.Catalyzer of the present invention is an active ingredient with nickel tungsten, with titanium dioxide (TiO
2) and silicon-dioxide (SiO
2) nano composite oxide be carrier, this compound be the compound of molecular level.
Catalyst metal content provided by the invention is in oxide compound, and the content of tungsten is 10～18% (weight), and the content of nickel is 1.5～3% (weight).The basic physical properties parameter is: specific surface area is 70～90m
2.g
-1, pore volume is 0.2～0.3ml.g
-1, the aperture is 12～14nm.
Catalyzer provided by the invention needs to carry out prevulcanized before use.For guaranteeing tight cure, curing time is preferably greater than 4 hours.
Preparation of catalysts method provided by the invention is to adopt the technology of soaking altogether, and with the nano combined carrier of solution impregnation of tungsten and nickel compound, drying and roasting is prepared catalyzer then.
The mixed solution of preferred metatungstic acid ammonia of the steeping fluid of above-mentioned tungsten and nickel compound and nickelous nitrate, preferred dipping temperature is 30～40 ℃, preferred 4～6 hours of dipping time; After filtering 110～120 ℃ of dryings 4～8 hours.Maturing temperature is 450～800 ℃; Roasting time was got 3～4 hours.Getting 60～80 orders part or extrusion molding after sieving can preparation cost invention catalyzer.
Catalyst metal content of the present invention reduces greatly than the catalyzer of prior art, but still has a good low temperature active (＜240 ℃), under the condition of temperature of reaction lower (200～240 ℃), with existing be that the higher catalyzer of metal content is compared with the aluminum oxide, catalyzer provided by the invention has higher catalytic activity; And under the temperature conditions of higher, with existing be that the catalyzer of the high metal content of carrier is compared with titanium dioxide, what then show is active and stable.Catalyzer of the present invention can satisfy the hydrorefined needs of different petroleum fractionss, is applicable to the unifining process of gasoline fraction and diesel oil distillate, and hydrogenating desulfurization, the alkene that is specially adapted to vapour, diesel oil is saturated, hydrogenation dearomatization etc.Its hydroprocessing condition can be adjusted according to the requirement of raw material oil properties and oil quality: 200～300 ℃ of temperature of reaction, hydrogen dividing potential drop 2～4MPa, volume space velocity 1～4h
-1, hydrogen-oil ratio 400～1000.
Embodiment:
For reducing discharge of harmful gases amount in light Fuel such as gasoline, the diesel oil use, improve the quality of oil fuel, require to reduce sulfide, alkene and aromaticity content in the oil product, wherein the most effective means are hydrogenation, and employed catalyst performance plays a part crucial in hydrogenation process.What primarily require is that catalyzer will have higher desulfurization, denitrogenation and olefin saturation performance energy, next is also to have higher catalytic performance under the demulcent reaction conditions, to reduce the running cost of hydrogenation process, simplify technical process and equipment (as a large amount of off-set facility of heat transfer process and the reduction that equipment material is required) greatly.
The preparation of embodiment 1 hydrogenation Ti-Si composite oxide catalyst
Prepare ammonium tungstate solution with deionized water, concentration is 84.97g/100ml (being called for short AMT solution).In the 100ml volumetric flask, move into AMT solution 54ml, add Ni (NO
3)
26H
2O 17g is diluted to scale marks and shakes up with deionized water and promptly gets steeping fluid.
The TiO that is announced with Chinese patent CN1316486A
2-SiO
2Composite oxides are carrier, flood in steeping fluid 4～5 hours under 30～40 ℃ of conditions, after filtering 110-120 ℃ of drying 4～6 hours, 450～800 ℃ of roastings 3～4 hours.After sieving, get 60～80 orders and partly be catalyzer of the present invention.
The preparation and the metal content analysis of embodiment 2 hydrogenation Ti-Si composite oxide catalysts
Get 3gTiO
2-SiO
2Composite oxide carrier, under 35 ℃ of conditions in embodiment 1 described steeping fluid dipping 4.5 hours, after filtering 120 ℃ of dryings 5 hours, 500 ℃ of roastings 3.5 hours.After sieving, get 60～80 order parts.Analyze active component content through chemical method, NiO% (weight) is 2.0%, WO
3% (weight) is 15.3%.
The preparation and the metal content analysis of embodiment 3 hydrogenation Ti-Si composite oxide catalysts
Get 2gTiO
2-SiO
2The composite granule carrier, under 30 ℃ of conditions dipping in embodiment 1 described steeping fluid 5 hours, after filtering 110 ℃ of dryings 4 hours, 500 ℃ of roastings 3 hours.After sieving, get 60～80 order parts.Analyze active component content through chemical method, NiO% (weight) is 1.8%, WO
3% (weight) is 17.2%
Table 1 catalyst activity component concentration and physical properties
| Catalyzer | ????NiO％ | ????WO3％ | Specific surface area/m 2g -1 | Pore volume/ml.g -1 | Aperture/nm |
| ?NiW/TiO 2 | ????3.76 | ????30.63 | ????---- | ????---- | ????---- |
| Embodiment 2 | ????1.8 | ????17.2 | ????84.3 | ????0.3 | ????13.7 |
| Embodiment 3 | ????2.0 | ????15.3 | ????70.2 | ????0.2 | ????12.4 |
As can be seen from Table 1, catalyzer (NiW/TiO of the present invention
2-SiO
2) have lower metal content, in oxide weight, NiO% is 1.8～2.0%, WO
3% is 15～18%.
The hydrogenation reaction catalytic activity of embodiment 4 Ti-Si composite oxide catalyzer under differing temps
With the thiophene is model compound, with 2W
t% thiophene-98W
tThe % hexanaphthene is a reaction system, at reaction pressure and the 2h of 4MPa
-1Down reaction 4 hours of reaction velocity, utilize the content of sulphur in the sulphur blood urea/nitrogen analyzer off-line analysis reaction product, its analytical results sees Table 2.
The relation of table 2 thiophene hydrogenating desulfurization rate and temperature of reaction (unit: ng/ μ l)
As can be seen from Table 2, (1) NiW/TiO of the present invention
2-SiO
2Catalyzer has very high catalytic activity, far above with Al
2O
3Catalyst n iW/Al for carrier
2O
3(2) catalyst n iW/TiO of the present invention
2-SiO
2Has very high low temperature active (desulfurization degree reaches 96%).(3) NiW/TiO of the present invention
2-SiO
2Catalyzer compares NiW/TiO
2Catalyzer has better reaction stability (300 ℃ time desulfurization degree do not descend).
| Catalyzer | ????200℃ | ??240℃ | ??280℃ | ??300℃ |
| ??NiW/TiO 2-SiO 2 | ????96.46 | ??94.96 | ??97.18 | ??96.79 |
| ??NiW/TiO 2 | ????96.23 | ??97.07 | ??97.68 | ??44.12 |
| ??NiW/Al 2O 3 | ????----- | ??66.75 | ??77.52 | ??77.47 |
Embodiment 5 Ti-Si composite oxide catalyzer are in the catalytic activity of differential responses time
With the thiophene is model compound, with 2W
t% thiophene-98W
tThe % hexanaphthene is a reaction system, at reaction pressure and the 2h of 300 ℃ temperature of reaction, 4MPa
-1Reaction velocity down the reaction different time investigate the reaction stability of catalyzer of the present invention, utilize the content of sulphur in the sulphur blood urea/nitrogen analyzer off-line analysis reaction product, its analytical results sees Table 3.
Table 3 catalyst n iW/TiO
2-SiO
2The relation in hydrodesulfurization activity and reaction times
| Reaction times/h | ????6 | ????18 | ????24 | ????30 | ????39 |
| Desulfurization degree/% | ??97.06 | ??98.43 | ??97.16 | ??97.53 | ??98.77 |
As seen from Table 3: catalyst desulfurizing activity of the present invention can be kept very high hydrodesulfurization activity level in the investigation time.
The test of embodiment 6 Ti-Si composite oxide catalyst activities
Heavily urging raw gasline with grand celebration is raw material (raw material S content is 653.599ng/ μ l), NiW/TiO
2-SiO
2Catalyzer, reaction conditions is: 300 ℃ of temperature, pressure 4MPa, air speed is 2h
-1, hydrogen-oil ratio is 600, reacts after 4 hours, the desulfurization degree of gasoline is 84.3%.
The test of embodiment 7 Ti-Si composite oxide catalyst activities
Gasoline with the huge port crude production is raw material (sulphur content is 130.6ng/ μ l), investigates NiW/TiO
2-SiO
2Catalyzer desulphurizing activated, 240 ℃ of temperature of reaction, pressure 4MPa, air speed is 2h
-1, hydrogen-oil ratio is 600, reacts and analyzes after 4 hours, the results are shown in Table 4.
Table 4 NiW/TiO
2-SiO
2The reactive behavior of catalyzer is investigated
| Temperature/℃ | Pressure/MPa | Sulphur content/ng/ μ l | Desulfurization degree/% |
| ????240 | ????4 | ????15.5 | ????88.1 |
| ????240 | ????3.5 | ????＜5 | ????＞96 |
Table 4 explanation catalyzer of the present invention also has very high low-temp desulfurization activity for huge port gasoline; And higher desulfurization degree arranged under the low pressure.
Claims (5)
1. a petroleum fractions hydrogenation catalyst is characterized in that described catalyzer is an active ingredient with nickel tungsten, with titanium dioxide (TiO
2) and silicon-dioxide (SiO
2) nano composite oxide be carrier.
2. the described catalyzer of claim 1, the content of tungsten is 10～18% (weight), the content of nickel is 1.5～3% (weight); The basic physical properties parameter is: specific surface area is 70～90m
2.g
-1, pore volume is 0.2～0.3ml.g
-1, the aperture is 12～14nm.
3. claim 1 or 2 described Preparation of catalysts methods are the nano combined carriers of solution impregnation with tungsten and nickel compound, and drying and roasting then sieves the solid matter of gained.
4. the described Preparation of catalysts method of claim 3, the mixed solution of preferred metatungstic acid ammonia of the steeping fluid of wherein said tungsten and nickel compound and nickelous nitrate.
5. the described Preparation of catalysts method of claim 3, wherein said dipping temperature is preferably 30～40 ℃, preferred 4～6 hours of dipping time; After filtering 110～120 ℃ of dryings 4～8 hours.Maturing temperature is 450～800 ℃, roasting time 3～4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021168512A CN1194075C (en) | 2002-04-12 | 2002-04-12 | Hydrogenation Ti-Si composite oxide catalyst and method for preparing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021168512A CN1194075C (en) | 2002-04-12 | 2002-04-12 | Hydrogenation Ti-Si composite oxide catalyst and method for preparing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1451717A true CN1451717A (en) | 2003-10-29 |
| CN1194075C CN1194075C (en) | 2005-03-23 |
Family
ID=29221058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021168512A Expired - Fee Related CN1194075C (en) | 2002-04-12 | 2002-04-12 | Hydrogenation Ti-Si composite oxide catalyst and method for preparing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1194075C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004037408A1 (en) * | 2002-10-10 | 2004-05-06 | China Petroleum & Chemical Corporation | A silicon-containing alumina support, preparation thereof and a catalyst comprising the alumina support |
| CN102091652A (en) * | 2010-12-10 | 2011-06-15 | 中国石油天然气股份有限公司 | Selective hydrodesulfurization catalyst and application |
| CN102091651A (en) * | 2010-12-10 | 2011-06-15 | 中国石油天然气股份有限公司 | Preparation method of selective hydrodesulfurization catalyst |
| CN108126702A (en) * | 2017-12-27 | 2018-06-08 | 上海迅凯新材料科技有限公司 | A kind of load-type nickel series catalysts and its preparation method and application |
-
2002
- 2002-04-12 CN CNB021168512A patent/CN1194075C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004037408A1 (en) * | 2002-10-10 | 2004-05-06 | China Petroleum & Chemical Corporation | A silicon-containing alumina support, preparation thereof and a catalyst comprising the alumina support |
| CN102091652A (en) * | 2010-12-10 | 2011-06-15 | 中国石油天然气股份有限公司 | Selective hydrodesulfurization catalyst and application |
| CN102091651A (en) * | 2010-12-10 | 2011-06-15 | 中国石油天然气股份有限公司 | Preparation method of selective hydrodesulfurization catalyst |
| CN102091652B (en) * | 2010-12-10 | 2013-04-24 | 中国石油天然气股份有限公司 | Selective hydrodesulfurization catalyst and application |
| CN108126702A (en) * | 2017-12-27 | 2018-06-08 | 上海迅凯新材料科技有限公司 | A kind of load-type nickel series catalysts and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1194075C (en) | 2005-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1230251C (en) | Metal nitride catalyst preparing method and catalyst | |
| CN101733151A (en) | Distillate oil hydrorefining catalyst | |
| CN1772846A (en) | Coal tar hydrogenating modification catalyst and its prepn and application | |
| CN102166520A (en) | Hydrorefining catalyst | |
| CN108067243B (en) | Hydrotreating catalyst and preparation method and application thereof | |
| EP3023147A1 (en) | Iron-based hydrogenation catalyst and applications thereof | |
| CN1778873A (en) | Inferior diesel oil hydrotreating catalyst | |
| CN105521791A (en) | Method for preparing sulfuration-type gasoline selective hydro-desulfurization catalyst | |
| CN108786869B (en) | Diesel oil deep hydrogenation catalyst, preparation method and application thereof | |
| CN1237150C (en) | Sulfurated hydrogenation catalyst and its preparing process | |
| CN101049564A (en) | Diene selection hydrogenation catalyst, and preparation method | |
| CN1194075C (en) | Hydrogenation Ti-Si composite oxide catalyst and method for preparing same | |
| CN102423712B (en) | Preparation method of high-activity inferior diesel oil hydrorefining catalyst | |
| CA2258563C (en) | A hydrofining catalyst of a distillate oil and production method | |
| CN1853779A (en) | Fluorinated hydrogenation catalyst with silicon oxide-alumina as carrier and its production | |
| CN1143890C (en) | Catalyst for hydromodifying poor middle distillate oil and its preparing process | |
| CN106701177A (en) | Method for producing super clean gasoline | |
| CN101058748A (en) | Diesel oil hydrofining catalyst containing phosphorous or molecular sieve and preparation method thereof | |
| CN1766047A (en) | Selective hydrogenation desulfuration catalyst for catalytically cracking gasoline and its preparation method | |
| CN1916121A (en) | Method for preparing diene selective hydrotreating catalyst for gasoline | |
| CN112657522B (en) | Hydrogenation catalyst, preparation method and application thereof | |
| CN115845866A (en) | Preparation method of hydrofining catalyst | |
| CN1169458A (en) | Catalyst for distillate hydro-cracking and preparation thereof | |
| CN1393528A (en) | Catalyst for hydrorefining paraffin wax and its preparing process and usage | |
| CN112473718A (en) | Preparation method and application of ultra-deep gasoline and diesel hydrodesulfurization catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| 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 | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |