CN100478423C - Selective hydrogenation desulfuration catalyst for catalytically cracking gasoline and its preparation method - Google Patents
Selective hydrogenation desulfuration catalyst for catalytically cracking gasoline and its preparation method Download PDFInfo
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Abstract
The invention discloses a selective hydrogenation desulfuration catalyst for catalytically cracking gasoline, wherein the carrying agent is the compound of potassium oxide with two selected from the following: metallic oxide titanium dioxide, aluminium oxide, silica dioxide and magnesium oxide. the active constituents include the metallic combination of two selected from cobalt, molybdenum, nickel and wolfram. The invention also discloses the process for preparing the catalyst.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst and hydrogenating desulfurization technology.Relating in particular to a kind of is the Hydrobon Catalyst And Its Preparation Method of carrier with composite oxides, and catalyzer of the present invention has hydrodesulfurization activity and the saturated performance of inhibition alkene preferably to catalytic cracking (FCC) gasoline.
Technical background
Along with the raising day by day of environmental protection requirement, also strict further to the restriction of motor vehicle emission, content of harmful controlling index such as sulphur, aromatic hydrocarbons also improve constantly in the clean fuel specification.Catalytically cracked gasoline is the main blend component of gasoline product, and the sulfide in the processed oil mainly comes from catalytically cracked gasoline, and the sulphur content that therefore reduces in the catalytically cracked gasoline becomes the key that clean gasoline is produced.Hydrogenation is to realize the most effective means of gasoline desulfur, and still, traditional gasoline hydrodesulfurizationmethod catalyzer also makes a large amount of alkene saturated in desulfurization, thereby causes the decline significantly of gasoline octane rating, has restricted the production of high-grade gasoline.
So employed catalyst performance plays a part crucial to the state of the art of hydrogenation technique in the hydrogenation process.Ideal catalytic gasoline hydrogenation catalyzer to have higher desulphurizing activated, suppress the olefin saturation performance energy preferably, to reduce the loss of octane number that causes because of alkene is saturated in the hydrodesulfurization process.
At present domestic and international employed gasoline hydrodesulfurizationmethod catalyzer major part is to be carrier with aluminum oxide or aluminum oxide blending molecular sieve, with cobalt, molybdenum, nickel, tungsten is active ingredient, in order to improve the desulfuration selectivity of catalyzer, at aspects such as the employing of support modification, novel material and preparation methods, the insider has carried out a lot of trials.
US.Pat.2,853,429 and US.Pat.3,269,938 disclose a kind of catalyzer respectively, their employed catalyzer be with magnesium oxide, silicon oxide and aluminum oxide as carrier, contain 4wt%CoO and 10wt%MoO among wherein a kind of catalyst B ASFK8-11
3, the hydrogenating desulfurization rate of this catalyzer with respect to traditional catalyst (with γ-Al
2O
3Be carrier) low, mainly be less because introduce behind the magnesium oxide specific surface area of carrier, active ingredient can not fine dispersion on carrier surface, thereby has caused the catalyst desulfurizing activity not high.
US.Pat.4,140,626 disclose a kind of catalyzer, and magnesian content is greater than 70% in its carrier, and active ingredient is the Mo and the Co of group vib and VIII family.This catalyzer can retained part alkene in hydrogenating desulfurization, thereby avoid the remarkable decline of octane value, but weak point is that the magnesium oxide physical strength is relatively poor, has limited its industrialized application.
US.Pat.4,132,632 disclosed be to be the hydrogenation catalyst of carrier with pure zirconia magnesium, the loading of active metal component molybdenum is 4～6%, the loading of cobalt is 0.5～2%.Test-results shows that catalyzer can reach 80% to the hydrogenating desulfurization rate of gasoline, but simultaneously the alkene saturation exponent is nearly 40%, 1.6 units of loss of octane number.If catalyzer is used for the heavy oil fluid catalytic cracking gasoline hydrodesulfurizationmethod of high olefin content, what alkene will be by by a larger margin is saturated, and loss of octane number is also bigger.
US.Pat.4 in 880, the 524 petroleum hydrocarbon hydroprocessing processs that propose, adopts a kind of highly active hydrogenation catalyst that has.This catalyzer belongs to Ni-Mo/Al
2O
3Type is to adopt the gelling process preparation.This specific surface area of catalyst is greater than 300m
2/ g, less than the aperture of 7nm greater than 70%.Because the aperture is less than normal, this catalyzer can only be used for the hydrodesulfurization process of light-end products, and also more complicated of this Preparation of catalysts process.
Be subjected to the restriction of catalyst activity, when FCC gasoline is implemented the hydrogenating desulfurization processing,, generally can improve the temperature and pressure of reaction for reaching the deep desulfuration effect as far as possible, can improve degree of olefin saturation in the gasoline after the desulfurization this moment inevitably, still influence the quality of gasoline.
In sum, currently reported aluminum oxide or magnesium oxide and modifier thereof are that the catalyzer of carrier is when carrying out the catalytic gasoline hydrogenation desulfurization, be difficult to have concurrently simultaneously good hydrogenating desulfurization character and suppress the saturated performance of alkene, and for the heavy oil fluid catalytic cracking gasoline of high olefin content, catalyzer does not have the desulfuration selectivity of height and suppresses the olefin saturation performance energy preferably, will cause the decline significantly of octane value inevitably.Even had report to have the catalyzer of desulfuration selectivity preferably, its preparation method and work-ing life also be difficult to satisfy the needs of heavy industrialization.
Summary of the invention
The invention provides the novel hydrogenation catalyst of a class, can be implemented in and handle catalytically cracked gasoline under lesser temps and the pressure, in deep desulfuration, degree of olefin saturation and loss of octane number are all less.
The present invention also provides the method for preparing described hydrogenation catalyst, by rational process combination, make catalyzer have suitable particle diameter and higher active ingredient supports rate, and preparation technology is simple, is easy to operate and control.
The present invention more provides and has utilized the treatment process of above-mentioned catalyzer realization to catalytic gasoline selective hydrodesulfurizationmodification.
Hydrogenation catalyst provided by the invention, based on the requirement of catalyzer to the catalytic gasoline hydrogenation desulfuration selectivity, carrier is two kinds of mixtures that form with potassium oxide that are selected from titanium dioxide, aluminum oxide, silicon-dioxide and the magnesium oxide, and K
2The weight percent of O in carrier is 0.1～5%, and active ingredient is two kinds of metallic combinations in cobalt, molybdenum, nickel and the tungsten, and the pore volume of this catalyzer is 0.2～0.7ml/g, and specific surface area is at 100～210m
2/ g.
The contriver finds by a large amount of test contrasts, utilize the compound of described potassium oxide that carrier is carried out modification, and the pore volume of the catalyzer behind the control load and specific surface area are proper range (being not to be the bigger the better), resulting catalyzer has higher activity, especially the activity that has higher selective hydrodesulfurization, in hydrogenating desulfurization, reach effective inhibition degree of olefin saturation, the catalytically cracked gasoline after guaranteeing to handle still has the effect of higher octane value.
In the catalyzer provided by the invention, the preferred proportion that forms the metal oxide of support of the catalyst is respectively with the atoms metal ratio: Al/Mg:0.08～1, Ti/Si:0.12～6, Ti/Al:0.5～2, Ti/Mg:0.1～4, Si/Mg:0.2～3.5, for example, can adopt Al
2O
3-MgO-K
2O, TiO
2-SiO
2-K
2O, TiO
2-Al
2O
3-K
2Composite oxides such as O are as the carrier of catalyzer.
Because the improvement of carrier, charge capacity and the dispersiveness of active ingredient on carrier all improved, and also helps the raising of catalytic efficiency.Preferably, the content of described reactive metal in catalyzer is respectively in oxide content: NiO 1～3%, WO
310～30%, CoO 1～5%, MoO
310～18%.
The pore volume of catalyzer of the present invention is 0.2～0.7ml/g, and specific surface area is at 100～210m
2/ g, that is, catalyzer of the present invention should have certain graininess, and preferably, this catalyzer is the particle of 3～3.6mm.
Preparation of catalysts method of the present invention comprises:
Adopt sol-gel method or coprecipitation method or mechanical mixing that two kinds of oxide compounds in described titanium dioxide, aluminum oxide, silicon-dioxide and the magnesium oxide are made complex body earlier, adopt pickling process to make complex body with potassium oxide after the drying again, dry roasting becomes described complexes carrier;
Adopt the solution impregnation technology determined active ingredient to be supported on the complexes carrier for preparing dry roasting.
Preparation process of the present invention has comprised the preparation and the Preparation of catalysts of carrier, in the preparation of carrier, is to make the complex body that contains two kinds of metal oxides earlier, and then utilizes pickling process further to obtain the complexes carrier of potassium oxide modification.Described sol-gel method is that the salt with described metal is dissolved in ethanol or the aqueous isopropanol, drips deionized water and hydrolysis inhibitor, and behind the stable sol to be formed, leaving standstill becomes gel; Described coprecipitation method is that the salt of described metal is dissolved into the aqueous solution, drips basic solution and forms precipitation.Drying means can be CO 2 supercritical drying or any feasible methods such as heated drying or lyophilize.
Detailed process can be:
Sol-gel method: with a certain amount of described metal-salt, for example organic titanium salt or organosilicon salt or aluminium salt or their mixture are dissolved in the alcoholic solution, and used alcoholic solution is an ethanol, also can be Virahols.Drip deionized water and hydrolysis inhibitor in mixed solution, hydrolysis inhibitor is nitric acid or acetate or ammoniacal liquor, and purpose is the hydrolysis rate of the above-mentioned salt of control, with the sol system that obtains mixing, settles into till the gel;
Coprecipitation method: with a certain amount of described metal-salt, for example inorganic aluminate, magnesium salts or titanium salt are dissolved in the aqueous solution, in the aqueous solution, drip basic solution, preferably using pH is 8～10 weakly alkaline solution, to regulate the hydrolysis and the sedimentation speed of metal-salt, for example can be solution of potassium carbonate, potassium nitrate solution, sodium carbonate solution, sodium nitrate solution, also can be ammonia soln etc., after treating that precipitation forms, filter and obtain precipitation;
Mechanical mixing: get two or three in pre-determined powder titanium dioxide, silicon-dioxide, aluminum oxide, the magnesium oxide and mix according to ratio separately.
Complex body product with method for preparing, utilize potassium salt soln to make complex carrier of the present invention again by pickling process, described sylvite is generally inorganic salt, for example: saltpetre, vitriolate of tartar, salt of wormwood etc., when adopting CO 2 supercritical drying or heated drying or lyophilize to handle, with substantially anhydrous branch in the desciccate or not have the organism smell be basic demand.Controllable Temperature was built in 40～60 ℃ when CO 2 supercritical was dry, pressure 8.0～12.0MPa, and get final product 1～3 hour time of drying; The heated drying condition generally is controlled to be higher than under 100 ℃ of (for example about 110～120 ℃) conditions carries out the heat oven dry to gel or precipitation; Lyophilize can be to dry 2～6 hours of gel or precipitation under-20～-40 ℃, 10KPa condition.Dried product or mechanically mixing product also need be under 400～650 ℃ of air atmosphere roasting 3～8 hours, preferred maturing temperature is 500～600 ℃, roasting time 3～5 hours.
The employing of drying means can be determined according to practical situation and operational condition, generally, preferably adopt the CO 2 supercritical drying means when adopting the Prepared by Sol Gel Method complex carrier, preferably adopt the heated drying method when adopting coprecipitation method to prepare complex carrier.Supercritical carbon dioxide fluid exsiccant method and device are routine techniques, and the heated drying process can be warm air drying known technologies such as (for example utilizing baking oven), repeats no more herein.
It is to adopt dipping technique that the present invention prepares catalyzer, can be synchronous pickling process, complexes carrier be impregnated in the mixing solutions of active metal salt, dipping time under the room temperature 4～6 hours, for example, when being active ingredient, adopt the mixing solutions of the salts solution of Ni, W to flood composite oxide carrier synchronously with Ni-W; Also can adopt step impregnation method,, two kinds of active ingredients be supported on carrier respectively through twice dip operation.Preferably, when supporting one of active ingredient on carrier is molybdenum, adopt step impregnation method, complexes carrier floods the solution that contains molybdenum earlier, floods the solution of another kind of reactive metal after drying, the roasting again, after drying and roasting, for example, when being active ingredient, composite oxide carrier being flooded earlier contain Mo solution with Co, Mo or Ni, Mo, flood again behind the drying and roasting and contain Co or Ni solution, after drying, roasting.The preferred metatungstic acid ammonia of the steeping fluid of described active ingredient, nickelous nitrate, Xiao Suangu, ammonium molybdate etc.
After the complexes carrier dipping active ingredient preferably 110～120 ℃ of dryings 4～8 hours, 450～650 ℃ of roastings 3～8 hours.Identical with usual method, the product after the roasting through overmolding, grind, sieve, become the final catalyst product, the present invention preferably collects the granular product of 3～3.6mm after sieving, this moment, its pore volume and specific surface area all met the needs of catalytic hydrogenation reaction.
According to a further aspect in the invention, the application of above-mentioned catalyzer in the FCC gasoline desulfur is handled is provided, promptly, using hydrogenation catalyst of the present invention that FCC gasoline is carried out hydrogenating desulfurization handles, show good selectivity, when realizing deep desulfuration, effectively suppress the saturation ratio of alkene, reduce the loss of gasoline octane rating.
In the catalyzer provided by the invention, metal active constituent must could better performance catalytic activity with the form of sulfide, thereby catalyzer needs to carry out prevulcanized before use, and concrete vulcanization process can adopt technique known.So, catalytic gasoline hydrogenation sulfur method provided by the invention comprise adopt above-mentioned hydrogenation catalyst after sulfidizing with pending catalytically cracked gasoline contact reacts, 200～350 ℃ of temperature of reaction, be preferably 240～320 ℃, be preferably 240～280 ℃, reaction pressure 1～6MPa is preferably 2～4MPa, liquid hourly space velocity 1～10h
-1, 1～4h preferably
-1
Wherein, sulfidizing is preferably used CS
2Cyclohexane solution handle described catalyzer, CS
2Cyclohexane solution concentration be 2～6wt%, 260～360 ℃ of curing temperatures, sulfide stress 2～6MPa, curing time 2～10 hours, solution feed air speed 2～10h
-1, hydrogen is 300～800 with the volume ratio of sulfuration liquor charging.
Treatment process of the present invention mainly is a catalytically cracked gasoline for the selection of reaction raw materials oil, can contain 10～70% alkane, 20～70% alkene, 10～50% aromatic hydrocarbons and a spot of sulfur-bearing and nitrogenous compound, its cut scope is 35～205 ℃, also can be the cut that cuts arbitrarily in above scope, wherein sulfide content can be 100～4000 μ g/g.
In the selection of reactor, can use fluidized-bed or ebullated bed, but preferably use fixed bed.
Embodiment
Below further describe technical characterstic of the present invention by specific embodiment, with the beneficial effect that helps the reader to understand enforcement of the present invention better and produced, but do not constitute any qualification to the scope of the present invention.
Embodiment 1
Sol-gel method prepares TiO
2-SiO
2, TiO
2-Al
2O
3Composite oxide carrier
The positive tetraethyl orthosilicate of the tetrabutyl titanate of 34.0g and 20.8g is dissolved in forms mixed solution in the ethanolic soln, drip the deionized water of 19ml and the acetate of 41.2ml in this mixed solution, stable sol to be formed settles into till the gel.It is dry to adopt supercritical carbon dioxide fluid that this gel is implemented, drying conditions is 40～60 ℃ of temperature, pressure 8.0～12.0MPa, and the time is approximately 1～2 hour (detect less than aqueous vapor or organism smell substantially this moment) in tail gas, 500～600 ℃ of following roastings 3～4 hours, obtain TiO then
2-SiO
2Carrier, Ti/Si atomic ratio wherein is 1: 1 substantially, is expressed as TS-1.
Take by weighing the tetrabutyl titanate of 54.4g and the positive tetraethyl orthosilicate of 8.3g, perhaps the tetrabutyl titanate of the aluminum nitrate of 30g and 40.8g according to same quadrat method, obtains TiO respectively
2-SiO
2Carrier, Ti/Si atomic ratio wherein is 4: 1 substantially, is expressed as TS-4, TiO
2-Al
2O
3Composite oxide carrier, Ti/Al atomic ratio wherein is 2: 1 substantially, is expressed as TA-2.
The character of gained composite oxides is as shown in table 1.
Table 1
Embodiment 2
Coprecipitation method prepares Al
2O
3-MgO composite oxide carrier
In the water-soluble solution of magnesium nitrate hexahydrate with the ANN aluminium nitrate nonahydrate of 14.856g and 40.618g, temperature is elevated to 70～80 ℃ (preferably 75 ℃), dropping ammonia solution in the aqueous solution, treat that precipitation forms after, obtain precipitation through reflux and filter.Adopt the heated drying method, in baking oven, precipitation is carried out drying, 110～120 ℃ of hot blast temperatures, the time is approximately 1～2 hour (detect less than aqueous vapor or organism smell substantially this moment) in tail gas.Under 500～600 ℃, roasting 3～4 hours obtains Al
2O
3-MgO composite oxide carrier, Al/Mg atomic ratio 1: 8.
Change the ratio of aluminum nitrate and magnesium nitrate, according to the carrier for preparing different atomic ratios with quadrat method.
The character of gained composite oxides is as shown in table 2, and the numeral in the sample unquote is the Al/Mg atomic ratio.
Table 2Al
2O
3-MgO composite oxides specific surface area, pore volume and aperture
Embodiment 3
TiO
2-SiO
2-K
2The preparation of O carrier
The tetrabutyl titanate of 34.0g and the positive tetraethyl orthosilicate of 20.8g be dissolved in (also can use Virahol) in the ethanolic soln and form mixed solution, in this mixed solution, drip the deionized water of 19ml and the nitric acid of 41.2ml, stable sol to be formed, settle into till the gel, adopt CO 2 supercritical drying (referring to embodiment 1).
With 0.3g saltpetre and 12ml deionized water wiring solution-forming, adopt equi-volume impregnating and above-mentioned dry thing to mix, the employing heated drying carries out drying, is calcination process 3～4 hours under 500～600 ℃, air atmosphere in temperature, obtains TiO
2-SiO
2-K
2O carrier (K wherein
2The weight ratio of O is: 1%).
Perhaps, make TiO with embodiment 1, embodiment 2
2-Al
2O
3And Al
2O
3The method that the composite oxides of-MgO adopt and present embodiment is same further prepares TiO
2-Al
2O
3-K
2O and Al
2O
3-MgO-K
2The O carrier, K
2The weight percent of O is 0.3～1.5%.
Embodiment 4
NiW/TiO
2-SiO
2-K
2The O Preparation of catalysts
Get 4.2ml ammonium metatungstate solution (0.8823g WO
3/ ml) be made into steeping fluid with the 7ml deionized water, get the 1.36g Nickelous nitrate hexahydrate, be made into steeping fluid with the 6ml deionized water.The TiO that makes with embodiment 3
2-SiO
2-K
2O (be expressed as TSK-n, n represents the atomic ratio of Ti and Si) composite oxides are carrier, under the room temperature condition, get the 10g carrier, and above two kinds of steeping fluids are mixed, and flood 4～5 hours, 110～120 ℃ of dryings 4～6 hours, 450～650 ℃ of roastings 3～4 hours.Get 60～80 orders after sieving and partly be catalyst n iW/TiO of the present invention
2-SiO
2-K
2O (being expressed as NiW/TSK-n).
Table 3 is that to utilize the Ti/Si atomic ratio be two kinds of TiO of 1 and 4
2-SiO
2-K
2The essential property of the catalyzer that the O composite oxide carrier makes.
Table 3NiW/TiO
2-SiO
2-K
2The essential property of O catalyzer
Embodiment 5
CoMo/TiO
2-SiO
2-K
2The O Preparation of catalysts
Get the 1.4g Cobaltous nitrate hexahydrate and be made into steeping fluid, get the 2.23g Ammonium Molybdate Tetrahydrate and be made into steeping fluid with 13ml ammoniacal liquor with the 13ml deionized water.The TiO that makes with embodiment 3
2-SiO
2-K
2The O composite oxides are carrier, get the 10g carrier.First dipping ammonium molybdate ammonia soln 4～6 hours at ambient temperature is 110～120 ℃ of dryings 4～6 hours, 450～650 ℃ of roastings 3～4 hours; And then dipping cobalt nitrate solution 4～6 hours, 110～120 ℃ of dryings 4～6 hours, 450～650 ℃ of roastings 3～4 hours.Get 60～80 orders after sieving and partly be CATALYST Co Mo/TiO of the present invention
2-SiO
2-K
2O (being expressed as CoMo/TSK-n).
Table 4 is that the Ti/Si atomic ratio is two kinds of TiO of 1 and 4
2-SiO
2-K
2The essential property of the catalyzer that the O composite oxide carrier makes.
The Al that makes with embodiment 3
2O
3-MgO-K
2O is that carrier (being expressed as AMK-n) adopts the method same with embodiment 4 or embodiment 5 when preparing catalyzer.
The essential property of table 4CoMo/TSK catalyzer
Embodiment 6
The hydrodesulfurization activity of various catalyzer
To carry out the evaluation of reactivity worth according to the various catalyzer (fixed bed) on the hydrogenation micro-reactor of the foregoing description 4, embodiment 5 preparations, at first catalyzer is carried out sulfidizing: sulfuration liquid is CS
2Cyclohexane solution, concentration 2～3%, 300 ℃ of curing temperatures, sulfide stress 4.0MPa, curing time 4 hours, sulfuration liquid charging air speed 2h
-1Hydrogen is 600 with the volume ratio of sulfuration liquid charging.
The temperature of catalytic gasoline hydrogenation desulphurization reaction is between 200～300 ℃, and reaction pressure is between 1～6MPa, and liquid hourly space velocity is 1～10h
-1In temperature is 280 ℃, and pressure is 3MPa, and air speed is 2h
-1The time the hydrodesulfurization activity result as shown in table 5.With desulfurization degree (HDS), alkene saturation exponent (HYD) and select the factor (Z) as evaluation index.The calculation formula of selectivity factor is as follows:
Select the factor (Z)=ln (1-HDS%)/ln (1-HYD%)
The hydrodesulfurization performance evaluation result of table 5 catalyzer
Embodiment 7
The hydrodesulfurization activity of catalyzer under the differing temps
Among the embodiment 6, CoMo/TSK-1 and CoMo/AMK-1/10 show hydrogenating desulfurization selectivity preferably, have therefore further investigated CoMo/AMK-1/10 reactivity worth under the differing temps, and reaction pressure is 3MPa, and air speed is 2h
-1, temperature range is 220～320 ℃, and preferably 240～300 ℃, especially 260～280 ℃, temperature optionally influences hydrogenating desulfurization, and its reactivity worth is as shown in table 6.
The reactivity worth of table 6CoMo/AMK-1/10 catalyzer under differing temps
Embodiment 8
The hydrodesulfurization activity of catalyzer under the different air speeds
Adopting the CoMo/AMK-1/10 catalyzer of preparation among the embodiment 5, is 3MPa at pressure, when temperature is 280 ℃, investigates air speed and hydrogenating desulfurization is optionally influenced air speed scope 1～10h in the little performance of carrying out on anti-of hydrogenation
-1, the result shows it better is 1～4h
-1, 2～4h preferably
-1Its reactivity worth is as shown in the table.
The reactivity worth of table 7CoMo/AMK-1/10 catalyzer under different air speeds
Embodiment 9
The hydrodesulfurization activity of catalyzer under the different pressures
Adopting the CoMo/AMK-10 catalyzer of preparation among the embodiment 5, when temperature is 280 ℃, is 2h in air speed
-1, investigate pressure hydrogenating desulfurization is optionally influenced in the little performance of carrying out on anti-of hydrogenation, pressure range 1～6MPa, 2～4MPa preferably, its reactivity worth is as shown in table 8.
The reactivity worth of table 8CoMo/AMK-1/10 catalyzer under different pressures
Embodiment 10
The contrast of gasoline property before and after selective hydrodesulfurization is handled
Select the CoMo/AMK-1/10 catalyzer of using shown in the embodiment 9 for use, when temperature of reaction was 280 ℃, pressure was 2MPa, and air speed is 2h
-1Condition under, the character of the gasoline products after selective hydrodesulfurization is handled and the contrast of stock oil character are as shown in table 9.
Character after table 9 catalytic gasoline hydrogenation is refining
In sum, catalyzer of the present invention not only has hydrogenating desulfurization effect preferably to catalytically cracked gasoline, and the saturated and loss of octane number of alkene can also be controlled at lower level, be a kind of new catalytic selective hydrogenation desulfurization of cracked gasoline catalyzer of complete function.
Claims (8)
1, a kind of hydrogenation catalyst, its carrier are to be selected from titanium dioxide, aluminum oxide, silicon-dioxide and the magnesium oxide two kinds of mixtures with potassium oxide, and K
2The weight percent of O in carrier is 0.1～5%, and active ingredient is two kinds of metallic combinations in cobalt, molybdenum, nickel and the tungsten, and the pore volume of this catalyzer is 0.2～0.7ml/g, and specific surface area is 100～210m
2/ g.
2, the described hydrogenation catalyst of claim 1, wherein, the ratio that forms the metal oxide of support of the catalyst is respectively in the atoms metal ratio: Al/Mg:0.08～1, Ti/Si:0.12～6, Ti/Al:0.5～2, Ti/Mg:0.1～4; S i/Mg:0.2～3.5.
3, the described hydrogenation catalyst of claim 1, wherein, the content of described reactive metal in catalyzer is respectively in oxide content: NiO 1～3%, WO
310～30%, CoO 1～5%, MoO
310～18%.
4, prepare the method for each described hydrogenation catalyst of claim 1～3, it comprises:
Adopt sol-gel method or coprecipitation method or mechanical mixing that two kinds of oxide compounds in described titanium dioxide, aluminum oxide, silicon-dioxide and the magnesium oxide are made complex body earlier, adopt pickling process to make complex body with potassium oxide after the drying again, dry roasting, become described complexes carrier, described roasting condition is: under the 400-650 ℃ of air atmosphere roasting 3-8 hour;
Adopt the solution impregnation technology that determined active ingredient is supported on the complexes carrier for preparing, 110-120 ℃ after dry 4-8 hour, at 450-650 ℃ of roasting 3-8 hour.
5, the described preparation method of claim 4, wherein,
Described sol-gel method is that the salt with described metal is dissolved in ethanol or the aqueous isopropanol, drips deionized water and hydrolysis inhibitor, and behind the stable sol to be formed, leaving standstill becomes gel;
Described coprecipitation method is that the salt of described metal is dissolved into the aqueous solution, drips basic solution and forms precipitation.
6, the described preparation method of claim 4 wherein, can adopt CO 2 supercritical drying, heated drying or lyophilize during the preparation complexes carrier, and temperature was controlled at 40～60 ℃, pressure 8.0～12.0MPa when CO 2 supercritical was dry.
7, the described preparation method of claim 4, wherein, described solution impregnation technology is synchronous pickling process, complexes carrier be impregnated in the mixing solutions of active metal salt the dipping time under the room temperature 4～6 hours.
8, the described preparation method of claim 4, wherein, supporting one of active ingredient on carrier is molybdenum, adopt step impregnation method, complexes carrier floods the solution that contains molybdenum, solution, after drying and the roasting of flooding another kind of reactive metal after drying, the roasting more earlier.
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| CN101766984B (en) * | 2008-12-31 | 2012-05-30 | 中国石油化工股份有限公司 | Desulfuration adsorbent containing phosphorus and preparation method and application thereof |
| CN101816918B (en) * | 2009-02-27 | 2012-08-29 | 中国石油化工股份有限公司 | Alkali metal-containing desulfurization adsorbent and preparation method and application thereof |
| WO2010075672A1 (en) | 2008-12-31 | 2010-07-08 | 中国石油化工股份有限公司 | Desulfurizing adsorbent and preparation method and use thereof |
| CN101722008B (en) * | 2009-11-10 | 2012-05-30 | 浙江大学 | Preparation method of catalyzer for tar carbon dioxide reforming |
| CN102806089A (en) * | 2012-08-15 | 2012-12-05 | 中国海洋石油总公司 | Preparation method of reformer feed hydrotreating catalyst |
| TWI630954B (en) | 2014-12-09 | 2018-08-01 | 財團法人工業技術研究院 | Method for hydrogenating bisphenol a or derivatives thereof and method for hydrogenating terephthalic acid or derivatives thereof |
| CN106669783B (en) * | 2015-11-11 | 2019-06-11 | 中国石油化工股份有限公司 | The preparation method of hydrocracking catalyst |
| CN110935460B (en) * | 2018-09-21 | 2023-02-28 | 中国石油天然气股份有限公司 | High-selectivity hydrodesulfurization catalyst and preparation method thereof |
| CN110013852A (en) * | 2019-04-23 | 2019-07-16 | 营口理工学院 | A kind of absorbing desulfurization catalyst and preparation method thereof based on catalysis with cracking fuel oil |
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2004
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