CN100389178C - Fluorine-containing hydrogenation catalyst and method for preparing the same - Google Patents
Fluorine-containing hydrogenation catalyst and method for preparing the same Download PDFInfo
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- CN100389178C CN100389178C CNB2005100020542A CN200510002054A CN100389178C CN 100389178 C CN100389178 C CN 100389178C CN B2005100020542 A CNB2005100020542 A CN B2005100020542A CN 200510002054 A CN200510002054 A CN 200510002054A CN 100389178 C CN100389178 C CN 100389178C
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Abstract
The present invention relates to a fluorine-containing hydrogenation catalyst and a preparation method thereof. The preparation method of the catalyst comprises: fluorine and hydrogenated active metal components are led into a carrier, wherein the method for leading in the fluorine comprises: the carrier contacts a solution of a fluorine-containing compound for 0.5 to 5 hours under an airtight condition at the temperature of 60 to 250DEG C, and the fluorine content in the final catalyst is from 0.5 to 25 wt% by using the catalyst as the reference according to the concentration and the consumption of the solution of the fluorine-containing compound. Compared with the existing method, the activity of the catalyst provided by the method of the present invention is obviously improved.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst and preparation method thereof, more specifically to a kind of fluorine-containing hydrogenation catalyst and preparation method thereof.
Background technology
In recent years, crude oil heavy and poor qualityization tendency are obvious day by day in the world wide, meanwhile, and to the but constantly increase of demand of middle distillate and reformation, steam crack material.This impels the hydrocracking technology that turns to purpose with the high-quality of heavy distillate and lightweight to be developed rapidly, and hydrogenation catalyst comprises that hydrofining, hydrotreatment and hydrocracking catalyst are wherein important and The key factor.
Normally a kind of dual-function catalyst of hydrotreatment and hydrocracking catalyst, it has lytic activity and hydrogenation activity simultaneously, promptly contains acidic components and hydrogenation activity component simultaneously.Acidic components can be heat-resistant inorganic oxide and/or the various zeolites that constitutes carrier; The hydrogenation activity component generally is metal, metal oxide and/or the metallic sulfide that is selected from group vib and VIII family in the periodic table of elements.In addition, in catalyzer, introduce, can regulate and improve catalyst performance and make it satisfy the requirement of different process process as adjuvant components such as silicon, boron, titanium, zirconium or halogens.
CN85104438 discloses a kind of catalyzer of being made by nickel, tungsten, fluorine and aluminum oxide.This catalyzer is owing to introduce the auxiliary agent fluorine on alumina supporter, make catalyst surface acidity that to a certain degree enhancing be arranged, and makes it have good hydrofining performance.
CN 1056514A discloses a kind of catalyst for hydro-processing heavy distillate, it is characterized in that it is the purity made by aluminum alkyls and the aluminum alkoxide hydrolysis method diaspore greater than 65 heavy %, the carrier that obtains with high-temperature roasting after zeolite through cationic exchange mixes, fluorine auxiliary agent and nickel, tungsten active ingredient constitute, and each component concentration (with the catalyzer is benchmark, heavy %) is: fluorine 0.5-5.0%, nickel oxide 2.5-6.0%, Tungsten oxide 99.999 10-32%, all the other are carriers, its preparation method is:
(1) with purity greater than 65% diaspore and zeolite through cationic exchange, press 1-13: the mixed of 1-3 (weight) is even, 500-700 ℃ roasting 3-5 hour, obtain carrier;
(2) carrier that (1) is obtained, with fluorine-containing solution impregnation, 100-130 ℃ of oven dry, 100-600 ℃ roasting 3-5 hour, obtain fluorine-containing carrier;
(3) the fluorine-containing carrier that (2) are obtained, through containing the solution impregnation of tungsten and nickel, 100-300 ℃ of oven dry, 400-60 ℃ roasting 3-5 hour, obtain catalyzer.
US6,174,429B1 discloses a kind of catalyzer, this catalyzer contains: the amorphous aluminum matrix that contains of at least a tart of 1-99 weight %, 0.1-80 at least a Y zeolite of weight, this zeolite lattice constant is greater than 2.438nm, total silica is less than 8, the skeleton silica is less than 21 greater than total mol ratio, and at least a group VIII metal component that is selected from, its content are 0.1-30 weight %, at least a group vib metal component, its content is 1-40 weight %, the phosphorus of 0.1-20 weight %, at least a VIIA family element of 0-20 weight %.Described VIIA family metal is a fluorine, and fluorine is to adopt the method for the solution impregnation of fluorochemicals to introduce, and fluorine cpd can be hydrofluoric acid, hydrofluoric acid ammonium or the fluorochemicals that can discharge fluorine anion in the aqueous solution.For example ammonium silicofluoride, silicon tetrafluoride etc.
In hydrogenation catalyst, introduce fluorine, catalyst performance is improved, but its activity is still on the low side.
Summary of the invention
The objective of the invention is at existing fluorine-containing activity of hydrocatalyst shortcoming on the low side, a kind of new active higher hydrogenation catalyst and preparation method thereof is provided.
The method that the present invention carries is included in and introduces fluorine and hydrogenation active metals component in the carrier, wherein, it is under 60-250 ℃ and the air tight condition that the method for introducing fluorine is included in temperature, carrier is contacted 0.5-5 hour with a kind of solution of fluorochemicals, with the catalyzer is benchmark, and it is 0.5-25 weight % that the concentration of the solution of described fluorochemicals and consumption make the content of fluorine in the final catalyzer.
Catalyzer provided by the invention contains carrier, fluorine and hydrogenation active metals component, the method preparation that this catalyzer is provided by the invention described above.
Compare with existing method, obviously improve by the activity of such catalysts that the invention provides the method preparation.
For example, adopt same materials oil and reaction conditions, (alumina content is 59.7 weight % to a kind of catalyst B that evaluation is prepared by the inventive method, USY content is 5.3 weight %, nickel oxide content is 7 weight %, tungsten oxide content is 25 weight %, fluorine content is 3 weight %) and a kind of reference catalyst BN (alumina content is 59.6 weight %, USY content is 5.3 weight %, nickel oxide content is 7 weight %, tungsten oxide content is 25 weight %, fluorine content is 3.1 weight %), it is 38.46% that the inventive method provides the transformation efficiency of catalyst B, and the transformation efficiency of reference catalyst only is 28.57%.
Embodiment
According to method provided by the invention, described fluorochemicals can be to be selected from fluorine-containing mineral compound, as HF, NH
4F, (NH
4)
2SiF
6, (NH
4)
2ZrF
6, (NH
4)
2TiF
6, (NH
4)
2AlF
6In one or more, can be fluorine-containing organism also, as C
6H
5F, gifblaar poison.Be preferably (NH
4)
2SiF
6, (NH
4)
2AlF
6Or (NH
4)
2TiF
6The solution of described fluorochemicals can be the aqueous solution of fluorochemicals, in the organic solution one or more, the preferred aqueous solution wherein.In element and with the catalyzer is benchmark, and it is 1-10 weight % that the concentration of the solution of fluorochemicals and consumption preferably make the content of fluorine in the final catalyzer.Described contact temperature is preferably 85-150 ℃, is preferably 0.5-3 hour duration of contact.
Describedly in confined conditions carrier is contacted with the solution of fluorochemicals, can adopt any one ordinary method to carry out, for example, described carrier and described solution are mixed, place sealable tank reactor to flood afterwards.
According to method provided by the invention, when the fluorochemicals that is adopted when in described carrier, introducing fluorine, when also introducing other components such as silicon, preferably include the step of washing, roasting.Described washing, drying and roasting method are ordinary method and the condition in the Preparation of Catalyst, are 100-300 ℃ as drying temperature, are preferably 105-250 ℃, and be 1-24 hour time of drying, is preferably 2-12 hour; Maturing temperature is 350-600 ℃, is preferably 400-550 ℃, and roasting time is 1-10 hour, is preferably 2-8 hour.
According to method provided by the invention, wherein said carrier can be any one carrier that is commonly used for the preparation catalyzer, for example, is selected from the various heat-resistant inorganic oxides that are commonly used for support of the catalyst and/or matrix one or more.The optional self-alumina of described heat-resistingization thing, silicon oxide, zirconium white, titanium oxide, magnesium oxide, Thorotrast, beryllium oxide, aluminium oxide-silicon oxide, aluminium oxide-titanium oxide, aluminum oxide-magnesium oxide, silicon oxide-magnesium oxide, silicon oxide-zirconium white, silicon oxide-Thorotrast, silicon oxide-beryllium oxide, silicon oxide-titanium oxide, oxidation titania-zirconia, silica-alumina-zirconium white, silica-alumina-Thorotrast, silica-alumina-titanium oxide or silica-alumina-magnesium oxide are preferably aluminum oxide, aluminium oxide-silicon oxide.With the catalyzer is benchmark, and the content of described carrier is 5-90 weight %, is preferably 40-80 weight %.
According to method provided by the invention, also contain molecular sieve in the wherein said carrier, described molecular sieve can be to be selected from the zeolite-type molecular sieves that is commonly used for active component of cracking catalyst in the prior art, in the non-zeolite molecular sieve one or more.For example, be selected from ZRP, Y zeolite, beta zeolite, mordenite, ZSM-5, MCM-41, Ω, ZSM-12, the MCM-22 zeolite molecular sieve one or more.Among preferred Y zeolite, beta zeolite, mordenite, the ZSM-5 one or more.The mixture of one or more in the further preferred Y zeolite, beta zeolite, ZSM-5 wherein.Described molecular sieve can be commercially available commodity, also can adopt any one prior art for preparing.With the catalyzer is benchmark, and the content of described molecular sieve is 0.5-85 weight %, is preferably 1-40 weight %.
Described carrier is looked different the forming composition that require can be made into various easy handlings, for example microballoon, sphere, tablet or bar shaped etc.Moulding can be carried out according to a conventional method, for example, for the complex carrier of a kind of molecular sieve and inorganic refractory oxides, can be with described heat-resistant inorganic oxide or its precursor is mixed, the preparation of the method for extruded moulding and roasting with described molecular sieve.Wherein, the precursor of described heat-resistant inorganic oxide refers to can form after the roasting compound of described heat-resistant inorganic oxide, typically refers to oxyhydroxide, hydrous oxide, contains the gel of its oxide compound, oxyhydroxide and in the colloidal sol one or more.For example, the precursor of aluminum oxide can be selected from one or more in various hydrated aluminum oxides, the aluminium colloidal sol.When extrusion moulding, can add an amount of extrusion aid and/or tackiness agent, extrusion moulding then.The kind of described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, do not give unnecessary details at this.The temperature of described roasting is 350-800 ℃, is preferably 450-650 ℃, and roasting time is 1-10 hour, is preferably 2-8 hour.
According to method provided by the invention, the kind of described hydrogenation active metals component and content are habitually practised by conventional hydrocracking catalyst, are selected from iron, cobalt or nickel and at least a molybdenum or the tungsten that is selected from group vib of at least a group VIII as the hydrogenation active metals component.In oxide compound and with the catalyzer is benchmark, and the content of group vib metal component is 5-40 weight %, and the content of group VIII metal component is 1-10 weight %.The content of preferred group vib metal component is 10-36 weight %, and the content of group VIII metal component is 1-8 weight %.
Described Preparation of catalysts method comprises described carrier under the condition that is enough to iron, cobalt or the nickel of at least a group VIII and at least a molybdenum that is selected from group vib or tungsten metal component be deposited on the carrier, described carrier and the iron that contains at least a group VIII, cobalt or nickel are selected from the molybdenum of group vib or the solution of tungsten metallization compound contacts with at least a, for example prepare by methods such as ion-exchange, dipping, co-precipitation.
The metallic compound of the described iron that contains group VIII, cobalt, nickel is selected from one or more in the soluble compound of these metals, can be in the nitrate, acetate, soluble carbon hydrochlorate, muriate, soluble complexes of these metals one or more as them.
Describedly containing in molybdenum in the group vib, the soluble compound that the tungsten metallization compound is selected from these metals one or more, can be in molybdate, paramolybdate, tungstate, metatungstate, the ethyl metatungstate one or more as them.
According to the ordinary method in this area, catalyzer provided by the invention is before using, usually can be in the presence of hydrogen, under 140-370 ℃ temperature, carry out prevulcanized with sulphur, hydrogen sulfide or sulfur-bearing raw material, this prevulcanized can be carried out also can original position vulcanizing in device outside device, is translated into sulfide type.
Catalyzer provided by the invention is applicable to all kinds of hydrogenation processes that hydrocarbon raw material is carried out, when catalyzer contains this class lytic activity component of molecular sieve, be specially adapted to have hydrocracking reaction than the hydrocarbon fraction hydrocarbons raw oil of lower boiling and lower molecular weight with production.Described hydrocarbon raw material can be various heavy mineral oils or synthetic oil or their mixed fraction oil, as straight run gas oil (straight run gasoil), vacuum gas oil (vacuum gas oil), metal removal oil (demetallized oils), long residuum (atmospheric residue), diasphaltene vacuum residuum (deasphalted vacuumresidue), coker distillate (coker distillates), catalytic cracking distilled oil (catc rakerdistillates), shale oil (shale oil), asphalt sand oil (tar sand oil), liquefied coal coil (coal liquid) etc.
To the present invention be described by embodiment below.
Agents useful for same among the embodiment except that specifying, is chemically pure reagent.
Embodiment 1
The method of the invention provides and the catalyzer that is prepared by the present invention are described.
With SB powder (pseudo-boehmite, German Sasol company product) 251.0 grams, (silica-alumina, German Sasol company product consists of: SiO Siral 40
239.6%, Al
2O
360.3%) 375.3 grams, beta molecular sieve (SiO
2/ Al
2O
3=13.7, Chang Ling catalyst plant product) 19.1 grams mix, extruded moulding, wet bar is in 120 ℃ of dryings 4 hours, 650 ℃ of following roastings 3 hours obtain carrier Z1.110.5 gram carrier Z1 are placed reactor, add the aqueous solution of 150 milliliters of fluorine-containing ammonium silicate 7.75 grams, sealing was also reacted 5 hours under 150 ℃.Filtering the wet bar in back dried 6 hours down in 105 ℃, obtain fluorine-containing carrier Z1, ammonium metawolframate 46.1 restrains with containing, 95 milliliters of fluorine-containing carrier Z1 of dipping of the aqueous solution of nickelous nitrate 45.2 grams, and wet afterwards bar was dried 3 hours down in 120 ℃, 450 ℃ of following roastings 3 hours obtain catalyst A.The composition of catalyst A is listed in the table 1.
Embodiment 2
The method of the invention provides and the catalyzer that is prepared by the present invention are described.
With CL powder (pseudo-boehmite, Chang Ling catalyst plant product descend together) 251.0 grams, USY molecular sieve (a
024.45
, CR 78.4%, Na
2O 0.21%, down with) 19.1 grams mix, extruded moulding, wet bar is in 120 ℃ of dryings 4 hours, 650 ℃ of following roastings 3 hours obtain carrier Z2.109.7 gram carrier Z2 are placed reactor, add the aqueous solution of 150 milliliters of fluorine-containing ammonium silicate 7.75 grams, sealing was also reacted 5 hours under 90 ℃.Filtering the back washs 2 times with 1000 ml deionized water, wet bar was dried 6 hours down in 105 ℃, 400 ℃ of following roastings 1 hour, obtain fluorine-containing carrier Z2, with 103 milliliters of fluorine-containing carrier Z2 of dipping of the aqueous solution that contains ammonium metawolframate 46.1 grams, nickelous nitrate 45.2 grams, wet afterwards bar is in 120 ℃ of oven dry 3 hours down, and 450 ℃ of following roastings 3 hours obtain catalyst B.The composition of catalyst B is listed in the table 1.
Comparative Examples 1
Reference method and the catalyzer that is prepared by the reference method are described.
With CL powder 251.0 gram, USY molecular sieve 19.1 grams mix, extruded moulding, and wet bar is in 120 ℃ of dryings 4 hours, and 650 ℃ of following roastings 3 hours obtain carrier N.Restrain carriers N2 hour with 150 milliliters of dippings of the aqueous solution that contains 9.8 gram Neutral ammonium fluorides 110.5 under the room temperature.Wet bar is in 105 ℃ of oven dry 6 hours down, and 450 ℃ of following roastings 1 hour obtain fluorine-containing carrier N, with 105 milliliters of fluorine-containing carrier N of dipping of the aqueous solution that contains ammonium metawolframate 46.1 grams, nickelous nitrate 45.2 grams, wet afterwards bar is in 120 ℃ of oven dry 3 hours down, and 400 ℃ of following roastings 3 hours obtain catalyst B N.The composition of catalyst B N is listed in the table 1.
Embodiment 3
The method of the invention provides and the catalyzer that is prepared by the present invention are described.
With CL powder (pseudo-boehmite, Chang Ling catalyst plant product descend together) 234.7 grams, USY molecular sieve (a
024.45
, CR 78.4%, Na2O 0.21%, down with) 37.7 grams mix, extruded moulding, wet bar is in 120 ℃ of dryings 4 hours, 650 ℃ of following roastings 3 hours obtain carrier Z 3.110.5 gram carrier Z3 are placed reactor, add the aqueous solution of 150 milliliters of fluorine-containing ammonium silicate 17.0 grams, sealing was also reacted 6 hours under 75 ℃.Filter the wet bar in back in 105 ℃ of oven dry 6 hours down, 450 ℃ of following roastings 1 hour obtain fluorine-containing carrier Z3, with 97 milliliters of fluorine-containing carrier Z3 of dipping of the aqueous solution that contains ammonium metawolframate 46.1 grams, nickelous nitrate 45.2 grams, wet afterwards bar is in 120 ℃ of oven dry 3 hours down, and 450 ℃ of following roastings 3 hours obtain catalyzer C.The composition of catalyzer C is listed in the table 1.
Embodiment 4
The method of the invention provides and the catalyzer that is prepared by the present invention are described.
With the CL powder (pseudo-boehmite, Chang Ling catalyst plant product, down with) 251.0 grams, SD powder (pseudo-boehmite, Shandong Aluminum Plant's product) 107.8 grams mix, extruded moulding, wet bar is in 120 ℃ of dryings 4 hours, 650 ℃ of following roastings 3 hours obtain carrier Z4.110.5 gram carrier Z4 are placed reactor, add the aqueous solution of 150 milliliters of fluorine-containing ammonium silicate 17.8 grams, sealing was also reacted 3 hours under 150 ℃.Filtering the back washs 2 times with 1000 ml deionized water, wet bar was dried 6 hours down in 105 ℃, 430 ℃ of following roastings 3 hours, obtain fluorine-containing carrier Z4, with 91 milliliters of fluorine-containing carrier Z4 of dipping of the aqueous solution that contains ammonium metawolframate 46.1 grams, nickelous nitrate 45.2 grams, wet afterwards bar is in 120 ℃ of oven dry 3 hours down, and 450 ℃ of following roastings 3 hours obtain catalyzer D.The composition of catalyzer D is listed in the table 1.
Embodiment 5
The method of the invention provides and the catalyzer that is prepared by the present invention are described.
With CL powder (pseudo-boehmite, Chang Ling catalyst plant product descend together) 251.0 grams, USY molecular sieve (a
024.45
, CR 78.4%, Na
2O 0.21%, down with) 19.1 grams mix, extruded moulding, wet bar is in 120 ℃ of dryings 4 hours, 650 ℃ of following roastings 3 hours obtain carrier Z5.110.5 gram carrier Z5 are placed reactor, add 150 milliliters of aqueous solution that contain ammonium titanium fluoride 17.3 grams, sealing was also reacted 1 hour under 160 ℃.Filtering the wet bar in back dried 6 hours down in 105 ℃, 350 ℃ of following roastings 3 hours, obtain fluorine-containing carrier Z5, with 104 milliliters of fluorine-containing carrier Z5 of dipping of the aqueous solution that contains ammonium metawolframate 46.1 grams, nickelous nitrate 45.2 grams, wet afterwards bar was dried 3 hours down in 120 ℃, 450 ℃ of following roastings 3 hours obtain catalyzer E.The composition of catalyzer E is listed in the table 1.
Embodiment 6
The method of the invention provides and the catalyzer that is prepared by the present invention are described.
With CL powder (pseudo-boehmite, Chang Ling catalyst plant product descend together) 251.0 grams, USY molecular sieve (a
024.45
, CR 78.4%, Na 2O 0.21%, down with) 19.1 grams mix, extruded moulding, wet bar is in 120 ℃ of dryings 4 hours, 650 ℃ of following roastings 3 hours obtain carrier Z6.110.5 gram carrier Z6 are placed reactor, add 150 milliliters of aqueous solution that contain ammonium titanium fluoride 10.9 grams, sealing was also reacted 4 hours under 95 ℃.Filtering the back washs 1 time with 500 ml deionized water, wet bar was dried 6 hours down in 105 ℃, 300 ℃ of following roastings 5 hours, obtain fluorine-containing carrier Z6, with 101 milliliters of fluorine-containing carrier Z6 of dipping of the aqueous solution that contains ammonium metawolframate 46.1 grams, nickelous nitrate 45.2 grams, wet afterwards bar is in 120 ℃ of oven dry 3 hours down, and 450 ℃ of following roastings 3 hours obtain catalyzer F.The composition of catalyzer F is listed in the table 1.
Table 1
| Example | Catalyzer | The heavy % of aluminum oxide | The heavy % of silica-alumina | The heavy % of molecular sieve | The heavy % of NiO | WO 3Heavy % | The heavy % of F |
| 1 | A | 24 | 39 | 2 | 7 | 25 | 3 |
| 2 | B | 59.7 | / | 5.3 | 7 | 25 | 3 |
| Comparative Examples 1 | BN | 59.6 | / | 5.3 | 7 | 25 | 3.1 |
| 3 | C | 51.5 | / | 9.8 | 7 | 25 | 6.7 |
| 4 | D | 61.0 | / | / | 7 | 25 | 7.0 |
| 5 | E | 57.3 | / | 5.1 | 7 | 25 | 5.6 |
| 6 | F | 59.4 | / | 5.1 | 7 | 25 | 3.5 |
Embodiment 7
The performance that the invention provides catalyzer is described.
Raw material oil properties: density (20 ℃) 0.9198g/cm3, N:776 μ g/g, initial boiling point, 298 ℃, 10%, 377 ℃, 50%, 468 ℃, 90%, 511 ℃, FBP, 570 ℃.
Evaluating catalyst method: the particle that catalyst B is broken into diameter 0.5-1.0 millimeter, in 20 milliliters of small stationary bed bioreactors, pack into 20 milliliters of this catalyzer, before the logical oil, catalyzer is at first at hydrogen dividing potential drop 8.0MPa, sulfuration is 28 hours under 300 ℃ of conditions, afterwards at hydrogen dividing potential drop 14.0MPa, volume space velocity 0.75h
- 1, hydrogen-oil ratio 900v/v, temperature of reaction is 395 ℃ and feeds stock oil down, reacts sampling after 8 hours, the sample underpressure distillation.Calculate turnover ratio and intermediate oil selectivity by following relation, the results are shown in Table 2.
Transformation efficiency=[(in the raw material＞350 ℃ of yield-products in＞350 ℃ of yields)/raw material in＞350 ℃ of yields] * 100%
Intermediate oil selectivity=[(132 ℃～371 ℃ product yields)/＜371 ℃ of product yields] * 100%
Comparative Examples 2
Adopt with embodiment 7 identical stock oils and method and estimate reference catalyst BN, the results are shown in Table 2.
Table 2
| Embodiment | Catalyzer | Transformation efficiency % | Selectivity % |
| 7 | B | 38.46 | 89.31 |
| Comparative Examples 2 | BN | 28.57 | 88.6 |
The result that table 2 provides shows, compares with reference catalyst, is obviously improved by the activity of such catalysts that the invention provides the method preparation.
Claims (12)
1. fluorine-containing hydrogenization catalyst preparation method, this method is included in and introduces fluorine and hydrogenation active metals component in the carrier, it is characterized in that, it is under 60-250 ℃ and the air tight condition that the method for described introducing fluorine is included in temperature, carrier is contacted 0.5-5 hour with a kind of solution of fluorochemicals, with the catalyzer is benchmark, and it is 0.5-25 weight % that the concentration of the solution of described fluorochemicals and consumption make the content of fluorine in the final catalyzer.
2. method according to claim 1 is characterized in that described fluorochemicals is selected from HF, NH
4F, (NH
4)
2SiF
6, (NH
4)
2ZrF
6, (NH
4)
2TiF
6, (NH
4)
2AlF
6, C
6H
5In F, the gifblaar poison one or more.
3. method according to claim 2 is characterized in that, described fluorochemicals is (NH
4)
2SiF
6, (NH
4)
2AlF
6Or (NH
4)
2TiF
6
4. method according to claim 1 is characterized in that the solution of described fluorochemicals is the aqueous solution, is benchmark with the catalyzer, and it is 0.5-10 weight % that the concentration of described solution and consumption make the content of fluorine in the final catalyzer.
5. method according to claim 1 is characterized in that, described temperature is 85-150 ℃, and the time is 0.5-3 hour.
6. method according to claim 1 is characterized in that described carrier contains heat-resistant inorganic oxide, is benchmark with the catalyzer, and the content of described heat-resistant inorganic oxide is 5-90 weight %.
7. method according to claim 6 is characterized in that, described heat-resistant inorganic oxide is aluminum oxide, aluminium oxide-silicon oxide or its mixture, is benchmark with the catalyzer, and its content is 40-80 weight %.
8. method according to claim 1 is characterized in that described carrier contains molecular sieve, is benchmark with the catalyzer, and the content of described molecular sieve is 0.5-85 weight %.
9. method according to claim 8 is characterized in that, one or more the mixture of described molecular screening in Y zeolite, beta zeolite, ZSM-5 is benchmark with the catalyzer, and the content of described molecular sieve is 1-40 weight %.
10. method according to claim 1 is characterized in that, described hydrogenation active metals component is selected from iron, cobalt or nickel and at least a molybdenum or the tungsten that is selected from group vib of at least a group VIII.In oxide compound and with the catalyzer is benchmark, and the content of group vib metal component is 5-40 weight %, and the content of group VIII metal component is 1-10 weight %.
11. method according to claim 10 is characterized in that, the content of described group vib metal component is 10-36 weight %, and the content of group VIII metal component is 1-8 weight %.
12. a fluorine-containing hydrogenation catalyst, this catalyzer contain carrier, auxiliary agent fluorine and hydrogenation active metals component, described catalyzer is according to any described method preparation among the claim 1-11.
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| CN1302847A (en) * | 2000-01-04 | 2001-07-11 | 中国石油化工集团公司 | Catalyst for hydrotransforming diesel oil and its preparing process |
| CN1470608A (en) * | 2003-07-01 | 2004-01-28 | 中国石油天然气集团公司 | Molecular sieve containing catalyst for deep hdyrogenation of middle distillate and its preparing method |
| CN101020903A (en) * | 2007-01-24 | 2007-08-22 | 中国农业科学院油料作物研究所 | Left boundary flanking sequence of exogenous event inserting vector for transgenic rape Oxy-235 and its application |
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