CN101157056A - Hydrogenation catalysts carrier with nickel and cobalt, hydro-catalyst and its preparing method - Google Patents
Hydrogenation catalysts carrier with nickel and cobalt, hydro-catalyst and its preparing method Download PDFInfo
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Abstract
The invention provides a carrier of pre-impregnating metal components, and hydrotreating catalyst containing the carrier, wherein carrier materials are Al 2 O 3, SiO 2, TiO 2, and a composite oxide of two of the Al 2 O 3, the SiO 2, and the TiO 2 which are prepared by a sol-gel method, a certain amount of molecular sieve is added into the carrier, saline solution containing nickel and cobalt is inducted in the process of the carrier materials prepared by a sol method, in order that the content of NiO and CoO in the carrier is 0.1 to 5 wt percent, the specific surface area of the obtained carrier containing the nickel or the cobalt is in 250 to 400 m <2> * g <-1>, and the pore volume is in 0.5 to 1.0 ml * g <-1>. The invention also provides a preparation method for the catalyst, group 6B metals and group 8 metals are taken as active components, the adoption of an equivalent-volumetric impregnation method produces the petroleum fraction hydrotreating catalyst, and the catalyst of the invention has excellent activity of hydrogen desulfurization and hydrodenitrification.
Description
Technical field
The invention provides a kind of in carrier pre-preg nickel or cobalt catalyst carrier for hydrgenating, contain the Catalysts and its preparation method of the carrier of this pre-preg nickel or cobalt.Specifically, be to prepare in the process of carrier at sol-gel, the metal active constituent nickel of catalyst or the part of cobalt are incorporated in the preparing carriers system, form the novel pre-preg nickel or the carrier of cobalt, metal component nickel or the existence of cobalt in carrier had so both been changed, improved the interaction between carrier and other metal components again, the dispersiveness and the curability of metal component have been improved, thereby making the hydrogenation catalyst of the carrier that contains this pre-preg nickel or cobalt, hydrogenation catalyst of the present invention has good hydrodesulfurization and hydrodenitrogeneration performance to petroleum distillate.
Background technology
Aggravation along with crude oil heaviness, inferiorization trend in the world wide, the ratio of inferior heavy oil constantly increases, the light-end products that effectively inferior heavy oil are processed as cleaning are cores of oil Refining Technologies development, and hydrotreatment then is the most effectively one of technology of cleaning Oil Production.
The key of decision hydrotreatment technical merit is the catalyst performance level, especially the inferior heavy oil hydrotreating catalyst requires that good hydrodesulfurization, hydrodenitrogeneration and arene saturating activity are arranged, and this just requires the metal active constituent of catalyst at carrier surface good dispersiveness and dispersion stabilization to be arranged.But the method for preparing catalyst that generally adopts both at home and abroad adopts solution dipping method that active metal component is supported on the carrier exactly at present, obtains corresponding catalyst by steps such as oven dry, roastings then.Though this preparation method is easy to implement, be unfavorable for the further raising of catalyst performance.This is because the capillarity of carrier micropore, makes metal impregnation liquid stop up the micropore of carrier, has both reduced the dispersiveness of metal component, has reduced the specific area and the pore volume of catalyst again; Unfavorable interaction has caused the degree of scatter of metal component not high between carrier and metal component, is difficult for forming the active phase of sulphided state.
Reunion, the dispersiveness that improves metal component and curability between the interaction between modulation carrier and metal active constituent for this reason,, inhibition metallic particles are the effective ways that promote catalyst performance.Carry out extensive work both at home and abroad in this regard, obtained certain effect.
CN1916120 discloses a kind of hydrotreating catalyst of heavy distillate, this catalyst is a carrier with the Ti-Si composite oxide that contains molecular sieve, prepared a kind of hydrotreating catalyst with solution dipping method, this catalyst has higher hydrodesulfurization and hydrodenitrogeneration reactivity.
EP0181693 has related to a kind of hydrotreating catalyst that contains chromium and preparation method thereof, this method is impregnated into the chromium component on the carrier earlier, after the carrier oven dry roasting, again metal active constituent is impregnated on the carrier, the catalyst that this method prepares has been regulated interaction between metal active constituent and the carrier by chromium, promoted highly active activity to form mutually, so catalyst have higher hydrodenitrogeneration performance.But this method is because through repeatedly roasting, cause the specific area of carrier and the decline of pore volume, and the hydrodesulfurization performance of catalyst improves and is not obvious, uses the catalyst of this method preparation simultaneously because the adding of the third non-hydrogenation activity component chromium has also improved catalyst production cost to a certain extent.
It is hydrotreating catalyst of carrier and preparation method thereof that RU2246987 has related to a kind of aluminium oxide or silica with the titanium oxide modification.This method is introduced titanium elements by the method by solution impregnation in aluminium oxide or silica support, can bring into play the effect of titanium in hydrogenation process, improved the dispersiveness of metal, promoted the formation of metal active phase, prepared catalyst has higher hydrodesulfurization activity.But because in the Preparation of catalysts process, unavoidably have aluminium oxide and nickle atom is had an effect, generate SA nickel aluminate structure, be unfavorable for the giving full play to of hydrogenation activity of metal active constituent on the catalyst; And, can not give full play to the effect of titanium oxide in hydrogenation catalyst because the introducing mode of titanium elements causes the content of titanium oxide in catalyst can be very not high.
The common feature of above-mentioned method for preparing catalyst is to have introduced the inactive metal component in carrier or catalyst, and the corresponding problem that this class preparation method brings is specific area and the pore volume that has increased the consumption of metal component or reduced catalyst.
Summary of the invention
The objective of the invention is to develop a kind of catalyst preparation technology of carrier pre-preg metal component, comprise a kind of novel pre-preg nickel of exploitation or the carrier of cobalt, this carrier is through flooding the preparation catalyst altogether, make this catalyst that good metal dispersiveness and curability be arranged, be applicable to the hydrofinishing of petroleum distillate, especially heavier petroleum fraction had good hydrodesulfurization and hydrodenitrogeneration performance.
Characteristics of the present invention are the pre-preg technology that adopt in the forming process of oxide carrier, the part of catalyst activity metallic nickel or cobalt consumption is incorporated in the carrier system, make the metal component high degree of dispersion, for hydrofining reaction provides more metal active center; Avoided the influence of the introducing of other metal components simultaneously, and reduced the consumption of metal component the catalyst performance generation.
The method for preparing catalyst that the present invention proposes can be incorporated into metal active constituent in the structure of oxide carrier, make firm being fixed on the carrier structure of metallic or atom, improved the stability of the anti-sintering of metal component, made the preparation carrier have bigger specific area and pore volume; Simultaneously, the metal modulation of pre-preg in the carrier interaction between carrier and metal component, improved the dispersion and the curability of metal component.
In the catalyst provided by the invention, carrier is the conventional catalyst carrier for hydrgenating that adopts the sol-gel method preparation, comprises Al
2O
3, SiO
2, TiO
2Or composite oxides of the two wherein, under the situation of needs, in carrier, can also add the molecular sieve that is no more than carrier gross weight 40wt%, preferred Y zeolite; Metal component in the catalyst of the present invention mainly is the W of group vib or the Ni or the Co of Mo and VIII family, and wherein the content of group vib metal oxide in catalyst is 10～30wt%, the content 1～10wt% of group VIII metal oxide.
The invention provides a kind of catalyst carrier for hydrgenating that contains nickel or cobalt, wherein, this carrier contains NiO or the CoO with the total restatement 0.1～5wt% of carrier.
The carrier that contains nickel or cobalt of the present invention comprises the Al of sol-gel process preparation for adopting the carrier of sol-gel process preparation
2O
3, SiO
2, TiO
2Or composite oxides of the two wherein, preferably in this carrier, also comprise the molecular sieve that is no more than 40wt% with the total restatement of carrier.Above-mentioned carrier can be by preparing in sol-gel process in the process of carrier, especially adds the salt that contains nickel or cobalt in the step before obtaining colloidal sol, again through wearing out, obtaining after the drying; Prepared its specific area of catalyst carrier for hydrgenating of nickel or cobalt that contains is at 250～400m
2G
-1Between, pore volume is 0.5～1.0mlg
-1Between.
Compare with the carrier of prior art, the specific area of above-mentioned carrier of the present invention and pore volume all increase to some extent.
The present invention also provide a kind of in carrier the hydrogenation catalyst of pre-preg active metal component, this catalyst has comprised the above-mentioned catalyst carrier for hydrgenating that contains nickel or cobalt.
In hydrogenation catalyst of the present invention, with the total restatement of this catalyst, comprised the group vib metal oxide of 10～30wt%, the group VIII metal oxide of 1～10wt%; Described group vib metal is tungsten or molybdenum, and described group VIII metal is nickel or cobalt.
The present invention also provides above-mentioned hydrogenization catalyst preparation method, comprising:
(1) adopt sol-gel method to prepare carrier, added the salt that contains nickel or cobalt before obtaining the step of colloidal sol, make dried carrier contain NiO or the CoO with the total restatement 0.1～5wt% of carrier, described carrier comprises Al
2O
3, SiO
2, TiO
2Or composite oxides of the two wherein;
(2) 400～800 ℃ of roastings of dried carrier obtain carrier material;
(3) salt with a certain amount of group vib and group VIII metal joins in the deionized water, obtain mixed solution H, a certain amount of carrier material of weighing, adopt the equal-volume co-impregnation that Solution H is impregnated on the carrier material, 100～150 ℃ of oven dry, 400～800 ℃ of roastings obtain above-mentioned hydrogenation catalyst.
In above-mentioned preparation method of the present invention, joining " salt of a certain amount of group vib and group VIII metal " in the deionized water and be in the catalyst gross weight is 100%, the group vib metal oxide that comprises 10～30wt% according to catalyst, the ratio of the group VIII metal oxide of 1～10wt% will join in the deionized water with the group vib of the proportional quantity after this ratio conversion and the salt of group VIII metal.
In preparation method of the present invention, the salt of group VIII metal is soluble salt, comprises nickel nitrate, nickelous carbonate, nickel acetate, cobalt nitrate, cobalt acetate; The salt of group vib metal (soluble salt) comprises ammonium metatungstate, ethyl ammonium metatungstate, metatungstic acid nickel, ammonium heptamolybdate, ammonium tetramolybdate, ammonium paramolybdate, ammonium dimolybdate.
In a preferred embodiment of the invention, hydrogenation catalyst is the catalyst that contains molecular sieve/complex carrier, preferably contains Y molecular sieve, more preferably contains the TiO of Y molecular sieve
2-SiO
2Complex carrier.The TiO that contains Y molecular sieve with preparation
2-SiO
2Complex carrier is an example, and concrete preparation method is as follows:
(1) molecular sieve is distributed in the ethanolic solution, obtains solution A; The salt that will contain titanium and silicon or titanium and aluminium be dissolved in respectively evenly mix again after the solution A solution B; In addition water, acetic acid and ethanol are mixed solution C, the described salt that contains titanium, silicon, aluminium is butyl titanate, ethyl orthosilicate, aluminum nitrate;
Above-mentioned steps titanium and silicon or titanium and aluminium: water: ethanol: the mol ratio of acetate is preferably 1: 1-5: 10-18: 1-3; More preferably this mol ratio is 1: 2.5: 13: 1.8;
(2) under agitation, solution C is dropwise splashed among the B react; Obtain colloidal sol behind the reaction certain hour, the aging under field conditions (factors) certain hour of colloidal sol just obtains Y/TiO
2-SiO
2Gel E;
(3) or in the solution A of step (1) preparation, add the salt of a certain amount of containing metal Ni, perhaps at the salt of a certain amount of containing metal Ni of middle adding of step (1) preparation solution C, other step is constant.
(4) gel that obtains in step (2) or the step (3) is carried out heated drying, vacuum drying or CO
2Supercritical fluid drying, the condition of heated drying are 120 ℃ of temperature, and be 2～8 hours drying time; Vacuum drying condition is 50 ℃, and vacuum is 0.1kPa, and be 2～8 hours drying time; CO
2The supercritical fluid drying condition is 40～60 ℃ of temperature, pressure 8.0～12.0MPa, 2～6 hours time, obtains carrier powder F;
(5) 400～800 ℃ of roastings of carrier powder that step (4) obtained, preferably in Muffle furnace in 400～800 ℃ of roastings 3～6 hours, obtain containing (not pre-preg Ni or pre-preg Ni) titanium-silicon composite oxide carrier material G of Y molecular sieve;
(6) be 100% in the catalyst gross weight, this catalyst comprises the group vib metal oxide of 10～30wt%, the group VIII metal oxide of 1～10wt%, to join in the deionized water with the group vib of the proportional quantity after this ratio conversion and the salt of group VIII metal, obtain mixed solution H, a certain amount of carrier G of weighing, adopt the equal-volume co-impregnation that Solution H is impregnated on the carrier G, dry then, roasting, preferably in baking oven 100～150 ℃ the oven dry 2～5 hours, 400～800 ℃ of roastings 3～6 hours just obtain needed catalyst H;
Wherein, the group VIII metal soluble salts in the above-mentioned steps is nickel nitrate, nickelous carbonate, nickel acetate, cobalt nitrate, cobalt acetate etc.; Group vib metal soluble salts is ammonium metatungstate, ethyl ammonium metatungstate, metatungstic acid nickel, ammonium heptamolybdate, ammonium tetramolybdate, ammonium paramolybdate, ammonium dimolybdate etc.
In the Preparation of catalysts method of the present invention, the preferred CO of above-mentioned drying condition
2Supercritical fluid drying, CO
2Supercritical fluid drying can help the giving full play to of hydrogenation activity of metal active constituent on the catalyst so that dry back carrier is avoided producing or forming SA nickel aluminate structure in the process of preparation catalyst.And prior art RU2246987 for example, the inapplicable CO of its preparation condition
2Supercritical fluid drying, and by introduce titanium in carrier, not only increased cost because of additionally having added Titanium also has certain SA nickel aluminate structure and forms, and is unfavorable for the giving full play to of hydrogenation activity of metal active constituent on the catalyst.
The above-mentioned catalyst that has comprised the catalyst carrier for hydrgenating that contains nickel or cobalt of the present invention and prior art for example CN1916120 are compared, greatly improve the dispersiveness of reactive metal in carrier to a certain extent, avoided metal to support in the process that catalyst duct that the gathering owing to reactive metal causes is stopped up and the problem of specific area decline; And compare with the EP0181693 that relates to " a kind of hydrotreating catalyst that contains chromium and preparation method thereof ", it at first is the use that has reduced the third metal, avoided the obstruction in the catalyst duct that too much metal loading causes and the decline of specific area, the catalyst that the present invention simultaneously makes has reduced production cost; Secondly, production technology of the present invention has reduced the bakes to burn the article process, has also reduced the adverse effect that roasting brings the specific area and the pore volume of catalyst to a certain extent; It is compared with the RU2246987 that has related to " a kind of aluminium oxide or silica with the titanium oxide modification is hydrotreating catalyst of carrier and preparation method thereof ", because the present invention adopts the mode of collosol and gel to prepare catalyst carrier, can greatly improve the content of titanium oxide in carrier, give full play to the effect of titanium oxide in hydrogenation catalyst, improve the dispersiveness of metal, in the sulfidation of catalyst, impel the generation of high activity sulphided state metal, improve the hydrogenation reaction activity of catalyst.Simultaneously, in the preparing carriers process, adopt the mode of pre-preg to support the part active metal component, improve the decentralization of metal component, can avoid in catalyst preparation process owing to the not high formation that causes nickel aluminate of nickle atom dispersiveness.
The specific embodiment
Further set forth characteristics of the present invention below by embodiment, but not thereby limiting the invention.
The preparation of embodiment 1,2 explanation carrier matrix materials, the preparing carriers method of two kinds of pre-preg Ni of embodiment 3～9 explanations, embodiment 10 explanation Preparation of catalysts methods.
Comparing embodiment 1
The ethyl orthosilicate of 109.2g butyl titanate and 16.8g is dissolved in respectively behind the ethanol of 72ml solution A; With 19ml water, 41.2ml acetic acid and 40ml absolute ethyl alcohol mix solution B; Solution B is dropwise splashed among the A, and stirring reaction 10～30min obtains colloidal sol, the aging under field conditions (factors) gel that just obtains of colloidal sol; Gel is through CO
2Supercritical fluid drying obtains white powder; 500～600 ℃ of roastings of white powder 3 hours obtain TiO
2-SiO
2Composite carrier A-1, specific area and pore volume, aperture that the method for employing BET records this sample are respectively: SBET=282m
2G
-1, V=0.82mlg
-1, D=14.6nm.
Comparing embodiment 2
The ethyl orthosilicate of 109.2g butyl titanate and 16.8g is dissolved in respectively behind the ethanol of 72ml solution A; With 3g HY molecular sieve dispersed with stirring in solution A, with 19ml water, 41.2ml acetic acid and 40ml absolute ethyl alcohol mix solution B; Solution B is dropwise splashed among the A, and stirring reaction 10～30min obtains colloidal sol, the aging under field conditions (factors) gel that just obtains of colloidal sol; Gel is through CO
2Supercritical fluid drying obtains white powder; White powder 500～600 ℃ of roastings 3 hours obtain HY content and are 10% TiO
2-SiO
2Composite carrier A-2, specific area and pore volume, aperture that the method for employing BET records this sample are respectively: S
BET=280m
2G
-1, V=0.80mlg
-1, D=11.4nm.
Embodiment 3
The 2g nickel nitrate is dissolved in the ethanol of 72ml, obtains solution A; The ethyl orthosilicate of 109.2g butyl titanate and 16.8g is added in the solution A, and with 3g HY molecular sieve dispersed with stirring in solution A, evenly mix solution B; With 19ml water, 41.2ml acetic acid and 40ml absolute ethyl alcohol mix solution C.Solution C added dropwise stirring reaction 10～30min obtains colloidal sol among the B, the aging under field conditions (factors) certain hour of colloidal sol just obtains gel; Gel drying and roasting condition obtain containing the carrier material B-1 of NiO 1% with embodiment 1, and specific area, pore volume, aperture that the method for employing BET records this sample are respectively SBET=321m2g-1, V=0.72mlg-1, D=9.0nm.
Embodiment 4
The ethyl orthosilicate of 109.2g butyl titanate and 16.8g is dissolved in respectively in the ethanol of 72ml, gets solution A; 3g HY molecular sieve dispersed with stirring in solution A, is obtained solution B; The 2g nickel nitrate is dissolved in the ethanol of 40ml and obtains green solution C; With water, the 41.2ml acetic acid of 19ml mix with solution C solution D.Solution D splashed into dropwise stirring reaction 10～30min obtains colloidal sol among the A, the aging under field conditions (factors) certain hour of colloidal sol just obtains gel; Gel drying and roasting condition obtain containing the carrier material C-1 of NiO 1% with embodiment 1, and specific area, pore volume, aperture that the method for employing BET records this sample are respectively: SBET=328m2g-1, V=0.73mlg-1, D=8.9nm.
Embodiment 5
The quality of the nickel nitrate among the embodiment 2 is become 4g, all the other steps and preparation condition are constant, make the carrier B-2 that contains NiO 2%, and specific area and pore volume, aperture that the method for employing BET records this carrier material are respectively: SBET=321m2g-1, V=0.71mlg-1, D=8.5nm.
Embodiment 6
2g nickel nitrate among the embodiment 2 is become the 6g cobalt nitrate, all the other steps and reaction condition are constant, make the carrier B-3 that contains CoO 3%, and specific area and pore volume, aperture that the method for employing BET records this carrier material are respectively: SBET=296m2g-1, V=0.63mlg-1, D=8.4nm.
Embodiment 7
The quality of the nickel nitrate among the embodiment 2 is become 8g, all the other steps and reaction condition are constant, make the carrier B-4 that contains NiO 4%, and specific area and pore volume, aperture that the method for employing BET records this carrier material are respectively: SBET=292m2g-1, V=0.55mlg-1, D=6.8nm.
Embodiment 8
The quality of the nickel nitrate among the embodiment 3 is become 4g, and all the other steps and reaction condition are constant, make the support C-2 that contains NiO 2%, adopt the method for BET to record the specific area of this carrier material and pore volume, aperture, be respectively: SBET=338m2g-1, V=0.74mlg-1, D=9.0nm.
Embodiment 9
2g nickel nitrate among the embodiment 3 is become the 6g cobalt nitrate, and all the other steps and reaction condition are constant, make the support C-3 that contains CoO 3%, adopt the method for BET to record the specific area of this carrier material and pore volume, aperture, be respectively: SBET=309m2g-1, V=0.76mlg-1, D=9.8nm.
Embodiment 10
The quality of the nickel nitrate among the embodiment 3 is become 8g, and all the other steps and reaction condition are constant, make the support C-4 of NiO 4%, adopt the method for BET to record the specific area of this carrier material and pore volume, aperture, be respectively: SBET=300m2g-1, V=0.64mlg-1, D=8.5nm.
Embodiment 11
Present embodiment is introduced Preparation of catalysts process and activity rating process.
Adopt equi-volume impregnating, all the other metal components are loaded on the carrier.WO3 content is 24wt% in the catalyst of present embodiment preparation, a NiO part joins in the carrier by the foregoing description in the mode of pre-preg, remainder is supported on the carrier in the mode of routine dipping, and the total content of NiO in the catalyst (or CoO) is defined as 4% at present embodiment.Be about to the 11.5g ammonium metatungstate and be dissolved in the 30ml water,, will remain the Ni (NO after NiO (or CoO) converts based on the content of pre-preg NiO (or CoO) in the different carriers
3)
2(or Co (NO
3)
2) join and make common maceration extract in the ammonium metatungstate solution, at room temperature will be total to maceration extract and be added drop-wise in the carrier, behind 120 ℃ of oven dry 3h, 500 ℃ of roasting 3h, make catalyst then.
With Liaohe River wax tailings is raw material (nitrogen content is 4000 μ gg-1, and sulfur content is 2402 μ gg-1), the comparative evaluation hydrodesulfurization and the denitrification activity of the catalyst that makes of the foregoing description.With the cyclohexane of 2wt%CS2 is sulfuration liquid, under pressure 4.0MPa, temperature are 300 ℃, air speed 6h-1 condition, to catalyst vulcanization 4h.Catalyst to the condition of Liaohe River wax tailings hydrotreatment is: hydrogen dividing potential drop 6.0MPa, 380 ℃ of temperature, air speed 1.0h-1, hydrogen/oil volume are than 1000, and reaction back oil sample carries out sulphur, analysis of nitrogen content, the results are shown in Table 1.
The evaluation of table 1 activity of such catalysts
| Embodiment | Catalyst | Sulfur content/μ gg-1 | HDS/％ | Nitrogen content/μ gg-1 | HDN/％ |
| 1 | A1 | 227 | 91.4 | 2289 | 42.9 |
| A2 | 204 | 91.5 | 2132 | 46.7 | |
| 2 | B1 | 74 | 96.9 | 878 | 78.1 |
| 4 | B2 | 77 | 96.7 | 748 | 81.2 |
| 5 | B3 | 100 | 95.9 | 1050 | 73.8 |
| 6 | B4 | 92 | 96.2 | 1002 | 75.0 |
| 3 | C1 | 85 | 96.5 | 982 | 75.5 |
| 7 | C2 | 86 | 96.4 | 995 | 75.1 |
| 8 | C3 | 72 | 97.0 | 1120 | 73.3 |
| 9 | C4 | 74 | 96.9 | 1054 | 73.7 |
As can be seen from Table 1: the catalyst that adopts the preparation of pre-preg technology and the carrier not catalyst that makes of impregnating metal are compared, and have shown good hydrodesulfurization activity and hydrodenitrogenationactivity activity.Therefore, catalyst provided by the invention is applicable to the hydrotreatment process of petroleum distillate, is particularly useful for the hydrotreatment process of heavy distillate.
Claims (9)
1. the catalyst carrier for hydrgenating of a nickeliferous or cobalt wherein, is 100% in the carrier gross weight, and this carrier contains NiO or the CoO of 0.1～5wt%.
2. catalyst carrier for hydrgenating as claimed in claim 1, wherein, the specific area of this carrier is 250～400m
2G
-1, pore volume is 0.5～1.0mlg
-1
3. catalyst carrier for hydrgenating as claimed in claim 1, wherein, this carrier is by adopting sol-gel process to prepare in the process of carrier, added the salt that contains nickel or cobalt before obtaining colloidal sol, through what wear out, obtain after the drying, described carrier comprises Al again
2O
3, SiO
2, TiO
2Or composite oxides of the two wherein.
4. catalyst carrier for hydrgenating as claimed in claim 1 wherein, is 100% in the carrier gross weight, also comprises the molecular sieve that is no more than 40wt% in this carrier.
5. hydrogenation catalyst, wherein, this catalyst comprises each described carrier of claim 1-4.
6. hydrogenation catalyst as claimed in claim 5 wherein, is 100% in this catalyst gross weight, and this catalyst comprises the group vib metal oxide of 10～30wt%, the group VIII metal oxide of 1～10wt%; Described group vib metal is tungsten or molybdenum, and described group VIII metal is nickel or cobalt.
7. claim 5 or 6 described hydrogenization catalyst preparation method, comprising:
(1) adopt sol-gel process to prepare carrier, added the salt that contains nickel or cobalt before obtaining the step of colloidal sol, make dried carrier contain NiO or the CoO with the total restatement 0.1～5wt% of carrier, described carrier comprises Al
2O
3, SiO
2, TiO
2Or composite oxides of the two wherein;
(2) dried carrier obtains carrier material with 400～800 ℃ of roastings;
(3) salt with group vib and group VIII metal joins in the deionized water, obtains mixed solution H, adopts the equal-volume co-impregnation that Solution H is impregnated on the carrier material, 100～150 ℃ of oven dry, and 400～800 ℃ of roastings obtain above-mentioned hydrogenation catalyst.
8. preparation method as claimed in claim 7, wherein, the salt of group VIII metal comprises nickel nitrate, nickelous carbonate, nickel acetate, cobalt nitrate, cobalt acetate; The salt of group vib metal comprises ammonium metatungstate, ethyl ammonium metatungstate, metatungstic acid nickel, ammonium heptamolybdate, ammonium tetramolybdate, ammonium paramolybdate, ammonium dimolybdate.
9. preparation method as claimed in claim 7 wherein, is 100% in this carrier gross weight, and described carrier is the TiO that contains the molecular sieve that is no more than 40wt%
2-SiO
2Perhaps TiO
2-Al
2O
3Complex carrier, this preparation method comprises:
(1) molecular sieve is distributed in the ethanolic solution, obtains solution A; The salt that will contain titanium and silicon or titanium and aluminium be dissolved in respectively evenly mix after the solution A solution B; In addition water, acetic acid and ethanol are mixed solution C, the described salt that contains titanium, silicon, aluminium is butyl titanate, ethyl orthosilicate, aluminum nitrate;
(2) in the solution A of step (1) preparation or C, add the salt of nickel metal or cobalt;
(3) under agitation, solution C is splashed among the B react; Obtain colloidal sol afterwards, the aging under field conditions (factors) molecular sieve/TiO that obtains of colloidal sol
2-SiO
2Gel E;
(4) gel E is carried out drying, obtain carrier powder F;
(5), obtain containing the titanium silicon or the titania-alumina mixed oxide material G of molecular sieve with 400～800 ℃ of roastings of carrier powder F;
(6) be 100% in the catalyst gross weight, this catalyst comprises the group vib metal oxide of 10～30wt%, the group VIII metal oxide of 1～10wt%, to join in the deionized water with the group vib after this ratio conversion and the salt of group VIII metal, obtain mixed solution H, adopt the equal-volume co-impregnation that Solution H is impregnated on the carrier material G, then oven dry, 400～800 ℃ of roastings obtain described hydrogenation catalyst;
Wherein, the salt of VII I family metal is nickel nitrate, nickelous carbonate, nickel acetate, cobalt nitrate, cobalt acetate, and the salt of group vib metal is ammonium metatungstate, ethyl ammonium metatungstate, metatungstic acid nickel, ammonium heptamolybdate, ammonium tetramolybdate, ammonium paramolybdate, ammonium dimolybdate.
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| CN104069884A (en) * | 2014-06-20 | 2014-10-01 | 中国石油天然气集团公司 | Heavy oil hydrogenation catalyst and preparation method thereof |
| CN104549346A (en) * | 2014-12-22 | 2015-04-29 | 中国石油天然气集团公司 | Hydrotreating catalyst for petroleum fraction oil as well as preparation method and application of catalyst |
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