CN102764665B - A kind of hydrogenation catalyst of active metal component non-uniform Distribution and preparation thereof - Google Patents
A kind of hydrogenation catalyst of active metal component non-uniform Distribution and preparation thereof Download PDFInfo
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Abstract
A kind of hydrogenation catalyst of active metal component non-uniform Distribution and preparation thereof, the non-noble metal slaine that this catalyst contains shaping aqua oxidation alumina supporter, load at least one is on this carrier selected from VIII and at least one are selected from the slaine of group vib metal, wherein, along the distribution of catalyst radial section, the outer surface concentration of described group VIII metal component is 0.1-0.9 with the ratio of centre concentration; The outer surface concentration of described group vib metal component is 0.1-0.8 with the ratio of centre concentration.Compared with existing technical method, hydrogenating catalyst composition provided by the invention not only has excellent heavy oil hydrogenation demetal performance, has simultaneously and well holds metallicity.In addition, determined by its preparation method, the preparation method that the invention provides catalyst is simple, production cost is starkly lower than catalyst prepared by existing method.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst Catalysts and its preparation method.
Background technology
Not only containing the impurity such as sulphur, nitrogen in heavy oil, also containing the metal impurities such as a large amount of Ni, V, Fe, Ca and asphalitine and colloid.In the hydroprocessing processes of this type of feedstock oil, these impurity can be adsorbed in catalyst surface covering activated centre or be deposited in catalyst duct and block duct, thus cause the inactivation of catalyst.Therefore, for the appearance metal ability of the catalyst of residual hydrocracking process and coking resistivity, the direct life cycle etc. to catalyst is had an impact.
CN101768470A discloses a kind of heavy oil hydrogenating treatment catalyst, at least one containing carrier and effective dose is selected from the metal component that VIII and at least one are selected from group vib, it is characterized in that, the concentration of described group VIII metal component is non-uniform Distribution along catalyst radial section, wherein, the concentration of outer surface metal component is 0.1-0.85 with the ratio of the concentration of central metal component; The concentration of described group vib metal component is evenly distributed along catalyst radial section, and wherein, the concentration of outer surface metal component is 0.90-1.5 with the ratio of the concentration of central metal component.
CN101462080A discloses a kind of preparation method of catalyst with non-uniform distribution of active metal component, comprise at least one adopting the method for dipping to introduce effective dose on carrier and be selected from the metal component that VIII and at least one are selected from group vib, it is characterized in that, described dipping comprises the steps: that (1) order will be selected from nitric acid, phosphoric acid, oxalic acid, twist rubber acid, tartaric acid, pimelic acid, in adipic acid one or more acid be selected from the compound of metal component of at least one containing group vib, at least one is mixed into solution containing the compound of metal component of VIII and water, wherein, the ratio of the compound molal quantity sum of the molal quantity of described acid and the metal component containing group vib and the metal component containing VIII is 0.1-0.92, the consumption of described water makes the amount of final solution by volume be 0.85 η-1.1 η, η is the water absorption rate of carrier, (2) under room temperature with the mixed solution impregnated carrier that step (1) is prepared, dip time is 1-5 hour, (3) carrier after step (2) being flooded is in being greater than 60-160 DEG C of dry 2-10 hour, 400-600 DEG C roasting 2-5 hour.
US4760045 discloses a kind of heavy oil hydrogenating treatment catalyst, this catalyst contains porous refractory oxides carrier and load at least one is on this carrier selected from periodic table of elements VB, the hydrogenation active metals component of VIB and VIII, it is characterized in that, meet Cr along the distribution of metal concentration described in catalyst cross section
1< Cr
2and R
1> R
2, wherein R
1and R
2represent the ratio of distance r1 from kernel of section to respective point and r2 and the distance from kernel of section to outer surface respectively, Cr
1and Cr
2represent the concentration of the described metal component of described respective point respectively.The preparation method of this catalyst, comprising: be enough to make described hydrogenation active metals component meet Cr along the CONCENTRATION DISTRIBUTION of catalyst cross section (radial section)
1< Cr
2and R
1> R
2maceration extract A is adopted to flood described carrier under condition, separation maceration extract A, further with maceration extract B dipping, dry also roasting after being separated maceration extract B, wherein, R
1and R
2represent the ratio of distance r1 from kernel of section to respective point and r2 and the distance from kernel of section to outer surface respectively, Cr
1and Cr
2represent the concentration of the described metal component of described respective point respectively, described solution A is for being selected from periodic table of elements VB containing at least one, the aqueous solution of the hydrogenation active metals component of VIB and VIII, or be a kind ofly selected from containing active metal and at least one the anion be made up of VIIA race element, ammonium ion, nitrate ion, sulfate ion, hydroxide ion, phosphate anion borate ion and organic acid mixed liquor solution B are a kind of water or are selected from containing at least one the anion be made up of VIIA race element, ammonium ion, nitrate ion, sulfate ion, hydroxide ion, phosphate anion, borate ion and the organic acid aqueous solution, described solution B is not containing active metal component, described anion is contained at least one solution in described solution A and B.
Practical application shows, in residual hydrocracking process, and the catalyst evenly better stability in use of similar above-mentioned active metal component non-uniform Distribution.
Summary of the invention
The technical problem to be solved in the present invention is to provide hydrogenation catalyst of a kind of new active metal component non-uniform Distribution and preparation method thereof.
The present invention relates to following invention:
1. the hydrogenation catalyst of an active metal component non-uniform Distribution, the slaine that the non-noble metal slaine of VIII and at least one are selected from group vib metal is selected from containing shaping aqua oxidation alumina supporter, load at least one on this carrier, wherein, along the distribution of catalyst radial section, the outer surface concentration of described group VIII metal component is 0.1-0.9 with the ratio of centre concentration; The outer surface concentration of described group vib metal component is 0.1-0.8 with the ratio of centre concentration.
2. the catalyst according to 1, is characterized in that, along the distribution of catalyst radial section, the outer surface concentration of described group VIII metal component is 0.4-0.8 with the ratio of centre concentration; The outer surface concentration of described group vib metal component is 0.3-0.7 with the ratio of centre concentration.
3. the catalyst according to 1, is characterized in that, is benchmark with oxide basis and with catalyst, and the content of described group VIII metal is 1-8 % by weight, and the content of group vib metal is 3-20 % by weight.
4. the catalyst according to 3, is characterized in that, is benchmark with oxide basis and with catalyst, and the content of described group VIII metal is 1.5-4.5 % by weight, and the content of group vib metal is 5-18 % by weight.
5. the catalyst according to 1, is characterized in that, described hydrated alumina is selected from one or more in hibbsite, monohydrate alumina, boehmite and amorphous hydroted alumina.
6. the catalyst according to 5, is characterized in that, described hydrated alumina is boehmite.
7. the catalyst according to 1, it is characterized in that, the described non-noble metal slaine being selected from VIII is selected from one or more in the soluble complexes of the soluble complexes of cobalt nitrate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and cobalt, nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and nickel, and the slaine of described group vib metal is selected from one or more in molybdate, paramolybdate, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, ethyl metatungstate.
8. the catalyst according to 7, it is characterized in that, the described non-noble metal slaine being selected from VIII is selected from one or more in cobalt nitrate, basic cobaltous carbonate, nickel nitrate and basic nickel carbonate, and the slaine of described group vib is selected from one or more in ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, ammonium tungstate.
9. the catalyst according to 1, it is characterized in that, described shaping aqua oxidation alumina supporter is hydrated alumina and the mixture helping forming agent, the described forming agent that helps is selected from sesbania powder, starch, polyvinyl alcohol, PVOH, hydroxyethylcellulose, methyl hydroxyethylcellulose, methylcellulose, ethyl cellulose, hydroxypropyl methylcellulose, one or more replacement in hydroxypropyl methylcellulose high, with described article shaped for benchmark, described in help the content of forming agent to be 1-15 % by weight.
10. the catalyst according to 9, it is characterized in that, one or more helping forming agent to be selected from sesbania powder, PVOH, polyvinyl alcohol, hydroxypropyl methylcellulose, methylcellulose, HEMC, hydroxyethylcellulose, ethyl cellulose described, with described article shaped for benchmark, described in help the content of forming agent to be 2-10 % by weight.
The preparation method of 11. 1 kinds of hydrogenation catalysts, comprise the shaping water of preparation and alumina support load at least one on this carrier and be selected from the slaine that the non-noble metal slaine of VIII and at least one are selected from group vib metal, wherein, the method of the water that described preparation is shaping and alumina support comprises hydrated alumina and water, forming agent is helped to mix, shaping and the step of drying, the described forming agent that helps is selected from sesbania powder, starch, polyvinyl alcohol, PVOH, hydroxyethylcellulose, methyl hydroxyethylcellulose, methylcellulose, ethyl cellulose, hydroxypropyl methylcellulose, one or more replacement in hydroxypropyl methylcellulose high, with described article shaped for benchmark, the described content of forming agent that helps is 1-15 % by weight, the temperature of described drying is for being greater than 180 DEG C to being less than or equal to 300 DEG C, drying time is 1-48 hour.
12. methods according to 11, it is characterized in that, one or more helping forming agent to be selected from sesbania powder, PVOH, polyvinyl alcohol, hydroxypropyl methylcellulose, methylcellulose, HEMC, hydroxyethylcellulose, ethyl cellulose described, with described article shaped for benchmark, the described content of forming agent that helps is 2-10 % by weight, the temperature of described drying is 200-260 DEG C, and drying time is 2-14 hour.
13. methods according to 11, it is characterized in that, it is described that to be selected from supported on carriers at least one the method that the non-noble metal slaine of VIII and at least one be selected from the slaine of group vib metal be infusion process, dry step is comprised after described dipping, the condition of described drying comprises: temperature is 100-200 DEG C, and the time is 1-15 hour; Be benchmark with oxide basis and with catalyst, in described dipping, the consumption of each component to make in described catalyst with the content of the group VIII metal of oxide basis for 1-8 % by weight, and the content of group vib metal is 3-20 % by weight.
14. methods according to 13, it is characterized in that, the condition of described drying comprises: temperature is 120-150 DEG C, and the time is 3-10 hour; Be benchmark with oxide basis and with catalyst, the consumption of each component to make in described catalyst with the content of the group VIII metal of oxide basis for 1.5-4.5 % by weight, with the content of the group vib metal of oxide basis for 5-18 % by weight.
15. methods according to 11, it is characterized in that, described hydrated alumina is selected from one or more in hibbsite, monohydrate alumina, boehmite and amorphous hydroted alumina.
16. methods according to 15, it is characterized in that, described hydrated alumina is boehmite.
17. methods according to 11, it is characterized in that, the described non-noble metal slaine being selected from VIII is selected from one or more in the soluble complexes of cobalt nitrate, cobalt acetate, basic cobaltous carbonate, cobalt chloride, the soluble complexes of cobalt, nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride, nickel, and the slaine of described group vib is selected from one or more in molybdate, paramolybdate, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, ethyl metatungstate.
18. methods according to 17, it is characterized in that, the described non-noble metal slaine being selected from VIII is selected from one or more in cobalt nitrate, basic cobaltous carbonate, nickel nitrate, basic nickel carbonate, and the slaine of described group vib is selected from one or more in ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, ammonium tungstate.
According to catalyst provided by the invention, wherein, described hydrated alumina can be selected from one or more in hibbsite, monohydrate alumina, boehmite and amorphous hydroted alumina, preferably boehmite wherein.They can be that commercially available commodity also can be prepared by any one method in prior art.
According to catalyst provided by the invention, described shaping aqua oxidation alumina supporter optionally can be made into the shape of arbitrary convenient operation, as spherical, compressing tablet and bar shaped.Describedly shapingly can to carry out according to a conventional method, as methods such as compressing tablet, spin, extrusions.Such as, when described shaping aqua oxidation alumina supporter is bar shaped, its preparation method comprises: (1) is also dry by described hydrated alumina extruded moulding, wherein, when extrusion molding, water, extrusion aid can be added in described hydrated alumina, then extrusion molding, the kind of described extrusion aid and consumption are conventionally known to one of skill in the art, such as common extrusion aid can be selected from sesbania powder, methylcellulose, starch, polyvinyl alcohol, PVOH, hydroxyethylcellulose, methylcellulose, methyl hydroxyethylcellulose, ethyl cellulose, hydroxypropyl methylcellulose, one or more replacement in hydroxypropyl methylcellulose high, preferably wherein described in help forming agent to be selected from hydroxypropyl methylcellulose, methylcellulose, HEMC, hydroxyethylcellulose, one or more and they in ethyl cellulose and mixture that is independent or two or more and sesbania powder.
The non-noble metal components of described VIII is cobalt wherein and/or nickel preferably, described slaine is selected from one or more in their soluble-salt and complex compound, as their nitrate, chloride, acetate, one or more in subcarbonate, be selected from one or more in the solubility of cobalt nitrate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and cobalt for cobalt salt, be selected from one or more and the cobalt salt in the solubility of nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and nickel and nickel salt admixture for nickel salt.The metal component of described group vib is molybdenum wherein and/or tungsten preferably, and described slaine is selected from one or more in their soluble-salt.Such as, be selected from molybdate, paramolybdate, one or more in tungstates, metatungstate, ethyl metatungstate, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, ethyl metatungstate.
Under the prerequisite that the slaine being selected from group vib metal at the non-noble metal slaine and at least one that are enough to described at least one to be selected from VIII loads on described carrier, the method of the present invention to described load is not particularly limited, such as, the method for dipping is adopted.Described dipping method is conventional method, such as, prepares the solution of the non-noble metal slaine being selected from VIII and the slaine being selected from group vib, the method dipping afterwards by soaking or spray.By adjusting concentration and the consumption of described dipping solution, be selected from the method that load capacity that the non-noble metal slaine of VIII and at least one be selected from the slaine of group vib metal meets the demands to be well known to those skilled in the art to make described at least one, do not repeat here.
According to catalyst provided by the invention, the material of the catalytic performance of catalyst provided by the invention maybe can also can be improved containing any material not affecting the catalytic performance that the invention provides catalyst.As contained auxiliary agent phosphorus, be benchmark in element and with catalyst, the content of described auxiliary agent is no more than 10 % by weight, is preferably 0.5-5 % by weight.
When in described catalyst also containing when being selected from the components such as phosphorus, described in be selected from the components such as phosphorus introducing method can be arbitrary method, as can be by containing as described in auxiliary agent compound directly with as described in hydrated alumina mix, shaping and dry; Can be by the compound containing described auxiliary agent be selected from VIII non-noble metal slaine and be selected from group vib slaine be mixed with mixed solution after flood described carrier.
According to the conventional method in this area, described catalyst before the use, usually can be in presence of hydrogen, presulfurization is carried out with sulphur, hydrogen sulfide or sulfur-bearing raw material at the temperature of 140-370 DEG C, this presulfurization can be carried out outside device also can be In-situ sulphiding in device, and the active metal component of its load is converted into metal sulfide component.
The invention provides catalyst is suitable for heavy hydrocarbon feedstocks, comprises the raw materials such as crude oil, reduced crude, decompression residuum and carries out hydrotreatment reaction, react especially for HDM.
Compared with existing technical method, hydrogenating catalyst composition provided by the invention not only has excellent heavy oil hydrogenation demetal performance, has simultaneously and well holds metallicity.In addition, determined by its preparation method, the preparation method that the invention provides catalyst is simple, production cost is starkly lower than catalyst prepared by existing method.
Detailed description of the invention
The present invention will be further described for example below, but therefore do not limit content of the present invention.
Agents useful for same in example, except as expressly described, is chemically pure reagent.
Unless otherwise indicated, the content of hydrogenation active metals component is by XRF fluorescence spectrometry.
Adopt SEM-EDX to measure hydrogenation active metals component along carrier radial distribution, and calculate metal component at the ratio of particle appearance with center concentration by characterization result.Wherein, outer surface concentration is: the mean value of outer surface 20 numerical point counting rates; Center concentration: the mean value (note: the counting rate along the radial every bit of carrier in SEM-EDX characterization result is mutually corresponding with this tenor of central spot 20 numerical point counting rates, the size of counting rate reflects this tenor height, but does not represent the real content of this metal).
In embodiment and comparative example, hydrated alumina forming matter used wets the preparation of bar:
2400g boehmite powder (Shandong Zibo neat cyclopentadienyl catalyst Co., Ltd produce) and 120g sesbania powder and 120g hydroxypropyl methylcellulose and 2880ml water are mixed, the butterfly boehmite obtaining diameter 1.1mm through extrusion molding wets bar, is divided into 6 deciles for subsequent use.
Comparative example 1
Get aforementioned boehmite and wet bar portion in 120 DEG C of dryings 4 hours.Get 143g wherein in 500 DEG C of roasting 3h (burn tinctuer of 500 DEG C of roasting 3h is 28%), obtain the carrier through roasting.Measuring its water absorption rate is 1.1ml/g.
Weigh 4.0g basic nickel carbonate (containing NiO 51%), 9.0g molybdenum oxide, 1.7g phosphoric acid, the heating for dissolving that adds water becomes 110 milliliters of nickel-molybdenum-phosphorus solution, and with carrier after this roasting of described solution impregnation 1 hour.Afterwards, in 120 DEG C of dryings 4 hours, 400 DEG C of roastings 3 hours, obtain catalyst A 1.Table 1 is listed in catalyst A 1 tenor and distribution.
Comparative example 2
Get aforementioned boehmite and wet bar portion in 120 DEG C of dryings 4 hours.Get 143g wherein in 500 DEG C of roasting 3h, obtain the carrier through roasting.Measuring its water absorption rate is 1.1ml/g.
Weigh 5.0g basic cobaltous carbonate (containing CoO 70%), 7.9g molybdenum oxide, 0.9g phosphoric acid, the heating for dissolving that adds water becomes 110 milliliters of cobalt molybdenum phosphorus solutions, and with this carrier of described solution impregnation 1 hour.Afterwards, in 120 DEG C of dryings 4 hours, 400 DEG C of roastings 3 hours, obtain catalyst A 2.Table 1 is listed in catalyst A 2 tenor and distribution.
Embodiment 1
Get aforementioned boehmite and wet bar portion in 200 DEG C of dryings 5 hours.Surveying its water absorption rate is 0.76.
Weigh 4.0g basic nickel carbonate, 9.0g molybdenum oxide, 1.7g phosphoric acid, the heating for dissolving that adds water becomes 109ml nickel-molybdenum-phosphorus solution, and with the aforesaid carrier of described solution impregnation 143g 1 hour.Afterwards, in 120 DEG C of dryings 4 hours, catalyst B 1 is obtained.Table 1 is listed in catalyst B 1 tenor and distribution.
Embodiment 2
Get aforementioned boehmite and wet bar portion in 240 DEG C of dryings 5 hours.Surveying its water absorption rate is 0.76.
Weigh 2.5g basic cobaltous carbonate, 6.0g molybdenum oxide, 1.2g phosphoric acid, the heating for dissolving that adds water becomes 109ml cobalt molybdenum phosphorus solution, and with the aforesaid carrier of described solution impregnation 143g 1 hour.Afterwards, in 120 DEG C of dryings 4 hours, catalyst B 2 is obtained.Table 1 is listed in catalyst B 2 tenor and distribution.
Embodiment 3
Get aforementioned boehmite and wet bar portion in 240 DEG C of dryings 5 hours.Surveying its water absorption rate is 0.76.
Weigh 25.2g basic nickel carbonate, 64.4g molybdenum oxide, 12.0g phosphoric acid, the heating for dissolving that adds water becomes 429ml nickel-molybdenum-phosphorus solution, and floods the aforesaid carrier of 143g 5 hours with described solution supersaturation.After filtering, in 120 DEG C of dryings 4 hours, catalyst B 3 is obtained.Table 1 is listed in catalyst B 3 tenor and distribution.
Embodiment 4
Get aforementioned boehmite and wet bar portion in 200 DEG C of dryings 5 hours.Surveying its water absorption rate is 0.76.
Weigh 16.8g Ni (NO
3)
26H
2o, 17.3g (NH
4)
12w
12o
415H
2o, is dissolved in water into 109ml nickel-molybdenum-phosphorus solution, and with the aforesaid carrier of described solution impregnation 143g 1 hour.Afterwards, in 120 DEG C of dryings 4 hours, catalyst B 4 is obtained.Table 1 is listed in catalyst B 4 tenor and distribution.
Table 1
Embodiment 4-6 illustrates and the invention provides catalyst performance.
Be that raw material is evaluated catalyst B 1, B2, B3 respectively with decompression residuum, the feedstock oil character of decompression residuum lists in table 2, evaluates and carries out in magnetic agitation autoclave device.Reaction condition comprises: agent oil quality ratio is 0.05, and reaction temperature is 400 DEG C, and reaction initial pressure is 8MPa, reacts sample analysis after 6 hours.Plasma emission spectrum (AES/ICP) method is adopted to measure the content generating nickel, vanadium in oil.Calculate demetallization per, the results are shown in table 3.
Adopt SEM-EDX to characterize the vanadium radial distribution on a catalyst that post catalyst reaction deposits, and calculate vanadium metal at the ratio of particle appearance with center concentration by characterization result, the results are shown in table 4.
Comparative example 3-4
According to method evaluation reference catalyst A1, A2 identical with embodiment 4.Calculate demetallization per, the results are shown in table 3.Measure the distribution of vanadium metal, the results are shown in Table 4.
Table 2
Table 3
Table 3 illustrates, catalyst provided by the invention, compared with reference catalyst, has higher HDM active.
Table 4
The result of table 4 can illustrate, catalyst provided by the invention is compared with reference catalyst, and when heavy oil hydrogenation demetal reacts, V trends towards the center deposition at catalyst, and reference catalyst does not show such feature.The feature that the invention provides catalyst activity metal component non-uniform Distribution is favourable to the appearance metal ability improving Hydrodemetalation catalyst.
Claims (17)
1. the hydrogenation catalyst of an active metal component non-uniform Distribution, the slaine that the non-noble metal slaine of VIII and at least one are selected from group vib metal is selected from containing shaping aqua oxidation alumina supporter, load at least one on this carrier, wherein, along the distribution of catalyst radial section, the outer surface concentration of described group VIII metal component is 0.1-0.9 with the ratio of centre concentration; The outer surface concentration of described group vib metal component is 0.1-0.8 with the ratio of centre concentration, described shaping aqua oxidation alumina supporter is hydrated alumina and the mixture helping forming agent, the described forming agent that helps is selected from sesbania powder, starch, polyvinyl alcohol, PVOH, hydroxyethylcellulose, methyl hydroxyethylcellulose, methylcellulose, ethyl cellulose, hydroxypropyl methylcellulose, one or more replacement in hydroxypropyl methylcellulose high, with described article shaped for benchmark, described in help the content of forming agent to be 1-15 % by weight.
2. catalyst according to claim 1, is characterized in that, along the distribution of catalyst radial section, the outer surface concentration of described group VIII metal component is 0.4-0.8 with the ratio of centre concentration; The outer surface concentration of described group vib metal component is 0.3-0.7 with the ratio of centre concentration.
3. catalyst according to claim 1, is characterized in that, is benchmark with oxide basis and with catalyst, and the content of described group VIII metal is 1-8 % by weight, and the content of group vib metal is 3-20 % by weight.
4. catalyst according to claim 3, is characterized in that, is benchmark with oxide basis and with catalyst, and the content of described group VIII metal is 1.5-4.5 % by weight, and the content of group vib metal is 5-18 % by weight.
5. catalyst according to claim 1, is characterized in that, described hydrated alumina is selected from one or more in hibbsite, monohydrate alumina, boehmite and amorphous hydroted alumina.
6. catalyst according to claim 5, is characterized in that, described hydrated alumina is boehmite.
7. catalyst according to claim 1, it is characterized in that, the described non-noble metal slaine being selected from VIII is selected from one or more in the soluble complexes of the soluble complexes of cobalt nitrate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and cobalt, nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and nickel, and the slaine of described group vib metal is selected from one or more in molybdate, paramolybdate, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, ethyl metatungstate.
8. catalyst according to claim 7, it is characterized in that, the described non-noble metal slaine being selected from VIII is selected from one or more in cobalt nitrate, basic cobaltous carbonate, nickel nitrate and basic nickel carbonate, and the slaine of described group vib is selected from one or more in ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, ammonium tungstate.
9. catalyst according to claim 1, it is characterized in that, one or more helping forming agent to be selected from sesbania powder, PVOH, polyvinyl alcohol, hydroxypropyl methylcellulose, methylcellulose, HEMC, hydroxyethylcellulose, ethyl cellulose described, with described article shaped for benchmark, described in help the content of forming agent to be 2-10 % by weight.
10. the preparation method of a hydrogenation catalyst, comprise the shaping water of preparation and alumina support load at least one on this carrier and be selected from the slaine that the non-noble metal slaine of VIII and at least one are selected from group vib metal, wherein, the method of the water that described preparation is shaping and alumina support comprises hydrated alumina and water, forming agent is helped to mix, shaping and the step of drying, the described forming agent that helps is selected from sesbania powder, starch, polyvinyl alcohol, PVOH, hydroxyethylcellulose, methyl hydroxyethylcellulose, methylcellulose, ethyl cellulose, hydroxypropyl methylcellulose, one or more replacement in hydroxypropyl methylcellulose high, with described article shaped for benchmark, the described content of forming agent that helps is 1-15 % by weight, the temperature of described drying is for being greater than 180 DEG C to being less than or equal to 300 DEG C, drying time is 1-48 hour.
11. methods according to claim 10, it is characterized in that, one or more helping forming agent to be selected from sesbania powder, PVOH, polyvinyl alcohol, hydroxypropyl methylcellulose, methylcellulose, HEMC, hydroxyethylcellulose, ethyl cellulose described, with described article shaped for benchmark, the described content of forming agent that helps is 2-10 % by weight, the temperature of described drying is 200-260 DEG C, and drying time is 2-14 hour.
12. methods according to claim 10, it is characterized in that, it is described that to be selected from supported on carriers at least one the method that the non-noble metal slaine of VIII and at least one be selected from the slaine of group vib metal be infusion process, dry step is comprised after described dipping, the condition of described drying comprises: temperature is 100-200 DEG C, and the time is 1-15 hour; Be benchmark with oxide basis and with catalyst, in described dipping, the consumption of each component to make in described catalyst with the content of the group VIII metal of oxide basis for 1-8 % by weight, and the content of group vib metal is 3-20 % by weight.
13. methods according to claim 12, is characterized in that, the condition of described drying comprises: temperature is 120-150 DEG C, and the time is 3-10 hour; Be benchmark with oxide basis and with catalyst, the consumption of each component to make in described catalyst with the content of the group VIII metal of oxide basis for 1.5-4.5 % by weight, with the content of the group vib metal of oxide basis for 5-18 % by weight.
14. methods according to claim 10, is characterized in that, described hydrated alumina is selected from one or more in hibbsite, monohydrate alumina, boehmite and amorphous hydroted alumina.
15. methods according to claim 14, is characterized in that, described hydrated alumina is boehmite.
16. methods according to claim 10, it is characterized in that, the described non-noble metal slaine being selected from VIII is selected from one or more in the soluble complexes of cobalt nitrate, cobalt acetate, basic cobaltous carbonate, cobalt chloride, the soluble complexes of cobalt, nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride, nickel, and the slaine of described group vib is selected from one or more in molybdate, paramolybdate, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, ethyl metatungstate.
17. methods according to claim 16, it is characterized in that, the described non-noble metal slaine being selected from VIII is selected from one or more in cobalt nitrate, basic cobaltous carbonate, nickel nitrate, basic nickel carbonate, and the slaine of described group vib is selected from one or more in ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, ammonium tungstate.
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|---|---|---|---|---|
| CN103801348B (en) * | 2012-11-08 | 2016-03-02 | 中国石油化工股份有限公司 | A kind of catalyst for hydrogenating hydrocarbon oil and preparation method thereof |
| CN103143367B (en) * | 2013-03-26 | 2014-12-24 | 沈阳三聚凯特催化剂有限公司 | Reformed pre-hydrogenation catalyst and preparation method thereof |
| CN104437571B (en) * | 2013-09-16 | 2017-06-06 | 中国石油化工股份有限公司 | A kind of Hydrobon catalyst, preparation method and applications |
| CN104667962B (en) * | 2013-11-26 | 2017-04-12 | 中国石油化工股份有限公司 | A catalyst for diesel oil hydrogenation modification and a preparing method thereof |
| CN104667959B (en) * | 2013-11-26 | 2017-03-22 | 中国石油化工股份有限公司 | A catalyst for diesel oil hydrogenation modification and a preparing method thereof |
| CN113559893B (en) * | 2020-04-28 | 2022-09-27 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof |
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