CN103418441B - A kind of Hydrobon catalyst and Synthesis and applications thereof - Google Patents
A kind of Hydrobon catalyst and Synthesis and applications thereof Download PDFInfo
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Abstract
A kind of Hydrobon catalyst and Synthesis and applications thereof, described catalyst contains and shaping is selected from containing charcoal aqua oxidation alumina supporter, load at least one on this carrier the slaine that the non-noble metal slaine of VIII and at least one are selected from group vib metal, be benchmark with oxide basis and with catalyst, group VIII metal content is 2 % by weight ~ 10 % by weight, and group vib tenor is 15 % by weight ~ 45 % by weight.The preparation method of this catalyst comprise preparation shaping containing charcoal aqua oxidation alumina supporter and load at least one is on this carrier selected from the slaine that the non-noble metal slaine of VIII and at least one are selected from group vib metal, carry out drying afterwards.Compared with existing technical method, hydrogenation catalyst provided by the invention not only has excellent hydrocarbon oil hydrogenation and refines performance, and preparation method is simple simultaneously, production cost is low.
Description
Technical field
The present invention relates to a kind of Hydrobon Catalyst And Its Preparation Method.
Background technology
The conventional flow process preparing hydrogenation catalyst comprises prepares shaping carrier and supported active metals component on this carrier.For catalyst prepared by alumina support, comprise shaping for hydrated alumina (as boehmite), drying roasting becomes γ-Al
2o
3, afterwards with the solution impregnation γ-Al containing active metal component compound
2o
3carrier, dry also roasting make catalyst.
In addition, as the method preparing heavy-oil hydrogenation catalyst that Richard A.Kemp reports, that active metal component solution is directly joined in boehmite gel, extrusion molding afterwards, drying and roasting makes catalyst (bibliography: [1] Richard A.Kemp, Charles T.Adam, Applied CatalysisA:general, 134 (1996) 299-317); The method preparing Hydrobon catalyst of D.minoux report, use nickel nitrate and ammonium molybdate and boehmite dried bean noodles to mix, then shaping, drying and roasting (bibliography: [2] D.minoux, F.Diehl, P.Euzen, Jean-Pierre Jolivetb, Edmond Payen, Studies in Surface Science and Catalysis 143 (2002), 767-775).
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of new Hydrobon Catalyst And Its Preparation Method.
The present invention relates to following invention:
1. a Hydrobon catalyst, the slaine that the non-noble metal slaine of VIII and at least one are selected from group vib metal is selected from containing carrier, load at least one on this carrier, be benchmark with oxide basis and with catalyst, group VIII metal content is 2 % by weight ~ 10 % by weight, group vib tenor is 15 % by weight ~ 45 % by weight, wherein, described carrier is the article shaped containing charcoal, cellulose ether and hydrated alumina.
2. the catalyst according to 1, is characterized in that, is benchmark with oxide basis and with catalyst, and group VIII metal content is 4 % by weight ~ 8 % by weight, and group vib tenor is 20 % by weight ~ 40 % by weight.
3. the catalyst according to 1, is characterized in that, the radial crushing strength of the described article shaped containing charcoal, cellulose ether and hydrated alumina is more than or equal to 12 Newton/millimeter, and water absorption rate is that 0.4 ~ 1.5, δ value is for being less than or equal to 10%; Wherein, δ=((Q1-Q2)/Q1) × 100%, Q1 is the radial crushing strength of article shaped, and Q2 is that article shaped is through water soaking 30 minutes, through the radial crushing strength of 120 DEG C of dryings after 4 hours.
4. the catalyst according to 3, is characterized in that, the radial crushing strength of described article shaped is 15 Newton/millimeter ~ 30 Newton/millimeter, and water absorption rate is that 0.6 ~ 1, δ is less than or equal to 5%.
5. the catalyst according to 3 or 4, is characterized in that, with described article shaped for benchmark, the mass fraction of described cellulose ether is 0.5% ~ 8%, in the mass fraction of element charcoal for 0.2% ~ 10%.
6. the catalyst according to 5, is characterized in that, with described article shaped for benchmark, the mass fraction of described cellulose ether is 1% ~ 6%, in the mass fraction of element charcoal for 0.5% ~ 9%.
7. the catalyst according to 6, is characterized in that, with described article shaped for benchmark, the mass fraction of described cellulose ether is 2% ~ 5%, in the mass fraction of element charcoal for 1% ~ 8%.
8. the catalyst according to 3, is characterized in that, described cellulose ether is selected from one or more in methylcellulose, HEMC, hydroxypropyl methylcellulose; Described charcoal is selected from one or more in charcoal powder, coke powder, active carbon powder, carbon black.
9. the catalyst according to 8, is characterized in that, described cellulose ether is methylcellulose, HEMC and their mixture.
10. the catalyst according to 3, is characterized in that, described hydrated alumina is selected from one or more in boehmite, boehmite, aluminium hydroxide, three water-aluminum hydroxides.
11. catalyst according to 10, it is characterized in that, described hydrated alumina is boehmite.
12. catalyst according to 3, is characterized in that, containing starch in described article shaped, with described article shaped for benchmark, the mass fraction of described starch is no more than 8%.
13. catalyst according to 12, it is characterized in that, described starch is sesbania powder, and with described article shaped for benchmark, the mass fraction of described starch is no more than 5%.
14. catalyst according to 1, it is characterized in that, the non-noble metal slaine of described 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, the slaine of described group vib metal be selected from molybdate, paramolybdate, containing molybdenum heteropolyacid, containing one or more in molybdenum heteropolyacid salt, tungstates, metatungstate, paratungstate, ethyl metatungstate, heteropoly acid containing tungsten, heteropoly acid containing tungsten salt.
15. catalyst according to 14, it is characterized in that, the non-noble metal slaine of described VIII is selected from one or more in cobalt nitrate, basic cobaltous carbonate, nickel nitrate and basic nickel carbonate, the slaine of described group vib be selected from ammonium molybdate, ammonium paramolybdate, containing molybdenum heteropolyacid, containing one or more in molybdenum heteropolyacid salt, ammonium metatungstate, ammonium tungstate, heteropoly acid containing tungsten, heteropoly acid containing tungsten salt.
The preparation method of 16. 1 kinds of Hydrobon catalysts, comprise and prepare carrier 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, carry out drying afterwards, wherein, described carrier is the hydrated alumina forming matter containing charcoal, with described catalyst for benchmark, it is 2 % by weight ~ 10 % by weight that the consumption of each component to make in described catalyst with the group VIII metal content of oxide basis, group vib tenor is 15 % by weight ~ 45 % by weight, the condition of described drying comprises: temperature is 100 DEG C ~ 200 DEG C, time is 1 hour ~ 15 hours.
17. methods according to 16, it is characterized in that, with described catalyst for benchmark, it is 4 % by weight ~ 8 % by weight that the consumption of each component to make in described catalyst with the group VIII metal content of oxide basis, group vib tenor is 20 % by weight ~ 40 % by weight, the condition of described drying comprises: temperature is 120 DEG C ~ 150 DEG C, and the time is 3 hours ~ 10 hours.
18. methods according to 16, it is characterized in that, described hydrated alumina is selected from one or more in hibbsite, monohydrate alumina and amorphous hydroted alumina.
19. methods according to 18, it is characterized in that, described hydrated alumina is boehmite.
20. methods according to 16, it is characterized in that, the non-noble metal slaine of described 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, the slaine of described group vib metal be selected from molybdate, paramolybdate, containing molybdenum heteropolyacid, containing one or more in molybdenum heteropolyacid salt, tungstates, metatungstate, paratungstate, ethyl metatungstate, heteropoly acid containing tungsten, heteropoly acid containing tungsten salt.
21. methods according to 20, it is characterized in that, the non-noble metal slaine of described VIII is selected from one or more in cobalt nitrate, basic cobaltous carbonate, nickel nitrate, basic nickel carbonate, the slaine of described group vib be selected from ammonium molybdate, ammonium paramolybdate, containing molybdenum heteropolyacid, containing one or more in molybdenum heteropolyacid salt, ammonium metatungstate, ammonium tungstate, heteropoly acid containing tungsten, heteropoly acid containing tungsten salt.
22. methods according to 16, is characterized in that, the described preparation method containing charcoal hydrated alumina forming matter comprises hydrated alumina, charcoal, cellulose ether mixing, shaping and dry; Wherein, the radial crushing strength of described article shaped is more than or equal to 12 Newton/millimeter, and water absorption rate is that 0.4 ~ 1.5, δ value is for being less than or equal to 10%; Wherein, δ=((Q1-Q2)/Q1) × 100%, Q1 is the radial crushing strength of article shaped, and Q2 is article shaped through water soaking 30 minutes, radial crushing strength after drying.
23. methods according to 22, it is characterized in that, the radial crushing strength of described article shaped is 15 Newton/millimeter ~ 30 Newton/millimeter, and water absorption rate is that 0.6 ~ 1, δ is less than or equal to 5%.
24. methods according to 22 or 23, it is characterized in that, with described article shaped for benchmark, the mass fraction of described cellulose ether is 0.5% ~ 8%, in the mass fraction of element charcoal for 0.2% ~ 10%; Described drying condition comprises: temperature 60 C to being less than 350 DEG C, 1 hour ~ 48 hours drying time.
25. methods according to 24, it is characterized in that, with described article shaped for benchmark, the mass fraction of described cellulose ether is 1% ~ 6%, in the mass fraction of element charcoal for 0.5% ~ 9%; Described drying condition comprises: temperature 80 DEG C ~ 150 DEG C, 2 hours ~ 14 hours drying time.
26. methods according to 25, it is characterized in that, with described article shaped for benchmark, the mass fraction of described cellulose ether is 2% ~ 5%, in the mass fraction of element charcoal for 1% ~ 8%; Described drying condition comprises: temperature 100 DEG C ~ 130 DEG C, 3 hours ~ 10 hours drying time.
27. methods according to 22, it is characterized in that, described cellulose ether is selected from one or more in methylcellulose, HEMC, hydroxypropyl methylcellulose; Described charcoal is selected from one or more in charcoal powder, coke powder, active carbon powder, carbon black.
28. methods according to 27, it is characterized in that, described cellulose ether is methylcellulose, HEMC and their mixture.
29. methods according to 16 or 22, it is characterized in that, described hydrated alumina is selected from one or more in boehmite, boehmite, aluminium hydroxide, three water-aluminum hydroxides.
30. methods according to 29, it is characterized in that, described hydrated alumina is boehmite.
31. methods according to 22, is characterized in that, comprise the step that is introduced starch in forming process, and with described article shaped for benchmark, the mass fraction that described starch is introduced is no more than 8%.
32. methods according to 31, it is characterized in that, described starch is sesbania powder, and with described article shaped for benchmark, the mass fraction of the introducing of described starch is no more than 5%.
33. 1 kinds of hydrofinishing process, under being included in hydrofining reaction condition, reacting feedstock oil and catalyst exposure, it is characterized in that, described catalyst is the catalyst described in aforementioned 1-15 any one.
According to catalyst provided by the invention, wherein, the radial crushing strength of the described article shaped (carrier) containing hydrated alumina, charcoal and cellulose ether is more than or equal to 12 Newton/millimeter, be preferably 15 Newton/millimeter ~ 30 Newton/millimeter, water absorption rate is 0.6 ~ 1, δ value, for being less than or equal to 10%, is preferably less than or equal to 5%.Described δ=((Q1-Q2)/Q1) × 100%, Q1 is for containing charcoal hydrated alumina forming matter (carrier) radial crushing strength, Q2 for containing charcoal hydrated alumina forming matter (carrier) through water soaking 30 minutes, through the radial crushing strength of 120 DEG C of heating, dryings after 4 hours.The size of δ value represents containing charcoal hydrated alumina forming matter (carrier) through the change (or be called loss of strength rate) of water soaking anteroposterior diameter to crushing strength.
Here, the measuring method of described article shaped (carrier) radial crushing strength is carried out according to RIPP 25-90 catalyst compressive resistance determination method, the concrete steps measured about the radial crushing strength of article shaped have detailed introduction at RIPP 25-90, do not repeat here.
Described water absorption rate is adopted and is measured with the following method: first dried 4 hours by testing sample 120 DEG C.Take out sample, be positioned in drier and be cooled to room temperature, with 40 mesh standard sieve screenings, take oversize 20 grams (numbering: w1) testing sample, adds 50 grams of deionized waters, soak 30 minutes, filter, solid phase drains 5 minutes, weighs solid phase weight (numbering: w2), water absorption rate=(w2-w1)/w1, dimensionless.In practical operation, the density of water is in 1, and water absorption rate also can be tried to achieve by water suction volume/vehicle weight, and its dimension is volume/weight, such as ml/g.
Be enough under the prerequisite that the radial crushing strength of article shaped (carrier), water absorption rate and loss of strength rate are met the demands, the content of the present invention to cellulose ether is not particularly limited, in a particular embodiment, with described article shaped total amount for benchmark, the mass fraction of cellulose ether is preferably 0.5% ~ 8%, more preferably 1% ~ 6%, be more preferably 2% ~ 5%.Described cellulose ether preferably in methylcellulose, HEMC, hydroxypropyl methylcellulose one or more, further preferably methylcellulose, HEMC and their mixture wherein.
According to catalyst provided by the invention, wherein, with described article shaped total amount for benchmark, in the mass fraction of element charcoal for 0.2% ~ 10%, more preferably 0.5% ~ 9%, be more preferably 1% ~ 8%.Described charcoal is selected from one or more in charcoal powder, coke powder, active carbon powder, carbon black.
According to catalyst provided by the invention, wherein, described containing can containing the adjuvant component not affecting or be of value to radial crushing strength, water absorption rate and the δ value of improving described article shaped in charcoal hydrated alumina forming matter (carrier).Such as, containing starch addO-on therapy, described starch can be the powder obtained through pulverizing by vegetable seeds arbitrarily, as sesbania powder.
According to catalyst provided by the invention, wherein, described hydrated alumina is selected from the hydrated alumina that any one can be used as adsorbent and catalyst carrier precursor, such as, can be boehmite, boehmite, aluminium hydroxide, three water-aluminum hydroxides, preferred boehmite.
According to preparation method provided by the invention, wherein, the described shaping forming method containing charcoal aqua oxidation alumina supporter can be arbitrary known method.Such as, the forming method of extrusion, round as a ball, compressing tablet and their combination.For ensureing shaping carrying out smoothly, can in aforesaid material (mixture of hydrated alumina, charcoal and cellulose ether), introduce water, contain or not contain auxiliary agent etc. when shaping, such as, when adopting extrusion method shaping, comprise by described hydrated alumina, charcoal and cellulose ether and water, containing or do not mix containing extrusion aid, then obtain wet bar through extrusion molding, then drying obtains article shaped of the present invention.Described auxiliary agent is selected from starch, and described starch can be the powder obtained through pulverizing by vegetable seeds arbitrarily, as sesbania powder.Preferred forming method is the method for extruded moulding.Described drying condition comprises: temperature 60 C is to being less than 350 DEG C, 1 hour ~ 48 hours drying time, preferable temperature is 80 DEG C ~ 150 DEG C, and drying time is 1 hour ~ 15 hours, further preferable temperature is 100 DEG C ~ 130 DEG C, and drying time is 2 hours ~ 10 hours.
The base metal 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 preferred molybdenum of described group vib metal and/or tungsten, described slaine is selected from one or more (comprise and obtaining by being transformed with acid or alkali reaction in the solution by their oxide) in their soluble-salt, preferably molybdenum salt wherein and/or tungsten salt, such as, be selected from molybdate, paramolybdate, one or more in tungstates, metatungstate, paratungstate, ethyl metatungstate and their heteropoly acid and salt thereof.
It is described that to be selected from containing charcoal hydrated alumina 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 can be arbitrary conventional method shaping, be preferably the method for dipping, described dipping method is conventional method, such as preparation is selected from the non-noble metal slaine of VIII and is selected from the solution of slaine of group vib, method dipping afterwards by soaking or spray, with described catalyst for benchmark, it is 2 % by weight ~ 10 % by weight that the consumption of each component to make in described catalyst with the content of the group VIII metal of oxide basis, be preferably 4 % by weight ~ 8 % by weight, the content of group vib metal is 15 % by weight ~ 45 % by weight, be preferably 20 % by weight ~ 40 % by weight.The condition of described drying comprises: temperature is 100 DEG C ~ 200 DEG C, and be preferably 120% ~ 150 DEG C, the time is 1 hour ~ 15 hours, is preferably 3 hours ~ 10 hours.
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 phosphorus, be benchmark with oxide basis and with catalyst, the content of above-mentioned auxiliary agent is no more than 10 % by weight, is preferably 0.5 % by weight ~ 5 % by weight.
When in described catalyst also containing when being selected from the components such as phosphorus, described in be selected from the component such as phosphorus or silicon introducing method can be arbitrary method, as can be by containing as described in auxiliary agent compound directly with as described in contain charcoal 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 DEG C ~ 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.
Hydrobon catalyst provided by the invention is adopted to be suitable for the hydrofinishing of all kinds of hydrocarbon oil crude material.Described hydrocarbon oil crude material can be various heavy mineral oil or artificial oil or their mixed fraction oil, is such as selected from one or more in crude oil, distillate, solvent-refined oil, slack wax, sweat oil, Fischer-Tropsch synthesis oil, liquefied coal coil, frivolous coal tar and heavy deasphalted oil.
Compared with existing technical method, Hydrobon catalyst provided by the invention not only has excellent hydrocarbon oil hydrogenation and refines performance, determined by its preparation method, the preparation method of Hydrobon catalyst provided by the invention 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.
Embodiment 1
Get 100 grams, the boehmite powder that catalyst Chang Ling branch company produces, add 4.0 grams of methylcellulose, 3.0 grams of sesbania powder, 4.5 grams of carbon blacks and 95 ml deionized water, fully be uniformly mixed, by banded extruder kneading and extruded moulding, the article shaped obtaining hydrated alumina wets bar.Wet bar is placed in baking oven 150 DEG C of dryings 12 hours.Measure the radial crushing strength of dry aftershaping carrier, water absorption rate and δ value, the results are shown in table 1.
Embodiment 2
Get 50 grams, the boehmite powder that catalyst Chang Ling branch company produces, 50 grams, self-control unformed aluminium hydroxide powder, add 2.0 grams of methylcellulose, 3.0 grams of HEMCs, 8.5 grams of charcoal powder and 95 ml deionized water, fully be uniformly mixed, by banded extruder kneading and extruded moulding, obtain the wet article shaped of aluminium hydroxide.Wet hydrogen aluminium oxide article shaped to be positioned in baking oven 220 DEG C of dryings 6 hours.Measure the radial crushing strength of dry aftershaping carrier, water absorption rate and δ value, the results are shown in table 1.
Embodiment 3
Get 60 grams, the boehmite powder that catalyst Chang Ling branch company produces, three water-aluminum hydroxides 40 grams, add 1.0 grams of methylcellulose, 2.0 grams of hydroxypropyl methylcelluloses, 3.0 grams of sesbania powder, 2 grams of active carbon powders and 95 ml deionized water, be fully uniformly mixed, by banded extruder kneading and extruded moulding, obtain the wet article shaped of aluminium hydroxide.Wet hydrogen aluminium oxide article shaped to be positioned in baking oven 80 DEG C of dryings 12 hours.Measure the radial crushing strength of dry aftershaping carrier, water absorption rate and δ value, the results are shown in table 1.
Embodiment 4
Get 100 grams, the boehmite SB powder that Sasol company produces, add 3.0 grams of HEMCs, 4 grams of coke powders and 80 ml deionized water, be fully uniformly mixed, and by banded extruder kneading and extruded moulding, obtains formation wet bar.Wet shaping bar to be positioned in baking oven 150 DEG C of dryings 12 hours.Measure the radial crushing strength of dry aftershaping carrier, water absorption rate and δ value, the results are shown in table 1.
Embodiment 5
Get 100 grams, the boehmite SB powder that Sasol company produces, add 3.0 grams of HEMCs, 2 grams of hydroxypropyl methylcelluloses, 3.0 grams of sesbania powder, 14.2 grams of carbon blacks and 90 ml deionized water, be fully uniformly mixed, by banded extruder kneading and extruded moulding, obtain formation wet bar.Wet shaping bar to be positioned in baking oven 250 DEG C of dryings 4 hours.Measure the radial crushing strength of dry aftershaping carrier, water absorption rate and δ value, the results are shown in table 1.
Embodiment 6
Get 100 grams, the boehmite powder that Yantai, Shandong Heng Hui Chemical Co., Ltd. produces, add 5.0 grams of hydroxypropyl methylcelluloses, 3.0 grams of sesbania powder, 1.5 grams of carbon blacks and 90 ml deionized water, fully be uniformly mixed, by banded extruder kneading and extruded moulding, obtain wet shaping bar.Wet shaping bar to be positioned in baking oven 120 DEG C of dryings 4 hours.Measure the radial crushing strength of dry aftershaping carrier, water absorption rate and δ value, the results are shown in table 1.
Comparative example 1
Get 100 grams, the boehmite powder that catalyst Chang Ling branch company produces, add red fuming nitric acid (RFNA) 2.5 milliliters, 3.0 grams of sesbania powder, 4.5 grams of carbon blacks and 95 ml deionized water, be fully uniformly mixed, and by banded extruder kneading and extruded moulding, obtains wet shaping bar.Wet shaping bar to be positioned in baking oven 80 DEG C of dryings 4 hours.Measure the radial crushing strength of dry aftershaping carrier, water absorption rate and δ value, the results are shown in table 1.
Comparative example 2
Get 100 grams, the boehmite SB powder that Sasol company produces, add 20 ml aluminium colloidal sols, 3.0 grams of sesbania powder, 14.2 grams of carbon blacks and 90 ml deionized water, be fully uniformly mixed, and after even by banded extruder kneading, extruded moulding obtains shaping bar.Shaping bar to be positioned in baking oven 150 DEG C of dryings 4 hours.Measure the radial crushing strength of dry aftershaping carrier, water absorption rate and δ value, the results are shown in table 1.
Comparative example 3
Get 100 grams, the boehmite powder that Yantai, Shandong Heng Hui Chemical Co., Ltd. produces, add 5.0 milliliters of acetic acid, 3.0 grams of sesbania powder, 1.5 grams of carbon blacks and 90 ml deionized water, fully be uniformly mixed, after even by banded extruder kneading, extruded moulding obtains shaping bar.Shaping bar to be positioned in baking oven 180 DEG C of dryings 4 hours.Measure the radial crushing strength of dry aftershaping carrier, water absorption rate and δ value, the results are shown in table 1.
Comparative example 4
Get 100 grams, the boehmite powder that catalyst Chang Ling branch company produces, add red fuming nitric acid (RFNA) 2.5 milliliters, 3.0 grams of sesbania powder, 4.5 grams of carbon blacks and 95 ml deionized water, be fully uniformly mixed, and after even by banded extruder kneading, extruded moulding obtains shaping bar.Shaping bar to be positioned in baking oven 80 DEG C of dryings 4 hours.Dried strip 600 DEG C of roastings 4 hours.Measure the radial crushing strength of roasting aftershaping carrier, water absorption rate and δ value, the results are shown in table 1.
Table 1
| Embodiment | Support strength, Newton/millimeter | Water absorption rate | δ value, % |
| 1 | 21.7 | 0.84 | 3.2 |
| 2 | 19.6 | 0.77 | 2.3 |
| 3 | 15.4 | 0.88 | 2.8 |
| 4 | 20.2 | 0.74 | 2.5 |
| 5 | 25.2 | 0.67 | 2.6 |
| 6 | 18.6 | 0.85 | 4.2 |
| Comparative example 1 | 21.6 | 0.86 | 61.2 |
| Comparative example 2 | 21.4 | 0.69 | 74.2 |
| Comparative example 3 | 22.5 | 0.86 | 46.6 |
| Comparative example 4 | 24.8 | 0.94 | 3.2 |
Embodiment 7 ~ 9 and comparative example 5 illustrate catalyst provided by the invention, reference catalyst and their preparation method respectively.
Embodiment 7
Prepare 95 grams of cylindrical vectors (diameter is 1.1 millimeters, and particle length is 2 millimeters ~ 5 millimeters, and 600 DEG C of roastings are after 4 hours in Muffle furnace for this article shaped, and recording butt is 70.6%) according to the method for embodiment 1, measuring its water absorption rate is 0.84.Flood 4 hours with 80 milliliters containing molybdenum oxide 25 grams, nickel oxide 5 grams, the ammonium molybdate of phosphorous oxide 3 grams, basic nickel carbonate, phosphoric acid mixed solution, afterwards in 120 DEG C of dryings 4 hours, obtain catalyst B 1.Adopt the tenor in XRF mensuration catalyst, in table 2.
Comparative example 5
Prepare 67 grams of cylindrical vectors (diameter is 1.1 millimeters, and particle length is 2 millimeters ~ 5 millimeters) according to the method for comparative example 4, measuring its water absorption rate is 0.94 ml/g.Flood 4 hours with 63 milliliters containing molybdenum oxide 25 grams, nickel oxide 5 grams, the ammonium molybdate of phosphorous oxide 3 grams, basic nickel carbonate, phosphoric acid mixed solution, afterwards in 120 DEG C of dryings 4 hours, 400 DEG C of roastings obtain catalyst A 1 in 3 hours.Adopt the tenor in XRF mensuration catalyst, in table 2.
Embodiment 8
Prepare 94 grams of cylindrical vectors (diameter is 1.1 millimeters, and particle length is 2 millimeters ~ 5 millimeters, and 600 DEG C of roastings are after 4 hours in Muffle furnace for this article shaped, and recording butt is 71.3%) according to the method for embodiment 2, measuring its water absorption rate is 0.77.Flood 4 hours with 73 milliliters containing molybdenum oxide 25 grams, cobalt oxide 5 grams, the ammonium molybdate of phosphorous oxide 3 grams, basic cobaltous carbonate, phosphoric acid mixed solution, afterwards in 120 DEG C of dryings 4 hours, obtain catalyst B 2.Adopt the tenor in XRF mensuration catalyst, in table 2.
Embodiment 9
Prepare 96.5 grams of cylindrical vectors (diameter is 1.1 millimeters, and particle length is 2 millimeters ~ 5 millimeters, and 600 DEG C of roastings are after 4 hours in Muffle furnace for this article shaped, and recording butt is 69.4%) according to the method for embodiment 3, measuring its water absorption rate is 0.88.Flood 1 hour with 85 milliliters containing tungsten oxide 25 grams, nickel oxide 4.4 grams, the ammonium metatungstate of phosphorous oxide 3.6 grams, nickel nitrate, phosphoric acid mixed solution, afterwards in 120 DEG C of dryings 4 hours, obtain catalyst B 3.Adopt the tenor in XRF mensuration catalyst, in table 2.
Embodiment 10
Prepare 115 grams of cylindrical vectors (diameter is 1.1 millimeters, and particle length is 2 millimeters ~ 5 millimeters, and 600 DEG C of roastings are after 4 hours in Muffle furnace for this article shaped, and recording butt is 68.9%) according to the method for embodiment 4, measuring its water absorption rate is 0.74.Flood 4 hours with 85 milliliters containing molybdenum oxide 15 grams, nickel oxide 3 grams, the ammonium molybdate of phosphorous oxide 3 grams, basic nickel carbonate, phosphoric acid mixed solution, afterwards in 120 DEG C of dryings 4 hours, obtain catalyst B 4.Adopt the tenor in XRF mensuration catalyst, in table 2.
Embodiment 11
Prepare 91.5 grams of cylindrical vectors (diameter is 1.1 millimeters, and particle length is 2 millimeters ~ 5 millimeters, and 600 DEG C of roastings are after 4 hours in Muffle furnace for this article shaped, and recording butt is 76.5%) according to the method for embodiment 5, measuring its water absorption rate is 0.67.Flood 4 hours with 62 milliliters containing molybdenum oxide 22.7 grams, nickel oxide 4.2 grams, the ammonium molybdate of phosphorous oxide 3.1 grams, basic nickel carbonate, phosphoric acid mixed solution, afterwards in 120 DEG C of dryings 4 hours, obtain catalyst B 5.Adopt the tenor in XRF mensuration catalyst, in table 2.
Embodiment 12
Prepare 64 grams of cylindrical vectors (diameter is 1.1 millimeters, and particle length is 2 millimeters ~ 5 millimeters, and 600 DEG C of roastings are after 4 hours in Muffle furnace for this article shaped, and recording butt is 70.3%) according to the method for embodiment 6, measuring its water absorption rate is 0.85.Flood 4 hours with 55 milliliters containing molybdenum oxide 42.3 grams, nickel oxide 8.6 grams, the ammonium molybdate of phosphorous oxide 4.1 grams, basic nickel carbonate, phosphoric acid mixed solution, afterwards in 120 DEG C of dryings 4 hours, obtain catalyst B 6.Adopt the tenor in XRF mensuration catalyst, in table 2.
Table 2
| Embodiment | Catalyst is numbered | NiO, CoO, % by weight | MoO 3、WO 3, % by weight |
| 7 | B1 | NiO，5.0 | MoO 3，25.0 |
| Comparative example 5 | A1 | NiO，5.0 | MoO 3，25.0 |
| 8 | B2 | CoO，5.0 | MoO 3，25.0 |
| 9 | B3 | NiO，4.4 | WO 3，25.0 |
| 10 | B4 | NiO，3.0 | MoO 3，15.0 |
| 11 | B5 | NiO，4.2 | MoO 3，22.7 |
| 12 | B6 | NiO，8.6 | MoO 3，42.3 |
Embodiment 10-12 and comparative example 6 illustrate the performance that the invention provides catalyst, reference catalyst respectively.
4,6-dimethyl Dibenzothiophene (4, the 6-DMDBT) hydrodesulfurization activity of evaluate catalysts on high-pressure hydrogenation micro-reactor.
Reaction raw materials: 4,6-DMDBT mass fraction is the n-decane solution of 0.45%.
Catalyst vulcanization condition: temperature 360 DEG C, pressure 4.2MPa, sulfurized oil adopts CS
2mass fraction is the cyclohexane solution of 5%, and sulfurized oil feed rate 0.4 ml/min, sulfuration carries out 3 hours altogether.
Reaction condition: reaction temperature is 270 DEG C, pressure 4.2MPa, reaction oil feed rate is 0.2 ml/min, and stable reaction is sample analysis after 3 hours.
Desulfurization degree=4,6-DMDBT conversion ratio × (S
dMBC hour+ S
dMC hour B+ S
dMBP) × 100%, wherein, S
dMBC hour, S
dMC hour B, S
dMBPbe respectively 4,6-DMDBT hydrogenation afterproduct dimethyl connection cyclohexane, Dimethylcyclohexyl benzene, dimethyl diphenyl selective.The results are shown in table 3.
Table 3
| Embodiment | Catalyst | Desulfurization degree, % |
| 13 | B1 | 75.5 |
| Comparative example 6 | A1 | 51.1 |
| 14 | B2 | 70.2 |
| 15 | B3 | 63.4 |
As seen from Table 3, employing directly contains charcoal γ-Al as hydrogenation catalyst desulphurizing activated being obviously better than of carrier containing the shaping boehmite of charcoal
2o
3catalyst.In addition, in the preparation process that the invention provides catalyst, eliminate carrier calcination and catalyst roasting, Catalyst Production technique can be made to simplify, reduce the production cost of catalyst.
Claims (29)
1. a Hydrobon catalyst, containing carrier, load at least one is on this carrier selected from the slaine that the non-noble metal slaine of VIII and at least one are selected from group vib metal, be benchmark with oxide basis and with catalyst, group VIII metal content is 2 % by weight ~ 10 % by weight, group vib tenor is 15 % by weight ~ 45 % by weight, wherein, described carrier is for containing charcoal, the article shaped of cellulose ether and hydrated alumina, described containing charcoal, the radial crushing strength of the article shaped of cellulose ether and hydrated alumina is more than or equal to 12 Newton/millimeter, water absorption rate is 0.4 ~ 1.5, δ value is for being less than or equal to 10%, wherein, δ=((Q1-Q2)/Q1) × 100%, Q1 is the radial crushing strength of article shaped, and Q2 is that article shaped is through water soaking 30 minutes, through the radial crushing strength of 120 DEG C of dryings after 4 hours.
2. catalyst according to claim 1, is characterized in that, is benchmark with oxide basis and with catalyst, and group VIII metal content is 4 % by weight ~ 8 % by weight, and group vib tenor is 20 % by weight ~ 40 % by weight.
3. catalyst according to claim 1, is characterized in that, the radial crushing strength of described article shaped is 15 Newton/millimeter ~ 30 Newton/millimeter, and water absorption rate is that 0.6 ~ 1, δ is less than or equal to 5%.
4. the catalyst according to claim 1 or 3, is characterized in that, with described article shaped for benchmark, the mass fraction of described cellulose ether is 0.5% ~ 8%, in the mass fraction of element charcoal for 0.2% ~ 10%.
5. catalyst according to claim 4, is characterized in that, with described article shaped for benchmark, the mass fraction of described cellulose ether is 1% ~ 6%, in the mass fraction of element charcoal for 0.5% ~ 9%.
6. catalyst according to claim 5, is characterized in that, with described article shaped for benchmark, the mass fraction of described cellulose ether is 2% ~ 5%, in the mass fraction of element charcoal for 1% ~ 8%.
7. catalyst according to claim 1, is characterized in that, described cellulose ether is selected from one or more in methylcellulose, HEMC, hydroxypropyl methylcellulose; Described charcoal is selected from one or more in charcoal powder, coke powder, active carbon powder, carbon black.
8. catalyst according to claim 7, is characterized in that, described cellulose ether is methylcellulose, HEMC and their mixture.
9. catalyst according to claim 1, is characterized in that, described hydrated alumina is selected from one or more in boehmite, boehmite, aluminium hydroxide, three water-aluminum hydroxides.
10. catalyst according to claim 9, is characterized in that, described hydrated alumina is boehmite.
11. catalyst according to claim 1, is characterized in that, containing starch in described article shaped, with described article shaped for benchmark, the mass fraction of described starch is no more than 8%.
12. catalyst according to claim 1, it is characterized in that, the non-noble metal slaine of described 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, the slaine of described group vib metal be selected from molybdate, paramolybdate, containing molybdenum heteropolyacid, containing one or more in molybdenum heteropolyacid salt, tungstates, metatungstate, paratungstate, ethyl metatungstate, heteropoly acid containing tungsten, heteropoly acid containing tungsten salt.
13. catalyst according to claim 12, it is characterized in that, the non-noble metal slaine of described VIII is selected from one or more in cobalt nitrate, basic cobaltous carbonate, nickel nitrate and basic nickel carbonate, the slaine of described group vib be selected from ammonium molybdate, ammonium paramolybdate, containing molybdenum heteropolyacid, containing one or more in molybdenum heteropolyacid salt, ammonium metatungstate, ammonium tungstate, heteropoly acid containing tungsten, heteropoly acid containing tungsten salt.
The preparation method of 14. 1 kinds of Hydrobon catalysts, comprise and prepare carrier 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, carry out drying afterwards, wherein, described carrier is for containing charcoal, the article shaped of cellulose ether and hydrated alumina, with described catalyst for benchmark, it is 2 % by weight ~ 10 % by weight that the consumption of each component to make in described catalyst with the group VIII metal content of oxide basis, group vib tenor number is 15 % by weight ~ 45 % by weight, the condition of described drying comprises: temperature is 100 DEG C ~ 200 DEG C, time is 1 hour ~ 15 hours, described containing charcoal, the preparation method of the article shaped of cellulose ether and hydrated alumina comprises hydrated alumina, charcoal, cellulose ether mixes, shaping and dry, wherein, the radial crushing strength of described article shaped is more than or equal to 12 Newton/millimeter, and water absorption rate is that 0.4 ~ 1.5, δ value is for being less than or equal to 10%, wherein, δ=((Q1-Q2)/Q1) × 100%, Q1 is the radial crushing strength of article shaped, and Q2 is that article shaped is through water soaking 30 minutes, through the radial crushing strength of 120 DEG C of dryings after 4 hours.
15. methods according to claim 14, it is characterized in that, with described catalyst for benchmark, it is 4 % by weight ~ 8 % by weight that the consumption of each component to make in described catalyst with the group VIII metal content of oxide basis, group vib tenor is 20 % by weight ~ 40 % by weight, describedly be selected from supported on carriers at least one the slaine that the non-noble metal slaine of VIII and at least one are selected from group vib metal, carry out dry condition afterwards to comprise: temperature is 120 DEG C ~ 150 DEG C, and the time is 3 hours ~ 10 hours.
16. methods according to claim 14, is characterized in that, described hydrated alumina is selected from one or more in hibbsite, monohydrate alumina and amorphous hydroted alumina.
17. methods according to claim 16, is characterized in that, described hydrated alumina is boehmite.
18. methods according to claim 14, it is characterized in that, the non-noble metal slaine of described 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, the slaine of described group vib metal be selected from molybdate, paramolybdate, containing molybdenum heteropolyacid, containing one or more in molybdenum heteropolyacid salt, tungstates, metatungstate, paratungstate, ethyl metatungstate, heteropoly acid containing tungsten, heteropoly acid containing tungsten salt.
19. methods according to claim 18, it is characterized in that, the non-noble metal slaine of described VIII is selected from one or more in cobalt nitrate, basic cobaltous carbonate, nickel nitrate, basic nickel carbonate, the slaine of described group vib be selected from ammonium molybdate, ammonium paramolybdate, containing molybdenum heteropolyacid, containing one or more in molybdenum heteropolyacid salt, ammonium metatungstate, ammonium tungstate, heteropoly acid containing tungsten, heteropoly acid containing tungsten salt.
20. methods according to claim 14, is characterized in that, the radial crushing strength of described article shaped is 15 Newton/millimeter ~ 30 Newton/millimeter, and water absorption rate is that 0.6 ~ 1, δ is less than or equal to 5%.
21. methods according to claim 14 or 20, it is characterized in that, with described article shaped for benchmark, the mass fraction of described cellulose ether is 0.5% ~ 8%, in the mass fraction of element charcoal for 0.2% ~ 10%; Described drying condition comprises: temperature 60 C to being less than 350 DEG C, 1 hour ~ 48 hours drying time.
22. methods according to claim 21, is characterized in that, with described article shaped for benchmark, the mass fraction of described cellulose ether is 1% ~ 6%, in the mass fraction of element charcoal for 0.5% ~ 9%; Described drying condition comprises: temperature 80 DEG C ~ 150 DEG C, 2 hours ~ 14 hours drying time.
23. methods according to claim 22, is characterized in that, with described article shaped for benchmark, the mass fraction of described cellulose ether is 2% ~ 5%, in the mass fraction of element charcoal for 1% ~ 8%; Described drying condition comprises: temperature 100 DEG C ~ 130 DEG C, 3 hours ~ 10 hours drying time.
24. methods according to claim 14, is characterized in that, described cellulose ether is selected from one or more in methylcellulose, HEMC, hydroxypropyl methylcellulose; Described charcoal is selected from one or more in charcoal powder, coke powder, active carbon powder, carbon black.
25. methods according to claim 24, is characterized in that, described cellulose ether is methylcellulose, HEMC and their mixture.
26. methods according to claim 14, is characterized in that, described hydrated alumina is selected from one or more in boehmite, boehmite, aluminium hydroxide, three water-aluminum hydroxides.
27. methods according to claim 26, is characterized in that, described hydrated alumina is boehmite.
28. methods according to claim 14, is characterized in that, comprise the step that is introduced starch in forming process, and with described article shaped for benchmark, the mass fraction that described starch is introduced is no more than 8%.
29. 1 kinds of hydrofinishing process, under being included in hydrofining reaction condition, reacting feedstock oil and catalyst exposure, it is characterized in that, described catalyst is the catalyst described in claim 1-13 any one.
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