CN102861601A - Hydrogenation catalyst containing fluorine and preparation method thereof - Google Patents
Hydrogenation catalyst containing fluorine and preparation method thereof Download PDFInfo
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Abstract
Provided are a hydrogenation catalyst containing fluorine and a preparation method thereof. The catalyst comprises a formed hydrated alumina carrier containing fluorine, at least one metal salt selected from VIII non-precious metals and at least one metal salt selected from VIB non-precious metals, wherein the metal salts are loaded on the carrier, the mass fraction of the VIII non-precious metals is 2-10%, and the mass fraction of the VIB non-precious metals is15-45% with an oxide as a unit and based on the catalyst. The preparation method of the catalyst comprises the steps of preparing the formed hydrated alumina carrier, loading at least one metal salt selected from the VIII non-precious metals and at least one metal salt selected from the VIB non-precious metals on the carrier and then performing drying. Compared with the prior art, the hydrogenation catalyst containing fluorine has excellent hydrocarbon oil hydrofining performance. In addition, the preparation method is simple, and the production cost is low.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst carbon monoxide-olefin polymeric and preparation method thereof.
Background technology
The flow process of conventional preparation hydrogenation catalyst comprises the preparation shaping carrier and supported active metal component on this carrier.Take the catalyst of alumina support preparation as example, comprise that drying and roasting become γ-Al with water and aluminium oxide (such as boehmite) moulding
2O
3, afterwards with the solution impregnation γ that contains the active metal component compound-Al
2O
3Catalyst is made in carrier, dry also roasting.
In addition, the method for preparing heavy-oil hydrogenation catalyst such as Richard A.Kemp report, that active metal component solution is directly joined in the boehmite gel, afterwards extrusion molding, drying and roasting is made catalyst (list of references: [1] Richard A.Kemp, Charles T.Adam, Applied Catalysis A:General, 134 (1996) 299-317); The method for preparing Hydrobon catalyst of D.Minoux report, to use nickel nitrate and ammonium molybdate and boehmite dried bean noodles mixed, then moulding, drying and roasting (list of references: [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 provides a kind of new hydrogenation catalyst carbon monoxide-olefin polymeric and preparation method thereof.
The present invention relates to following invention:
1. fluorine-containing hydrogenation catalyst, contain carrier, load on non-noble metal slaine and at least a slaine that is selected from the group vib metal of at least a VIII of the being selected from family on this carrier, in oxide and take catalyst as benchmark, the mass fraction of VIII family metal is 2-10%, the mass fraction of group vib metal is 15-45%, wherein, described carrier is fluorine-containing hydrated alumina forming matter.
2. according to 1 described catalyst, it is characterized in that, in oxide and take catalyst as benchmark, the mass fraction of VIII family metal is 4-8%, and the mass fraction of group vib metal is 20-40%.
3. according to 1 described catalyst, it is characterized in that, described fluorine-containing hydrated alumina forming matter contains hydrated alumina, fluorochemical and cellulose ether, and the radially crushing strength of described article shaped is more than or equal to 12N/mm, water absorption rate is 0.4-1.5, and the δ value is less than or equal to 10%; Wherein, δ=((Q1-Q2)/Q1) * 100%, Q1 are the radially crushing strength of article shaped, and Q2 is article shaped through water soaking 30 minutes, after drying radially crushing strength.
4. according to 3 described catalyst, it is characterized in that, the radially crushing strength of described article shaped is 15N/mm-30N/mm, and water absorption rate is 0.6-1, and δ is less than or equal to 5%.
5. according to 3 or 4 described catalyst, it is characterized in that, take described article shaped as benchmark, the mass fraction of described cellulose ether is 0.5-8%, take the mass fraction of the fluorochemical of element as 0.2-10%.
6. according to 5 described catalyst, it is characterized in that, take described article shaped as benchmark, the mass fraction of described cellulose ether is 1-6%, take the mass fraction of the fluorochemical of element as 0.5-9%.
7. according to 6 described catalyst, it is characterized in that, take described article shaped as benchmark, the mass fraction of described cellulose ether is 2-5%, take the mass fraction of the fluorochemical of element as 1%-8%.
8. according to 3 described catalyst, it is characterized in that, described cellulose ether is selected from methylcellulose, HEMC, the hydroxypropyl methylcellulose one or more; Described fluorochemical is selected from HF, NH
4F, C
6H
5In F, ten difluoro enanthol, polytetrafluorethylepowder powder, perfluoro caprylic acid, the fluoroacetic acid one or more.
9. according to 8 described catalyst, it is characterized in that, described cellulose ether is methylcellulose, HEMC and their mixture; Described fluorochemical is NH
4One or more of F, ten difluoro enanthol, perfluoro caprylic acid.
10. according to 3 described catalyst, it is characterized in that, described hydrated alumina is selected from one or more in boehmite, boehmite, aluminium hydroxide, three water-aluminum hydroxides.
11. according to 10 described catalyst, it is characterized in that, described hydrated alumina is boehmite.
12. according to 3 described catalyst, it is characterized in that, contain starch in the described article shaped, take described article shaped as benchmark, the mass fraction of described starch is no more than 8%.
13. according to 12 described catalyst, it is characterized in that, described starch is the sesbania powder, take described article shaped as benchmark, the mass fraction of described starch is no more than 5%.
14. according to 1 described catalyst, it is characterized in that, the non-noble metal slaine of described VIII family is selected from one or more in the soluble complexes of soluble complexes, nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and nickel of cobalt nitrate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and cobalt, and the slaine of described group vib metal is selected from one or more in molybdate, paramolybdate, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, the ethyl metatungstate.
15. according to 14 described catalyst, it is characterized in that, the non-noble metal slaine of described VIII family is selected from one or more in cobalt nitrate, basic cobaltous carbonate, nickel nitrate and the basic nickel carbonate, and the slaine of described group vib is selected from one or more in ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, the ammonium tungstate.
16. the preparation method of the described catalyst of aforementioned 1-15, comprise the preparation carrier and non-noble metal slaine and at least a slaine that is selected from the group vib metal of at least a VIII of being selected from of load family on this carrier, carry out afterwards drying, wherein, described carrier is fluorine-containing hydrated alumina forming matter, take described catalyst as benchmark, the consumption of each component makes in the described catalyst mass fraction take the VIII family metal of oxide as 2-10%, the mass fraction of group vib metal is 15-45%, the condition of described drying comprises: temperature is 100-200 ℃, and the time is 1-15 hour.
17. according to 16 described methods, it is characterized in that, take described catalyst as benchmark, the consumption of each component makes in the described catalyst mass fraction take the VIII family metal of oxide as 4-8%, the mass fraction of group vib metal is 20-40%, the condition of described drying comprises: temperature is 120-150 ℃, and the time is 3-10 hour.
18. according to 16 described methods, it is characterized in that, described hydrated alumina is selected from one or more in hibbsite, monohydrate alumina and the amorphous hydroted alumina.
19. according to 18 described methods, it is characterized in that, described hydrated alumina is boehmite.
20. according to 16 described methods, it is characterized in that, the non-noble metal slaine of described VIII family is selected from one or more in the soluble complexes of soluble complexes, nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride, nickel of cobalt nitrate, cobalt acetate, basic cobaltous carbonate, cobalt chloride, cobalt, and the slaine of described group vib is selected from one or more in molybdate, paramolybdate, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, the ethyl metatungstate.
21. according to 20 described methods, it is characterized in that, the non-noble metal slaine of described VIII family is selected from one or more in cobalt nitrate, basic cobaltous carbonate, nickel nitrate, the basic nickel carbonate, and the slaine of described group vib is selected from one or more in ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, the ammonium tungstate.
22. according to 16 described methods, it is characterized in that, the preparation method of described fluorinated water and aluminium oxide article shaped comprises hydrated alumina, fluorochemical, cellulose ether mixing, moulding and dry; Or with hydrated alumina, cellulose ether mixed-forming and dry, in this article shaped, introduce fluorochemical and dry in the mode of dipping afterwards; Wherein, the radially crushing strength of described article shaped is more than or equal to 12N/mm, and water absorption rate is 0.4-1.5, and the δ value is less than or equal to 10%; Wherein, δ=((Q1-Q2)/Q1) * 100%, Q1 are the radially crushing strength of article shaped, and Q2 is article shaped through water soaking 30 minutes, after drying radially crushing strength.
23. according to 22 described methods, it is characterized in that, the radially crushing strength of described article shaped is 15N/mm-30N/mm, water absorption rate is 0.6-1, and δ is less than or equal to 5%.
24. according to 22 or 23 described methods, it is characterized in that, take described article shaped as benchmark, the mass fraction of described cellulose ether is 0.5-8%, take the mass fraction of the fluorochemical of element as 0.2-10%; Described drying condition comprises: temperature 60 C is to less than 350 ℃, 1-48 hour drying time.
25. according to 24 described methods, it is characterized in that, take described article shaped as benchmark, the mass fraction of described cellulose ether is 1%-6%, take the mass fraction of the fluorochemical of element as 0.5%-9%; Described drying condition comprises: temperature 80-150 ℃, and 2-14 hour drying time.
26. according to 25 described methods, it is characterized in that, take described article shaped as benchmark, the mass fraction of described cellulose ether is 2%-5%, take the mass fraction of the fluorochemical of element as 1%-8%; Described drying condition comprises: temperature 100-130 ℃, and 3-10 hour drying time.
27. according to 22 described methods, it is characterized in that, described cellulose ether is selected from methylcellulose, HEMC, the hydroxypropyl methylcellulose one or more; Described fluorochemical is selected from HF, NH
4F, C
6H
5In F, ten difluoro enanthol, polytetrafluorethylepowder powder, perfluoro caprylic acid, the fluoroacetic acid one or more.
28. according to 27 described methods, it is characterized in that, described cellulose ether is methylcellulose, HEMC and their mixture; Described fluorochemical is NH
4One or more of F, ten difluoro enanthol, perfluoro caprylic acid.
29. according to 16 or 22 described methods, it is characterized in that, described hydrated alumina is selected from one or more in boehmite, boehmite, aluminium hydroxide, three water-aluminum hydroxides.
30. according to 29 described methods, it is characterized in that, described hydrated alumina is boehmite.
31. according to 22 described methods, it is characterized in that, comprise a step of introducing starch in forming process, take described article shaped as benchmark, the mass fraction that described starch is introduced is no more than 8%.
32. according to 31 described methods, it is characterized in that, described starch is the sesbania powder, take described article shaped as benchmark, the mass fraction of the introducing of described starch is no more than 5%.
According to catalyst provided by the invention, wherein, the radially crushing strength of the fluorinated water of described moulding and the article shaped of aluminium oxide (carrier) is more than or equal to 12N/mm, be preferably 15N/mm-30N/mm, water absorption rate is 0.6-1, and the δ value is less than or equal to 10%, is preferably less than or equal to 5%.Described δ=((Q1-Q2)/Q1) * 100%, Q1 is radially crushing strength of fluorine-containing hydrated alumina forming matter (carrier), Q2 is fluorine-containing hydrated alumina forming matter (carrier) through water soaking 30 minutes, through the radially crushing strength of 120 ℃ of heating, dryings after 4 hours.The size of δ value is representing fluorine-containing hydrated alumina forming matter (carrier) through the variation (or be called loss of strength rate) of water soaking anteroposterior diameter to crushing strength.
Here, described article shaped (carrier) the radially measuring method of crushing strength is carried out according to RIPP 25-90 catalyst compressive resistance determination method, about article shaped radially the concrete steps measured of crushing strength at RIPP25-90 detailed introduction is arranged, do not give unnecessary details here.
Described water absorption rate refers to that dry fluorine-containing hydrated alumina forming matter (carrier) soaks Unit Weight value added behind the 30min with excessive deionized water.The present invention adopts following method to measure: first with 120 ℃ of oven dry of testing sample 4 hours.Take out sample, be positioned over and be cooled to room temperature in the drier, with the screening of 40 mesh standard sieves, (numbering: w1) testing sample adds the 50g deionized water to take by weighing oversize 20g, soak 30min, filter, solid phase drains 5min, weighing solid phase weight (numbering: w2), water absorption rate=(w2-w1)/w1, dimensionless.In the practical operation, the density of water is in 1, and water absorption rate also can be tried to achieve by suction volume/vehicle weight, and its dimension is volume/weight, for example ml/g.
Under the prerequisite that the radially crushing strength that is enough to make article shaped (carrier), water absorption rate and loss of strength rate meet the demands, the present invention is not particularly limited the content of cellulose ether, in concrete embodiment, take described article shaped total amount as benchmark, the mass fraction of cellulose ether is preferably 0.5%-8%, more preferably 1%-6% more is preferably 2%-5%.Described cellulose ether preferably in methylcellulose, HEMC, hydroxypropyl methylcellulose one or more, further preferred methylcellulose, HEMC and their mixture wherein.
According to catalyst provided by the invention, wherein, take described article shaped total amount as benchmark, take the mass fraction of the fluorochemical of element as 0.2%-10%, more preferably 0.5%-9% is more preferably 1%-8%.Described fluorochemical is preferably from HF, NH
4F, C
6H
5In F, ten difluoro enanthol, polytetrafluorethylepowder powder, perfluoro caprylic acid, the fluoroacetic acid one or more are further preferably from NH
4One or more of F, ten difluoro enanthol, perfluoro caprylic acid.
According to catalyst provided by the invention, wherein, can contain the adjuvant component that does not affect or be of value to radially crushing strength, water absorption rate and the δ value of improving described article shaped in the described fluorine-containing hydrated alumina forming matter (carrier).For example, contain starch and add component, described starch can be the powder that is obtained through pulverizing by vegetable seeds arbitrarily, such as the sesbania powder.
According to catalyst provided by the invention, wherein, described hydrated alumina is selected from any hydrated alumina that can be used as adsorbent and catalyst carrier precursor, for example, can be boehmite, boehmite, aluminium hydroxide, three water-aluminum hydroxides, preferred boehmite.
According to preparation method provided by the invention, wherein, the fluorinated water of described moulding and the forming method of alumina support can be known methods arbitrarily.For example, the forming method of extrusion, spraying, round as a ball, compressing tablet and their combination.Described fluorochemical can be directly also dry with hydrated alumina, cellulose ether mixing aftershaping, also can be at first that hydrated alumina, cellulose ether mixed-forming is also dry, in this article shaped, introduce fluorochemical and drying in the mode of dipping afterwards.For guaranteeing carrying out smoothly of moulding, can be to the aforesaid material (mixture of hydrated alumina, fluorochemical and cellulose ether when moulding; Or hydrated alumina mixes with cellulose ether) in introducing and water, contain or do not contain auxiliary agent etc., for example, when adopting the moulding of extrusion method, comprise with described hydrated alumina and cellulose ether with water, contain or do not contain extrusion aid and mix, then obtain wet bar through extrusion molding, drying obtains article shaped of the present invention again.Described auxiliary agent is selected from starch, and described starch can be the powder that is obtained through pulverizing by vegetable seeds arbitrarily, such as the sesbania powder.Preferred forming method is the method for extruded moulding.Described drying condition comprises: temperature 60 C is extremely less than 350 ℃, and 1-48 hour drying time, preferred temperature is 80-150 ℃, and be 1-15h drying time, and further preferred temperature is 100-130 ℃, and be 2-10h drying time.
Preferred cobalt and/or the nickel wherein of the base metal of described VIII family, described slaine is selected from their soluble-salt and one or more in the complex compound, such as in their nitrate, chloride, acetate, subcarbonate one or more, be selected from one or more in the solubility of cobalt nitrate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and cobalt as an example of cobalt salt example, be selected from one or more and cobalt salt and nickel salt admixture in the solubility of nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and nickel as an example of nickel salt example.The preferred molybdenum of described group vib metal and/or tungsten, described slaine is selected from one or more in their soluble-salt, preferred molybdenum salt and/or tungsten salt wherein, for example, be selected from molybdate, paramolybdate, one or more in tungstates, metatungstate, ethyl metatungstate, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, the ethyl metatungstate.
Described in moulding water and alumina support on the non-noble metal slaine of at least a VIII of being selected from of load family and at least a method that is selected from the slaine of group vib can be conventional method arbitrarily, be preferably the method for dipping, described dipping method is conventional method, for example preparation is selected from the non-noble metal slaine and the solution that is selected from the slaine of group vib of VIII family, flood by the method for soaking or spraying afterwards, take described carbon monoxide-olefin polymeric as benchmark, the consumption of each component makes in the described composition content take the VIII family metal of oxide as the 2-10 % by weight, be preferably the 4-8 % by weight, the content of group vib metal is the 15-45 % by weight, is preferably the 20-40 % by weight.The condition of described drying comprises: temperature is 100-200 ℃, is preferably 120-150 ℃, and the time is 1-15 hour, is preferably 3-10 hour.
According to catalyst provided by the invention, can also contain the material that any material that does not affect the catalytic performance that the invention provides catalyst maybe can improve the catalytic performance of catalyst provided by the invention.As containing phosphorus, in element and take catalyst as benchmark, the content of above-mentioned auxiliary agent is no more than 10 % by weight, is preferably the 0.5-5 % by weight.
When also containing components such as being selected from phosphorus in the described catalyst, the described introducing method that is selected from the components such as phosphorus or silicon can be method arbitrarily, as can be with the compound of auxiliary agent as described in containing directly with as described in hydrated alumina mixes, moulding drying also; It can be the described carrier of dipping behind the mixed solution that is mixed with of the compound that will contain described auxiliary agent and the non-noble metal slaine that is selected from VIII family and the slaine that is selected from group vib.
According to the conventional method in this area, described catalyst is before using, usually can be in the presence of hydrogen, under 140-370 ℃ temperature, carry out presulfurization with sulphur, hydrogen sulfide or sulfur-bearing raw material, this presulfurization can be carried out outside device also can original position sulfuration in device, and the active metal component of its load is converted into the metal sulfide component.
Adopt hydrogenating catalyst composition provided by the invention to be suitable for the hydrofinishing of all kinds of hydrocarbon oil crude materials.Described hydrocarbon oil crude material can be various heavy mineral oils or artificial oil or their mixed fraction oil, such as be selected from crude oil, distillate, solvent-refined oil, slack wax, sweat oil, Fischer-Tropsch synthesis oil, liquefied coal coil, frivolous coal tar and the heavy deasphalted oil one or more.
Compare with existing technical method, hydrogenating catalyst composition provided by the invention not only has the refining performance of excellent hydrocarbon oil hydrogenation, determined the catalyst that the preparation method of hydrogenating catalyst composition provided by the invention is simple, production cost is starkly lower than existing method preparation by its preparation method.
The specific embodiment
The present invention will be further described for following example, but therefore do not limit content of the present invention.
Agents useful for same in the example except specifying, is chemically pure reagent.
Embodiment 1
Get the boehmite powder 100g that catalyst Chang Ling branch company produces, add the 4.0g methylcellulose, 3.0g sesbania powder, 4.5g NH
4F and 95mL deionized water fully mix, by the banded extruder kneading evenly after, extruded moulding obtains the wet bar of article shaped of hydrated alumina.The bar that will wet placed 150 ℃ of dryings of baking oven 12 hours.Measure radially crushing strength, water absorption rate and the δ value of dry aftershaping carrier, the results are shown in table 1.
Embodiment 2
Get the boehmite powder 50g that catalyst Chang Ling branch company produces, self-control unformed aluminium hydroxide powder 50g adds the 2.0g methylcellulose, 3.0g HEMC, 8.5g NH
4F and 95mL deionized water fully mix, by the banded extruder kneading evenly after, extruded moulding obtains the wet article shaped of aluminium hydroxide.Wet hydrogen aluminium oxide article shaped is positioned in the baking oven 220 ℃ of dryings 6 hours.Measure radially crushing strength, water absorption rate and the δ value of dry aftershaping carrier, the results are shown in table 1.
Embodiment 3
Get the boehmite powder 60g that catalyst Chang Ling branch company produces, three water-aluminum hydroxide 40g, add the 1.0g methylcellulose, 2.0g hydroxypropyl methylcellulose, 3.0g the sesbania powder, 40.0%HF solution 5mL and 95mL deionized water fully mix, after even by the banded extruder kneading, extruded moulding obtains the wet article shaped of aluminium hydroxide.Wet hydrogen aluminium oxide article shaped is positioned in the baking oven 80 ℃ of dryings 12 hours.Measure radially crushing strength, water absorption rate and the δ value of dry aftershaping carrier, the results are shown in table 1.
Embodiment 4
Get the boehmite SB powder 100g that Sasol company produces, add the 3.0g HEMC, 40.0%HF solution 10mL and 80mL deionized water fully mix, by the banded extruder kneading evenly after, extruded moulding obtains the moulding bar.Aluminium hydroxide moulding bar is positioned in the baking oven 150 ℃ of dryings 12 hours.Measure radially crushing strength, water absorption rate and the δ value of dry aftershaping carrier, the results are shown in table 1.
Embodiment 5
Get the boehmite SB powder 100g that Sasol company produces, add the 3.0g HEMC, 2g hydroxypropyl methylcellulose, 3.0g sesbania powder, 14.2g NH
4F and 90mL deionized water fully mix, by the banded extruder kneading evenly after, extruded moulding obtains the moulding bar.Aluminium hydroxide moulding bar is positioned in the baking oven 250 ℃ of dryings 4 hours.Measure radially crushing strength, water absorption rate and the δ value of dry aftershaping carrier, the results are shown in table 1.
Embodiment 6
Get the boehmite powder 100g that Yantai, Shandong permanent brightness chemical industry Co., Ltd produces, add the 5.0g hydroxypropyl methylcellulose, 3.0g sesbania powder, 1.5g NH
4F and 90mL deionized water fully mix, by the banded extruder kneading evenly after, extruded moulding obtains the moulding bar.The moulding bar is positioned in the baking oven 120 ℃ of dryings 4 hours.Measure radially crushing strength, water absorption rate and the δ value of dry aftershaping carrier, the results are shown in table 1.
Comparative Examples 1
Get the boehmite powder 100g that catalyst Chang Ling branch company produces, add red fuming nitric acid (RFNA) 2.5mL, 3.0g sesbania powder, 4.5g NH
4F and 95mL deionized water fully mix, by the banded extruder kneading evenly after, extruded moulding obtains the moulding bar.The moulding bar is positioned in the baking oven 80 ℃ of dryings 4 hours.Measure the intensity of dried strip.Take by weighing 10g gained dried strip and add the 50mL deionized water, be soaked in water 30 minutes, measure radially crushing strength, water absorption rate and the δ value of dry aftershaping carrier, the results are shown in table 1.
Comparative Examples 2
Get the boehmite SB powder 100g that Sasol company produces, add 20ml aluminium colloidal sol, 3.0g sesbania powder 14.2g NH
4F and 90mL deionized water fully mix, by the banded extruder kneading evenly after, extruded moulding obtains the moulding bar.The moulding bar is positioned in the baking oven 150 ℃ of dryings 4 hours.The moulding bar is positioned in the baking oven 150 ℃ of dryings 4 hours.Measure the intensity of dried strip.Take by weighing 10g gained dried strip and add the 50mL deionized water, be soaked in water 30 minutes, measure radially crushing strength, water absorption rate and the δ value of dry aftershaping carrier, the results are shown in table 1.
Comparative Examples 3
Get the boehmite powder 100g that Yantai, Shandong permanent brightness chemical industry Co., Ltd produces, add 5.0mL acetic acid, 3.0g sesbania powder, 1.5g NH
4F and 90mL deionized water fully mix, by the banded extruder kneading evenly after, extruded moulding obtains the moulding bar.The moulding bar is positioned in the baking oven 180 ℃ of dryings 4 hours.Measure the intensity of dried strip.Take by weighing 10g gained dried strip and add the 50mL deionized water, be soaked in water 30 minutes, measure radially crushing strength, water absorption rate and the δ value of dry aftershaping carrier, the results are shown in table 1.
Comparative Examples 4
Get the boehmite powder 100g that catalyst Chang Ling branch company produces, add red fuming nitric acid (RFNA) 2.5mL, 3.0g sesbania powder, 4.5g NH
4F and 95mL deionized water fully mix, by the banded extruder kneading evenly after, extruded moulding obtains the moulding bar.The moulding bar is positioned in the baking oven 80 ℃ of dryings 4 hours.600 ℃ of roastings of dried strip 4 hours.Measure radially crushing strength, water absorption rate and the δ value of roasting aftershaping carrier, the results are shown in table 1.
Table 1
| Embodiment | Support strength, N/mm | Water absorption rate | The δ value, % |
| 1 | 22.8 | 0.85 | 3.3 |
| 2 | 19.7 | 0.79 | 2.4 |
| 3 | 14.7 | 0.89 | 2.9 |
| 4 | 25.1 | 0.71 | 2.0 |
| 5 | 20.2 | 0.66 | 2.7 |
| 6 | 19.5 | 0.83 | 4.3 |
| Comparative Examples 1 | 21.6 | 0.87 | 60.2 |
| Comparative Examples 2 | 20.7 | 0.68 | 75.2 |
| Comparative Examples 3 | 23.5 | 0.85 | 46.0 |
| Comparative Examples 4 | 24.9 | 0.93 | 3.1 |
Embodiment 7-9 and Comparative Examples 5 illustrate respectively catalyst provided by the invention, reference catalyst and their preparation method.
Embodiment 7
Method according to embodiment 1 prepares 20.00g cylindrical vector (diameter is 1.1mm, and particle length is 2-5mm, and 600 ℃ of roastings are after 4 hours in Muffle furnace for this article shaped, and recording butt is 70.6%).Weighing basic nickel carbonate 4.71 grams (containing NiO 51%), molybdenum oxide 12.00 grams, phosphatase 11 .12 gram adds the water heating for dissolving and becomes 60ml nickel-molybdenum-phosphorus solution, and floods this carrier 4h with described solution supersaturation.Afterwards, in 120 ℃ of dryings 4 hours, obtain catalyst B 1.Adopt the tenor in the XRF mensuration catalyst, see Table 2.
Comparative Examples 5
Method according to Comparative Examples 4 prepares 14.24g cylindrical vector (diameter is 1.1mm, and particle length is 2-5mm).Measuring its water absorption rate is 0.93 ml/g.Weighing basic nickel carbonate 2.03 gram (containing NiO 51%), molybdenum oxide 5.18 grams, phosphoric acid 0.48 gram adds the water heating for dissolving and becomes 13.2ml nickel-molybdenum-phosphorus solution, and with this carrier of the saturated dipping of described solution 4h.Afterwards, in 120 ℃ of dryings 4 hours, 400 ℃ of roasting 3h obtained catalyst A 1.Adopt the tenor in the XRF mensuration catalyst, see Table 2.
Embodiment 8
Method according to embodiment 2 prepares 20.00g cylindrical vector (diameter is 1.1mm, and particle length is 2-5mm, and 600 ℃ of roastings are after 4 hours in Muffle furnace for this article shaped, and recording butt is 71.3%).Weighing basic cobaltous carbonate 3.43 grams (containing CoO 70%), molybdenum oxide 12.00 grams, phosphatase 11 .12 gram adds the water heating for dissolving and becomes 60ml nickel-molybdenum-phosphorus solution, and floods this carrier 4h with described solution supersaturation.Afterwards, in 120 ℃ of dryings 4 hours, obtain catalyst B 2.Adopt the tenor in the XRF mensuration catalyst, see Table 2.
Embodiment 9
Method according to embodiment 3 prepares 20.00g cylindrical vector (diameter is 1.1mm, and particle length is 2-5mm, and 600 ℃ of roastings are after 4 hours in Muffle furnace for this article shaped, and recording butt is 69.4%).Measuring its water absorption rate is 0.89, weighing nickel nitrate (Ni (NO
3)
26H
2O) 3.85 grams, ammonium metatungstate ((NH
4)
6W
7O
244H
2O) 5.65 grams add the water heating for dissolving and become, 17.8ml nickel tungsten solution, and with this carrier of the saturated dipping of described solution 1 hour.Afterwards, in 120 ℃ of dryings 4 hours, obtain catalyst B 3.Adopt the tenor in the XRF mensuration catalyst, see Table 2.
Embodiment 10
Method according to embodiment 4 prepares 20.00g cylindrical vector (diameter is 1.1mm, and particle length is 2-5mm, and 600 ℃ of roastings are after 4 hours in Muffle furnace for this article shaped, and recording butt is 68.9%).Weighing basic nickel carbonate 1.18 grams (containing NiO 51%), molybdenum oxide 3.00 grams, phosphoric acid 0.28 gram adds the water heating for dissolving and becomes 60ml nickel-molybdenum-phosphorus solution, and floods this carrier 4h with described solution supersaturation.Afterwards, in 120 ℃ of dryings 4 hours, obtain catalyst B 4.Adopt the tenor in the XRF mensuration catalyst, see Table 2.
Embodiment 11
Method according to embodiment 5 prepares 20.00g cylindrical vector (diameter is 1.1mm, and particle length is 2-5mm, and 600 ℃ of roastings are after 4 hours in Muffle furnace for this article shaped, and recording butt is 76.5%).Weighing basic nickel carbonate 3.53 grams (containing NiO 51%), molybdenum oxide 9.00 grams, phosphoric acid 0.84 gram adds the water heating for dissolving and becomes 60ml nickel-molybdenum-phosphorus solution, and floods this carrier 4h with described solution supersaturation.Afterwards, in 120 ℃ of dryings 4 hours, obtain catalyst B 5.Adopt the tenor in the XRF mensuration catalyst, see Table 2.
Embodiment 12
Method according to embodiment 6 prepares 20.00g cylindrical vector (diameter is 1.1mm, and particle length is 2-5mm, and 600 ℃ of roastings are after 4 hours in Muffle furnace for this article shaped, and recording butt is 70.3%).Weighing basic nickel carbonate 14.12 grams (containing NiO 51%), molybdenum oxide 36.00 grams, phosphoric acid 3.35 grams add the water heating for dissolving and become 60ml nickel-molybdenum-phosphorus solution, and flooded this carrier 4 hours with 60 ℃ of supersaturation of described solution.Afterwards, in 120 ℃ of dryings 4 hours, obtain catalyst B 6.Adopt the tenor in the XRF mensuration catalyst, see Table 2.
Table 2
| Embodiment | The catalyst numbering | NiO、CoO，w％ | MoO 3、WO 3，w％ |
| 7 | B1 | NiO，4.9 | MoO 3，25.0 |
| Comparative Examples 5 | A1 | NiO，5.0 | MoO 3，25.0 |
| 8 | B2 | CoO，5.2 | MoO 3，25.8 |
| 9 | B3 | NiO，4.3 | WO 3，25.2 |
| 10 | B4 | NiO，2.78 | MoO 3，15.8 |
| 11 | B5 | NiO，4.20 | MoO 3，22.70 |
| 12 | B6 | NiO，8.56 | MoO 3，42.3 |
The result in the analysis result of the VIII of oxide and group vib metal component respectively with comprise in the F of element with in Al, the VIII of oxide and group vib metal component and each component analysis of phosphorus percent value of sum as a result.
Embodiment 10-12 and Comparative Examples 6 illustrate respectively the performance that the invention provides catalyst, reference catalyst.
On the high-pressure hydrogenation micro-reactor 4 of evaluate catalysts, and the 6-dimethyl Dibenzothiophene (4,6-DMDBT) hydrodesulfurization activity.
Reaction raw materials: 4,6-DMDBT mass fraction is 0.45% n-decane solution.
Catalyst fluidization condition: 360 ℃ of temperature, pressure 4.2MPa, H
2Flow velocity 400ml/min, sulfurized oil adopts CS
2Mass fraction is 5% cyclohexane solution, sulfurized oil feed rate 0.4ml/min, and 3h is carried out in sulfuration altogether.
Reaction condition: reaction temperature is 270 ℃, pressure 4.2MPa, H
2Flow velocity is 400ml/min, and the reaction oil feed rate is 0.2ml/min, sample analysis behind the stable reaction 3h.
Desulfurization degree=4,6-DMDBT conversion ratio * (S
DMBCH+ S
DMCHB+ S
DMBP) * 100%, wherein, S
DMBCH, S
DMCHB, S
DMBPRespectively the selective of 4,6-DMDBT hydrogenation afterproduct dimethyl connection cyclohexane, Dimethylcyclohexyl benzene, dimethyl diphenyl.The results are shown in table 3.
Table 3
| Embodiment | Catalyst | Desulfurization degree, % |
| 13 | B1 | 75.5 |
| Comparative Examples 6 | A1 | 51.1 |
| 14 | B2 | 70.2 |
| 15 | B3 | 63.4 |
As seen from Table 3, adopt fluorine-containing moulding boehmite obviously to be better than fluorine-containing γ-Al as the hydrogenation catalyst HDS activity of carrier
2O
3Catalyst.In addition, in the invention provides the preparation process of catalyst, remove carrier roasting and catalyst roasting from, can make the Catalyst Production work simplification, reduced the production cost of catalyst.
Claims (32)
1. fluorine-containing hydrogenation catalyst, contain carrier, load on non-noble metal slaine and at least a slaine that is selected from the group vib metal of at least a VIII of the being selected from family on this carrier, in oxide and take catalyst as benchmark, the mass fraction of VIII family metal is 2-10%, the mass fraction of group vib metal is 15-45%, wherein, described carrier is fluorine-containing hydrated alumina forming matter.
2. catalyst according to claim 1 is characterized in that, in oxide and take catalyst as benchmark, the mass fraction of VIII family metal is 4-8%, and the mass fraction of group vib metal is 20-40%.
3. catalyst according to claim 1, it is characterized in that, described fluorine-containing hydrated alumina forming matter contains hydrated alumina, fluorochemical and cellulose ether, and the radially crushing strength of described article shaped is more than or equal to 12N/mm, water absorption rate is 0.4-1.5, and the δ value is less than or equal to 10%; Wherein, δ=((Q1-Q2)/Q1) * 100%, Q1 are the radially crushing strength of article shaped, and Q2 is article shaped through water soaking 30 minutes, after drying radially crushing strength.
4. catalyst according to claim 3 is characterized in that, the radially crushing strength of described article shaped is 15N/mm-30N/mm, and water absorption rate is 0.6-1, and δ is less than or equal to 5%.
5. according to claim 3 or 4 described catalyst, it is characterized in that, take described article shaped as benchmark, the mass fraction of described cellulose ether is 0.5-8%, take the mass fraction of the fluorochemical of element as 0.2-10%.
6. catalyst according to claim 5 is characterized in that, take described article shaped as benchmark, the mass fraction of described cellulose ether is 1-6%, take the mass fraction of the fluorochemical of element as 0.5-9%.
7. catalyst according to claim 6 is characterized in that, take described article shaped as benchmark, the mass fraction of described cellulose ether is 2-5%, take the mass fraction of the fluorochemical of element as 1%-8%.
8. catalyst according to claim 3 is characterized in that, described cellulose ether is selected from methylcellulose, HEMC, the hydroxypropyl methylcellulose one or more; Described fluorochemical is selected from HF, NH
4F, C
6H
5In F, ten difluoro enanthol, polytetrafluorethylepowder powder, perfluoro caprylic acid, the fluoroacetic acid one or more.
9. catalyst according to claim 8 is characterized in that, described cellulose ether is methylcellulose, HEMC and their mixture; Described fluorochemical is NH
4One or more of F, ten difluoro enanthol, perfluoro caprylic acid.
10. catalyst according to claim 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 claim 10 is characterized in that, described hydrated alumina is boehmite.
12. catalyst according to claim 3 is characterized in that, contains starch in the described article shaped, take described article shaped as benchmark, the mass fraction of described starch is no more than 8%.
13. catalyst according to claim 12 is characterized in that, described starch is the sesbania powder, and take described article shaped as benchmark, the mass fraction of described starch is no more than 5%.
14. catalyst according to claim 1, it is characterized in that, the non-noble metal slaine of described VIII family is selected from one or more in the soluble complexes of soluble complexes, nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and nickel of cobalt nitrate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and cobalt, and the slaine of described group vib metal is selected from one or more in molybdate, paramolybdate, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, the ethyl metatungstate.
15. catalyst according to claim 14, it is characterized in that, the non-noble metal slaine of described VIII family is selected from one or more in cobalt nitrate, basic cobaltous carbonate, nickel nitrate and the basic nickel carbonate, and the slaine of described group vib is selected from one or more in ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, the ammonium tungstate.
16. the preparation method of the described catalyst of claim 1-15, comprise the preparation carrier and non-noble metal slaine and at least a slaine that is selected from the group vib metal of at least a VIII of being selected from of load family on this carrier, carry out afterwards drying, wherein, described carrier is fluorine-containing hydrated alumina forming matter, take described catalyst as benchmark, the consumption of each component makes in the described catalyst mass fraction take the VIII family metal of oxide as 2-10%, the mass fraction of group vib metal is 15-45%, the condition of described drying comprises: temperature is 100-200 ℃, and the time is 1-15 hour.
17. method according to claim 16, it is characterized in that, take described catalyst as benchmark, the consumption of each component makes in the described catalyst mass fraction take the VIII family metal of oxide as 4-8%, the mass fraction of group vib metal is 20-40%, the condition of described drying comprises: temperature is 120-150 ℃, and the time is 3-10 hour.
18. method according to claim 16 is characterized in that, described hydrated alumina is selected from one or more in hibbsite, monohydrate alumina and the amorphous hydroted alumina.
19. method according to claim 18 is characterized in that, described hydrated alumina is boehmite.
20. method according to claim 16, it is characterized in that, the non-noble metal slaine of described VIII family is selected from one or more in the soluble complexes of soluble complexes, nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride, nickel of cobalt nitrate, cobalt acetate, basic cobaltous carbonate, cobalt chloride, cobalt, and the slaine of described group vib is selected from one or more in molybdate, paramolybdate, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, the ethyl metatungstate.
21. method according to claim 20, it is characterized in that, the non-noble metal slaine of described VIII family is selected from one or more in cobalt nitrate, basic cobaltous carbonate, nickel nitrate, the basic nickel carbonate, and the slaine of described group vib is selected from one or more in ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, the ammonium tungstate.
22. method according to claim 16 is characterized in that, the preparation method of described fluorinated water and aluminium oxide article shaped comprises hydrated alumina, fluorochemical, cellulose ether mixing, moulding and dry; Or with hydrated alumina, cellulose ether mixed-forming and dry, in this article shaped, introduce fluorochemical and dry in the mode of dipping afterwards; Wherein, the radially crushing strength of described article shaped is more than or equal to 12N/mm, and water absorption rate is 0.4-1.5, and the δ value is less than or equal to 10%; Wherein, δ=((Q1-Q2)/Q1) * 100%, Q1 are the radially crushing strength of article shaped, and Q2 is article shaped through water soaking 30 minutes, after drying radially crushing strength.
23. method according to claim 22 is characterized in that, the radially crushing strength of described article shaped is 15N/mm-30N/mm, and water absorption rate is 0.6-1, and δ is less than or equal to 5%.
24. according to claim 22 or 23 described methods, it is characterized in that, take described article shaped as benchmark, the mass fraction of described cellulose ether is 0.5-8%, take the mass fraction of the fluorochemical of element as 0.2-10%; Described drying condition comprises: temperature 60 C is to less than 350 ℃, 1-48 hour drying time.
25. method according to claim 24 is characterized in that, take described article shaped as benchmark, the mass fraction of described cellulose ether is 1%-6%, take the mass fraction of the fluorochemical of element as 0.5%-9%; Described drying condition comprises: temperature 80-150 ℃, and 2-14 hour drying time.
26. method according to claim 25 is characterized in that, take described article shaped as benchmark, the mass fraction of described cellulose ether is 2%-5%, take the mass fraction of the fluorochemical of element as 1%-8%; Described drying condition comprises: temperature 100-130 ℃, and 3-10 hour drying time.
27. method according to claim 22 is characterized in that, described cellulose ether is selected from methylcellulose, HEMC, the hydroxypropyl methylcellulose one or more; Described fluorochemical is selected from HF, NH
4F, C
6H
5In F, ten difluoro enanthol, polytetrafluorethylepowder powder, perfluoro caprylic acid, the fluoroacetic acid one or more.
28. method according to claim 27 is characterized in that, described cellulose ether is methylcellulose, HEMC and their mixture; Described fluorochemical is NH
4One or more of F, ten difluoro enanthol, perfluoro caprylic acid.
29. according to claim 16 or 22 described methods, it is characterized in that, described hydrated alumina is selected from one or more in boehmite, boehmite, aluminium hydroxide, three water-aluminum hydroxides.
30. method according to claim 29 is characterized in that, described hydrated alumina is boehmite.
31. method according to claim 22 is characterized in that, comprises a step of introducing starch in forming process, take described article shaped as benchmark, the mass fraction that described starch is introduced is no more than 8%.
32. method according to claim 31 is characterized in that, described starch is the sesbania powder, and take described article shaped as benchmark, the mass fraction of the introducing of described starch is no more than 5%.
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