CN1211157C - Hydrocracking after-treatment catalyst and preparing method thereof - Google Patents
Hydrocracking after-treatment catalyst and preparing method thereof Download PDFInfo
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Abstract
The present invention discloses a hydrocracking post-treatment catalyst and a preparation method thereof. In the catalyst, aluminum oxide is used as a carrier, active constituents comprise molybdenum (Mo) and/or tungsten, nickel (Ni) and cobalt (Co), and phosphorus (P) is used as a catalysis promoting component. The catalyst is prepared by firstly loading a part of nickel on the carrier with a kneading method and by secondly impregnating the nickel with a Ni-Mo-Co-P mixed solution. The obtained catalyst has the advantages of high NiO content, high Ni/Ni+Mo atomic ratio, high saturated activity of hydrodesulphurized alcohol and hydrodesulphurized olefine, and high stability. The catalyst is especially suitable for the process of the hydrocracking post-treatment production of a low-sulfur alcohol product.
Description
Technical field
The present invention relates to a kind of hydrotreating catalyst and preparation method thereof, particularly a kind of hydrocracking post-processing catalyst and preparation method thereof.
Background technology
Hydrocracking is a kind of petroleum refining process process that high-boiling hydrocarbon is formed little molecule, low boiling purpose product by the C-C bond fission.The cracking of raw material process produces the H in a spot of alkene and the system in the hydrocracking process
2The S reaction generates mercaptan.Usually, reaction temperature is too high will be unfavorable for that alkene is saturated and be easier to form mercaptan.And the existence of mercaptan not only can make product generation stench and make oil quality and stability decline in the product, and mercaptan itself also has corrosivity.Along with the increase of sour crude refining amount and the enhancing of environmental protection standard, make the handling problem of mercaptan seem more outstanding.
At present, industrial owing to raw material and processing technology difference, the removal methods of mercaptan is not quite similar.Usually can comprise soda acid electrochemical treating technology, oxidation deodorizing technology, hydrofining technology and hydrocracking aftertreatment technology.
Soda acid electrochemical treating technology belongs to early stage desulfurizing oil alcohol technology, because the soda acid consumption is big, waste residue environmental pollution, equipment corrosion and product colour unstability and seldom be used.
Air sweetening technology endangers the mercaptan subtractive process that less disulphide can be applicable to some intermediate oils by mercaptan is changed into, but this method raw material is suitable relatively poor, and the process conditions restriction is comparatively strict.
Hydrofinishing is a kind of comparatively effectively mercaptan removing process, and this method (as illuminating kerosene, aviation kerosine, FCC gasoline) when handling intermediate oil and light-end products is used comparatively general.Because this method needs independent reactor to carry out hydrofinishing (reaction condition restriction), thereby be used for hydrocracking process meeting increase equipment investment and energy consumption.
Hydrocracking aftertreatment technology (post-treatment) be meant the hydrocracking reactor back segment add a small amount of hydrocracking post-processing catalyst with remove mercaptan, saturation of olefins satisfies product index and environmental requirement, it is the mercaptan method that removes that generally adopts on the industrial hydrocracking unit.The hydrocracking post processing is carried out under higher relatively reaction temperature usually, and is higher about 15 ℃ even higher than common hydrofinishing temperature.The hydrocracking post-processing catalyst that adopts on the industrialized unit is common Hydrobon catalyst mostly.Nickel/(nickel+molybdenum) atomic ratio hangs down common Hydrobon catalyst and the high influence of hydrogenation post processing reaction temperature makes the effect of mercaptan deep removal undesirable owing to being subjected to.
Chinese patent CN 1229835A discloses a kind of be used for containing on the light-end products load alumina support tungsten oxide and/or molybdenum oxide, nickel oxide, cobalt oxide hydrotreating catalyst, the content 4% of described tungsten oxide and/or molybdenum oxide is to less than 10% (weight), nickel oxide content 1%～5% (weight), cobalt oxide content 0.01%～1% (weight), nickel and cobalt total atom number are 0.3～0.9 with the ratio of the total atom number of nickel, cobalt, tungsten and/or molybdenum, catalyst carrier contain auxiliary agent be in fluorine, phosphorus, the magnesium one or more.Chinese patent CN 1229838A improves on this basis, make hydrofinishing take off to heat up in a steamer alcohol not only can and carry out under 150～260 ℃ of the lower reaction temperatures, has lower hydrogen-oil ratio (5～30) simultaneously, though the method reaction condition comparatively relaxes, the mercaptan removal effect is preferable, but the unifining process that is adopted with usually the hydrocracking post-treatment condition that adopts different, and can not directly mate with hydrocracking process.
U.S. Pat 3338819 discloses a kind of hydrocracking back end hydrogenation process for refining.At generating mercaptan with alkene at the interval H2S of hydrocracking reaction, the existence of mercaptan has reduced the problem of the oil quality of respective regions, and this patent adopts the mode of further post processing, with a spot of hydrotreating catalyst (Ni-Mo/Al
2O
3) be loaded on the hydrocracking reactor bottom, reduce the mercaptan in the petroleum benzin (end point of distillation is 230 promptly 110 ℃), but the effect of not mentioned other fractional oil desulfurizing alcohol.
Since mercaptan during with the sulfur-containing compound desulfurization required desulfurization depth different, being specifically designed to the hydrocracking post-processing catalyst has higher (nickel and cobalt)/(nickel+cobalt+tungsten and/or molybdenum) atomic ratio usually.Chinese patent CN1071136C, CN 1072706C and U.S. Pat 6231753 all have comparatively detailed description.In addition, during preparation Mo-Ni-P solution, at P/MoO
3Under the certain prerequisite of mass ratio, Ni/ (Mo+Ni) atomic ratio＜0.3 o'clock, solution is solvable, further improves Ni content, and solution will produce precipitation.Usually,, adopt a few step impregnation methods more, increased operation, complicated technology for reaching higher Ni/ (Mo+Ni) ratio.
Summary of the invention
The purpose of this invention is to provide a kind of Catalysts and its preparation method with hydrocracking post processing of high NiO content, high Ni/ (Mo+Ni) atomic ratio, this catalyst has proper pore structure, hydro-sweetening activity and alkene saturated activity height, good stability, and Preparation of catalysts technology is simple, cost is low.
Catalyst of the present invention is to be carrier with the aluminium oxide, and active component is the base metal of group vib and group VIII.Described base metal is respectively the nickel and the cobalt of group vib molybdenum and/or tungsten and group VIII, adds phosphate builder.With the catalyst weight is benchmark, molybdenum oxide and/or tungsten oxide content are 5%～20%, be preferably 5%～15%, nickel oxide content is 7%～15%, be preferably 7%～10%, cobalt oxide content is 0.01%～1.0%, is preferably 0.05%～1.0%, phosphorus content is 0.8%～2.5%, is preferably 1.2%～2.0%.The nickle atom number is 0.3～0.9 with the ratio of the total atom number of nickel, molybdenum and/or tungsten, is preferably 0.4～0.9.The cobalt atom number is 0.005～0.1 with the ratio of the total atom number of nickel, cobalt, molybdenum and/or tungsten, is preferably 0.01～0.1.
Specific surface area of catalyst of the present invention is 200～400m
2/ g, pore volume are 0.35～0.55ml/g.
Preparation of catalysts method of the present invention comprises: mix macroporous aluminium oxide (1) with little porous aluminum oxide and nickel compound containing, after adding adhesive (little porous aluminum oxide get with peptizing agent making beating peptization), warp is mixed to be pinched, moulding, drying, roasting make catalyst carrier of the present invention; Or earlier macroporous aluminium oxide is mixed with the aperture aluminium oxide, add again and mixedly behind the adhesive of nickel compound containing pinch, make catalyst carrier of the present invention after the moulding, drying, roasting.(2) Preparation of catalysts: flood the alumina carrier containing Ni of above-mentioned preparation with the aqueous solution that contains molybdenum and/or tungsten and nickel, phosphorus and cobalt compound, catalyst of the present invention is made in dipping back drying, roasting.
The concrete preparation process of catalyst of the present invention is as follows:
(1) preparation of catalyst carrier
A, macroporous aluminium oxide, little porous aluminum oxide are mixed with nickel compound containing.
Add in b, the raw material after mixed mix behind adhesive, the extrusion aid pinch, roll, extrusion.
C, above-mentioned extrusion is dried under room temperature naturally, in 60～200 ℃ of dryings, preferably 100～150 ℃, be generally drying time 0.5～24 hour, be preferably 1～8 hour; Pulverize and obtain the dried strip that length is 3～8mm.
D, with the roasting in Muffle furnace of above-mentioned dried strip, sintering temperature is generally 350～700 ℃, preferably 450～650 ℃, roasting time was generally 0.5～24 hour, was preferably 1～8 hour, obtained catalyst carrier.
(2) Preparation of catalysts
E, be that raw material adds phosphorus-containing compound and distilled water with nickel compound containing and/or tungsten, cobalt compound, molybdate compound, stirred 0.5～4 hour at 90～99 ℃ of following azeotropic, solution transfers bottle green to by initial yellow green and forms the cosolvency aqueous solution of nickeliferous, cobalt of while, molybdenum, phosphorus.
F, adopt the prepared catalyst carrier of the present invention, with the solution impregnation of above-mentioned configuration 1～6 hour.The dipping back leaches maceration extract with funnel, and will flood under the strip room temperature and dry naturally, in 60～200 ℃ of dryings, preferably 100～150 ℃, be generally drying time 0.5～24 hour, be preferably 1～8 hour; With the roasting in Muffle furnace of above-mentioned dried strip, sintering temperature is generally 350～700 ℃, preferably 450～650 ℃.Roasting time was generally 0.5～24 hour, was preferably 1～8 hour, can obtain the catalyst finished product.
The specific area of the little porous aluminum oxide described in the step (1) is 250～500m
2/ g is preferably 280～450m
2/ g, pore volume are 0.28～0.53ml/g.The specific area of macroporous aluminium oxide is 380～700m
2/ g is preferably 400～700m
2/ g, pore volume are 0.88～1.10ml/g.Little porous aluminum oxide and macroporous aluminium oxide weight ratio are 80: 20～50: 50.Macropore wherein and little porous aluminum oxide all can be wherein one or more.Described specific surface and pore volume adopt B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature to measure.
The specific area of the prepared catalyst carrier of step (1) is 300～400m
2/ g, pore volume are 0.35～0.60ml/g, and it is 2～7% that NiO accounts for vehicle weight percentage.
Adhesive component involved in the present invention comprises little porous aluminum oxide and peptizing agent, and the specific area of wherein little porous aluminum oxide is 250～500m
2/ g, pore volume are 0.28～0.53ml/g; Peptizing agent is one or more in aluminum sulfate, citric acid, nitric acid, acetic acid and the oxalic acid.
Involved in the present invention to extrusion aid can be: sesbania powder, citric acid, oxalic acid, cellulose, starch, one or more in the high molecular surfactant.
Support shapes after the described moulding can be sheet, spherical, cylinder bar and special-shaped bar (clover, bunge bedstraw herb), preferably cylinder bar and special-shaped bar (clover, bunge bedstraw herb).The diameter of carrier can be 0.8～2.0mm slice and＞the thick bar of 2.5mm.
Described Tungstenic compound is selected from ammonium metatungstate, ammonium tungstate or its mixture, and molybdate compound is selected from ammonium molybdate, molybdenum oxide or its mixture.Nickel compound containing can be selected from one or more in its water-soluble nitrate, acetate, carbonate, the subcarbonate, preferred nickel nitrate and/or basic nickel carbonate.Cobalt compound can be selected from one or more in its water-soluble nitrate, acetate, carbonate, the subcarbonate, preferred cobalt nitrate and/or cobalt acetate.Phosphorus-containing compound is selected from one or more in phosphoric acid, ammonium hydrogen phosphate and the ammonium dihydrogen phosphate (ADP).
The characteristics of Preparation of catalysts method provided by the invention are that the nickel content of making earlier that contains the Ni carrier is relatively low, and afterwards soak in the Ni step mode that adopts Ni-Mo to soak altogether, can effectively be suppressed at like this and soak the phenomenon that the Ni on the carrier runs off because of dissolving in the Mo process.The catalyst that makes like this has higher Ni/ (Ni+Mo) atomic ratio, improves the hydrogenation performance, and it is saturated to help alkene, suppresses mercaptan and generates.And, to compare with the multistep infusion process, it is dry that Preparation of catalysts method provided by the invention can reduce several steps, and a few one-step baking steps have been simplified preparation technology, have reduced cost.
Compared with prior art, the present invention is used for catalyst oxidation nickel content height, the nickel/(nickel+molybdenum) atomic ratio height of hydrocracking post processing, under the higher reaction temperature of hydrocracking post processing, characteristics with hydro-sweetening, alkene saturated activity height and good stability, and catalyst preparation process is simple, cost is low.
Catalyst provided by the invention is applicable to that the boiling range scope is the hydrofinishing of 70～380 ℃ fraction oil of petroleum, be specially adapted to hydrocracking and generate oily removal of mercaptans process, this process comprises refining desulfurization alcohol process behind the hydrogenation at least, also can comprise one or several other hydrofinishings and hydrocracking process, be preferably used in the hydrocracking post processing and produce low thioalcohol product process.
The specific embodiment
Further set forth feature of the present invention below in conjunction with instantiation.
Embodiment 1～4
The character of used various macropores and little porous aluminum oxide sees Table 1 among the embodiment 1～4.
The character of table 1 aluminium oxide
| Raw material | Macroporous aluminium oxide A | Boehmite | Macroporous aluminium oxide B | Germany SB aluminium oxide |
| Specific area, m 2/g | 570 | 329 | 420 | 358 |
| Pore volume, ml/g | 1.09 | 0.28 | 0.90 | 0.48 |
| Butt, wt% | 0.72 | 0.80 | 0.75 | 0.72 |
Embodiment 1
The preparation of catalyst carrier DT-1 provided by the invention.
Get macroporous aluminium oxide A111 gram, boehmite 100 grams, macroporous aluminium oxide B 6.6 grams, basic nickel carbonate (Ni content is 40wt%) 16.7 grams mixed 15 minutes, add 200 gram adhesives (German SB aluminium oxide 47.2 grams, with 6.46 gram volumetric concentrations be that 65% nitric acid making beating is prepared from, adhesive solid content 17wt%), and extrusion aid 2 restrains, and the sesbania powder are mixed to be pinched and rolls 30 minutes, it is 1.6mm clover bar that extrusion gets diameter, again through 120 ℃ of dryings 2 hours, 500 ℃ of roastings 4 hours obtain carrier DT-1.Specific area, the pore volume of carrier DT-1 are listed in the table 2.Described specific area and pore volume adopt cryogenic nitrogen absorption BET method to measure (down together).
Embodiment 2
The preparation of catalyst carrier DT-2 provided by the invention.
Get macroporous aluminium oxide A150 gram, boehmite 67.5 grams, German SB aluminium oxide 80.8 grams, nickel nitrate (Ni (NO
3)
26H
2O) 44.33 grams mixed 15 minutes, (German SB aluminium oxide 69.2 grams and 8.4 gram volumetric concentrations are that 65% nitric acid making beating is prepared to add 317.6 gram adhesives, adhesive solid content 17wt%), and 3 the gram citric acids mix and to pinch and to roll 30 minutes, it is 1.6mm clover bar that extrusion gets diameter, again through 110 ℃ of dryings 4 hours, 550 ℃ of roastings 4 hours obtain carrier DT-2.Specific area, the pore volume of carrier DT-2 are listed in the table 2.
Embodiment 3
The preparation of catalyst carrier DT-3 provided by the invention.
Get industrial macroporous aluminium oxide A83.3 gram, Germany SB aluminium oxide 166.7 grams, boehmite 60 grams, basic nickel carbonate (Ni content is 40wt%) 35.26 grams mixed 15 minutes, (boehmite 90 grams and 8.0 gram volumetric concentrations are that 65% nitric acid making beating is prepared to add 352.9 gram adhesives, adhesive solid content 17wt%), and extrusion aid 3 gram sesbania powder, 3 restrain citric acids, mix and pinched and roll 30 minutes, it is 1.6mm clover bar that extrusion gets diameter, again through 150 ℃ of dryings 2 hours, 560 ℃ of roastings 4 hours obtain carrier DT-3.Specific area, the pore volume of carrier DT-3 are listed in the table 2.
Embodiment 4
The preparation of catalyst carrier DT-4 provided by the invention.
Get industrial macroporous aluminium oxide A138.8 gram, boehmite 125 grams, Germany SB aluminium oxide 95 grams, basic nickel carbonate (Ni content is 40wt%) 31.03 grams mixed 15 minutes, (German SB aluminium oxide 83.3 grams and 7.5 gram volumetric concentrations are that 65% nitric acid making beating is prepared to add 294.1 gram adhesives, adhesive solid content 17wt%), and extrusion aid 3 gram sesbania powder, 3 restrain citric acids, mix and pinched and roll 30 minutes, it is 1.6mm clover bar that extrusion gets diameter, again through 140 ℃ of dryings 3 hours, 570 ℃ of roastings 4 hours obtain carrier DT-4.Specific area, the pore volume of carrier DT-4 are listed in the table 2.
The physico-chemical property of table 2 catalyst carrier
| The embodiment numbering | 1 | 2 | 3 | 4 |
| Bearer number | DT-1 | DT-2 | DT-3 | DT-4 |
| NiO，wt％ | 3.12 | 4.11 | 6.58 | 5.79 |
| Specific area, m 2/g | 340.0 | 339.9 | 311.2 | 325.2 |
| Pore volume, ml/g | 0.575 | 0.564 | 0.523 | 0.519 |
| Average pore size, nm | 8.02 | 7.41 | 7.25 | 7.05 |
Embodiment 5
The preparation of present embodiment explanation Ni-Mo-Co-P maceration extract.
Solution R-A: with 400g molybdenum oxide (MoO
3Purity is 92%), 133g basic nickel carbonate (Ni content is 40wt%), the 45ml volumetric concentration is the water that 85% phosphoric acid places 300ml, is heated to 95 ℃ and stirs down, adds 12g cobalt nitrate (Co (NO again
3)
26H
2O), stirred 2 hours, dissolving is placed in the beaker of 500ml, is diluted to 500ml and promptly gets solution again.
Solution R-B: with 385g molybdenum oxide (MoO
3Purity is 92%), 142g basic nickel carbonate (Ni content is 40wt%), the 45ml volumetric concentration is the water that 85% phosphoric acid places 300ml, is heated to 99 ℃ and stirs down, adds 7.35g cobalt nitrate (Co (NO again
3)
26H
2O), stirred 3 hours, dissolving is placed in the beaker of 500ml, is diluted to 500ml and promptly gets solution again.
Embodiment 6
Present embodiment illustrates Preparation of catalysts provided by the invention.
The carrier 30 as one kind gram DT-1 of the diameter 1.6mm that makes is placed the solution R-A of the above-mentioned configuration of 60ml, room temperature dipping 2 hours, the dipping back leaches maceration extract with funnel, to flood bar dries under room temperature naturally, in 110 ℃ of dryings 8 hours, with the 480 ℃ of roastings 6 hours in Muffle furnace of above-mentioned dried strip, can obtain catalyst finished product C-1.The catalyst physico-chemical property sees Table 3.
Embodiment 7
Present embodiment illustrates Preparation of catalysts provided by the invention.
The carrier 30 as one kind gram DT-2 of the diameter 1.6mm that makes is placed the solution R-A of the above-mentioned configuration of 60ml, room temperature dipping 5 hours, the dipping back leaches maceration extract with funnel, to flood bar dries under room temperature naturally, in 150 ℃ of dryings 8 hours, with the 500 ℃ of roastings 4 hours in Muffle furnace of above-mentioned dried strip, can obtain catalyst finished product C-2.The catalyst physico-chemical property sees Table 3.
Embodiment 8
Present embodiment illustrates Preparation of catalysts provided by the invention.
The carrier 30 as one kind gram DT-3 of the diameter 1.6mm that makes is placed the solution R-B of the above-mentioned configuration of 60ml, room temperature dipping 3 hours, the dipping back leaches maceration extract with funnel, to flood bar dries under room temperature naturally, in 120 ℃ of dryings 6 hours, with the 550 ℃ of roastings 4 hours in Muffle furnace of above-mentioned dried strip, can obtain catalyst finished product C-3.The catalyst physico-chemical property sees Table 3.
Embodiment 9
Present embodiment illustrates Preparation of catalysts provided by the invention.
The carrier 30 as one kind gram DT-4 of the diameter 1.6mm that makes is placed the solution R-B of the above-mentioned configuration of 60ml, room temperature dipping 2 hours, the dipping back leaches maceration extract with funnel, to flood bar dries under room temperature naturally, in 145 ℃ of dryings 8 hours, with the 480 ℃ of roastings 6 hours in Muffle furnace of above-mentioned dried strip, can obtain catalyst finished product C-4.The catalyst physico-chemical property sees Table 3.
Comparative Examples 1
Reference agent A is a present effect hydrocracking post-processing catalyst preferably.
Table 3 catalyst physico-chemical property
| The catalyst numbering | C-1 | C-2 | C-3 | C-4 | The reference agent |
| The used carrier numbering | DT-1 | DT-2 | DT-3 | DT-4 | |
| NiO，wt％ | 7.10 | 7.11 | 10.2 | 12.1 | 3.08 |
| CoO，wt％ | 0.34 | 0.36 | 0.23 | 0.26 | 0.33 |
| P，wt％ | 1.50 | 1.61 | 1.37 | 1.37 | 1.51 |
| MoO 3，wt％ | 9.72 | 11.16 | 8.35 | 5.15 | 14.68 |
| Specific area, m 2/g | 254 | 253 | 209 | 228 | 204 |
| Pore volume, ml/g | 0.447 | 0.444 | 0.386 | 0.392 | 0.4328 |
| Ni/ (Ni+Mo) atomic ratio | 0.583 | 0.550 | 0.701 | 0.819 | 0.287 |
Embodiment 10
Present embodiment illustrates the hydro-sweetening activity of catalyst provided by the invention.
The employing boiling range is that the hydrocracking of 73.6～355.1 ℃ laboratory simulation preparation generates oily removal of mercaptans and the hydrogenation of olefins activity of feedstock oil evaluate catalysts C-1～C-4 that be.The raw material oil properties sees Table 4.Reaction condition is: 385 ℃ of reaction temperatures, hydrogen dividing potential drop 14.7MPa, liquid hourly space velocity (LHSV) 10.0 hours
-1, hydrogen to oil volume ratio 1500.The character of products obtained therefrom is listed in table 5.
Table 4 raw material oil properties
| Feedstock oil character | |
| d 4 20，g/cm 3 | 0.8254 |
| Boiling range/℃ | |
| IBP/10％ | 73.6/135.3 |
| 30％/50％ | 228.7/311.7 |
| 90％/EBP | 341.7/355.1 |
| Sulfur content, μ g/g | 3300 |
| Mercaptan sulfur content, μ g/g | 46.1 |
| The bromine valency, gBr/100ml | 1.50 |
The character of table 5 product
| The catalyst numbering | C-1 | C-2 | C-3 | C-4 | The reference agent |
| Mercaptan sulfur content, μ g/g | 7.8 | 6.9 | 5.0 | 4.8 | 10.1 |
| Total sulfur content, μ g/g | 70.3 | 66.4 | 30.6 | 42.1 | 86.1 |
| The bromine valency, gBr/100ml | 0.69 | 0.48 | 0.36 | 0.28 | 0.70 |
By the evaluation result of the hydrogenation activity of table 5 catalyst as seen, the hydrocracking that to adopt catalyst treatment boiling range of the present invention be 73.6～355.1 ℃ of scopes generates oil, mercaptan sulfur in the products obtained therefrom, sulfur content and bromine valency are all low than with the reference agent time, illustrate that the catalyst that contains higher Ni/ (Ni+Mo) atomic ratio for preparing has higher desulfuration, removal of mercaptans effect than reference agent, reach olefin saturation performance energy preferably.
Embodiment 11
Present embodiment illustrates the activity stability of catalyst hydrogenation removal of mercaptans provided by the invention.
The employing boiling range is that the hydrocracking of 73.6～355.1 ℃ laboratory simulation preparation generates oily removal of mercaptans and the hydrogenation of olefins activity stability of feedstock oil evaluate catalysts C-1 that be.Reaction condition is: 385 ℃ of reaction temperatures, hydrogen dividing potential drop 14.7MPa, liquid hourly space velocity (LHSV) 10.0 hours
-1, hydrogen to oil volume ratio 1500.The mercaptan sulfur content of product is listed in the table 6 with the variation in reaction time.
Comparative Examples 2
The activity stability of present embodiment explanation reference agent hydro-sweetening.
Adopting boiling range is the oily removal of mercaptans and the hydrogenation of olefins activity stability of estimating the reference agent for feedstock oil of hydrocracking generation of 73.6～355.1 ℃ laboratory simulation preparation.Reaction condition is: 385 ℃ of reaction temperatures, hydrogen dividing potential drop 14.7MPa, liquid hourly space velocity (LHSV) 10.0 hours
-1, hydrogen to oil volume ratio 1500.The content of mercaptan sulfur is listed in the table 6 with the variation in reaction time in the product.
The content of mercaptan sulfur is with the variation in reaction time in table 6 product
| Reaction time/hr | Generate oily mercaptan sulfur content, μ g/g | |
| Catalyst C-1 | The reference agent | |
| 133 | 7.0 | 10.0 |
| 324 | 7.8 | 11.0 |
| 549 | 8.0 | 10.7 |
| 705 | 7.0 | 11.0 |
| 1034 | 7.8 | 12.0 |
| 1470 | 8.0 | 12.6 |
| 1823 | 8.0 | 12.6 |
| 2002 | 8.0 | 12.4 |
The result of table 6 shows that catalyst provided by the invention not only has good active, and has good active stability.
Claims (7)
1, a kind of hydrocracking post-processing catalyst, with group vib and VIII family metal is active component, auxiliary agent is a phosphorus, with the aluminium oxide is carrier, it is characterized in that active component is molybdenum and/or tungsten and nickel and cobalt, is benchmark with the catalyst weight, molybdenum oxide and/or tungsten oxide content are 5%～20%, nickel oxide content is 7%～15%, and cobalt oxide content is 0.01%～1.0%, and phosphorus content is 0.8%～2.5%; The nickle atom number is 0.3～0.9 with the ratio of the total atom number of nickel, molybdenum and/or tungsten; The specific area of catalyst is 200～400m
2/ g, pore volume are 0.35～0.55ml/g.
2, hydrocracking post-processing catalyst according to claim 1, it is characterized in that with the catalyst weight being benchmark, molybdenum oxide and/or tungsten oxide content are 5%～15%, and nickel oxide content is 7%～10%, cobalt oxide content is 0.05%～1.0%, and phosphorus content is 1.2%～2.0%; The nickle atom number is 0.4～0.9 with the ratio of the total atom number of nickel, molybdenum and/or tungsten.
3, the preparation method of a kind of claim 1 or 2 described hydrocracking post-processing catalysts, its step is as follows:
(1) macroporous aluminium oxide, little porous aluminum oxide mix with nickel compound containing, add adhesive, and then pinch through mixing, moulding, drying, roasting make catalyst carrier, described is 60～200 ℃ in dry temperature, be 0.5～24 hour drying time; Sintering temperature is 350～700 ℃, and roasting time is 0.5～24 hour;
(2) flood the nickeliferous inorganic oxide carrier of above-mentioned preparation with the aqueous solution that contains molybdenum and/or tungsten and nickel, phosphorus and cobalt compound, catalyst is made in dipping back drying, roasting, and described baking temperature is 60～200 ℃, and be 0.5～24 hour drying time; Sintering temperature is 350～700 ℃, and roasting time is 0.5～24 hour;
Wherein the specific area of the described little porous aluminum oxide of step (1) is 250～500m
2/ g, pore volume are 0.28～0.53ml/g; The specific area of macroporous aluminium oxide is 380～700m
2/ g, pore volume are 0.88～1.10ml/g; The weight ratio of little porous aluminum oxide and macroporous aluminium oxide is 80: 20～50: 50.
4, preparation method according to claim 3, the specific area that it is characterized in that little porous aluminum oxide is 280～450m
2/ g; The specific area of macroporous aluminium oxide is 400～700m
2/ g.
5, preparation method according to claim 3, the specific area that it is characterized in that the catalyst carrier described in the step (1) is 300～400m
2/ g, pore volume are 0.35～0.60ml/g, and it is 2%～7% that NiO accounts for vehicle weight percentage.
6, preparation method according to claim 3 is characterized in that the nickel compound containing described in step (1) and (2) is nickel nitrate, basic nickel carbonate or its mixture.
7, preparation method according to claim 3, it is characterized in that the molybdate compound described in the step (2) is ammonium molybdate, molybdenum oxide or its mixture, Tungstenic compound is ammonium metatungstate, ammonium tungstate or its mixture, cobalt compound is cobalt nitrate, cobalt acetate or its mixture, and phosphorus-containing compound is selected from one or more in phosphoric acid, ammonium hydrogen phosphate and the ammonium dihydrogen phosphate (ADP).
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102451694B (en) * | 2010-10-15 | 2016-01-20 | 中国石油化工股份有限公司 | Hydro-sweetening Catalysts and its preparation method and application |
| CN103059963B (en) * | 2011-10-21 | 2014-12-31 | 中国石油化工股份有限公司 | Method for producing clean gasoline |
| CN103320159B (en) * | 2013-06-24 | 2015-08-12 | 大连理工大学 | A kind of method removing mercaptan sulfur in catalytically cracked gasoline |
| CN103316705B (en) * | 2013-06-24 | 2015-08-26 | 大连理工大学 | A kind of low temperature removes the Catalysts and its preparation method of mercaptan sulfur in catalytically cracked gasoline |
| CN107335469A (en) * | 2017-07-13 | 2017-11-10 | 武汉凯迪工程技术研究总院有限公司 | Hydrogenation catalyst suitable for producing low solidifying biodiesel and its preparation method and application |
| CN112742409B (en) * | 2019-10-31 | 2023-07-11 | 中国石油化工股份有限公司 | Catalyst for reducing mercaptan, preparation method and application thereof and method for reducing mercaptan in gasoline |
| CN111437823A (en) * | 2020-04-01 | 2020-07-24 | 深圳泰利能源有限公司 | Animal and vegetable oil hydrogenation catalyst composition and application thereof |
| CN113559870A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Heavy oil hydrogenation catalyst and preparation method and application thereof |
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2002
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