CN1508224A - 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 invention discloses a processing catalyzer after hydrogenated cracking and preparing method, adopting alumina as carrier, Mo and/or Wu as well as Ni and Co as active components, and P as catalyst promoting component. Firstly, it carries a part of Ni on the carrier by mixed kneading, and then uses Ni-Mo-Co-P mixed solution for dipping to make the catalyzer. It has higher NiO content, higher Ni/Ni+Mo atomic ratio, especially applied to processing the course of producing low-mercaptan product after hydrogenated cracking.
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 hydrocarbons is formed small molecules, lower boiling purpose product by the C-C bond rupture.Raw material generates mercaptan through the H2S reaction that cracking produces in a spot of alkene and the system in the hydrocracking process.Usually, temperature of reaction 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 corrodibility.Along with the increase of high-sulfur crude oil 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 complete processing 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 unstable 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 processing condition restriction is comparatively strict.
Hydrofining is a kind of comparatively effectively mercaptan removing process, and this method (as illuminating kerosene, aviation kerosene, FCC gasoline) when handling intermediate oil and light-end products is used comparatively general.Because this method needs independent reactor to carry out hydrofining (reaction conditions restriction), thereby be used for hydrocracking process meeting increase facility 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 hydroeracking unit.The hydrocracking aftertreatment is carried out under higher relatively temperature of reaction usually, and is higher about 15 ℃ even higher than common hydrofining 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 aftertreatment temperature of reaction 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 supporter Tungsten oxide 99.999 and/or molybdenum oxide, nickel oxide, cobalt oxide hydrotreating catalyst, the content 4% of described Tungsten oxide 99.999 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, support of the catalyst contain auxiliary agent be in fluorine, phosphorus, the magnesium one or more.Chinese patent CN 1229838A improves on this basis, make hydrofining take off to heat up in a steamer alcohol not only can and carry out under 150～260 ℃ of the lower temperature of reaction, has lower hydrogen-oil ratio (5～30) simultaneously, though this method reaction conditions 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 at the interval H of hydrocracking reaction
2S can generate mercaptan with alkene, and the existence of mercaptan has reduced the problem of the oil quality of respective regions, and this patent adopts the mode of further aftertreatment, with a spot of hydrotreating catalyst (Ni-Mo/Al
2O
3) be loaded on the hydrocracking reactor bottom, reduce the mercaptan in the light benzine (final boiling point is promptly 110 ℃ of 230F), but the effect of not mentioned other fractional oil desulfurizing alcohol.
Since mercaptan during with the sulfocompound 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 aftertreatment of high NiO content, high Ni/ (Mo+Ni) atomic ratio, this catalyzer has proper pore structure, hydro-sweetening activity and alkene saturated activity height, good stability, and Preparation of catalysts technology is simple, cost is low.
Catalyzer of the present invention is to be carrier with the aluminum oxide, and active ingredient 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 tackiness agent (little porous aluminum oxide get with peptizing agent making beating peptization), warp is mixed to be pinched, moulding, drying, roasting make support of the catalyst of the present invention; Or earlier macroporous aluminium oxide is mixed with the aperture aluminum oxide, add again and mixedly behind the tackiness agent of nickel compound containing pinch, make support of the catalyst 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, catalyzer of the present invention is made in dipping back drying, roasting.
The concrete preparation process of catalyzer of the present invention is as follows:
(1) preparation of support of the catalyst
A, macroporous aluminium oxide, little porous aluminum oxide are mixed with nickel compound containing.
Add in b, the raw material after mixed mix behind tackiness agent, 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 time of drying 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 retort furnace of above-mentioned dried strip, maturing temperature is generally 350～700 ℃, preferably 450～650 ℃, roasting time was generally 0.5～24 hour, was preferably 1～8 hour, obtained support of the catalyst.
(2) Preparation of catalysts
E, be that raw material adds P contained 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 deep green to by initial yellow-green colour and forms the cosolvency aqueous solution of nickeliferous, cobalt of while, molybdenum, phosphorus.
F, adopt the prepared support of the catalyst of the present invention, with the solution impregnation of above-mentioned configuration 1～6 hour.The dipping back leaches steeping fluid with funnel, and will flood bar and under room temperature, dry naturally, in 60～200 ℃ of dryings, preferably 100～150 ℃, be generally time of drying 0.5～24 hour, be preferably 1～8 hour; With the roasting in retort furnace of above-mentioned dried strip, maturing temperature is generally 350～700 ℃, preferably 450～650 ℃.Roasting time was generally 0.5～24 hour, was preferably 1～8 hour, can obtain the catalyzer finished product.
The specific surface 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 surface 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 surface area of the prepared support of the catalyst 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 per-cent.
Binder ingredients involved in the present invention comprises little porous aluminum oxide and peptizing agent, and the specific surface 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 Tai-Ace S 150, 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, Mierocrystalline cellulose, starch, one or more in the polymeric surface active agent.
Support shapes after the described moulding can be sheet, spherical, cylinder bar and special-shaped bar (trifolium, Herba Galii Bungei), preferably cylinder bar and special-shaped bar (trifolium, Herba Galii Bungei).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 metawolframate, 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 nickelous 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 Xiao Suangu and/or Cobaltous diacetate.P contained compound is selected from one or more in phosphoric acid, ammonium hydrogen phosphate and the primary ammonium phosphate.
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 catalyzer 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 pickling 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 aftertreatment, under the higher temperature of reaction of hydrocracking aftertreatment, characteristics with hydro-sweetening, alkene saturated activity height and good stability, and catalyst preparation process is simple, cost is low.
Catalyzer provided by the invention is applicable to that the boiling range scope is the hydrofining of 70～380 ℃ fraction oil of petroleum, be specially adapted to hydrocracking and generate oily mercaptan removal process, this process comprises refining desulfurization alcohol process behind the hydrogenation at least, also can comprise one or several other hydrofinings and hydrocracking process, be preferably used in the hydrocracking aftertreatment and produce low thioalcohol product process.
Embodiment
Further set forth feature of the present invention below in conjunction with specific examples.
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 aluminum oxide
| Raw material | Macroporous aluminium oxide A | Pseudo-boehmite | Macroporous aluminium oxide B | Germany SB aluminum oxide |
| Specific surface 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 support of the catalyst DT-1 provided by the invention.
Get macroporous aluminium oxide A111 gram, pseudo-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 tackiness agents (German SB aluminum oxide 47.2 grams, with 6.46 gram volumetric concentrations be that 65% nitric acid making beating is prepared from, tackiness agent 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 trifolium bar that extrusion gets diameter, again through 120 ℃ of dryings 2 hours, 500 ℃ of roastings 4 hours obtain carrier DT-1.Specific surface area, the pore volume of carrier DT-1 are listed in the table 2.Described specific surface area and pore volume adopt cryogenic nitrogen absorption BET method to measure (down together).
Embodiment 2
The preparation of support of the catalyst DT-2 provided by the invention.
Get macroporous aluminium oxide A150 gram, pseudo-boehmite 67.5 grams, German SB aluminum oxide 80.8 grams, nickelous nitrate (Ni (NO
3)
26H
2O) 44.33 grams mixed 15 minutes, (German SB aluminum oxide 69.2 grams and 8.4 gram volumetric concentrations are that 65% nitric acid making beating is prepared to add 317.6 gram tackiness agents, tackiness agent solid content 17wt%), and 3 the gram citric acids mix and to pinch and to roll 30 minutes, it is 1.6mm trifolium bar that extrusion gets diameter, again through 110 ℃ of dryings 4 hours, 550 ℃ of roastings 4 hours obtain carrier DT-2.Specific surface area, the pore volume of carrier DT-2 are listed in the table 2.
Embodiment 3
The preparation of support of the catalyst DT-3 provided by the invention.
Get industrial macroporous aluminium oxide A83.3 gram, Germany SB aluminum oxide 166.7 grams, pseudo-boehmite 60 grams, basic nickel carbonate (Ni content is 40wt%) 35.26 grams mixed 15 minutes, (pseudo-boehmite 90 grams and 8.0 gram volumetric concentrations are that 65% nitric acid making beating is prepared to add 352.9 gram tackiness agents, tackiness agent 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 trifolium bar that extrusion gets diameter, again through 150 ℃ of dryings 2 hours, 560 ℃ of roastings 4 hours obtain carrier DT-3.Specific surface area, the pore volume of carrier DT-3 are listed in the table 2.
Embodiment 4
The preparation of support of the catalyst DT-4 provided by the invention.
Get industrial macroporous aluminium oxide A138.8 gram, pseudo-boehmite 125 grams, Germany SB aluminum oxide 95 grams, basic nickel carbonate (Ni content is 40wt%) 31.03 grams mixed 15 minutes, (German SB aluminum oxide 83.3 grams and 7.5 gram volumetric concentrations are that 65% nitric acid making beating is prepared to add 294.1 gram tackiness agents, tackiness agent 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 trifolium bar that extrusion gets diameter, again through 140 ℃ of dryings 3 hours, 570 ℃ of roastings 4 hours obtain carrier DT-4.Specific surface area, the pore volume of carrier DT-4 are listed in the table 2.
The physico-chemical property of table 2 support of the catalyst
| 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 surface area, m 2/g | ????340.0 | ????339.9 | ????311.2 | ????325.2 |
| Pore volume, ml/g | ????0.575 | ????0.564 | ????0.523 | ????0.519 |
| Mean pore size, nm | ????8.02 | ????7.41 | ????7.25 | ????7.05 |
Embodiment 5
The preparation of present embodiment explanation Ni-Mo-Co-P steeping fluid.
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 Xiao Suangu (Co (NO again
3)
26H
2O), restir 2 hours, dissolving is placed in the beaker of 500ml, is diluted to 500ml and promptly gets solution.
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 Xiao Suangu (Co (NO again
3)
26H
2O), restir 3 hours, dissolving is placed in the beaker of 500ml, is diluted to 500ml and promptly gets solution.
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 steeping fluid with funnel, to flood bar dries under room temperature naturally, in 110 ℃ of dryings 8 hours, with the 480 ℃ of roastings 6 hours in retort furnace of above-mentioned dried strip, can obtain catalyzer finished product C-1.The catalyzer 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 steeping fluid with funnel, to flood bar dries under room temperature naturally, in 150 ℃ of dryings 8 hours, with the 500 ℃ of roastings 4 hours in retort furnace of above-mentioned dried strip, can obtain catalyzer finished product C-2.The catalyzer 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 steeping fluid with funnel, to flood bar dries under room temperature naturally, in 120 ℃ of dryings 6 hours, with the 550 ℃ of roastings 4 hours in retort furnace of above-mentioned dried strip, can obtain catalyzer finished product C-3.The catalyzer 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 steeping fluid with funnel, to flood bar dries under room temperature naturally, in 145 ℃ of dryings 8 hours, with the 480 ℃ of roastings 6 hours in retort furnace of above-mentioned dried strip, can obtain catalyzer finished product C-4.The catalyzer physico-chemical property sees Table 3.
Comparative Examples 1
Reference agent A is a present effect hydrocracking post-processing catalyst preferably.
Table 3 catalyzer physico-chemical property
| The catalyzer 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 surface 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 catalyzer provided by the invention.
The employing boiling range is that the hydrocracking of 73.6～355.1 ℃ laboratory simulation preparation generates oily mercaptan removal and the hydrogenation of olefins activity of stock oil evaluate catalysts C-1～C-4 that be.The raw material oil properties sees Table 4.Reaction conditions is: 385 ℃ of temperature of reaction, hydrogen dividing potential drop 14.7MPa, liquid hourly space velocity 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
| Stock 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 |
| Sulphur 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 catalyzer 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 catalyzer 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, sulphur content and bromine valency are all low than with the reference agent time, illustrate that the catalyzer that contains higher Ni/ (Ni+Mo) atomic ratio for preparing has higher desulfuration, mercaptan removal effect than reference agent, reach olefin saturation performance energy preferably.
Embodiment 11
Present embodiment illustrates the activity stability of catalyst hydrogenation mercaptan removal provided by the invention.
The employing boiling range is that the hydrocracking of 73.6～355.1 ℃ laboratory simulation preparation generates oily mercaptan removal and the hydrogenation of olefins activity stability of stock oil evaluate catalysts C-1 that be.Reaction conditions is: 385 ℃ of temperature of reaction, hydrogen dividing potential drop 14.7MPa, liquid hourly space velocity 10.0 hours
-1, hydrogen to oil volume ratio 1500.The mercaptan sulfur content of reaction product is listed in the table 6 with the variation in reaction times.
Comparative Examples 2
The activity stability of present embodiment explanation reference agent hydro-sweetening.
Adopting boiling range is the oily mercaptan removal and the hydrogenation of olefins activity stability of estimating the reference agent for stock oil of hydrocracking generation of 73.6～355.1 ℃ laboratory simulation preparation.Reaction conditions is: 385 ℃ of temperature of reaction, hydrogen dividing potential drop 14.7MPa, liquid hourly space velocity 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 times in the reaction product.
The content of mercaptan sulfur is with the variation in reaction times in table 6 reaction product
| Reaction times/hr | Generate oily mercaptan sulfur content, μ g/g | |
| Catalyzer 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 catalyzer provided by the invention not only has good active, and has good active stability.
Claims (10)
1, a kind of hydrocracking post-processing catalyst, with group vib and VIII family metal is active ingredient, auxiliary agent is a phosphorus, with the aluminum oxide is carrier, it is characterized in that active ingredient 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.
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, hydrocracking post-processing catalyst according to claim 1, the specific surface area that it is characterized in that described catalyzer is 200～400m
2/ g, pore volume are 0.35～0.55ml/g.
4, the preparation method of each described hydrocracking post-processing catalyst of a kind of claim 1～3, its step is as follows:
(1) macroporous aluminium oxide, little porous aluminum oxide mix with nickel compound containing, add tackiness agent, and then pinch through mixing, moulding, drying, roasting make support of the catalyst, described exsiccant temperature is 60～200 ℃, be 0.5～24 hour time of drying; Maturing 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, catalyzer is made in dipping back drying, roasting, and described drying temperature is 60～200 ℃, and be 0.5～24 hour time of drying; Maturing temperature is 350～700 ℃, and roasting time is 0.5～24 hour.
5, preparation method according to claim 4 is characterized in that the specific surface area of the described little porous aluminum oxide of described step (1) is 250～500m
2/ g, pore volume are 0.28～0.53ml/g; The specific surface area of macroporous aluminium oxide is 380～700m
2/ g, pore volume are 0.88～1.10ml/g.
6, preparation method according to claim 5, the specific surface area that it is characterized in that little porous aluminum oxide is 280～450m
2/ g; The specific surface area of macroporous aluminium oxide is 400～700m
2/ g.
7, preparation method according to claim 4, the weight ratio that it is characterized in that medium and small porous aluminum oxide of step (1) and macroporous aluminium oxide is 80: 20～50: 50.
8, preparation method according to claim 4, the specific surface area that it is characterized in that the support of the catalyst 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 per-cent.
9, preparation method according to claim 4 is characterized in that the nickel compound containing described in step (1) and (2) is nickelous nitrate, basic nickel carbonate or its mixture.
10, preparation method according to claim 4, 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 metawolframate, ammonium tungstate or its mixture, cobalt compound is Xiao Suangu, Cobaltous diacetate or its mixture, and P contained compound is selected from one or more in phosphoric acid, ammonium hydrogen phosphate and the primary ammonium phosphate.
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| CN 02144950 CN1211157C (en) | 2002-12-19 | 2002-12-19 | Hydrocracking after-treatment catalyst and preparing method thereof |
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| CN 02144950 CN1211157C (en) | 2002-12-19 | 2002-12-19 | Hydrocracking after-treatment catalyst and preparing method thereof |
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