CN105013498A - Hydrotreating catalyst and applications thereof - Google Patents
Hydrotreating catalyst and applications thereof Download PDFInfo
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Abstract
The invention relates to a hydrotreating catalyst and applications thereof, wherein the catalyst contains a carrier, at least a metal component selected from group VIII, and at least a metal component selected from group VIB, the carrier contains 10-90 wt% of silica-alumina and 10-90 wt% of alumina, and the catalyst is characterized in that silica-alumina and pseudo boehmite are subjected to mixing, molding, drying and calcining to obtain the carrier, the pseudo bohemite comprises PB1, the X-ray diffraction characterizing result shows that the kappa1 and the kappa2 of the PB1 are respectively more than 1 and less than or equal to 3, kappa1 is h2/h1, kappa2 is h3/h2 , and h1, h2 and h3 respectively are the peak heights of three diffraction peaks having the 2[theta] angle of 24-30 DEG, 35-41 DEG and 46-52 DEG in the X-ray diffraction map. Compared with the catalyst in the prior art, the catalyst of the present invention has the good hydrogenation dearomatization performance.
Description
Technical field
The present invention relates to a kind of hydrotreating catalyst and application thereof.
Background technology
Industry hydrocrack charge comprises the 350-540 such as VGO DEG C cut, and reaction temperature is generally between 350-440 DEG C, and in charging, high boiling component contacts with catalyst in liquid form when reacting.Catalyst pore passage structure just has prior effect, and this just needs the aperture increasing carrier, improves the ability that reaction molecular touches hydrogenation active metals in catalyst.Due to molecular sieve and metal sulfide pore volume less, particularly meet the middle macropore of macromolecule hydrocarbon feed needs required by PETROLEUM PROCESSING less, conventional method realizes by the method introducing large pore volume heat-resistant inorganic oxide matrix in carrier of hydrocracking catalyst, such as, introduce alumina host.
ZL97121663.0 discloses a kind of hydrocracking catalyst being specially adapted to produce intermediate oil, containing amorphous silica-alumina component and aperture alumina adhesive, the content of amorphous silica-alumina is 30-60 % by weight, at least one group vib element and at least one VIII race element, hydrogenation metal oxide total content is 20-35 % by weight, surplus is aperture alumina adhesive, it is characterized in that catalyst specific surface 150-300 rice
2/ gram, pore volume 0.25-0.50 ml/g, 4-15 nano-pore is distributed in 60-90%, infrared acidity 0.30-0.50 mM/gram.
ZL01123765.1 discloses a kind of catalyst for hydrogenation treatment of diesel oil, this catalyst contains a kind of carrier and load molybdenum on this carrier and/or tungsten and nickel and/or cobalt, it is characterized in that, described carrier is made up of aluminium oxide and zeolite, the weight ratio of aluminium oxide and zeolite is 90:10-50:50, described aluminium oxide is the aluminium oxide be composited according to the weight ratio of 75:25-50:50 by little porous aluminum oxide and macroporous aluminium oxide, wherein, little porous aluminum oxide is the aluminium oxide that pore volume that diameter is less than 80 dust holes accounts for total pore volume more than 95%, macroporous aluminium oxide is the aluminium oxide that the pore volume in diameter 60-600 dust hole accounts for total pore volume more than 70%.
Summary of the invention
The object of this invention is to provide hydrotreating catalyst and this catalyst application that a kind of performance obtains modification.
The content that the present invention relates to comprises:
1. a hydrotreating catalyst, the metal component that VIII race and at least one are selected from group vib is selected from containing carrier and at least one, described carrier is containing silica-alumina and aluminium oxide, take carrier as benchmark, the content of silica-alumina is 10-90 % by weight, the content of aluminium oxide is 10-90 % by weight, it is characterized in that, described carrier is mixed with boehmite by silica-alumina, shaping, dry also roasting obtains, described boehmite comprises PB1, characterize with X-ray diffraction, the κ of described PB1
1and κ
2be greater than 1 respectively to being less than or equal to 3, wherein, κ
1=h
2/ h
1, κ
2=h
3/ h
2, h
1, h
2and h
3to be respectively in the x-ray diffraction spectra of PB1 be 24-30 ° at 2 θ angles, the peak height of three diffraction maximums of 35-41 ° and 46-52 °.
2. the catalyst according to 1, is characterized in that, take carrier as benchmark, and the content of silica-alumina is 20-80 % by weight, and the content of aluminium oxide is 20-80 % by weight; Characterize with X-ray diffraction, the κ of described PB1
1and κ
2be respectively 1.02-2.4.
3. the catalyst according to 2, is characterized in that, characterizes, the κ of described PB1 with X-ray diffraction
1for 1.2-2.3, κ
2for 1.02-1.4.
4. the catalyst according to 1, is characterized in that, the specific area of described PB1 is 100-350 rice
2/ gram, pore volume is 0.7-1.2 ml/g.
5. the catalyst according to 4, is characterized in that, the specific area of described PB1 is 150-280 rice
2/ gram, pore volume is 0.85-1.12 ml/g.
6. the catalyst according to 1, is characterized in that, the specific area of described silica-alumina is 350-750 rice
2/ gram, pore volume is 0.4-1.2 ml/g.
7. the catalyst according to 6, is characterized in that, the specific area of described silica-alumina is 400-650 rice
2/ gram, pore volume is 0.45-0.95 ml/g.
8. the catalyst according to 1,6 or 7 any one, is characterized in that, with described silica-alumina for benchmark, in described silica-alumina, the content of silica is 10-80 % by weight.
9. the catalyst according to 8, is characterized in that, with described silica-alumina for benchmark, in described silica-alumina, the content of silica is 15-55 % by weight.
10. the catalyst according to 1, it is characterized in that, the metal component of described VIII race is selected from nickel and/or cobalt, the metal component of described group vib is selected from molybdenum/or tungsten, with oxide basis and with described catalyst for benchmark, the content of described nickel and/or cobalt is 1-15 % by weight, and the content of described molybdenum/or tungsten is 5-40 % by weight.
11. catalyst according to 10, it is characterized in that, with oxide basis and with described catalyst for benchmark, the content of described nickel and/or cobalt is 2.0-10 % by weight, and the content of described molybdenum/or tungsten is 10-35 % by weight.
12. catalyst according to 1, it is characterized in that, described boehmite is the mixture of PB1 and PB2, is benchmark in butt and with carrier, the content of PB1 is the content of 10-90 % by weight, PB2 is 5-60 % by weight, with infrared spectrum characterization, the δ value of PB2 is 1.5-4.5, wherein, and δ=I
1/ (I
2+ I
3), I
1for 3665-3680cm in the infrared hydroxyl spectrum of described boehmite
-1the peak height of place's absworption peak, I
2for 3720-3730cm
-1the peak height of place's absworption peak, I
3for 3760-3780cm
-1the peak height of place's absworption peak.
13. catalyst according to 12, it is characterized in that, be benchmark in butt and with carrier, and the content of PB1 is the content of 20-80 % by weight, PB2 is 10-50 % by weight, and the δ value of described PB2 is 1.8-3.8.
14. catalyst according to 1, it is characterized in that, described drying condition comprises: temperature is 50-350 DEG C, and the time is 1-24 hour; Described roasting condition comprises: temperature is 400-700 DEG C, and the time is 0.5-6 hour.
15. catalyst according to 14, it is characterized in that, described drying condition comprises: temperature is 80-200 DEG C, and the time is 1-6 hour; Described roasting condition comprises: temperature is 550-650 DEG C, and the time is 1-3 hour.
16. catalyst according to 12, it is characterized in that, described PB2 is that PB1 was in the modifier of 70-400 DEG C of dry 0.5-14 hour.
17. catalyst according to 16, it is characterized in that, described PB2 is that PB1 was in the modifier of 220-330 DEG C of dry 1-6 hour.
The application of 18. catalyst according to any one of 1-17 in hydrocarbon ils processing.
In the present invention, described silicaalumina carrier can be commercially available commodity or adopt any one prior art to prepare.Preferred specific area is 350-750 rice
2/ gram, pore volume is the silica-alumina of 0.4-1.2 ml/g, and more preferably specific area is 400-650 rice
2/ gram, pore volume is the silica-alumina of 0.45-0.95 ml/g.
Describedly shapingly to carry out according to a conventional method, such as extruded moulding.Appropriate extrusion aid and/or adhesive can be added, then extrusion molding when extrusion molding.The kind of described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, are not repeated herein.
The method of described drying and roasting is conventional method, and such as, adopt baking oven, guipure, converter heating means to carry out drying, drying condition comprises temperature 50-350 DEG C, preferred 70-200 DEG C, time 1-24 hour, preferred 2-6 hour; Adopt baking oven, guipure, converter heating means to carry out roasting, roasting condition comprises temperature 350-800 DEG C, preferred 400-700 DEG C, time 0.5-6 hour, preferred 1-4 hour.
The present inventor is surprised to find, and characterizes with X-ray diffraction, and employing comprises one and meets κ
1value is 1 to being less than or equal to 3 and κ
2value is 1 to the boehmite PB1 and the silica-alumina component that are less than or equal to 3, and preferably the specific area of silica-alumina component is wherein 400-650 rice
2/ gram, pore volume is 0.45-0.95 ml/g, and the content of silica is that 15-55 weight is prepared into carrier, and when preparing hydrotreating catalyst by this carrier, catalyst has higher aromatic conversion performance.
Wherein, κ
1=h
2/ h
1, κ
2=h
3/ h
2, h
1, h
2and h
3be respectively in the x-ray diffraction spectra of PB1 at the peak height that 2 θ angles are three diffraction maximums of 24-30,35-41 and 46-52.
According to the present invention, the κ of further preferred described PB1
1and κ
2value be respectively 1.02-2.3, be more preferably the κ of described PB1
1value be 1.2-2.3, κ
2value be 1.02-1.4.
Be enough under the prerequisite meeting application claims, the source of the present invention to PB1 is not particularly limited, and such as, can be commercially available commodity or adopts the preparation of arbitrary existing method.Boehmite prepared by the boehmite method that such as disclosed in CN100999328B, a class adopts aluminum sulfate and sodium metaaluminate neutralisation to prepare can meet requirement of the present invention, quotes as a reference here.
In the present invention, described PB1 is at κ
1and κ
2the prerequisite that meets the demands of value under, preferably wherein specific area is 100-350 rice
2/ gram, pore volume is 0.7-1.2 ml/g, and preferably specific area is 150-280 rice further
2/ gram, pore volume is the boehmite of 0.85-1.12 ml/g.
In the present invention, the pore volume, specific area etc. of described boehmite are that described boehmite after 4 hours in 600 DEG C of roastings, is characterized by BET N2 adsorption and obtained.
Inventor studies discovery further, will meet the boehmite of aforementioned claim in 70-400 DEG C of dry 0.5-14 hour, after being preferable over 220-330 DEG C of dry 1-6 hour, obtain the modifier PB2 of PB1, employing infrared absorption spectroscopy characterizes, and the δ value of PB2 is 1.5-4.5, is preferably 1.8-3.8.Adopt it to mix with PB1 and silica-alumina, the carrier of shaping preparation is when preparing hydrotreating catalyst, the performance of catalyst is further enhanced.Wherein, δ=I
1/ (I
2+ I
3), I
1for 3665-3680cm in the infrared hydroxyl spectrum of described boehmite
-1the peak height of place's absworption peak, I
2for 3720-3730cm
-1the peak height of place's absworption peak, I
3for 3760-3780cm
-1the peak height of place's absworption peak.
According to catalyst provided by the invention, the described content being selected from VIII race and the metal component that is selected from group vib is the usual content of hydrotreating catalyst, such as, be benchmark with catalyst and with oxide basis, described catalyst contains VIII race's metal component of 1-10 % by weight, the VI B race metal component of 5-40 % by weight; VIII race's metal component preferably containing 1.5-7 % by weight, the VI B race metal component of 7-35 % by weight.Described group vib metal is selected from one or more in Cr, Mo or W, preferred Mo and/or W, and described group VIII metal component is selected from one or more in Fe, Co or Ni, preferred Co and/or Ni.
Being enough to described at least one to be selected under the prerequisite that metal component that VIII race and at least one be selected from group vib is carried on described alumina support, concrete carrying method is not particularly limited.Preferred method is infusion process.Comprise the dipping solution prepared respectively or simultaneously containing the metal component compound being selected from VIII and group vib, described dipping can be excessive immersion stain, the saturated dipping in hole according to maceration extract consumption difference, can be infusion method leaching, spray impregnating according to the mode difference that dipping realizes.By the regulation and control of the concentration to dipping solution, consumption or carrier consumption, can prepare the described catalyst of specifying content, this is those skilled in the art institute easy understand, does not repeat here.
According to method for preparing catalyst provided by the invention, described group vib metallic compound is selected from one or more in the soluble compound of these metals, such as, can be one or more in silico-tungstic acid, silicotungstate, phosphomolybdic acid, phosphomolybdate, molybdate, paramolybdate, tungstates, metatungstate, ethyl metatungstate.
Described group VIII metal compound is selected from the salt of these metals, comprises their inorganic acid salt or organic salt.Such as, described inorganic salts are selected from one or more in the partially decomposed product of nitrate, carbonate, subcarbonate, hypophosphites, phosphate, sulfate, chloride and these salts, preferably, one or more in nitrate, carbonate or subcarbonate are selected from.Described organic salt is the salt that generates of organic matter and VIII race's corrupt split or soluble complexes, and described organic matter can be organic base, organic carboxyl acid, amine, ketone, ethers, alkyls, is preferably organic carboxylate.
According to catalyst provided by the invention, can also contain organic additive, with described catalyst for benchmark, and in carbon, the content of described organic additive is no more than 10 % by weight, further preferably more than 6 % by weight.
Described organic additive is selected from containing one or more in oxygen and/or nitrogenous organic matter.Described oxygenatedchemicals is selected from one or more in Organic Alcohol, organic acid, and organic compounds containing nitrogen is selected from one or more in organic amine, organic ammonium salt.Particularly, be selected from oxygen containing organic matter and be selected from ethylene glycol, glycerine, polyethylene glycol (molecular weight is 200 ~ 1500), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1, one or more in 2-CDTA, citric acid, tartaric acid, malic acid, wherein preferably ethylene glycol, glycerine, polyethylene glycol and citric acid; Nitrogenous organic matter is selected from one or more in ethylenediamine, diethylenetriamines, 1,2-diaminocyclohexane tetraacetic acid, amion acetic acid, NTA, EDTA and ammonium salt thereof, wherein preferred EDTA and NTA.Described organic additive also can comprise containing Organic Alcohol and organic acid simultaneously.
According to preparation method provided by the invention, when catalyst of the present invention is further containing organic compound, also comprise the step introducing organic compound, described organic compound can be introduced together with group VIII metal, also can introduce after introducing group VIII metal, and carry out drying, preferably organic matter and group VIII metal are mixed with mixed solution and are introduced by the mode of dipping simultaneously, carry out drying afterwards.The selection of described baking temperature and time is except being not enough to make group VIII metal salt or complex decomposes, also should allow to retain most of organic matter introduced in the catalyst, such as retain the organic matter of more than 50%, more preferably, retain the organic matter of more than 70%.Its method can be the method that in prior art, any one can realize above-mentioned purpose.Such as, heat drying, drying under reduced pressure and add the methods such as thermal drying under reduced pressure.When described drying means is heat drying, preferred baking temperature is no more than 250 DEG C, further preferably more than 200 DEG C, is more preferably and is no more than 180 DEG C.Such as, in one preferred embodiment, described baking temperature is 70 DEG C ~ 180 DEG C.
According to the present invention, when preparing the described catalyst containing organic compound, in carbon and with described catalyst for benchmark, make in final catalyst preferably by selecting the introduction volume of described organic compound, the content of described organic additive is no more than 10 % by weight, further preferably more than 6 % by weight.
According to the conventional method in this area, described hydrotreating catalyst before the use, usually can be in presence of hydrogen, presulfurization is carried out with sulphur, hydrogen sulfide or sulfur-bearing raw material at the temperature of 140-370 DEG C, this presulfurization can be carried out outside device also can be In-situ sulphiding in device, and the active metal component of its load is converted into metal sulfide component.
Catalyst provided by the invention can be used for hydrotreatment or the hydro-upgrading of all kinds of hydrocarbon oil crude material.Reaction condition for hydrotreatment or hydro-upgrading is usual hydrotreatment or hydro-upgrading reaction condition, such as reaction temperature is degree 200-420 DEG C, more preferably 220-400 DEG C, pressure is 2-18 MPa, more preferably 2-15 MPa, and liquid hourly space velocity (LHSV) is 0.3-10 hour
-1, more preferably 0.3-5 hour
-1, hydrogen to oil volume ratio is 50-5000, more preferably 50-4000.
The device of the reaction of described hydrotreatment or hydro-upgrading can fill in device in any reaction being enough to make described feedstock oil react with described catalyst exposure at hydrotreating reaction conditions and carry out, such as, at described fixed bed reactors, carry out in moving-burden bed reactor or fluidized bed reactor.
Compared with providing catalyst with prior art, the invention provides catalyst and there is better hydrogenation aromatics-removing performance.Such as, adopt catalyst provided by the invention to process catalytic cracking tail oil under press strip part in 6.4MPa, tail oil balance arene content relatively reduces and can reach 10-55%.
Accompanying drawing explanation
Accompanying drawing in order to a further understanding of the present invention, and forms a part for description, for illustration of the present invention together with detailed description of the invention below, but is not construed as limiting the invention.In the accompanying drawings:
PB1-1 in Fig. 1 (the XRD figure of boehmite) is the XRD spectra of the boehmite meeting application claims; PB2-2 is a kind of modifier of PB1-1; The boehmite that SB(Sasol company produces, commodity are called SB powder) be a kind of XRD spectra that can not meet the boehmite of application claims.
PB2-1 in Fig. 2 (the IR-OH figure of boehmite) is the IR-OH spectrogram of the modifier of a kind of PB1-1; PB2-2 is the IR-OH spectrogram of the modifier of another kind of PB1-1; PB2-3 is that PB1-1 is in the IR-OH spectrogram of 600 DEG C of product of roastings.
detailed description of the invention
The invention will be further described by the following examples.
In experiment, XRD carries out on the D5005 type X-ray diffractometer of Siemens, Cu target, Ka radiation, solid probe, 40kV, 40mA, step-scan, stride 0.02 °, sweep limits 5 ~ 70 °.
IR-OH spectrogram measures at U.S. BIO-RAD company FT3000 type Fourier transformation infrared spectrometer, the self-supporting sheet of 15mm, and vacuum to 10
-3pa, keeps 1h, scans 1000 ~ 4000cm after being chilled to room temperature
-1wave-number range.
The boehmite used in embodiment and comparative example, preparation method or source:
PB1-1
The sodium metaaluminate (causticity coefficient is 1.6) of to be the aluminum sulfate of 93g/L and concentration by the 500mL concentration of clear be 195g/L slowly adds in the reactor that 2L band stirs simultaneously, and controlling reaction temperature is 40 DEG C, pH value 7.3.After reacting completely, stirring that to add concentration be sodium carbonate to the solution ph of 0.5mol/L is 9.7.Constant temperature 50 DEG C reaction is after 1 hour, and filter, deionized water washs three times, and the dry 3hr of 120 DEG C of temperature of ventilating in baking oven, obtains boehmite PB1-1.The h1 of PB1-1, h2, h3, k
1, k
2and its pore volume lists in table 1.
PB1-2
Be that the ammoniacal liquor of the aluminum sulfate of 48g/L and concentration 8% slowly adds in the reactor that 2L band stirs simultaneously by the 600mL concentration of clear, reaction is filtered, then adding ammoniacal liquor, to control reaction temperature be 35 DEG C, pH value 6.0.After reacting completely, filter, pulled an oar by filter cake, it is 9.5 that stirring adds carbonic hydroammonium to solution ph.Constant temperature 35 DEG C reaction is after 12 hours, and filter, deionized water washs three times, and the dry 3hr of 120 DEG C of temperature of ventilating in baking oven, obtains boehmite PB1-2.The h1 of PB1-2, h2, h3, k
1, k
2and its pore volume lists in table 1.
PB1-3
Be that the aluminum sulfate of 93g/L and the ammoniacal liquor of concentration 8% slowly add in the reactor of 2L band stirring simultaneously by the 600mL concentration of clear, controlling reaction temperature is 50 DEG C, pH value 4.6.After reacting completely, filter, pulled an oar by filter cake, it is 8.4 that stirring adds sodium carbonate to solution ph.Constant temperature 35 DEG C reaction is after 0.5 hour, and filter, deionized water washs three times, and the dry 3hr of 120 DEG C of temperature of ventilating in baking oven, obtains boehmite PB1-3.The h1 of PB1-3, h2, h3, k
1, k
2and its pore volume lists in table 1.
SB
The boehmite that Sasol company produces, commodity are called SB powder.The h1 of SB, h2, h3, k
1, k
2and its pore volume lists in table 1.
Table 1
| h1 | h2 | h3 | k 1 | k 2 | Pore volume | |
| PB1-1 | 1300 | 2400 | 2913 | 1.85 | 1.21 | 1.0 |
| PB1-2 | 1223 | 2721 | 3730 | 2.22 | 1.37 | 0.85 |
| PB1-3 | 1860 | 2984 | 3211 | 1.60 | 1.08 | 1.10 |
| PB2-1 | 424 | 540 | 581 | 1.27 | 1.08 | 0.98 |
| PB2-2 | 514 | 615 | 674 | 1.20 | 1.10 | 0.98 |
| SB | 5740 | 4278 | 6089 | 0.74 | 1.42 | 0.55 |
Wherein, SB can not meet application claims.
Boehmite modifier used in embodiment and comparative example and preparation method thereof:
PB2-1
300 grams of PB1-1 are placed in Muffle furnace, are heated to 250 DEG C and constant temperature 3 hours at such a temperature, obtain PB2-1.The I1 of PB2-1, I2, I3 and δ value lists in table 2.
PB2-2
300 grams of PB1-1 are placed in Muffle furnace, are heated to 300 DEG C and constant temperature 3 hours at such a temperature, obtain PB2-2.The I1 of PB2-2, I2, I3 and δ value lists in table 2.
PB2-3
300 grams of PB1-1 are placed in Muffle furnace, are heated to 600 DEG C and constant temperature 3 hours at such a temperature, obtain PB2-3.The I1 of PB2-3, I2, I3 and δ value lists in table 2.
PB2-4
300 grams of PB1-2 are placed in Muffle furnace, are heated to 230 DEG C and constant temperature 5 hours at such a temperature, obtain PB2-4.The I1 of PB2-4, I2, I3 and δ value lists in table 2.
PB2-5
300 grams of PB1-3 are placed in Muffle furnace, are heated to 330 DEG C and constant temperature 2 hours at such a temperature, obtain PB2-5.The I1 of PB2-5, I2, I3 and δ value lists in table 2.
Table 2
| I1 | I2 | I3 | δ | |
| PB1-1 | 0.226 | 0.547 | 0.641 | 0.8 |
| PB2-1 | 0.041 | 0.314 | 0.807 | 2.3 |
| PB2-2 | 0.014 | 0.126 | 0.512 | 3.7 |
| PB2-3 | 0.056 | 0.204 | 0.2961 | 1.1 |
| PB2-4 | 0.081 | 0.351 | 0.792 | 1.8 |
| PB2-5 | 0.022 | 0.116 | 0.489 | 3.5 |
Comparative example 1
By 267 grams of boehmite SB(butts 0.75, butt assay method puts into Muffle furnace for a certain amount of former powder is inserted crucible with cover, after being warming up to 700 DEG C of constant temperature 1hr, calculate the ratio of residue with former powder, lower same) (German Condea company produces with 395 grams of silica-aluminas, trade name Sira-40, pore volume 0.88ml/g, specific surface 468m
2/ g, silica weight content 40%, butt 0.76), the mixing of 16 grams, sesbania powder, be extruded into the trilobal bar that circumscribed circle diameter is 1.6 millimeters, dry 3 hours for 120 DEG C, 600 DEG C of roasting temperatures 3 hours, obtain carrier, catalyst carrier composition is in table 3.
After being cooled to room temperature, get 100 grams of carriers with containing ammonium metatungstate (Zigong, Sichuan cemented carbide works, tungsten oxide content is 82 % by weight) 50 grams, basic nickel carbonate (Xu Chi Chemical Co., Ltd. of Jiangsu, nickel oxide content is 51 % by weight) 8.7 grams, 10.5g citric acid 78ml aqueous impregnation, 180 DEG C are dried 10 hours, obtain catalyst R-1.With catalyst total amount for benchmark, in R1, the mass fraction (being calculated value, lower same) of metal component lists in table 3.
Example 1
By 267 grams of boehmite powder PB1-1(butts 0.75) with 3695 grams of silica-aluminas (with comparative example 1), the mixing of 16 grams, sesbania powder, be extruded into the trilobal bar that circumscribed circle diameter is 1.6 millimeters, dry 3 hours for 120 DEG C, 600 DEG C of roasting temperatures 3 hours, obtain carrier, catalyst carrier composition is in table 3.
After being cooled to room temperature, get 100 grams of carriers with containing ammonium metatungstate (Zigong, Sichuan cemented carbide works, tungsten oxide content is 82 % by weight) 51 grams, basic nickel carbonate (Xu Chi Chemical Co., Ltd. of Jiangsu, nickel oxide content is 51 % by weight) 8.7 grams, 10.5g citric acid 87ml aqueous impregnation, 180 DEG C are dried 10 hours, obtain catalyst C-1.With catalyst total amount for benchmark, in C-1, the mass fraction of metal component lists in table 3.
Example 2
By 133 grams of boehmite powder PB1-1 with 109 grams of PB2-2(butts 0.92), 394g silica-alumina (with example 1), the mixing of 16 grams, sesbania powder, be extruded into the trilobal bar that circumscribed circle diameter is 1.6 millimeters, 120 DEG C of oven dry, 600 DEG C of roasting temperatures 3 hours, obtain carrier, catalyst carrier composition is in table 3.
After being cooled to room temperature, get 100g carrier with containing ammonium metatungstate (Zigong, Sichuan cemented carbide works, tungsten oxide content is 82 % by weight) 51 grams, basic nickel carbonate (Xu Chi Chemical Co., Ltd. of Jiangsu, nickel oxide content is 51 % by weight) 8.7 grams, 10.5g citric acid 94ml aqueous impregnation, 180 DEG C are dried 10 hours, obtain catalyst C-2.With catalyst total amount for benchmark, in C-2, the mass fraction of metal component lists in table 3.
Comparative example 2
With embodiment 2, difference replaces PB-2-2 with 100g PB2-3, obtains catalyst R-2.With catalyst total amount for benchmark, in R-2, the mass fraction of metal component lists in table 3.
Example 3
By 131.6g gram of boehmite powder PB1-3(butt 0.76) with 224.7g PB2-1(butt 0.89), (German Condea company produces 267g silica-alumina, trade name Sira-20, pore volume 0.49ml/g, specific surface 590m
2/ g, silica weight content 20%, butt 0.75), the mixing of 16 grams, sesbania powder, be extruded into the trilobal bar that circumscribed circle diameter is 1.6 millimeters, 120 DEG C of oven dry, 600 DEG C of roasting temperatures 3 hours, obtain carrier, catalyst carrier composition is in table 3.
After being cooled to room temperature, get 100g carrier with containing ammonium metatungstate (Zigong, Sichuan cemented carbide works, tungsten oxide content is 82 % by weight) 51 grams, basic nickel carbonate (Xu Chi Chemical Co., Ltd. of Jiangsu, nickel oxide content is 51 % by weight) 8.7 grams, 10.5g citric acid 92ml aqueous impregnation, 140 DEG C are dried 3 hours, obtain catalyst C-3.With catalyst total amount for benchmark, in C-3, the mass fraction of metal component lists in table 3.
Example 4
By 460g gram of boehmite powder PB1-3(butt 0.76) with 56g PB2-1(butt 0.89), (German Condea company produces 267g silica-alumina, trade name Sira-30, pore volume 0.78ml/g, specific surface 455m
2/ g, silica weight content 30%, butt 0.75), the mixing of 16 grams, sesbania powder, be extruded into the trilobal bar that circumscribed circle diameter is 1.6 millimeters, 120 DEG C of oven dry, 480 DEG C of roasting temperatures 8 hours, obtain carrier, catalyst carrier composition is in table 3.
After being cooled to room temperature, get 100g carrier with containing ammonium metatungstate (Zigong, Sichuan cemented carbide works, tungsten oxide content is 82 % by weight) 30 grams, basic nickel carbonate (Xu Chi Chemical Co., Ltd. of Jiangsu, nickel oxide content is 51 % by weight) 18 grams, 25g citric acid 94ml aqueous impregnation, 110 DEG C are dried 20 hours, obtain catalyst C-4.With catalyst total amount for benchmark, in C-4, the mass fraction of metal component is listed in
Table 3.
Table 3
Example 7
This example illustrates the performance that the invention provides catalyst.
Raw materials used oil is that sand gently subtracts two vacuum gas oil (VGO)s, and its physico-chemical property is in table 4.
In this example, the evaluation method of catalyst is: particle catalyst breakage being become diameter 2-3 millimeter, catalyst 20 milliliters is loaded in 30 milliliters of fixed bed reactors, first carry out sulfuration with the kerosene containing 2 heavy % carbon disulfide according to following program under a hydrogen atmosphere before reaction, then switch reaction raw materials reaction.
Sulfuration program: be warming up to 150 DEG C, introduces sulfurized oil, and constant temperature 1hr Wen Bo upon adsorption, by two reactors, is warming up to 230 DEG C with 60 DEG C/hr, stablizes 2hr, be warming up to 360 DEG C, stablize 6hr with 60 DEG C/hr.Displacement reaction oil, adjustment reaction temperature to 355 DEG C, at least stablizes 20hr.Reactive hydrogen dividing potential drop is 6.4 MPas, liquid hourly space velocity (LHSV) (LHSV) 1 hour
-1, hydrogen-oil ratio (volume) 800, the catalyst of evaluation and the results are shown in Table 5.
Table 4
| Feedstock oil | |
| Density (20 DEG C), g/cm 3 | 0.8885 |
| S, % by weight | 16000 |
| N，mg/l | 352 |
| Simulation distil (ASTM D-2887) | |
| IBP | 291 |
| 50 | 391 |
| 90 | 421 |
After reaction, products obtained therefrom is carried out decompression distillation by 350 DEG C, products obtained therefrom carries out mass spectrum PONA analysis, the results are shown in Table shown in 5:.
Table 5,
| Catalyst | Tail oil aromatic hydrocarbons | Aromatic hydrocarbons reduces |
| R-1 | 14.6 | Benchmark, % |
| C-1 | 13.2 | 10 |
| C-2 | 7.8 | 53 |
| R-2 | 15.8 | Aromatic hydrocarbons increase about 8% |
Because evaluating catalyst reaction pressure is lower, make tail oil aromatic hydrocarbons close to so-called thermodynamical equilibrium region, after adopting this method, tail oil arene content reduces 10-55% relatively.
Claims (18)
1. a hydrotreating catalyst, the metal component that VIII race and at least one are selected from group vib is selected from containing carrier and at least one, described carrier is containing silica-alumina and aluminium oxide, take carrier as benchmark, the content of silica-alumina is 10-90 % by weight, the content of aluminium oxide is 10-90 % by weight, it is characterized in that, described carrier is mixed with boehmite by silica-alumina, shaping, dry also roasting obtains, described boehmite comprises PB1, characterize with X-ray diffraction, the κ of described PB1
1and κ
2be greater than 1 respectively to being less than or equal to 3, wherein, κ
1=h
2/ h
1, κ
2=h
3/ h
2, h
1, h
2and h
3to be respectively in the x-ray diffraction spectra of PB1 be 24-30 ° at 2 θ angles, the peak height of three diffraction maximums of 35-41 ° and 46-52 °.
2. the catalyst according to 1, is characterized in that, take carrier as benchmark, and the content of silica-alumina is 20-80 % by weight, and the content of aluminium oxide is 20-80 % by weight; Characterize with X-ray diffraction, the κ of described PB1
1and κ
2be respectively 1.02-2.4.
3. the catalyst according to 2, is characterized in that, characterizes, the κ of described PB1 with X-ray diffraction
1for 1.2-2.3, κ
2for 1.02-1.4.
4. the catalyst according to 1, is characterized in that, the specific area of described PB1 is 100-350 rice
2/ gram, pore volume is 0.7-1.2 ml/g.
5. the catalyst according to 4, is characterized in that, the specific area of described PB1 is 150-280 rice
2/ gram, pore volume is 0.85-1.12 ml/g.
6. the catalyst according to 1, is characterized in that, the specific area of described silica-alumina is 350-750 rice
2/ gram, pore volume is 0.4-1.2 ml/g.
7. the catalyst according to 6, is characterized in that, the specific area of described silica-alumina is 400-650 rice
2/ gram, pore volume is 0.45-0.95 ml/g.
8. the catalyst according to 1,6 or 7 any one, is characterized in that, with described silica-alumina for benchmark, in described silica-alumina, the content of silica is 10-80 % by weight.
9. the catalyst according to 8, is characterized in that, with described silica-alumina for benchmark, in described silica-alumina, the content of silica is 15-55 % by weight.
10. the catalyst according to 1, it is characterized in that, the metal component of described VIII race is selected from nickel and/or cobalt, the metal component of described group vib is selected from molybdenum/or tungsten, with oxide basis and with described catalyst for benchmark, the content of described nickel and/or cobalt is 1-15 % by weight, and the content of described molybdenum/or tungsten is 5-40 % by weight.
11. catalyst according to 10, it is characterized in that, with oxide basis and with described catalyst for benchmark, the content of described nickel and/or cobalt is 2.0-10 % by weight, and the content of described molybdenum/or tungsten is 10-35 % by weight.
12. catalyst according to 1, it is characterized in that, described boehmite is the mixture of PB1 and PB2, is benchmark in butt and with carrier, the content of PB1 is the content of 10-90 % by weight, PB2 is 5-60 % by weight, with infrared spectrum characterization, the δ value of PB2 is 1.5-4.5, wherein, and δ=I
1/ (I
2+ I
3), I
1for 3665-3680cm in the infrared hydroxyl spectrum of described boehmite
-1the peak height of place's absworption peak, I
2for 3720-3730cm
-1the peak height of place's absworption peak, I
3for 3760-3780cm
-1the peak height of place's absworption peak.
13. catalyst according to 12, it is characterized in that, be benchmark in butt and with carrier, and the content of PB1 is the content of 20-80 % by weight, PB2 is 10-50 % by weight, and the δ value of described PB2 is 1.8-3.8.
14. catalyst according to 1, it is characterized in that, described drying condition comprises: temperature is 50-350 DEG C, and the time is 1-24 hour; Described roasting condition comprises: temperature is 400-700 DEG C, and the time is 0.5-6 hour.
15. catalyst according to 14, it is characterized in that, described drying condition comprises: temperature is 80-200 DEG C, and the time is 1-6 hour; Described roasting condition comprises: temperature is 550-650 DEG C, and the time is 1-3 hour.
16. catalyst according to 12, it is characterized in that, described PB2 is that PB1 was in the modifier of 70-400 DEG C of dry 0.5-14 hour.
17. catalyst according to 16, it is characterized in that, described PB2 is that PB1 was in the modifier of 220-330 DEG C of dry 1-6 hour.
The application of 18. catalyst according to any one of 1-17 in hydrocarbon ils processing.
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| CN113559885A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Vulcanized hydrogenation catalyst, and preparation method and application thereof |
| CN113559892A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Composite carrier and preparation method thereof, hydrogenation catalyst containing composite carrier and application of hydrogenation catalyst |
| CN113559888A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Modified vulcanization type hydrogenation catalyst, and preparation method and application thereof |
| CN113559887A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof |
| CN113862028A (en) * | 2020-06-30 | 2021-12-31 | 中国石油化工股份有限公司 | Residual oil hydrotreating catalyst grading method and residual oil hydrotreating method |
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| CN113559885A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Vulcanized hydrogenation catalyst, and preparation method and application thereof |
| CN113559892A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Composite carrier and preparation method thereof, hydrogenation catalyst containing composite carrier and application of hydrogenation catalyst |
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| CN113559892B (en) * | 2020-04-28 | 2023-05-05 | 中国石油化工股份有限公司 | Composite carrier, preparation method thereof, hydrogenation catalyst containing composite carrier and application of hydrogenation catalyst |
| CN113559887B (en) * | 2020-04-28 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof |
| CN113559888B (en) * | 2020-04-28 | 2023-05-05 | 中国石油化工股份有限公司 | Modified vulcanized hydrogenation catalyst, and preparation method and application thereof |
| CN113862028A (en) * | 2020-06-30 | 2021-12-31 | 中国石油化工股份有限公司 | Residual oil hydrotreating catalyst grading method and residual oil hydrotreating method |
| CN113862028B (en) * | 2020-06-30 | 2023-04-11 | 中国石油化工股份有限公司 | Residual oil hydrotreating catalyst grading method and residual oil hydrotreating method |
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