CN103157482A - Hydrotreatment catalyst with silicon oxide-alumina as carrier and preparation and application thereof - Google Patents
Hydrotreatment catalyst with silicon oxide-alumina as carrier and preparation and application thereof Download PDFInfo
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Abstract
A hydrotreatment catalyst with silicon oxide-alumina as a carrier and preparation and application thereof. The catalyst contains a silicon oxide-alumina carrier, at least one metal component selected from VIII group and at least one metal component selected from VIB group; the catalyst is characterized in that the VIB group metal component exists in the form of metal oxide, and the VIII group metal component exists in the form of metal salt. Compared with the prior art, the hydrotreatment catalyst provided by the invention has obviously improved hydrotreatment performance, and is suitable for hydrotreatment process of a variety of hydrocarbon oil.
Description
Technical field
The present invention relates to a kind of hydrotreating catalyst and preparation thereof and application.
Background technology
The hydrofinishing of hydrocarbon raw material or hydrotreatment are a kind of technical process of generally using in petroleum refining industry, and its effect is mainly to remove the impurity such as sulphur in hydrocarbon feed, nitrogen, metal, aromatic hydrocarbons, carbon residue.By hydrotreatment, perhaps can directly obtain the light-end products that clean, for example diesel oil is carried out can obtaining the clean diesel product after hydrofinishing; Perhaps can improve the character of hydrocarbon feed, for example the FCC raw material be carried out pretreatment, the improved hydrocarbon feed of character is re-used as the charging of FCC process, to improve the efficient of FCC process.The hydrogenation catalyst that uses in the hydrotreatment process is made of the carrier that comprises group vib (as molybdenum or tungsten) and group VIII metal (as cobalt or nickel) component usually.In various carriers, what comparatively generally use is alumina support and silica-alumina carrier.
Traditional Hydrobon catalyst or hydrotreating catalyst generally contain group vib metal oxide and VIII family metal oxide, catalyst usually carries out one or many by the solution that will contain group vib metallic compound and/or VIII family metallic compound with carrier and contacts, then the method for and roasting dry by one or many prepares.
Patent ZL97112397 discloses a kind of catalyst for hydrorefining distillate oil, and it consists of the heavy % of nickel oxide 1-5, the heavy % of tungsten oxide 12-35, and the heavy % of fluorine 1-9, all the other are aluminium oxide.This catalyst is used the precursor aqueous solution dipping of aqueous solution containing fluoride and nickel, tungsten successively by comprising the moulding of aluminium oxide precursor after roasting, the method preparation of drying and roasting after each dipping.
Patent ZL96194541 discloses a kind of hydrogenation catalyst, this catalyst contains with the VIII family metal oxide of carrier supported and VI family metal oxide, this catalyst is the additive of selected at least a compound in the polyethers of the compound of self-contained at least two hydroxyls and 2-10 carbon atom and these compounds also in addition, and wherein VIII family's metallic compound and VI family metallic compound are the form of oxide.
Patent ZL94103999 discloses a kind of hydrotreating catalyst take aluminium oxide as carrier, and it consists of: γ-Al
2O
360-80%, NiO 3-6%, MoO
315-27%, P
2O
52-5%, aluminium oxide used is for adopting the pH value swing method to make.Described catalyst passes through the Ni-Mo-P solution impregnation of alumina carrier, then obtains in 100-140 ℃ of drying and 450-650 ℃ of roasting.
The document (" CoMo/Al of distinct methods preparation
2O
3The sign of Hydrobon catalyst ", catalysis journal,, 26 the 8th phases of volume, 639 pages in 2005) reported preparation CoMo/Al
2O
3The various preparation methods of catalyst comprise: (1) wet mixing method: cobalt nitrate and ammonium molybdate and organic acid are made into homogeneous transparent solution, then form through kneading, extrusion, oven dry and roasting together with boehmite; (2) dry pigmentation: cobalt nitrate and ammonium molybdate are directly mixed with boehmite, then add binding agent, form through kneading, extrusion, oven dry and roasting; (3) infusion process: boehmite is made alumina support through kneading, extrusion, oven dry and roasting together with binding agent and expanding agent, then adopt equi-volume impregnating with cobalt nitrate and ammonium molybdate solution total immersion stain, then drying and roasting form.Said method has all comprised the roasting process of catalyst, and metal component all exists with oxide form in catalyst.
Document (" CoMo/ γ-Al
2O
3The preparation of catalyst and hydrogenation deoxidation performance thereof ", petrochemical industry,, 39 the 1st phases of volume, 42 pages in 2010) reported CoMo/ γ-Al
2O
3The preparation method of catalyst comprises: (1) with ammonium heptamolybdate aqueous solution oxide impregnation alumina supporter 2h in ultrasound field, dry 4h under 100 ℃, 500 ℃ of lower roasting 4h; (2) adopt same procedure, then flood for the second time with cobalt nitrate solution, carry out equally drying and roasting.
Patent ZL94114194 discloses a kind of with γ-Al
2O
3Be carrier, active component is the Hydrodevulcanizing catalyst for hydro-carbons of cobalt, molybdenum, and the preparation of this catalyst comprises: (1) at high temperature prepares the alumina support of Zn modification; (2) with the ammonia spirit dipping Zn modified support that contains ethylenediamine, ammonium molybdate and cobalt salt, then in 110-150 ℃ of oven dry 2-6 hour, 480-600 ℃ roasting 3-8 hour, thereby obtain described catalyst.
Patent ZL99113281 has disclosed a kind of preparation method of catalyst for hydrorefining distillate oil, comprise take aluminium oxide or silicon-containing alumina as carrier, take W, Mo, Ni as active component, add the P auxiliary agent, make W, Mo, Ni, P co-impregnated solution with W, Mo, Ni, P-compound, after 70-120 ℃ of heating, with the mode impregnated carrier of described co-impregnated solution with the gradation total immersion, finally by 80-150 ℃ of drying 8 hours, 450-550 ℃ made in roasting 2-5 hour.
Patent ZL01106041 discloses a kind of catalyst for hydrorefining distillate oil, contain silica alumina as carrier take porous, take Mo, Ni, Co as metal component, the preparation method of described catalyst comprises: with the ammonia spirit oxide impregnation silicon-alumina support that contains Ni, Mo, the drying roasting makes the catalyst intermediate; With the ammonia spirit dipping gained catalyst intermediate that contains Ni, Co, Mo, the drying roasting makes final catalyst prod.
A kind of catalyst of coal tar to prepare clean fuel oil by catalytic hydrogenation is addressed in patent application 200910074790, and its mass percent consists of: molybdenum oxide 4-15%, nickel oxide 3-9%, cobalt oxide 0.1-5%, tungsten oxide 10-25%, silica 2.5-40%, aluminium oxide 26-65%.The catalyst preparation is at first to prepare the silica-alumina carrier, by load C o, Mo, Ni and W active component, then drying, roasting, moulding on incipient impregnation normal direction carrier.Described catalyst can be used for the catalytic hydrogenation clean fuel oil processed of coal tar, the national standard that the gasoline that prepared fuel oil obtains after separating and diesel oil meet respectively 93# gasoline and 0# diesel oil.
(" different silica sources is to NiW/Al for document
2O
3-SiO
2The impact of catalyst hydrogenation desulfurization performance ", petroleum journal＜PETROLEUM PROCESSING 〉,, 25 the 3rd phases of volume, 307 pages in 2009) and reported NiW/Al
2O
3-SiO
2The preparation method, comprise Ludox or SiO
2Powder and Al
2O
3The powder extruded moulding is made silica-alumina supports after high-temperature roasting; Or ethyl orthosilicate is flooded Al
2O
3Carrier floods rear 100 ℃ of oven dry, the hydrolysis after in air atmosphere with higher temperature roasting 3h, prepare silica-alumina supports.Adopt afterwards the saturated infusion process in hole, the silica-alumina supports dipping NiW solution with above-mentioned preparation obtains NiW/Al after drying and roasting
2O
3-SiO
2Catalyst.
In the prior art, also have some reports to relate to the catalyst preparation technology that preparation process does not comprise calcination steps, in these catalyst, vib metal and VIII family metal obviously exist with the form of non-oxidized substance.Even adopted in preparation process metal oxide for example molybdenum oxide as precursor, due to its solubility extremely low in the aqueous solution, thereby also need to be converted into other compound effects salt or complex compound or the heteropoly acid etc. of solubility.
Patent ZL200710176737 discloses a kind of preparation method who exempts from the petroleum distillate oil hydrogenation catalysts of roasting, and the method comprises: (1) joins organic sequestering agent in deionized water, and organic sequestering agent is dissolved fully; (2) add the salt that contains VI B family and VIII family metal; (3) obtain the maceration extract of P H value 6-8, according to equi-volume impregnating dipping catalyst carrier for hydrgenating, 100～150 ℃ of dryings obtain described catalyst.Obviously, in described catalyst, VI B family and VIII family metal all exist with the slaine form.
Patent ZL200380106678 discloses a kind of catalyst for hydrotreatment light oil, this catalyst comprises on inorganic oxide carrier at least a metal, at least a metal that is selected from periodic table group VIII metal of 1～15 % by weight and the phosphorus of 1.5～8 % by weight that are selected from periodic table VI family metal of 10 % by weight in oxide～40 % by weight, and in the carbon of 2～14 % by weight of carbon, the preparation of this catalyst comprises that the solution that will contain said components is carried on inorganic oxide carrier, carries out drying afterwards at 200 ℃ or lower temperature.
(" citric acid is to NiW/Al for document
2O
3The impact of Hydrobon catalyst sulfidation ", petroleum journal (PETROLEUM PROCESSING), 2010,26 the 3rd phases of volume, 329 pages) reported a kind of NiW/Al
2O
3The preparation of catalyst comprises and adopts the saturated infusion process in hole, to contain the Ni-W solution impregnation commercial alumina carrier of citric acid, makes the NiW/Al that contains citric acid complexing agent after 120 ℃ of dryings
2O
3Catalyst.
Patent application 200780003235 discloses a kind of method that manufacturing is applicable to the catalyst of hydrodesulfurizationof of naphtha, comprise: (i) with (a) cobalt salt, (b) molybdenum salt and (c) aqueous solution dipping of at least a organic additive be that approximately 0.6-2.0 cubic centimetre/g, mean pore sizes are the about silica supports of 150-2000 based on the dioxide-containing silica of silica at least about 85wt%, pore volume, to form catalyst precarsor; (ii) less than dry this catalyst precarsor at the about temperature of 200 ℃ to form dried catalyst precursor; (iii) the described dried catalyst precursor of sulfuration is to form catalyst, and condition is that this dried catalyst precursor or catalyst are not calcined in sulfuration or before being used for hydrodesulfurization.
Patent application ZL 200780024100 discloses a kind of for hydrocarbon ils being carried out the Catalysts and its preparation method of hydrodesulfurization/dewaxing.Described preparation method comprises: the solution that will contain the 8th family's metal, the 6th family's metal, organic acid and phosphoric acid loads on the inorganic oxide that contains at least a crystallized silicon aluminate with one dimension or two-dimentional channel system, subsequently the dry catalyst that obtains at 200 ℃ or lower temperature.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of new, hydrogenation catalyst and preparation and application that performance is further improved.
The present inventor finds under study for action, compare with unfired catalyst with the metal oxide catalyst that roasting obtains, vib metal exists with oxide form in catalyst, and VIII family metal is when existing with the slaine form, and catalyst has higher activity.
The present invention relates to following content:
1, a kind of hydrotreating catalyst take silica-alumina as carrier, contain silica-alumina carrier and at least a VIII of being selected from family and at least a metal component that is selected from group vib, it is characterized in that, described group vib metal component exists with the form of metal oxide, and described VIII family metal component exists with the form of slaine.
2, according to 1 described catalyst, take catalyst as benchmark and with oxide, the content of described VIII family metal component is the 1-10 % by weight, and the content of group vib metal component is the 5-40 % by weight.
3, according to 2 described catalyst, take catalyst as benchmark and with oxide, the content of described VIII family metal component is the 1.5-7 % by weight, and the content of group vib metal component is the 7-35 % by weight.
4, according to 1 described catalyst, it is characterized in that, described group vib metal component is selected from one or more in Cr, Mo, W, and described VIII family metal component is selected from one or more in Fe, Co, Ni.
5, according to 4 described catalyst, it is characterized in that, described group vib metal is Mo and/or W, and described VIII family metal component is Co and/or Ni.
6, according to 1 described catalyst, it is characterized in that, described slaine is selected from the inorganic salts of VIII family metal component or one or more in organic salt.
7, according to 6 described catalyst, it is characterized in that, described inorganic salts are selected from one or more in carbonate, subcarbonate, nitrate; Described organic salt is organic carboxylate.
8, catalyst described according to 1-7, is characterized in that, described catalyst also contains one or more auxiliary agents that are selected from P, F, B, and in element and take catalyst as benchmark, the content of described auxiliary agent is no more than 10 % by weight.
9, catalyst described according to 1-7, is characterized in that, described catalyst also contains organic additive, and take described catalyst as benchmark, and in carbon, the content of described organic additive is no more than 10 % by weight.
10, according to 1 described catalyst, it is characterized in that, take described carrier as benchmark, in described silica-alumina carrier, the content of silica is the 1-50 % by weight, and the content of aluminium oxide is the 50-99 % by weight.
11, according to 10 described catalyst, it is characterized in that, take described carrier as benchmark, in described silica-alumina carrier, the content of silica is the 2-40 % by weight, and the content of aluminium oxide is the 60-98 % by weight,
12, according to 10 described catalyst, it is characterized in that, in oxide, in described silica-alumina carrier, the content of silica is the 3-35 % by weight, and the content of aluminium oxide is the 65-97 % by weight.
13, the preparation method of aforementioned 1 hydrogenation catalyst that relates to comprises:
(1) with the solution impregnation silica-alumina carrier that contains the group vib metallic compound, carry out afterwards drying and roasting, the condition of described roasting makes the described compound that contains the group vib metal be enough to be converted into oxide;
(2) product that obtains with the solution impregnation step (1) that contains VIII family slaine carries out drying afterwards, and the condition deficiency of described drying is so that VIII family slaine is decomposed into oxide.
14, according to 13 described methods, it is characterized in that, the baking temperature of described step (1) is 80-300 ℃, and be 1-12 hour drying time, and described sintering temperature is 350-550 ℃, and roasting time is 2-10 hour; The baking temperature of described step (2) is 30-250 ℃, 1-8 hour drying time.
15, according to 14 described methods, it is characterized in that, the baking temperature of described step (1) is 100-250 ℃, and be 2-8 hour drying time, and described sintering temperature is 400-500 ℃, and roasting time is 3-6 hour; The baking temperature of described step (2) is 60-200 ℃, and be 2-6 hour drying time.
16, according to 13 described methods, it is characterized in that, described method also comprises introduces the step that is selected from one or more components in the components such as boron, phosphorus or fluorine.
17, according to 13 described methods, it is characterized in that, described method also comprises the step of introducing organic additive.
18, a kind of method for hydrotreating hydrocarbon oil is included under the hydrotreatment reaction condition, with hydrocarbon ils and catalyst haptoreaction, it is characterized in that, described catalyst is the described catalyst of aforementioned 1-12 any one.
According to catalyst provided by the invention, take catalyst as benchmark and with oxide, the described VIII of being selected from family and the content that is selected from the metal component of group vib can be the usual content of hydrotreating catalyst, preferably, described catalyst contains the VIII family metal component of 1-10 % by weight, the group vib metal component of 5-40 % by weight; The VIII family metal component that further preferably contains the 1.5-7 % by weight, the group vib 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 VIII family metal component is selected from one or more in Fe, Co or Ni, preferred Co and/or Ni.
Take described carrier as benchmark, in preferred silica-alumina, the content of silica is the 2-40 % by weight, and the content of aluminium oxide is the 60-98 % by weight; Further the content of preferential oxidation silicon is the 3-35 % by weight, and the content of aluminium oxide is the 65-97 % by weight.
Described silica-alumina has specific surface and the pore volume of conventional silica-alumina carrier, and the specific surface of preferential oxidation silicon-aluminium oxide is 130-350 rice
2/ gram, more preferably 180-300 rice
2/ gram, the pore volume of preferential oxidation silicon-aluminium oxide are 0.4-1 ml/g, more preferably 0.5-0.8 ml/g.
Described silica-alumina carrier can be commercially available commodity, as business amorphous aluminum silicide or sial bead etc., or adopts any one prior art preparation.A method that preferably prepares silica-alumina, be with the precursor of aluminium oxide and/or aluminium oxide mix with the precursor of silica and/or silica, roasting obtains.The mixing of silicon-containing compound and aluminum contained compound can be by carrying out such as modes such as mediating, grind mixed, immersion, dipping, deposition, precipitation.In case of necessity, silicon-containing compound can be scattered in the middle of solvent, then mix with aluminum contained compound.Described sintering temperature is 500-650 ℃, and roasting time is 1-10 hour, and preferred sintering temperature is 550-620 ℃, and roasting time is 2-8 hour.Wherein, the consumption of silicon-containing compound should make that in final carrier, silica satisfies required requirement.
Described silicon-containing compound can be selected from inorganic silicon compound, as Ludox, silicon gel, silica gel, silicic acid, silica, silicon tetrachloride, waterglass, amorphous aluminum silicide, also can be selected from organo-silicon compound, as silester, butyl silicate, the derivative of silicone oil, silicone, silane and these compounds.
Described aluminum contained compound can be selected from one or more in aluminium oxide, hibbsite, monohydrate alumina and amorphous hydroted alumina, or one or more in hibbsite, monohydrate alumina and the amorphous hydroted alumina of titaniferous, boron, zirconium, thorium, niobium, rare earth.
Described carrier optionally can be made into the article shaped of convenient operation arbitrarily, as spherical, compressing tablet and bar shaped.Described moulding can be undertaken by conventional process, all can as methods such as compressing tablet, spin, extrusions.When adopting the customary way moulding, for guarantee moulding carry out smoothly introduce auxiliary agent allow in described mixture, for example when extrusion, can add appropriate extrusion aid and/or adhesive and water, then extrusion molding.The kind of described extrusion aid, peptizing agent and consumption are this area routine, and for example common extrusion aid can be selected from one or more in sesbania powder, methylcellulose, starch, polyvinyl alcohol, PVOH.
According to catalyst provided by the invention, can also contain any performance that the invention provides catalyst that do not affect and maybe can improve the material of catalyst performance provided by the invention.As containing one or both in the components such as phosphorus, boron or fluorine, in element and take catalyst as benchmark, the content of above-mentioned auxiliary agent is no more than 10 % by weight, is preferably the 0.5-5 % by weight.
According to catalyst provided by the invention, can also contain organic additive, take described catalyst as benchmark, and in carbon, the content of described organic additive is no more than 10 % by weight, further preferably is no more than 6 % by weight.
Described organic additive is selected from one or more that contain 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 preferred 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 simultaneously and contains organic pure and mild organic acid.
According to method for preparing catalyst provided by the invention, be enough to the described at least a VIII of being selected from family and at least a metal component that is selected from group vib is carried on described silica-alumina carrier and described group vib metal component is existed with the form of metal oxide, under the prerequisite that described VIII family metal component exists with the form of slaine, concrete operation step is not particularly limited.For example, the method that the described at least a VIII of being selected from family and at least a metal component that is selected from group vib is carried on described carrier is infusion process.Described dipping can be excessive liquid dipping, the saturated dipping in hole according to maceration extract consumption difference, and the mode difference that realizes according to dipping can be infusion method dipping, spray impregnating.By the regulation and control to concentration, consumption or the carrier consumption of dipping solution, can prepare the described catalyst of specifying content, it is intelligible that this is that those skilled in the art hold.
According to method for preparing catalyst provided by the invention, the described compound that contains the group vib metal is selected from one or more in the soluble compound of these metals, for example, can be one or more in silico-tungstic acid, silicotungstate, phosphomolybdic acid, phosphomolybdate, molybdate, paramolybdate, tungstates, metatungstate, ethyl metatungstate.
The described salt that contains the group VIII metal is organic salt at least a that contains the inorganic acid salt of group VIII metal or contain the group VIII metal, 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, be selected from one or more in nitrate, carbonate or subcarbonate.Described organic salt to be organic matter be combined with VIII family metal salt or the soluble complexes that generates, described organic matter can be organic base, organic carboxyl acid, amine, ketone, ethers, alkyls, is preferably organic carboxylate.
According to method for preparing catalyst provided by the invention, after the introducing group vib metal of step (1), need carry out drying and roasting, the method for described drying and condition can be usual method and conditions in the catalyst preparation, and there is no particular limitation to this present invention.For example, described drying means is the method for heat drying, and its baking temperature can be 80-300 ℃, and be 1-12 hour drying time, and preferred baking temperature is 100-250 ℃, and be 2-8 hour drying time.Described roasting be so that the group vib metallic compound of load can be decomposed into oxide is prerequisite, and preferred sintering temperature is 350～and to 550 ℃, more preferably 400-500 ℃, roasting time is 2-10 hour, is preferably 3-6 hour.Atmosphere for roasting does not have special requirement, can be the mixture of air, oxygen or nitrogen or above-mentioned gas, is preferably air.
Introduce the group VIII metal in step (2) after, need to carry out drying, selected drying condition answers deficiency so that VIII family's slaine or the complex compound of load are decomposed into oxide, adoptable baking temperature is 30-250 ℃, be preferably 60-200, more preferably 70-180 ℃, 1-8 hour drying time, preferred 2-6 hour.Drying is preferably carried out under air atmosphere.
According to preparation method provided by the invention, during one or both adjuvant components in also containing components such as being selected from boron, phosphorus or fluorine in described catalyst, comprise and introduce the step that is selected from one or more components in the components such as boron, phosphorus or fluorine, the described introducing method that is selected from the components such as boron, phosphorus or fluorine can pass through number of ways, as can be that compound with auxiliary agent as described in containing directly mixes with silicon-containing compound, aluminum contained compound or silicoaluminate, moulding and roasting; Can be the compound that to contain described auxiliary agent and contact with described carrier after the compound that contains the hydrogenation active metals component is mixed with mixed solution; Can also be to contact with described carrier after the independent obtain solution of the compound that contains auxiliary agent and roasting.When auxiliary agent and hydrogenation active metals are introduced described carrier respectively, preferably at first auxiliary compound solution contacts with described carrier and roasting with containing, introduce again afterwards the hydrogenation active metals component, described sintering temperature is 250-600 ℃, be preferably 350-500 ℃, roasting time is 2-8 hour, is preferably 3-6 hour.
According to preparation method provided by the invention, when catalyst of the present invention further contains organic compound, also comprise the step of introducing organic compound, described organic compound can be introduced together with the group VIII metal, also can introduce after introducing the group VIII metal, and carry out drying, and preferably organic matter and group VIII metal are mixed with mixed solution and introduce simultaneously by the mode of dipping, carry out afterwards drying.The selection of described baking temperature and time except deficiency so that VIII family's slaine or complex compound decompose, also should allow to keep most of organic matter of introducing in catalyst, for example keep the organic matter more than 50%, more preferably, keep the organic matter more than 70%.Its method can be any one method that can realize above-mentioned purpose in prior art.For example, heat drying, drying under reduced pressure and add the methods such as thermal drying under reduced pressure.When described drying means was heat drying, preferred baking temperature was no more than 250 ℃, further preferably is no more than 200 ℃, is more preferably and is no more than 180 ℃.For example, one preferred embodiment in, described baking temperature is 70 ℃-180 ℃.
According to the present invention, when preparation contains the described catalyst of organic compound, in carbon and take described catalyst as benchmark, preferably make in final catalyst by the introducing amount of selecting described organic compound, the content of described organic additive is no more than 10 % by weight, further preferably is no more than 6 % by weight.
According to the conventional method in this area, described hydrotreating catalyst is before using, usually can be under hydrogen exists, carry out presulfurization with sulphur, hydrogen sulfide or sulfur-bearing raw material at the temperature of 140-370 ℃, this presulfurization can be carried out outside device also can original position sulfuration in device, and the active metal component of its load is converted into the metal sulfide component.
In hydrotreating method provided by the invention, the device of described hydrotreatment reaction can be enough to make described feedstock oil to carry out under the hydrotreatment reaction condition with in the catalytic reaction dress of described catalyst device any, for example, at described fixed bed reactors, carry out in moving-burden bed reactor or fluidized bed reactor.Under the prerequisite that is enough to realize described hydrotreatment reaction purpose, to described hydroconversion condition without any special restriction.For example, the reaction temperature that can list is 200-420 ℃, more preferably 220-400 ℃, pressure 2-18 MPa, 2-15 MPa more preferably, liquid hourly space velocity (LHSV) 0.3-10 hour
-1, more preferably 0.3-5 hour
-1, hydrogen to oil volume ratio 50-5000,50-4000 more preferably.
Adopt hydrotreating method provided by the invention can directly process all kinds of hydrocarbon oil crude materials, so that it is carried out hydrofinishing, hydro-upgrading or hydrocracking.Described hydrocarbon oil crude material can be various heavy mineral oils or artificial oil or their mixed fraction oil, such as be selected from crude oil, distillate, solvent-refined oil, slack wax, sweat oil, Fischer-Tropsch synthesis oil, liquefied coal coil, frivolous coal tar and heavy deasphalted oil one or more.Be particularly suitable for the hydrotreatment of the hydrofinishing of diesel oil or poor ignition quality fuel and wax oil, residual oil.
Compared with prior art, the invention provides catalyst and have higher hydrotreatment activity.For example, in the identical situation of hydrogenation active metals content of catalyst, NiW/SiO provided by the invention
2-Al
2O
3Catalyst (contains WO
335 % by weight, NiO 3.6 % by weight), with the NiW/SiO that adopts the method for roasting preparation
2-Al
2O
3Catalyst and the NiW/SiO that exempts from the method for roasting preparation
2-Al
2O
3Catalyst is compared, and hydrodesulfurization activity improves respectively 40% and 7% relatively, and denitrification activity improves respectively 15% and 8% left and right relatively.
The specific embodiment
The present invention will be further described for following example, but therefore do not limit content of the present invention.
Carbon content in catalyst adopts analyses, and other components are except specifying, all adopt x-ray fluorescence spectrometry, the composition of all catalyst is provided by table 1.
Embodiment 1
The preparation of this example explanation catalyst of the present invention silica-alumina carrier S used A1:
First 800 gram boehmites (the triumphant benefit in Tianjin special company produce, butt 66%) and Ludox (are contained SiO
230% weight, the production of Beijing flying dragon horse company) after 618 grams, sesbania powder 20 grams mix, again with 16 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, Shantou west) and 295 milliliters of mixing of water, afterwards this mixture is continued kneading even on double screw banded extruder, be extruded into afterwards the butterfly bar of 1.3 millimeters of ф, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains silica-alumina carrier S A-1 through 120 ℃ of dryings.Adopt x-ray fluorescence method to measure the composition of SA-1, the total amount of silica and aluminium oxide is as benchmark in oxide and in the described composition, and silica content is 26 % by weight, and alumina content is 74% weight.
Adopt BET N
2Absorption method is analyzed the SA-1 carrier, and the specific area of this carrier is 256 meters squared per gram, 0.60 ml/g of pore volume.
Embodiment 2
The preparation of this example explanation catalyst of the present invention silica-alumina carrier S used A-2:
first with the 956 gram aluminum oxide dry glue powders (boehmite that Sinopec catalyst Chang Ling branch company produces, butt 70%) and amorphous aluminum silicide (Siral 40, butt 81%, Germany Condea company product) 400 grams, sesbania powder 37 grams mix, again with this mixture and 45 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, west, Shantou), 1500 ml waters mix, continue afterwards kneading even on double screw banded extruder, be extruded into afterwards the butterfly bar of 1.3 millimeters of ф, wet bar is through 120 ℃ of dryings after 4 hours, in 600 ℃ of roastings 3 hours, obtain silica-alumina carrier S A-2.Adopt x-ray fluorescence method to measure the composition of SA-2, the total amount of silica and aluminium oxide is as benchmark in oxide and in the described composition, and silica content is 15 % by weight, and alumina content is 85% weight.
Adopt BET N
2Absorption method is analyzed the SA-2 carrier, and the specific area of this carrier is 271 meters squared per gram, 0.66 ml/g of pore volume.
Embodiment 3
The preparation of this example explanation catalyst of the present invention silica-alumina carrier S used A-3:
(Tianjin permanent brightness chemical industry Co., Ltd produces with 800 gram business boehmites, butt 69%) mix with 20 gram sesbania powder, again this mixture is mixed with 18 milliliters of nitric acid, 700 ml waters, continue afterwards kneading even on double screw banded extruder, be extruded into afterwards the butterfly bar of 1.3 millimeters of ф, wet bar is through 120 ℃ of dryings after 4 hours, in 600 ℃ of roastings 3 hours, obtain 550 gram alumina supports, (Beijing chemical reagents corporation contains SiO with containing ethyl orthosilicate
228% weight is analyzed pure) 468 milliliters of above-mentioned alumina supports of dipping of the ethanolic solution of 103 grams, through 120 ℃ of dryings 4 hours and 500 ℃ of roastings 3 hours, obtain silica-alumina carrier S A-3 respectively.Adopt x-ray fluorescence method to measure the composition of SA-3, the total amount of silica and aluminium oxide is as benchmark in oxide and in the described composition, and silica content is 5 % by weight, and alumina content is 95% weight.
Adopt BET N
2Absorption method is analyzed the SA-3 carrier, and the specific area of this carrier is 236 meters squared per gram, 0.68 ml/g of pore volume.
Embodiment 4-6 explanation catalyst provided by the invention and preparation thereof
Comparative Examples 1-3 explanation comparative catalyst and preparation thereof
The raw material sources that Kaolinite Preparation of Catalyst uses are as follows: ammonium paramolybdate, Anqing moon metallurgy of copper chemical industry Co., Ltd product, technical grade; Ammonium metatungstate, Zhuzhou diamond tungsten product Co., Ltd product, technical grade; Nickel nitrate, Beijing Yili Fine Chemicals Co., Ltd.'s product is analyzed pure; Basic nickel carbonate, Yixing Xu Chi chemical industry Co., Ltd product, chemical pure; Cobalt nitrate, Beijing Yili Fine Chemicals Co., Ltd. analyzes pure; Phosphoric acid, Beijing Chemical Plant's product, analyze pure, 85% concentration; Ammoniacal liquor, 25% concentration, Beijing Chemical Plant's product is analyzed pure; Citric Acid Mono, Beijing Chemical Plant's product is analyzed pure; Ammonium fluoride, chemical plant, Jinan product is analyzed pure.
Embodiment 4
Get SA-1 carrier 150 grams, flooded 2 hours with 118 milliliters of dilute ammonia solutions (10% concentration) that contain ammonium paramolybdate 28 grams, in 120 ℃ of dryings 4 hours, 470 ℃ of roastings 4 hours, what make the load molybdenum oxide contains the molybdenum carrier, contain the molybdenum carrier 2 hours with 88 milliliters of aqueous solution dippings that contain cobalt nitrate 14 grams afterwards, in 120 ℃ of dryings 4 hours, make catalyst C-1.Take catalyst weight as benchmark, adopt the chemical composition in x-ray fluorescence method mensuration catalyst C1, measurement result is listed in table 1 (lower same).
Comparative Examples 1
Get SA-1 carrier 150 grams, flooded 2 hours with 116 milliliters of dilute ammonia solutions (10% concentration) that contain ammonium paramolybdate 28 grams, in 120 ℃ of dryings 4 hours, 470 ℃ of roastings 4 hours, contained the molybdenum carrier 2 hours with the 88 milliliters of dippings of the aqueous solution that contain cobalt nitrate 14 grams afterwards, in 120 ℃ of dryings 4 hours, 470 ℃ of roastings 4 hours obtained comparative catalyst DC-1A.
Comparative Examples 2
Get SA-1 carrier 150 grams, with 116 milliliters of dilute ammonia solutions (10% concentration) dippings that contain ammonium paramolybdate 28 grams, cobalt nitrate 14 grams 2 hours, in 120 ℃ of dryings 4 hours, obtain comparative catalyst DC-1B.
Embodiment 5
Get SA-2 carrier 150 grams, flooded 2 hours with 124 milliliters of aqueous solution that contain ammonium paramolybdate 60 grams, phosphatase 11 8 grams, in 120 ℃ of dryings 4 hours, 500 ℃ of roastings 4 hours, what make the load molybdenum oxide contains the molybdenum carrier, contain the molybdenum carrier 2 hours with the 73 milliliters of dippings of the aqueous solution that contain nickel nitrate 44 grams afterwards, in 120 ℃ of dryings 4 hours, obtain catalyst C-2.
Comparative Examples 3
Get SA-2 carrier 150 grams, with 124 milliliters of the aqueous solution dipping that contains ammonium paramolybdate 60 grams, nickel nitrate 44 grams, phosphatase 11 8 grams 2 hours, in 120 ℃ of dryings 4 hours, 500 ℃ of roastings 4 hours obtained comparative catalyst DC-2A.
Comparative Examples 4
Get SA-2 carrier 150 grams, with 124 milliliters of the aqueous solution dipping that contains ammonium paramolybdate 60 grams, nickel nitrate 44 grams, phosphatase 11 8 grams 2 hours, in 120 ℃ of dryings 4 hours, obtain comparative catalyst DC-2B.
Embodiment 6
Get SA-3 carrier 150 grams, with the aqueous solution of 121 milliliters of fluorinated ammonium 16 grams dipping 2 hours, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours obtained fluorine-containing carrier.
With fluorine-containing carriers of 113 milliliters of the aqueous solution that contains ammonium metatungstate 99 grams dipping 2 hours, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours made the fluorine-containing carrier of load tungsten oxide.
With the carrier of the above-mentioned fluorine-containing and tungsten of 55 milliliters of liquid of the aqueous solution that contains basic nickel carbonate 18 grams, citric acid 29 grams dipping 2 hours, in 150 ℃ of dryings 4 hours, obtain catalyst C-3.
Comparative Examples 5
Get SA-3 carrier 150 grams, with the aqueous solution of 121 milliliters of fluorinated ammonium 16 grams dipping 2 hours, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours obtained fluorine-containing carrier.
With fluorine-containing carriers of 113 milliliters of the aqueous solution that contains ammonium metatungstate 99 grams, basic nickel carbonate 18 grams, citric acid 29 grams dipping 2 hours, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours obtained comparative catalyst DC-3A.
Comparative Examples 6
Get SA-3 carrier 150 grams, with the aqueous solution of 121 milliliters of fluorinated ammonium 16 grams dipping 2 hours, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours obtained fluorine-containing carrier.
With fluorine-containing carriers of 113 milliliters of the aqueous solution that contains ammonium metatungstate 99 grams, basic nickel carbonate 18 grams, citric acid 29 grams dipping 2 hours, in 150 ℃ of dryings 4 hours, obtain comparative catalyst DC-3B.
Table 1
Embodiment 7-9 explanation the invention provides the effect of catalyst.
Comparative Examples 7-12 explanation comparative catalyst's effect.
Embodiment 7
The decompressed wax oil hydrotreatment performance of the present embodiment explanation catalyst C-1 of the present invention.
Catalyst breakage is become the 2-4 mm granules, evaluate catalysts C-1 on 250 milliliters of hydrogenation plants, raw materials used oil nature, reaction condition see Table 2, and reaction result sees Table 3.
Table 2
| Feedstock oil character | Decompressed wax oil |
| Density (20 ℃), g/cm 3 | 0.9113 |
| S，ppm | 17000 |
| N，ppm | 478 |
| Index of refraction (70 ℃) | 1.4875 |
| Boiling range (D1160), ℃ | |
| Initial boiling point | 276 |
| 50% point | 429 |
| 95% point | 490 |
| Reaction condition | |
| The hydrogen dividing potential drop, MPa | 8.0 |
| Catalyst volume, mL | 100 |
| Temperature, ℃ | 375 |
| Volume space velocity, h -1 | 1.6 |
| Hydrogen-oil ratio, v/v | 600 |
The assay method of sulphur is SH/T 0253-92, and the nitrogen determination method is SH/T 0657-1998.The hydrodesulfurization activity of catalyst calculates by 1.5 order reactions, and hydrodenitrogenationactivity activity is calculated by 1 order reaction, and related computing formula is as follows.
Comparative Examples 7
The decompressed wax oil hydrotreatment performance of this Comparative Examples explanation reference catalyst DC-1A.
According to the method evaluation comparative catalyst DC-1A of embodiment 7, reaction result sees Table 3, take the activity of DC-1A catalyst as 100.
Comparative Examples 8
The decompressed wax oil hydrotreatment performance of this Comparative Examples explanation reference catalyst DC-1B.
According to the method evaluation comparative catalyst DC-1B of embodiment 7, reaction result sees Table 3.
Table 3
Table 3 result shows, C-1 catalyst provided by the invention has better wax oil hydrogenation handling property than Comparative Examples catalyst DC-1A and DC-1B.
Embodiment 8
The straight-run diesel oil hydrofinishing performance of the present embodiment explanation catalyst C-2 provided by the invention.
Catalyst breakage is become the 2-4 mm granules, evaluate catalysts C-2 on 30 milliliters of hydrogenation plants, raw materials used oil nature, reaction condition see Table 4, and reaction result sees Table 5.The hydrodesulfurization activity of catalyst calculates by 1.65 order reactions, and related computing formula is as follows, and hydrodenitrogenationactivity activity is calculated by 1 order reaction, and computing formula is seen embodiment 7.
Table 4
| Feedstock oil character | Straight-run diesel oil |
| Density (20 ℃), g/cm 3 | 0.8471 |
| S，ppm | 8300 |
| N，ppm | 202 |
| Index of refraction (20 ℃) | 1.4765 |
| Reaction condition | |
| The hydrogen dividing potential drop, MPa | 3.2 |
| Catalyst volume, mL | 30 |
| Temperature, ℃ | 350 |
| Volume space velocity, h -1 | 2.0 |
| Hydrogen-oil ratio, v/v | 300 |
Comparative Examples 9
The straight-run diesel oil hydrofinishing performance of this Comparative Examples explanation reference catalyst DC-2A.
According to the method evaluation reference catalyst DC-2A of embodiment 8, reaction result is listed in table 5, take the activity of DC-2A catalyst as 100.
Comparative Examples 10
The straight-run diesel oil hydrofinishing performance of this Comparative Examples explanation reference catalyst DC-2B.
According to the method evaluation reference catalyst DC-2B of embodiment 8, reaction result is listed in table 5.
Table 5 result shows, C-2 catalyst provided by the invention has better straight-run diesel oil hydrofinishing performance than Comparative Examples catalyst DC-2A and DC-2B.
Table 5
Embodiment 9
The catalytic diesel oil hydrofinishing performance of the present embodiment explanation catalyst C-3 provided by the invention.
Catalyst breakage is become the 2-4 mm granules, evaluate catalysts C-3 on 30 milliliters of hydrogenation plants, raw materials used oil nature, reaction condition see Table 6, and reaction result sees Table 7.The hydrodesulfurization activity of catalyst calculates by 1.65 order reactions, and related computing formula is as follows, and hydrodenitrogenationactivity activity is calculated by 1 order reaction, and computing formula is seen embodiment 7.
Table 6
| Feedstock oil character | Catalytic diesel oil |
| Density (20 ℃), g/cm 3 | 0.9242 |
| S，ppm | 6800 |
| N，ppm | 902 |
| Index of refraction (20 ℃) | 1.5331 |
| Reaction condition | |
| The hydrogen dividing potential drop, MPa | 6.0 |
| Catalyst volume, mL | 30 |
| Temperature, ℃ | 340 |
| Volume space velocity, h -1 | 2.0 |
| Hydrogen-oil ratio, v/v | 300 |
Comparative Examples 11
The catalytic diesel oil hydrofinishing performance of this Comparative Examples explanation reference catalyst DC-3A.
According to the method evaluation reference catalyst DC-3A of embodiment 9, reaction result is listed in table 7, take the activity of DC-3A catalyst as 100.
Comparative Examples 12
The catalytic diesel oil hydrofinishing performance of this Comparative Examples explanation reference catalyst DC-3B.
According to the method evaluation reference catalyst DC-3B of embodiment 9, reaction result is listed in table 7.
Table 7
Table 7 result shows, C-3 catalyst provided by the invention has better catalytic diesel oil hydrofinishing performance than Comparative Examples catalyst DC-3A and DC-3B.
Claims (18)
1. hydrotreating catalyst take silica-alumina as carrier, contain silica-alumina carrier and at least a VIII of being selected from family and at least a metal component that is selected from group vib, it is characterized in that, described group vib metal component exists with the form of metal oxide, and described VIII family metal component exists with the form of slaine.
2. catalyst according to claim 1, take catalyst as benchmark and with oxide, the content of described VIII family metal component is the 1-10 % by weight, the content of group vib metal component is the 5-40 % by weight.
3. catalyst according to claim 2, take catalyst as benchmark and with oxide, the content of described VIII family metal component is the 1.5-7 % by weight, the content of group vib metal component is the 7-35 % by weight.
4. catalyst according to claim 1, is characterized in that, described group vib metal component is selected from one or more in Cr, Mo, W, and described VIII family metal component is selected from one or more in Fe, Co, Ni.
5. catalyst according to claim 4, is characterized in that, described group vib metal is Mo and/or W, and described VIII family metal component is Co and/or Ni.
6. catalyst according to claim 1, is characterized in that, described slaine is selected from the inorganic salts of VIII family metal component or one or more in organic salt.
7. catalyst according to claim 6, is characterized in that, described inorganic salts are selected from one or more in carbonate, subcarbonate, nitrate; Described organic salt is organic carboxylate.
8. according to claim 1-7 described catalyst, is characterized in that, described catalyst also contains one or more auxiliary agents that are selected from P, F, B, and in element and take catalyst as benchmark, the content of described auxiliary agent is no more than 10 % by weight.
9. according to claim 1-7 described catalyst, is characterized in that, described catalyst also contains organic additive, and take described catalyst as benchmark, and in carbon, the content of described organic additive is no more than 10 % by weight.
10. catalyst according to claim 1, is characterized in that, take described carrier as benchmark, in described silica-alumina carrier, the content of silica is the 1-50 % by weight, and the content of aluminium oxide is the 50-99 % by weight.
11. catalyst according to claim 10 is characterized in that, take described carrier as benchmark, in described silica-alumina carrier, the content of silica is the 2-40 % by weight, and the content of aluminium oxide is the 60-98 % by weight,
12. catalyst according to claim 10 is characterized in that, in oxide, in described silica-alumina carrier, the content of silica is the 3-35 % by weight, and the content of aluminium oxide is the 65-97 % by weight.
13. the preparation method of hydrogenation catalyst claimed in claim 1 comprises:
(1) with the solution impregnation silica-alumina carrier that contains the group vib metallic compound, carry out afterwards drying and roasting, the condition of described roasting makes the described compound that contains the group vib metal be enough to be converted into oxide;
(2) product that obtains with the solution impregnation step (1) that contains VIII family slaine carries out drying afterwards, and the condition deficiency of described drying is so that VIII family slaine is decomposed into oxide.
14. method according to claim 13 is characterized in that, the baking temperature of described step (1) is 80-300 ℃, and be 1-12 hour drying time, and described sintering temperature is 350-550 ℃, and roasting time is 2-10 hour; The baking temperature of described step (2) is 30-250 ℃, 1-8 hour drying time.
15. method according to claim 14 is characterized in that, the baking temperature of described step (1) is 100-250 ℃, and be 2-8 hour drying time, and described sintering temperature is 400-500 ℃, and roasting time is 3-6 hour; The baking temperature of described step (2) is 60-200 ℃, and be 2-6 hour drying time.
16. method according to claim 13 is characterized in that, described method also comprises introduces the step that is selected from one or more components in the components such as boron, phosphorus or fluorine.
17. method according to claim 13 is characterized in that, described method also comprises the step of introducing organic additive.
18. a method for hydrotreating hydrocarbon oil is included under the hydrotreatment reaction condition, with hydrocarbon ils and catalyst haptoreaction, it is characterized in that, described catalyst is the described catalyst of claim 1-12 any one.
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| CN109894107A (en) * | 2017-12-11 | 2019-06-18 | 中国石油化工股份有限公司 | For the catalyst carrier of residual hydrocracking, catalyst and preparation method thereof |
| CN111318286B (en) * | 2018-12-13 | 2023-08-01 | 中国石油化工股份有限公司 | Hydrotreating catalyst and preparation method thereof |
| CN111318286A (en) * | 2018-12-13 | 2020-06-23 | 中国石油化工股份有限公司 | Hydrotreating catalyst and preparation method thereof |
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