CN105688978A - Hydrogenation treatment catalyst, and applications thereof - Google Patents
Hydrogenation treatment catalyst, and applications thereof Download PDFInfo
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Abstract
The invention discloses a hydrogenation treatment catalyst, and applications thereof. The hydrogenation treatment catalyst comprises a carrier and a hydrogenation active metal ingredient loaded onto the carrier; and the carrier contains a heat-resistant inorganic oxide, a molecular sieve, and charcoal. The carrier is prepared via mixing the heat-resistant inorganic oxide and/or a predecessor of the heat-resistant inorganic oxide with the molecular sieve and carbon black powder and/or a predecessor of charcoal, moulding, drying, and activating. In the step of activating, (1) a molded material obtained via drying is subjected to heating treatment without air and/or in the presence of insert gas, wherein heating treatment temperature is controlled to be 400 to 800 DEG C, and time is controlled to be 0.5 to 8h; (2) a product obtained via the step (1) is subjected to heating treatment in the presence of water vapor and/or carbon dioxide, wherein heating temperature is controlled to be 600 to 950 DEG C, time is controlled to be 0.3 to 4h, and flux of water vapor and/or carbon dioxide is controlled to be 50 to 500 standard litre/kg.h. The hydrogenation treatment catalyst is suitable to be applied to hydrogenation treatment of hydrocarbon oil so as to prepare clean oil products.
Description
Technical field
The present invention is about a kind of hydrotreating catalyst and application thereof。
Background technology
The environmental consciousness day by day strengthened and increasingly stricter environmental regulation force oil refining circle more to focus on Clean Fuel Production technological development, and how producing super-low sulfur oil product economically has become one of problem of needing emphasis to solve in oil refining circle's current and expected future regular period。It is then produce one of most economical method of clear gusoline that exploitation has more high activity and selective novel hydrogenation process catalyst。
Hydrotreating catalyst is the sulfide of carrier loaded group vib (such as Mo and W) and VIII (such as Co and Ni) metal, and carrier is generally γ-Al2O3。
Carrier is as one of the important component part of hydrogenation catalyst, its surface nature performance important to catalyst。Its development trend is that carrier is modified increasing the dispersion of active component, interpolation auxiliary agent weakens the interaction between carrier and active component to avoid active component embed carrier or generate spinel structure with carrier, thus forming the more active phase with high intrinsic activity, improve catalyst activity；Having many researcheres to adopt and interact more weak activated carbon as carrier with active metal component, the additional advantage of absorbent charcoal carrier is that the transistion metal compound presoma of institute's load can relatively be completely converted into active sulfide and catalyst anticoking capability is good。
Unfortunately absorbent charcoal carrier has abundant microcellular structure and poor mechanical strength, and for the catalytic reaction of macromole, micropore application value is little, moreover amount of activated component also can be deposited in micropore, affects active component and plays one's part to the full。One effective ways overcoming disadvantages mentioned above is first to be coated with layer of active carbon at alumina surface before introducing active component。Thus combine activated carbon activity presoma can be made relatively to be fully converted into high activity sulfide, catalyst anticoking capability be good and alumina support has excellent pore passage structure, advantage that mechanical strength is high。
CN97100882.5 discloses a kind of by covering catalyst prepared by char combustion alumina supporter load hydrogenation active metals component, and this carbon covered carrier adopts hydrocarbons high temperature pyrolysis method to prepare。Compared with the catalyst adopting gama-alumina to prepare, its catalysis activity improves 7-8%。But, this catalyst only in containing the scope that charcoal mass fraction is 19.25-25.25% activity the highest。When charcoal mass fraction is lower than 19%, the activity of catalyst is still relatively low。
CN200410000952.X discloses a kind of catalyst for hydrorefining distillate oil and preparation method thereof, this method provide a kind of simple preparation method containing Pd/carbon catalyst, described containing the mixed-forming carrier that char combustion alumina supporter is charcoal and aluminium oxide, obtained by after the precursor of aluminium oxide and/or aluminium oxide and carbon powder and/or the precursor mechanical mixture of charcoal, molding, activation。Catalyst prepared by the carrier provided by this invention improves the catalysis activity of catalyst to a certain extent。
CN101733151A has reported for work and has first prepared alumina support, then adopts dipping method to introduce charcoal predecessor, then the method carrying out activating makes alumina surface cover charcoal。
The catalyst prepared with the load hydrogenation active metals component containing high-area carbon that prior art provides, when reacting for fraction oil hydrogenation refining, the performance of catalyst improves。But, when being used for the diesel oil hydrogenation deep desulfuration reaction that elimination is representative with 4,6-dimethyl Dibenzothiophene (4,6-DMDBT), the reactivity worth of this type of catalyst is still relatively low。In diesel deep desulfurization stage (in product, sulfur content is less than 500 μ g/g) and ultra-deep desulfurization stage (in product, sulfur content is less than 50 μ g/g), its medium sulphide content is mainly the dibenzothiophenes class sulfide that alkyl replaces。4,6-dimethyl Dibenzothiophene is exactly this compounds Typical Representative, owing to methyl adjacent with sulphur atom in molecule makes the not accessible catalyst active center of sulphur atom, cause that reaction rate is greatly reduced, 1/10th of its desulphurization reaction speed only about dibenzothiophenes。Bibliographical information, suitably the acid function of increase catalyst is conducive to the isomerization reaction of the methyl generation position transfer of 4,6 of 4,6-dimethyl Dibenzothiophene compounds of difficult desulfurization, thus being conducive to weakening space steric effect, improve the hydrodesulfurization activity of catalyst。
Summary of the invention
The technical problem to be solved in the present invention is on the basis of existing technology, it is provided that hydrotreating catalyst that a kind of hydrodesulfurization performance is higher and application thereof。
The content that the present invention relates to includes:
1. a hydrotreating catalyst, containing carrier and load hydrogenation active metals component on this carrier, it is characterized in that, described carrier contains heat-resistant inorganic oxide, molecular sieve and charcoal, the predecessor of heat-resistant inorganic oxide and/or heat-resistant inorganic oxide is mixed by including by described carrier with the predecessor of molecular sieve and carbon powder and/or charcoal, molding, prepared by the method drying and activating, with described carrier for benchmark, the consumption of each component makes the content of charcoal in final described carrier be 0.3-5 weight %, the content of molecular sieve is 2-15 weight %, the content of heat-resistant inorganic oxide is 80-95 weight %,
Wherein, described drying condition includes: temperature is 100-180 DEG C, and drying time is 0.5-10 hour；
Described activation includes: (1), under isolation air and/or noble gas exist, by dried article shaped heat treated, heat treatment temperature is 400-800 DEG C, and the time is 0.5-8 hour；(2) under steam and/or carbon dioxide atmosphere, the product heats of step (1) is processed, heating-up temperature is 600-950 DEG C, and the time is 0.3-4 hour, and the flow of described steam and/or carbon dioxide is 50-500 standard liter/(kilogram hour)。
2., according to the catalyst described in 1, it is characterised in that with described carrier for benchmark, the consumption of each component makes the content of charcoal in final described carrier be 0.5-3 weight %；The content of molecular sieve is 2.5-10 weight %, and the content of heat-resistant inorganic oxide is 87-97 weight %；The method of described activation includes: (1), under isolation air and/or noble gas exist, by dried article shaped heat treated, heat treatment temperature is 550-700 DEG C, and the time is 0.5-3 hour；(2) under steam and/or carbon dioxide atmosphere, the product heats of step (1) is processed, heating-up temperature is 750-850 DEG C, and the time is 0.5-3 hour, and the flow of described steam and/or carbon dioxide is 100-300 standard liter/(kilogram hour)。
3. according to the catalyst described in 1, it is characterised in that the predecessor of described charcoal is selected from can the Organic substance of carbonization in the step (1) of described activation。
4. according to the catalyst described in 3, it is characterised in that one or more in alcohol, sugar, organic acid of the predecessor of described charcoal。
5. according to the catalyst described in 4, it is characterised in that one or more in monohydric alcohol, dihydroxylic alcohols and polyhydric alcohol of described alcohol；One or more in lactose, galactose, beet sugar, fructose, glucose, sugar, sucrose, maltose, methylcellulose and starch of described sugar；One or more in formic acid, acetic acid, n Propanoic acid, 1,3-malonic acid, n-butyric acie, oxalic acid, citric acid, tartaric acid, malic acid of described organic acid。
6. the catalyst according to 1,3,4 or 5 any one, it is characterized in that, the predecessor of described charcoal is the mixture of small organic molecule and larger molecular organics, wherein the weight ratio of small organic molecule and larger molecular organics is 1-3, wherein, described small organic molecule refers to the predecessor in molecule containing the charcoal below 4 carbon atoms, and described larger molecular organics refers to the predecessor in molecule containing charcoals more than 5 carbon atoms。
7. according to the catalyst described in 6, it is characterised in that the weight ratio of described small organic molecule and larger molecular organics is 1.3-2.3。
8. the catalyst according to 1 or 2, it is characterised in that one or more in nitrogen, argon and helium of described noble gas。
9. according to the catalyst described in 1, it is characterized in that, one or more in aluminium oxide, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, silica-magnesias, silica-zirconia, silica thoria, silica-berylias, silica-titania, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia, silica-alumina, zirconia of described refractory oxides。
10. the catalyst according to 1 or 9, it is characterised in that described refractory oxides is selected from aluminium oxide。
11. according to the catalyst described in 1, it is characterised in that one or more in faujasite, modenite, L zeolite, omega zeolite, ZSM-5 zeolite, Beta zeolite etc. of described molecular screening。
12. according to the catalyst described in 11, it is characterised in that described faujasite is selected from y-type zeolite, it is preferable that HY type molecular sieve, USY type molecular sieve and/or rare earth Y type molecular sieve。
13. according to the catalyst described in 1, it is characterized in that, described hydrogenation active metals component is selected from the metal component of at least one group VIII and at least one vib, with described catalyst for benchmark, the content of the group VIII metal component counted with oxide is for 2-10 weight %, and the content of the vib metals component counted with oxide is for 13-30 weight %。
14. according to the catalyst described in 13, it is characterized in that, described group VIII metal component is nickel and cobalt, the metal component of vib is molybdenum, with described catalyst for benchmark, the content of the group VIII metal component counted with oxide is for 2-8 weight %, and the content of the vib metals component counted with oxide is for 13-27 weight %。
15. according to the catalyst described in 1, it is characterised in that described catalyst contains auxiliary agent phosphorus, count with oxide and with catalyst for benchmark, the content of phosphorus is 2-10 weight %。
16. according to the catalyst described in 15, it is characterised in that count with oxide and with catalyst for benchmark, the content of auxiliary agent phosphorus is 2-7 weight %。
17. according to the catalyst described in 1, it is characterised in that containing organic additive in described catalyst, with described catalyst for benchmark, the content of described organic additive is 2-20 weight %。
18. according to the catalyst described in 17, it is characterised in that containing organic additive in described catalyst, with described catalyst for benchmark, the content of described organic additive is 3-15 weight %。
19. a method for hydrotreating hydrocarbon oil, including at hydrotreating reaction conditions, by hydrocarbon oil crude material and catalyst haptoreaction, it is characterised in that described catalyst is the catalyst described in 1-18 any one。
In the present invention, one or more in aluminium oxide, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, silica-magnesias, silica-zirconia, silica thoria, silica-berylias, silica-titania, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia, silica-alumina, zirconia of described refractory oxides。It is preferably aluminium oxide。They can be commercially available commodity, it would however also be possible to employ prepared by any one existing method。
Described zeolite molecular sieve is selected from one or more having in the natural of acid catalysis function or the molecular sieve of synthetic known。Such as, faujasite, modenite, L zeolite, omega zeolite, ZSM-5 zeolite, Beta zeolite etc.。Wherein, described faujasite be selected from y-type zeolite and X-type zeolite, it is preferable that y-type zeolite therein, it is preferred that y-type zeolite be HY type molecular sieve, USY type molecular sieve and/or rare earth Y type molecular sieve。They can be commercially available commodity, it would however also be possible to employ prepared by any one existing method。
Carrier optionally can be made article shaped easy to operate and use arbitrarily, for instance spherical, tablet or bar shaped etc.。Molding carries out according to a conventional method, for instance, it is possible to be that the predecessor of heat-resistant inorganic oxide and/or heat-resistant inorganic oxide is mixed with the predecessor of molecular sieve and carbon powder and/or charcoal, after prepare through extruded moulding, method that is dry and that activate。For ensureing that described molding is smoothed out in extruded moulding, can to the predecessor of described heat-resistant inorganic oxide and/or heat-resistant inorganic oxide and addition water, extrusion aid and/or adhesive, then extrusion molding in the mixture of molecular sieve and the predecessor of carbon powder and/or charcoal。Described extrusion aid, the kind of peptizer and consumption are conventionally known to one of skill in the art, for instance common extrusion aid can be selected from one or more in sesbania powder, methylcellulose, starch, polyvinyl alcohol, and described peptizer can be mineral acid and/or organic acid。
In the present invention, the predecessor of described heat-resistant inorganic oxide is the compound that can transform into described heat-resistant inorganic oxide when the activation act of carrier of the present invention。For aluminium oxide, the mixture of one or more that its predecessor (also referred to as precursor or parent compound) can be chosen from Alumina hydrate, monohydrate alumina, boehmite and amorphous hydroted alumina, they can be commercially available commodity or be prepared by any one method in prior art。
Inventor have found that, by the precursor mix molding of the predecessor of heat-resistant inorganic oxide and/or heat-resistant inorganic oxide and molecular sieve and carbon powder and/or charcoal, dry and under isolation air and/or noble gas exist carrier after high-temperature activation, at the temperature of more than 600 DEG C, re-activation is carried out again under steam and/or carbon dioxide exist, 4,6-dimethyl Dibenzothiophene hydrodesulfurization activities of the catalyst thus prepared improve。
In the present invention, the predecessor of the predecessor of described heat-resistant inorganic oxide and/or heat-resistant inorganic oxide with molecular sieve and carbon powder and/or charcoal is mixed, molding, in the dry and operation that activates, with described carrier for benchmark, the consumption of each component makes carbon content in final described carrier be 0.3-5 weight %, excellent in 0.5-3 weight % further。The content of molecular sieve is 2-15 weight %, more preferably 3-10 weight %, and the content of heat-resistant inorganic oxide is 80-95 weight %, more preferably 87-97 weight %。
In the present invention, the drying means of described article shaped is conventional method, it is preferred that drying condition includes: temperature is 100-180 DEG C, more preferably 100-160 DEG C, and drying time is 0.5-10 hour, more preferably 3-6 hour。
In described support-activated step (1), it may occur however that reaction include the carbonization of predecessor of charcoal and the conversion to its oxide when heat-resistant inorganic oxide introduces with the form of predecessor。Wherein, described isolation air refers to that the oxygen content in described support-activated environment is less than 1 volume %, it is preferable that less than 0.5 volume %。It is being enough to realize in described support-activated step under the oxygen content premise less than 1 volume %, arbitrary existing method can be adopted to realize the operation of this isolation air, such as, it can be the method for evacuation, evacuation the method that system vacuum is held at less than 10Pa is carried out including the process system access vacuum pump at described carrier；The activation that described noble gas carries out under existing, can be adopt inert gas replacement air to oxygen content less than 1 volume %, it is preferably smaller than 0.5 volume % the activation carried out in the presence of an inert gas, the described noble gas gaseous mixture of one or more in nitrogen, argon and helium。
In the present invention, described can the Organic substance of carbonization can be arbitrary can the carbonaceous material of carbonization under support-activated operating condition of the present invention。Preferably can the Organic substance of carbonization selected from oxygen-bearing organic matter, for instance, it is possible to selected from alcohols (such as monohydric alcohol: methanol, ethanol, propanol, isopropanol, n-butyl alcohol, isobutanol, n-amyl alcohol, isoamyl alcohol；Dihydroxylic alcohols: ethylene glycol: 1,2-propylene glycol, 1,3-propylene glycol, 1,3 butylene glycol；Polyhydric alcohol: glycerol, polyvinyl alcohol etc.), one or more the mixture organic such as saccharide (such as lactose, galactose, beet sugar, fructose, glucose, sugar, sucrose, maltose, methylcellulose starch etc.) and/or organic acid (such as formic acid, acetic acid, n Propanoic acid, 1,3-malonic acid, n-butyric acie, oxalic acid, citric acid, tartaric acid, malic acid)。
In one preferred embodiment, the predecessor of described charcoal is the mixture including at least one small organic molecule and at least one larger molecular organics, wherein, the weight ratio of described small organic molecule and larger molecular organics is 1-3, more preferably 1.3-2.3。Here, described small organic molecule refers to the predecessor in molecule containing 4 or charcoal less than 4 carbon atoms, and described larger molecular organics refers to the predecessor in molecule containing charcoals more than 5 carbon atoms。
In the present invention, described carrier has the conventional specific surface area of general carrier and pore volume, for instance, specific surface area can be 150-300 rice2/ gram, be preferably 160-250 rice2/ gram, pore volume can be 0.4-1.1 ml/g, be preferably 0.6-1.0 ml/g。
Described hydrogenation active metals component is carried under the premise on described carrier being enough to, described carrying method is not particularly limited by the present invention, the method preferably employing dipping, including the preparation dipping solution containing described metallic compound, afterwards with the carrier described in this solution impregnation and dry。Described dipping method is conventional method, for instance, it is possible to it is excessive infusion process, the saturated infusion process in hole。Described dry method and condition are the conventional method and the condition that add hydrogen species catalyst preparing, for instance, described drying condition includes: described dry temperature can be 40-350 DEG C, it is preferred to 100-200 DEG C, the time is 1-24 hour, it is preferred to 2-12 hour。
Preferably, the present invention provides catalyst to contain auxiliary agent phosphorus and/or organic additive。With catalyst for benchmark, with P2O5The content of the auxiliary agent phosphorus of meter is 2-10 weight %, it is preferred to 2-7 weight %, the content of organic additive is 2-20 weight %, it is preferred to 3-15 weight %。
When in described catalyst containing auxiliary agent phosphorus and/or organic additive, including the step introducing auxiliary agent phosphorus and/or organic additive on the carrier。Being carried under the premise on described carrier by described auxiliary agent phosphorus and/or organic additive being enough to, the method for described load is not particularly limited by the present invention。Such as, prepare containing hydrogenation active metals component composition and phosphorous and/or organic additive impregnation liquid, afterwards with the carrier described in this solution impregnation。Described dipping method is conventional method, for instance, it is possible to it is excessive infusion process, the saturated infusion process in hole。Including the step dried after dipping, described drying condition includes: described dry temperature can be 100-300 DEG C, it is preferred to 100-280 DEG C, the time is 1-12 hour, it is preferred to 2-8 hour。
One or more in phosphoric acid, phosphorous acid, phosphate, phosphite of described phosphorus-containing compound, it is preferable that phosphoric acid or ammonium phosphate salt。
Described organic additive is one or more in oxygen-containing or organic compounds containing nitrogen, it is preferred that oxygen-containing organic compound is one or more in Organic Alcohol and organic acid；Preferred organic compounds containing nitrogen is one or more in organic amine。Such as, oxygen-containing organic compound can enumerate ethylene glycol, glycerol, 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, organic compounds containing nitrogen can enumerate ethylenediamine, ethylenediaminetetraacetic acid (EDTA) and ammonium salt thereof etc.。
According to the conventional method in this area, before the preparation method of hydrogenation catalyst provided by the invention is preferably also included in use, in presence of hydrogen, at the temperature of 140-400 DEG C, with sulfur, hydrogen sulfide or sulfur-bearing raw material, catalyst is carried out presulfurization, this presulfurization can carry out outside device also can be In-situ sulphiding in device, thus catalyst is converted into sulfide type。
According to method for hydrotreating hydrocarbon oil provided by the invention, wherein said hydrotreatment reaction condition is conventional hydrocarbon hydrotreatment reaction condition, such as, described hydrotreatment reaction condition includes: reaction temperature 200-650 DEG C, preferred 300-510 DEG C, hydrogen dividing potential drop 2-20 MPa, it is preferable that 3-15 MPa, liquid hourly space velocity (LHSV) 0.1-3 hour-1, it is preferable that 1-2 hour-1, hydrogen to oil volume ratio is 50-2000, it is preferable that 100-1000。Wherein, can be different depending on the difference of handled raw oil or purpose, this is that those skilled in the art are readily appreciated by。
The device of described hydrotreatment reaction can make described raw oil carry out with the catalytic reactor of described catalyst at hydrotreating reaction conditions any being enough to, such as, fixed bed reactors, moving-burden bed reactor, slurry bed system or fluidized bed reactor carry out。
Catalyst provided by the invention is applicable to hydrocarbon raw material is carried out hydrotreatment, to produce high-quality hydrocarbon fraction。Described hydrocarbon raw material can be various mineral oil or artificial oil or their mixed fraction oil, such as plant wet goods more than straight run gas oil, vacuum gas oil (VGO), metal removal oil, reduced crude, de-asphalted vacuum residue, coker distillate, catalytic treatment distillate oil, shale oil, asphalt sand oil, ICL for Indirect Coal Liquefaction oil, coal direct liquefaction oil, common vegetable oil or kitchen。
Compared with existing hydrogenation catalyst, the present invention provides the performance of catalyst to improve。Such as, under identical reaction conditions, the present invention provides the catalyst that 4,6-dimethyl Dibenzothiophene hydrodesulfurization activities of catalyst are prepared higher than prior art。
Detailed description of the invention
Example below will be further illustrated the present invention。
Agents useful for same in embodiment, unless otherwise indicated, is chemically pure reagent。The source of hydrated alumina and molecular sieve that following example and comparative example prepare carrier includes:
Chang Ling dry glue powder is the boehmite that Sinopec catalyst Chang Ling branch company produces, and butt is 0.73, and specific surface area is 300 meters2/ gram, pore volume is 0.97 ml/g。
The boehmite that SD Fen Shi Shandong Aluminum Plant produces, butt is 0.69, and specific surface area is 220 meters2/ gram, pore volume is 0.48 ml/g)。
SB powder is the boehmite powder that Sasol company of Germany produces, and butt is 0.74, and specific surface area is 230 meters2/ gram, pore volume is 0.50 ml/g。
USY type molecular sieve is produced by Sinopec catalyst Chang Ling branch company, and lattice constant 2.437 nanometers, butt is 0.74。
HY type molecular sieve is produced by Sinopec catalyst Chang Ling branch company, and lattice constant 2.453 nanometers, butt is 0.75。
HZSM-5 molecular sieve is produced by Sinopec catalyst Chang Ling branch company, n(SiO2)/n(Al2O3)Being 64, butt is 0.95。
Wherein, butt assay method is: weigh the testing sample (such as 30g) of constant weight, by this sample 600 DEG C of roasting 3h in muffle furnace, weighs after cooling, and before this weight and roasting, the ratio of weight (such as 30g) is butt。
Specific surface area and pore volume assay method are to adopt BET method (referring to GB/5816-1995) to measure above-mentioned 600 DEG C of pretreated dry glue powders。
In carrier, carbon content assay method is shown in " Petrochemical Engineering Analysis method (RIPP test method) ", Science Press, 1990,303-304
In catalyst, the content assaying method of active metal component is shown in " Petrochemical Engineering Analysis method (RIPP test method) ", Science Press, 1990,371-379
Embodiment 1
Weighing 493.0 grams of Chang Ling dry glue powders, 43.5 grams of HZSM-5 type molecular sieves, 32.6 grams of methylcellulose and 535 milliliters of aqueous solution containing 1.0 weight % nitric acid uniform, be extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters, 120 DEG C dry 4 hours。Weighing 300 grams of dried strip, be placed in tube furnace and completely cut off air, be warmed up to 580 DEG C with 4 DEG C/minute, carbonization processes 4 hours。Then, pass into the steam of 150 standard liters/(kilogram hour), be warmed up to 820 DEG C with 6 DEG C/minute, activate 60 minutes, prepare the alumina support S containing charcoal and molecular sievel。Wherein, containing charcoal 3.0 weight %, containing molecular sieve 10.0 weight %。
Weigh 100.0 grams of SlCarrier with 93 milliliters of aqueous impregnation containing ammonium paramolybdate 26.5 grams, nickel nitrate 12.0 grams, cobalt nitrate 6.0 grams and ethylenediamine 4.2 grams 2 hours, 120 DEG C dry 4 hours, 500 DEG C of roastings 4 hours, obtain catalyst C1。Catalyst C1Middle NiO, CoO and MoO3Weight content is in Table 1。
Embodiment 2
Weigh 493.0 grams of Chang Ling dry glue powders, 43.5 grams of HZSM-5 type molecular sieves, 13.0 grams of methylcellulose and 548 milliliters of aqueous solution containing 27.9 grams of oxalic acid and 1.0 weight % nitric acid uniform, being extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters, 120 DEG C dry 4 hours。The weight ratio of oxalic acid and methylcellulose is 2.14。Weighing 300 grams of dried strip, be placed in tube furnace and completely cut off air, be warmed up to 580 DEG C with 4 DEG C/minute, carbonization processes 4 hours。Then, pass into the steam of 150 standard liters/(kilogram hour), be warmed up to 820 DEG C with 6 DEG C/minute, activate 60 minutes, prepare the alumina support S containing charcoal and molecular sieve2。Wherein, containing charcoal 3.0 weight %, containing molecular sieve 10.0 weight %。
Weigh 100.0 grams of S2Carrier with 93 milliliters of aqueous impregnation containing ammonium paramolybdate 26.5 grams, nickel nitrate 12.0 grams, cobalt nitrate 6.0 grams and ethylenediamine 4.2 grams 2 hours, 120 DEG C dry 4 hours, 500 DEG C of roastings 4 hours, obtain catalyst C2。Catalyst C2Middle NiO, CoO and MoO3Weight content is in Table 1。
Embodiment 3
Weigh 500.0 grams of Chang Ling dry glue powders, 100.0 grams of SD powder, 44.0 grams of HY type molecular sieves and 614 milliliters of aqueous solution containing 4.7 grams of glucoses, 10.6 grams of oxalic acid and 1.0 weight % nitric acid uniform, being extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters, 120 DEG C dry 6 hours。The weight ratio of oxalic acid and glucose is 2.25。Weighing 300 grams, be placed in tube furnace and completely cut off air, be warmed up to 580 DEG C with 5 DEG C/minute, carbonization processes 4 hours。Then, pass into the steam of 200 standard liters/(kilogram hour), be warmed up to 790 DEG C with 4 DEG C/minute, activate 90 minutes, prepare the alumina support S containing charcoal and molecular sieve2。This carrier is containing charcoal 1.0 weight %, containing molecular sieve 7.0 weight %。
Weigh S2100 grams of carrier, impregnates 3 hours containing nickel nitrate 15.6 grams, cobalt nitrate 5.0 grams, ammonium paramolybdate 36.5 grams and 7.7 grams and 7.6 grams glycerin solutions of phosphoric acid with 90 milliliters, and 130 DEG C dry 4 hours, obtain catalyst C3。Catalyst C3Middle NiO, CoO, MoO3、P2O5With organic additive weight content in Table 1。
Embodiment 4
Weigh 300.0 grams of Chang Ling dry glue powders, 300.0 grams of SB powder, 35.2 grams of USY type molecular sieves, 7.5 grams of methylcellulose and 561 milliliters of aqueous solution containing 11.0 grams of ethylene glycol and 1.0 weight % nitric acid uniform, being extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters, 130 DEG C dry 5 hours。The weight ratio of ethylene glycol and methylcellulose is 1.48。Weighing 300 grams, be placed in tube furnace, pass into the nitrogen of 190 standard liters/(kilogram hour), be warmed up to 550 DEG C with 5 DEG C/minute, carbonization processes 5 hours。Then, pass into the steam of 140 standard liters/(kilogram hour), be warmed up to 800 DEG C with 4 DEG C/minute, activate 80 minutes, prepare the alumina support S containing charcoal and molecular sieve3。This carrier is containing charcoal 1.5 weight %, containing molecular sieve 5.5 weight %。
Weigh S3100.0 grams of carrier, with 83 milliliters of aqueous impregnation containing basic nickel carbonate 7.5 grams, basic cobaltous carbonate 3.8 grams, molybdenum trioxide 32.3 grams and phosphatase 11 1.8 grams 1 hour, 120 DEG C dry 5 hours, 420 DEG C of roastings 4 hours under logical condition of nitrogen gas。Again with 60 milliliters of aqueous impregnation containing ethylenediaminetetraacetic acid 16.2 grams 1.5 hours, 190 DEG C dry obtains catalyst C in 3 hours4。Catalyst C4Middle NiO, CoO, MoO3、P2O5With the weight content of organic additive in Table 1。
Embodiment 5
Weigh 430.0 grams of Chang Ling dry glue powders, 200.0 grams of SD powder, 40.1 grams of USY type molecular sieves and 625 milliliters of aqueous solution containing 10.9 grams of citric acids, 14.8 grams of formic acid and 1.0 weight % nitric acid uniform, being extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters, 140 DEG C dry 3 hours。The weight ratio of formic acid and citric acid is 1.36。Weighing 300 grams, be placed in tube furnace, pass into the nitrogen of 150 standard liters/(kilogram hour), be warmed up to 550 DEG C with 5 DEG C/minute, carbonization processes 4 hours。Then, the CO of 220 standard liters/(kilogram hour) is passed into2, it is warmed up to 810 DEG C with 3 DEG C/minute, activates 70 minutes, prepare the alumina support S containing charcoal and molecular sieve4。This carrier is containing charcoal 2.6 weight %, containing molecular sieve 6.0 weight %。
Weigh S4100.0 grams of carrier, with 87 milliliters of aqueous impregnation containing basic nickel carbonate 9.8 grams, basic cobaltous carbonate 1.9 grams, molybdenum trioxide 27.7 grams, phosphoric acid 6.7 grams and citric acid 13.4 grams 2 hours, 190 DEG C dry 3 hours, obtain catalyst C5。Catalyst C5Middle NiO, CoO, MoO3、P2O5With the weight content of organic additive in Table 1。
Embodiment 6
Weigh 380.0 grams of Chang Ling dry glue powders, 250.0 grams of SB powder, 55.4 grams of HY type molecular sieves and 628 milliliters containing 14.8 grams of sucrose, 19.8 gram 1, the aqueous solution of ammediol and 1.0 weight % nitric acid is uniform, being extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters, 150 DEG C dry 2 hours。The weight ratio of 1,3-propylene glycol and sucrose is 1.33。Weighing 300 grams, be placed in tube furnace and completely cut off air, be warmed up to 600 DEG C with 5 DEG C/minute, carbonization processes 3 hours。Then, pass into the steam of 200 standard liters/(kilogram hour), be warmed up to 780 DEG C with 4 DEG C/minute, activate 100 minutes, prepare the alumina support S containing charcoal and molecular sieve5。This carrier is containing charcoal 3.0 weight %, containing molecular sieve 8.0 weight %。
Weigh S5100.0 grams of carrier, with 85 milliliters containing nickel nitrate 14.2 grams, cobalt nitrate 5.8 grams, ammonium paramolybdate 28.6 grams, phosphoric acid 5.5 grams and the aqueous solution 88 milliliters of aminotriacetic acid 7.5 grams impregnate 1.5 hours, 160 DEG C are dry 4 hours, obtain catalyst C6。Catalyst C6Middle NiO, CoO, MoO3、P2O5With the weight content of organic additive in Table 1。
Comparative example 1
The method that in referenced patent ZL200410000952.X, embodiment 3 provides prepares comparative catalyst D1Carrier。
Weighing 493.0 grams of Chang Ling dry glue powders, 43.5 grams of HZSM-5 type molecular sieves, 32.6 grams of methylcellulose and 535 milliliters of aqueous solution containing 1.0 weight % nitric acid uniform, be extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters, 120 DEG C dry 4 hours。Weigh 300 grams of dried strip, be placed in tube furnace, roasting 2 hours under the condition of nitrogen gas of 450 DEG C of logical oxygenous 1.5 volume %。Then, oxygen, nitrogen mixed gas are changed into nitrogen and be warming up to 630 DEG C of activation 2 hours, obtains carrier S7。Wherein, containing charcoal 3.0 weight %, containing molecular sieve 10 weight %。
The method that in referenced patent CN201310198742.5, embodiment 4 provides introduces comparative catalyst D1Active metal component。
Weigh ammonium paramolybdate 26.5 grams, nickel nitrate 12.0 grams and cobalt nitrate 6.0 grams, put in the deionized water beaker filling 60 milliliters and be configured to solution, add ethylenediamine 4.2 grams, be diluted to 93 milliliters with deionized water。With this solution impregnation S7100.0 grams of carrier 2 hours, 120 DEG C dry 4 hours, 500 DEG C of roastings 4 hours, obtain comparative catalyst D1。Catalyst D1Middle NiO, CoO, MoO3、P2O5With the weight content of organic additive in Table 1。
Table 1
| Catalyst | NiO/% | CoO/% | MoO3/ % | P2O5/ % | Organic additive/% |
| C1 | 2.4 | 1.2 | 17.0 | 0 | 0 |
| C2 | 2.4 | 1.2 | 17.0 | 0 | 0 |
| C3 | 2.4 | 0.8 | 18.2 | 3.5 | 4.7 |
| C4 | 2.3 | 1.4 | 19.8 | 5.2 | 9.8 |
| C5 | 3.2 | 0.7 | 17.9 | 3.1 | 8.6 |
| C6 | 2.3 | 1.0 | 15.2 | 2.6 | 4.9 |
| D1 | 2.4 | 1.2 | 17.0 | 0 | 0 |
Embodiment 7-12 comparative example 2
Embodiment 7-12 comparative example 2 illustrates catalyst activity evaluation methodology and the evaluation result that the inventive method provides。
Catalyst activity evaluation carries out on flowing high-pressure micro-device continuously。Catalyst first carries out presulfurization process。Conditions of vulcanization: sulfurized oil is containing CS2Being the hexamethylene of 5 weight %, curing temperature 360 DEG C, hydrogen dividing potential drop is 4.14MPa。After vulcanizing 3 hours, pass into containing 4,6-dimethyl Dibenzothiophene (4,6-DMDBT) is the n-decane solution of 0.45 weight %, and catalyst loading amount is 0.15g, dilute with 1.0g quartz sand, reaction temperature is 280 DEG C, and hydrogen dividing potential drop is 4.14MPa, hydrogen to oil volume ratio 2000, feed rate 0.2 ml/min, in offgas outlet frozen water cooling sampling after reacting 3.0 hours。The 6890N type gas chromatograph that gained sample AgilentTechnologies company produces is analyzed。
If reaction carries out 4,6-DMDBT residual concentration C in t afterproductt, 4,6-DMDBT hydrodesulfurization reactions are processed by first order reaction, reaction rate constant is calculated by following method。
Response time is 4,6-DMDBT conversion ratio x during t:
X=(C0-Ct)/C0
C in formula0For 4,6-DMDBT concentration (C in reaction raw materials0It is 0.45%), CtIt is that (i.e. sample time for different catalysts, keeps 4,6-DMDBT concentration during identical response time t) to t for the response time。
4,6-DMDBT hydrodesulfurization reaction speed constant is:
K=1/t*Ln (1/ (1-x))
The relative hydrodesulfurization activity of catalyst represents with the ratio of 4,6-DMDBT hydrodesulfurization reaction speed constants on the catalyst with hydrogenation reaction speed constant on comparative example catalyst, and result is in Table 2。
Table 2
| Example | Catalyst | Relative hydrodesulfurization activity/the % of catalyst |
| 7 | C1 | 109 |
| 8 | C2 | 112 |
| 9 | C3 | 119 |
| 10 | C4 | 117 |
| 11 | C5 | 120 |
| 12 | C6 | 118 |
| Comparative example 2 | D1 | 100 |
Illustrated, by the NiCoMo catalyst prepared containing the heat-resistant inorganic oxide carrier of charcoal and molecular sieve provided by the invention, there are 4,6-DMDBT higher hydrodesulfurization activities by data in table 2。
Claims (19)
1. a hydrotreating catalyst, containing carrier and load hydrogenation active metals component on this carrier, it is characterized in that, described carrier contains heat-resistant inorganic oxide, molecular sieve and charcoal, the predecessor of heat-resistant inorganic oxide and/or heat-resistant inorganic oxide is mixed by including by described carrier with the predecessor of molecular sieve and carbon powder and/or charcoal, molding, prepared by the method drying and activating, with described carrier for benchmark, the consumption of each component makes the content of charcoal in final described carrier be 0.3-5 weight %, the content of molecular sieve is 2-15 weight %, the content of heat-resistant inorganic oxide is 80-95 weight %,
Wherein, described drying condition includes: temperature is 100-180 DEG C, and drying time is 0.5-10 hour；
Described activation includes: (1), under isolation air and/or noble gas exist, by dried article shaped heat treated, heat treatment temperature is 400-800 DEG C, and the time is 0.5-8 hour；(2) under steam and/or carbon dioxide atmosphere, being processed by the product heats of step (1), heating-up temperature is 600-950 DEG C, and the time is 0.3-4 hour, the flow of described steam and/or carbon dioxide be 50-500 standard liter/kilogram hour。
2. catalyst according to claim 1, it is characterised in that with described carrier for benchmark, the consumption of each component makes the content of charcoal in final described carrier be 0.5-3 weight %；The content of molecular sieve is 2.5-10 weight %, and the content of heat-resistant inorganic oxide is 87-97 weight %；The method of described activation includes: (1), under isolation air and/or noble gas exist, by dried article shaped heat treated, heat treatment temperature is 550-700 DEG C, and the time is 0.5-3 hour；(2) under steam and/or carbon dioxide atmosphere, the product heats of step (1) is processed, heating-up temperature is 750-850 DEG C, and the time is 0.5-3 hour, the flow of described steam and/or carbon dioxide be 100-300 standard liter/kilogram hour。
3. catalyst according to claim 1, it is characterised in that the predecessor of described charcoal is selected from can the Organic substance of carbonization in the step (1) of described activation。
4. catalyst according to claim 3, it is characterised in that one or more in alcohol, sugar, organic acid of the predecessor of described charcoal。
5. catalyst according to claim 4, it is characterised in that one or more in monohydric alcohol, dihydroxylic alcohols and polyhydric alcohol of described alcohol；One or more in lactose, galactose, beet sugar, fructose, glucose, sugar, sucrose, maltose, methylcellulose and starch of described sugar；One or more in formic acid, acetic acid, n Propanoic acid, 1,3-malonic acid, n-butyric acie, oxalic acid, citric acid, tartaric acid, malic acid of described organic acid。
6. the catalyst according to claim 1,3,4 or 5 any one, it is characterized in that, the predecessor of described charcoal is the mixture of small organic molecule and larger molecular organics, wherein the weight ratio of small organic molecule and larger molecular organics is 1-3, wherein, described small organic molecule refers to the predecessor in molecule containing the charcoal below 4 carbon atoms, and described larger molecular organics refers to the predecessor in molecule containing charcoals more than 5 carbon atoms。
7. catalyst according to claim 6, it is characterised in that the weight ratio of described small organic molecule and larger molecular organics is 1.3-2.3。
8. catalyst according to claim 1 and 2, it is characterised in that one or more in nitrogen, argon and helium of described noble gas。
9. catalyst according to claim 1, it is characterized in that, one or more in aluminium oxide, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, silica-magnesias, silica-zirconia, silica thoria, silica-berylias, silica-titania, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia, silica-alumina, zirconia of described refractory oxides。
10. the catalyst according to claim 1 or 9, it is characterised in that described refractory oxides is selected from aluminium oxide。
11. catalyst according to claim 1, it is characterised in that one or more in faujasite, modenite, L zeolite, omega zeolite, ZSM-5 zeolite, Beta zeolite etc. of described molecular screening。
12. catalyst according to claim 11, it is characterised in that described faujasite is selected from y-type zeolite, it is preferred to HY type molecular sieve, USY type molecular sieve and/or rare earth Y type molecular sieve。
13. catalyst according to claim 1, it is characterized in that, described hydrogenation active metals component is selected from the metal component of at least one group VIII and at least one vib, with described catalyst for benchmark, the content of the group VIII metal component counted with oxide is for 2-10 weight %, and the content of the vib metals component counted with oxide is for 13-30 weight %。
14. catalyst according to claim 13, it is characterized in that, described group VIII metal component is nickel and cobalt, the metal component of vib is molybdenum, with described catalyst for benchmark, the content of the group VIII metal component counted with oxide is for 2-8 weight %, and the content of the vib metals component counted with oxide is for 13-27 weight %。
15. catalyst according to claim 1, it is characterised in that described catalyst contains auxiliary agent phosphorus, counting with oxide and with catalyst for benchmark, the content of phosphorus is 2-10 weight %。
16. catalyst according to claim 15, it is characterised in that count with oxide and with catalyst for benchmark, the content of auxiliary agent phosphorus is 2-7 weight %。
17. catalyst according to claim 1, it is characterised in that containing organic additive in described catalyst, with described catalyst for benchmark, the content of described organic additive is 2-20 weight %。
18. catalyst according to claim 17, it is characterised in that containing organic additive in described catalyst, with described catalyst for benchmark, the content of described organic additive is 3-15 weight %。
19. a method for hydrotreating hydrocarbon oil, including at hydrotreating reaction conditions, by hydrocarbon oil crude material and catalyst haptoreaction, it is characterised in that described catalyst is the catalyst described in 1-18 any one。
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| WO2018160424A1 (en) * | 2017-03-03 | 2018-09-07 | Exxonmobil Research And Engineering Company | Trimetallic base metal hdn+hds+dewaxing catalysts, their preparation and use |
| CN112844466A (en) * | 2021-02-02 | 2021-05-28 | 华南农业大学 | Green biomass charcoal modified molecular sieve supported metal catalyst and preparation method and application thereof |
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| JP2002166181A (en) * | 2000-11-30 | 2002-06-11 | Tonengeneral Sekiyu Kk | Catalyst for hydrogenation processing and hydrogenation processing method for hydrocarbon oil using the catalyst |
| CN101015805A (en) * | 2007-02-07 | 2007-08-15 | 沈和平 | Catalyst for hydrorefining fraction oil and its prepn. |
| CN101733151A (en) * | 2008-11-20 | 2010-06-16 | 中国石油化工股份有限公司 | Distillate oil hydrorefining catalyst |
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| JP2002166181A (en) * | 2000-11-30 | 2002-06-11 | Tonengeneral Sekiyu Kk | Catalyst for hydrogenation processing and hydrogenation processing method for hydrocarbon oil using the catalyst |
| CN101015805A (en) * | 2007-02-07 | 2007-08-15 | 沈和平 | Catalyst for hydrorefining fraction oil and its prepn. |
| CN101733151A (en) * | 2008-11-20 | 2010-06-16 | 中国石油化工股份有限公司 | Distillate oil hydrorefining catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018160424A1 (en) * | 2017-03-03 | 2018-09-07 | Exxonmobil Research And Engineering Company | Trimetallic base metal hdn+hds+dewaxing catalysts, their preparation and use |
| US10632453B2 (en) | 2017-03-03 | 2020-04-28 | Exxonmobil Research And Engineering Company | Trimetallic base metal dewaxing catalyst |
| CN112844466A (en) * | 2021-02-02 | 2021-05-28 | 华南农业大学 | Green biomass charcoal modified molecular sieve supported metal catalyst and preparation method and application thereof |
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