CN1769376A - Hydrotreatment catalyst and its preparation method - Google Patents
Hydrotreatment catalyst and its preparation method Download PDFInfo
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- CN1769376A CN1769376A CN 200410050713 CN200410050713A CN1769376A CN 1769376 A CN1769376 A CN 1769376A CN 200410050713 CN200410050713 CN 200410050713 CN 200410050713 A CN200410050713 A CN 200410050713A CN 1769376 A CN1769376 A CN 1769376A
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Abstract
The invention discloses the hydrotreatment catalyst and preparing method. The catalyst contains the 1wt%-20wt% organic auxiliary agent, using the aluminum oxide modified by titanium and silicon as carrier, and using the metals in the VIB and VIII as active metal componemt. The method comprises the following steps: using the modified aluminum oxide as carrier, after soaking the catalyst carrier in the active metal and organic auxiliary agent, drying at the 200 DEG C, and getting the catalyst. The said catalyst can be used for hydrotreating process of fraction of petroleum, especially for hydrodesulphurization and hydrodenitrification process of middle distillate oil.
Description
Technical field
The present invention relates to a kind of hydrotreating catalyst, be specially adapted to the hydrogenating desulfurization and the hydrodenitrification process of distillate.The present invention has also related to this Preparation of catalysts method in addition.
Background technology
Along with the great attention of society to environment and human health, environmental regulation is more and more stricter to the requirement of sulphur content in the petroleum products, diesel oil distillate particularly, sulphur content in the diesel oil distillate is that 0.05wt%～0.1wt% is an acceptable at present, but will soon require sulphur content less than 0.05wt%, and foreseeable future will require sulphur content less than 350ppm even lower.Can this standard reach and depend on to a great extent and be difficult to for example 4-MDBT and 4 of the sulfocompound that removes in the raw material, the content of 6-dimethyl Dibenzothiophene etc. how much, and can relatively effectively it removed under the demulcent condition with high activated catalyst, reach the deep desulfuration purpose.
In general, the purpose of hydrotreatment is with all or part of the removing of impurities in raw materials.Reduce sulphur, nitrogen content in the diesel oil, to reduce harm on the one hand to environment, on the other hand, sulfur-bearing and nitrogen compound often can make poisoning of catalyst, for example cracking catalyst, hydrocracking catalyst and reforming catalyst, general before carrying out this reaction, to carry out hydrotreatment and remove wherein impurity, for example cracking process.Hydrotreatment is that raw material and catalyzer are contacted under hydrogen and pyritous condition.Under this condition, sulfur-bearing in the raw material and nitrogenous compound all are converted into the hydrogen sulfide or the ammonia that remove easily and remove from raw material.
In general, hydrotreating catalyst is made up of carrier and load VIB and group VIII active metal component in the above.The most frequently used group vib element is molybdenum and tungsten, the group VIII element is nickel and cobalt, often contains phosphorus in the catalyzer, and this Preparation of catalysts method of reporting in the document is exactly a reactive metal element in load on the carrier, for example dipping makes it to be transformed into oxidation state through high-temperature roasting then.Before being used for hydrotreatment, catalyzer makes it to be transformed into sulphided state through prevulcanized.
Because environmental regulation is more and more stricter to the requirement of sulphur in the petroleum products and nitrogen content, also just requires also more and more higher to activity of such catalysts.In addition, reach the product of same quality index, utilize highly active catalyzer can be under demulcent operational condition more operation or make catalyzer have longer life cycle.
Multiple effort and trial have been carried out in the document at present for improving the hydrotreating catalyst activity, great successes have also been obtained, for example CN 1052501A and CN 1086534A disclose the hydrogenation catalyst that contains three kinds of active metal components of W-Mo-Co, for improving the catalytic performance of catalyzer, introduce auxiliary agent F, P and B, adopted two sections dipping preparation catalyzer.The introducing of auxiliary agent not only activity of such catalysts is significantly improved, and the stability of catalyzer has also obtained improvement to a certain degree.
CN85104438 discloses a kind of method for preparing catalyst, this catalyst action carrier is the high purity aluminium oxide carrier with the fluorine modification, active metal component is W-Ni, catalyzer consist of 1wt%～9wt% F, 1wt%～5wt% NiO, 15wt%～38wt% WO
3With the aluminum oxide of surplus, compare with catalyzer in the past, improved the acidity of catalyzer, the hydrogenation performance of catalyzer is improved.
CN1105953 discloses and has a kind ofly handled through high-temperature vapor, and at the high purity aluminium oxide carrier that carries out modification with fluorine, active metal component is W-Ni then, catalyzer consist of 1wt%～9wt% F, 1wt%～5wt% NiO, 15wt%～38wt% WO
3Aluminum oxide with surplus.The pore structure and the specific surface of the catalyzer that obtains are improved, and activity of such catalysts obtains raising to a certain degree.
EP0523679 discloses a kind of technology that adopts two-stage method to produce low-sulfur diesel-oil, first section temperature is 350 ℃～450 ℃, second section temperature is 200 ℃～300 ℃, at first section, sulphur content in the product is reduced to below the 0.05wt%, second section color of improving product, catalyst system therefor are conventional hydrotreating catalyst, and employed active ingredient is that Co and/or Ni-Mo load on the alumina supporter among the embodiment.Improve oil quality, reduce the severity of device operation, the most important thing is to improve the activity of hydrotreating catalyst.
USP 6281333 discloses a kind of hydrotreating catalyst.This method for preparing catalyst is as follows: after one or more reactive metals of support of the catalyst load and the organic volatile component, make the precursor of catalyzer without roasting, in the presence of at least a sulfocompound, carry out sulfurized then and reduce volatiles simultaneously, wherein the organic volatile component is selected from one or more in aliphatic hydrocarbon, aromatic hydrocarbons, alcohols, the ketone, its content is not less than 0.5wt%, preferred 2wt%～25wt%.Though used catalyzer in this patent without roasting, make catalyst desulfurizing and denitrification activity aspect obtain certain raising, but because this support of the catalyst use is conventional carrier, the physico-chemical property of carrier is very not suitable for the bigger sulfur-bearing of some volumes (nitrogen) compound, causes its deep desulfuration and denitrogenation result not very good.
JP 04-166231 discloses a kind of preparation method of hydrotreatment catalyst, the support of the catalyst dipping contains reactive metal, preferred phosphorated steeping fluid, after the dipping, dry down less than 200 ℃, contact with polyol again, less than 200 ℃ of following dryings, make this hydrotreating catalyst afterwards.There is the same shortcoming with USP 6281333 in this catalyzer, is difficult to reach the requirement of deep desulfuration and denitrogenation.
Although the catalyzer that the top is mentioned is compared with catalyzer in the past, raising is in various degree arranged on activity, be mainly reflected in the desulphurizing activated raising that obtains to a certain degree to alkyl sulfocompound and dibenzothiophene, but sulfocompound for the structure more complicated, for example 4,6-dimethyl Dibenzothiophene etc., these catalyst system activity still seem abundant inadequately, to such an extent as to be difficult to satisfy more and more higher quality product requirement at present.
Summary of the invention
For overcoming the shortcoming of prior art, the invention provides a kind of high-activity hydrogenation catalyst and preparation method thereof.This catalyzer is specially adapted to hydrogenating desulfurization, the denitrification process of intermediate oil, has higher HDS, HDN activity under identical processing condition.
High-activity hydrogenation catalyst of the present invention is to be active metal component with in the metal of group vib and group VIII one or more, is carrier with the aluminum oxide through silicon and titanium modification, is benchmark with the weight of carrier, SiO
2Content is 0.1wt%～20.0wt%, TiO
2Content is 0.1wt%～20.0wt%.Weight with catalyzer is benchmark, alumina content through silicon and titanium modification is 30wt%～95wt%, is preferably 50wt%～80wt%, and the content of active metal component is counted 0.1wt%～50.0wt% with oxide compound, be preferably 2wt%～40wt%, more preferably 2wt%～30wt%.Also contain organic additive in this catalyzer, its content is 1wt%～20wt%, is preferably 2wt%～10wt%.This catalyzer loss on ignition (roasting condition is: 600 ℃ roasting 4 hours) is 1wt%～20wt%, is preferably 2wt%～10wt% (with respect to the roasting procatalyst), and the catalyzer XRD figure is that 8 °～10 ° positions have a strong diffraction peak 20.
Described aluminum oxide through silicon and titanium modification has following feature: (1) dioxide-containing silica is 0.1wt%～20wt%, and (2) content of titanium dioxide is 0.1wt%～20wt%, and (3) specific surface area is 310m
2/ g～380m
2/ g, (4) pore volume is 0.8cm
3/ g～1.2cm
3/ g, (5) aperture is that the pore volume of 8nm～15nm accounts for 75%～85% of total pore volume, and the meleic acid amount of (6) 〉=350 ℃ is 0.04mmol/g～0.10mmol/g, and wherein B acid accounts for 40%～60% of total acid.Wherein the aluminum oxide thing can be θ-aluminum oxide, gama-alumina or η-aluminum oxide mutually, is preferably gama-alumina.
The preparation method of modified aluminas of the present invention may further comprise the steps:
(1) prepares aluminum contained compound solution, silicon-containing compound solution and titanium-containing compound solution respectively;
(2) under agitation condition, aluminum contained compound solution and silicon-containing compound solution are mixed, add the precipitation agent aqueous solution then and be reacted into glue;
(3) after the cemented into bundles, adding acid reagent in the mixed serum that obtains in step (2), to regulate the pH value of slurries be 2～4, adds the pH value 9.0～10.5 of alkaline reagents adjusting slurries again, repeats above-mentioned adjusting pH value step 1～3 times then;
(4) add titanium-containing compound solution in the mixed serum of step (3), constant temperature is aging then;
(5) mixed serum after aging filters with step (4), and filter cake obtains the modified aluminas dry glue powder through washing, drying, passes through high-temperature roasting again, just can obtain modified aluminas of the present invention.
Organic additive of the present invention can adopt oxygen-containing hydrocarbon compounds commonly used, be selected from organic carboxyl acid, alcohols, ethers and ester class and have in the saccharide compound of a plurality of hydroxyls one or more, wherein carboxylic acid compound is acetate, propionic acid, oxalic acid, hexanodioic acid, tartrate and citric acid etc., preferred hexanodioic acid, tartrate and citric acid, more preferably citric acid; Alcohol compound is vinyl alcohol, vinylcarbinol, glycerol, diethyl enol, two vinylcarbinols, trimethylammonium glycerine, glycol ether, triethyl glycerine, tripropyl glycerine and polyvinyl alcohol etc., is preferably diethyl enol, two vinylcarbinols, glycol ether and molecular-weight average and is 150～300 polyvinyl alcohol; Ether compound is vinyl alcohol butyl ether, methyl tertiary butyl ether, diethyl enol methyl ether, diethyl enol ether, diethyl enol propyl ether, diethyl enol butyl ether etc.; The saccharide compound that has a plurality of hydroxyls is glucose, fructose, lactose, maltose and sucrose etc., is preferably glucose and fructose, more preferably glucose; Ester compound is ethyl acetate, glycerol mono acetate bulk etc.
The present invention also provides above-mentioned Preparation of catalysts method, this Preparation of catalysts is to adopt two-stage method, promptly prepare alumina supporter at first according to the method described above, then with required component in the impregnation method load, comprising active ingredient and auxiliary agent through titanium and silicon modification.After impregnation steps is finished, in room temperature～200 ℃, be preferably under 80 ℃～150 ℃ and carry out drying, promptly get hydrotreating catalyst of the present invention after the drying.Dried catalyzer loss on ignition (roasting condition is: 600 ℃ roasting 4 hours) is controlled at 1wt%～20wt% (with respect to the roasting procatalyst), is preferably 2wt%～10wt%.
On the catalyzer of the present invention, the content of organic additive will suit, and general content (with respect to catalyzer) is 1wt%～20wt%, is preferably 2wt%～10wt%.If auxiliary agent content is too low, advantage of the present invention just can not demonstrate fully; If auxiliary agent content is too high, advantage of the present invention can not be further improved yet, even influences activity of such catalysts, causes the waste of material on the contrary even owing to existing a large amount of organism to cause taking place coking on the catalyzer in application process.
Compare with the preparation process of the hydrogenation catalyst of routine, catalyzer of the present invention only needs under suitable temperature dryly after dipping, and does not need through high-temperature roasting.Contain organic additive on the catalyzer of the present invention, and do not contain similar compounds on the conventional catalyzer.Catalyzer of the present invention has very high activity, the present not clear highly active reason that causes, may be owing to the time avoid or reduced the gathering of reactive metal on the catalyzer in sulfuration, thereby make have in the catalyzer more active mutually or actively have higher dispersity mutually, improved the catalytic activity of catalyzer.
It is carrier that the present invention adopts the aluminum oxide through titanium and silicon modification, because its pore structure and acid matter are more suitable for the hydrogenation reaction of petroleum fractions, prepared catalyzer has higher HDS and HDN activity under the processing condition close with comparing catalyzer.
Catalyzer of the present invention can be widely used in the hydrotreatment process of petroleum fractions, and the hydrotreatment process of diesel oil, kerosene, petroleum naphtha, vacuum gas oil and heavy gas oil for example is particularly suitable for hydrogenating desulfurization, the hydrodenitrification process of diesel oil.
Catalyzer of the present invention is used for the hydrotreatment process, and its operational condition can be with conventional hydrotreatment operational condition, and for example: temperature is 250 ℃～450 ℃, and pressure is 0.5MPa～20MPa, and volume space velocity is 0.1h
-1～10h
-1, hydrogen to oil volume ratio is 50～2000.
Description of drawings
Fig. 1 is the XRD figure of comparative example 2 catalyzer.
Fig. 2 is the XRD figure of embodiment 1 catalyzer.
Fig. 3 is the XRD figure of embodiment 5 catalyzer.
Fig. 4 is the XRD figure of embodiment 9 catalyzer.
From these XRD figure as can be seen, be that 8～10 ° position has a strong diffraction peak (Fig. 2,3 and 4) at 2 θ on the XRD figure of catalyzer of the present invention, and through the comparative catalyst of high-temperature roasting, then this diffraction peak weaken (Fig. 1) greatly.
Embodiment
The concrete preparation process of the used modified aluminas of the present invention is as follows:
Silicon-containing compound described in the step (1) can be organism or inorganics, be preferably inorganics, more preferably water glass or silicon sol solution, silicon-dioxide in the silicon-containing compound solution (in silicon-dioxide) content is generally 5～40 grams per liters, be preferably 10～30 grams per liters, more preferably 15～25 grams per liters; Described aluminum contained compound can be in the strong acid salt of meta-aluminate or aluminium one or more, is preferably sodium metaaluminate and Tai-Ace S 150, and alumina content is (with Al in the sodium aluminate solution
2O
3Meter) be generally 20～80 grams per liters, be preferably 30～70 grams per liters, 40～60 grams per liters more preferably, alumina content is (with Al in the alum liquor
2O
3Meter) is generally 5～40 grams per liters, is preferably 10～20 grams per liters; Described titanium-containing compound can be preferably titanium sulfate or titanium tetrachloride for all solubility titanium-containing compounds, titanium sulfate more preferably, and the content of titanium oxide is (with TiO in the solution
2Meter) is generally 1～50 grams per liter, is preferably 5～20 grams per liters.
Said one-tenth glue process in the step (2), be the aluminum contained compound solution for preparing to be mixed with silicon-containing compound solution to place in the glue jar earlier, the add-on of silicon-containing compound solution is according to the requirement decision of product, in dioxide-containing silica in the finished product, be warmed up to 50～95 ℃ of constant temperature, under agitation condition, neutralize with containing the precipitation agent aqueous solution, when reaching 7.5～8.5, the pH value that contains aluminum hydroxide slurry stops to add, be controlled at 0.5～1.0 hour with the time in whole, continue constant temperature and stir; Described precipitation agent is can react with aluminum contained compound to generate all substances of aluminium hydroxide gel, for example aluminum contained compound is a sodium metaaluminate, precipitation agent can be selected from hydrolysis can produce hydrionic all compounds, is preferably carbonic acid gas or Tai-Ace S 150, more preferably Tai-Ace S 150.When being Tai-Ace S 150 as aluminum contained compound, precipitation agent can be selected from all compounds that hydrolysis can produce hydroxide ion, is preferably potassium hydroxide, sodium hydroxide, yellow soda ash, ammoniacal liquor and sodium metaaluminate etc., more preferably sodium metaaluminate.
It is specific as follows to regulate the pH process behind the described one-tenth glue of step (3): add acid reagent earlier, make the pH value of aluminium hydroxide slurries be reduced to 2～4, kept 5～10 minutes, add alkaline reagents then, make the pH value of aluminium hydroxide slurries be elevated to 9.0～10.5, kept repetitive operation 1～3 time 5～10 minutes.Described acid reagent can be selected from one or more that can produce hydrionic compound after organic acid, mineral acid and the dissolving, be preferably in mineral acid or the organic acid one or more, one or more in sulfuric acid, nitric acid and the acetic acid more preferably, its consumption are to reach the pH value decision of defined; Described alkaline reagents can be selected from one or more of compound that dissolving back generates hydroxide ion, is preferably one or more of mineral compound, more preferably one or more in sodium metaaluminate, sodium hydroxide and the ammoniacal liquor.
The described method of step (4) adds titanium-containing compound solution in the solution after the cemented into bundles, add-on is adjusted as required, adds speed control and adds at 5～30 minutes and finish, and constant temperature is aging 1～3 hour then.
The described filtration of step (5), washing, drying and roasting can be adopted method commonly used, for example suction filtration, 80～120 ℃ of dryings obtained modified aluminum hydroxide solid elastomer in 2～20 hours, and dried glue obtained modified aluminas of the present invention in 0.5～8 hour through 400～800 ℃ of roastings.
Active metal component in the catalyzer of the present invention is selected from one or more in the metal of group vib and group VIII in the periodic table of elements, and wherein the group vib metal refers generally to molybdenum and tungsten, and the group VIII metal refers generally to cobalt and nickel.If main purpose is desulfurization, active metal component is preferably molybdenum and cobalt, if main purpose is denitrogenation, active metal component is preferably molybdenum (or tungsten) and nickel.Group vib and the group VIII metal content (in oxide compound) in catalyzer is respectively 5wt%～35wt% and 1wt%～15wt%, is preferably 10wt%～20wt% and 4wt%～8wt%.If desired, can add other element, for example phosphorus, chlorine or boron etc., phosphorus particularly is benchmark with the weight of catalyzer, and the content of Vanadium Pentoxide in FLAKES is 1wt%～10wt%, be preferably 2wt%～6wt%, the adding of phosphorus can improve hydrogenating desulfurization, denitrogenation and the Tuo Fang performance of catalyzer.
In carrier loaded active ingredient and organic additive process, organic additive can together load on the catalyzer with other active ingredient, also can step load to catalyzer, during step load, can first supported active metal component, also can first load organic additive, be preferably first supported active metal component, behind the supported active metal component, carry out drying under ℃ condition of room temperature～200 to catalyzer, and then the load organic additive.If adding assistant phosphorus can together load on the support of the catalyst with active metal component.Carrying method can adopt an existing incision technology, and for example saturated dipping, unsaturated dipping, spraying dipping and dip etc. are preferably saturated dipping, and the steeping fluid that is about to saturated extent of adsorption joins in the carrier, is adsorbed fully until it.After impregnation steps is finished, catalyzer will carry out dry to remove solvent wherein, in drying process, want strict controlled temperature, avoid the volatilization and the decomposition of auxiliary agent as far as possible, concrete temperature should depend on the character of auxiliary agent, and general temperature will be lower than 200 ℃, is preferably 80 ℃～150 ℃, generally be controlled at 1wt%～20wt% (with respect to the roasting procatalyst) through dried catalyzer loss on ignition (600 ℃ roasting 4 hours), be preferably 2wt%～10wt%.
Give further instruction below by embodiment to technology of the present invention.
XRD result among the present invention adopts D/MAX-RA type x-ray diffractometer of science, and source of radiation is the copper target, the filtering of graphite monocrystalline, operation tube voltage 35KV, tube current 30～50mA, sweep velocity (2 θ) be 4 degree/minute, sweep limit is 4～35 degree.The specific surface area of carrier and catalyzer and pore volume are to adopt ASAP2400, and cryogenic nitrogen absorption (77K) calculates according to BET formula.Acid amount and acid matter adopt infrared spectrometer to record, and the sorbent material that uses is pyridine.SiO
2And TiO
2Content adopt weighting method and spectrophotometry to record respectively.
The embodiment of the invention is to adopt 100 milliliters of fixed-bed reactor, and employed raw material is grand celebration catalytic diesel oil (character sees Table 1).Catalyzer carries out prevulcanized by following conditions before use to be handled, vulcanized oil adopts and adds the virgin kerosene (character sees Table 1) that contains 1.5wt% sulphur (vulcanizing agent is a dithiocarbonic anhydride), directly carry out catalytic test after the prevulcanized, the condition of prevulcanized and test sees Table 2.
The character of table 1 virgin kerosene and catalytic diesel oil
| The stock oil title | Virgin kerosene | Catalytic diesel oil |
| Density (20 ℃), g/cm 3 | 0.8044 | 0.8643 |
| Sulphur content, μ g.g -1 | 460 | 6400 |
| Nitrogen content, μ g.g -1 | 18 | 450 |
| Boiling range, ℃ (ASTM D86) | ||
| Initial boiling point | 148 | 171 |
| 10％ | 174 | 208 |
| 50％ | 188 | 259 |
| 90％ | 216 | 329 |
Table 2 prevulcanized and test conditions
| The prevulcanized condition | Test conditions | |
| Temperature, ℃ | 320 | 330 |
| The hydrogen dividing potential drop, Mpa | 6.0 | 6.0 |
| LHSV，h -1 | 1 | 2 |
| Hydrogen to oil volume ratio | 300 | 300 |
| Time, h | 8 | 160 |
The desulphurization reaction speed K of each catalyzer
nCalculation formula by bottom calculates:
K
n＝LHSV*1/(n-1)*(1/S
n-1*1/S
0 n-1)
Here the sulphur content in the S representative products, S
0Represent the sulphur content in the raw material, n represents the reaction order of hydrogenating desulfurization, the volume space velocity of LHSV representative reaction, and in this reaction, the value of n is 1.75.Comparative catalyst's reaction constant is 100, and the desulphurization reaction speed of other catalyzer is relative value.
The denitrogenation rate constant K of catalyzer
nCalculation formula by bottom calculates:
K
n＝LHSV*ln(N
0*N)
Here the nitrogen content in the N representative products, N
0Represent the nitrogen content in the raw material, the volume space velocity of LHSV representative reaction, comparative catalyst's reaction constant is 100, the denitrification reaction speed of its catalyzer is relative value, the results are shown in Table 3.
Comparative example 1
Adopt conventional method for preparing catalyst to prepare the comparative catalyst, process is: (specific surface area is 278m with pseudo-boehmite
2/ g, pore volume are 0.76cm
3/ g, aperture be the pore volume of 8nm～15nm account for total pore volume 68%, 〉=350 ℃ meleic acid amount is 0.02mmol/g, wherein B acid account for total acid 38%) and suitable peptizing agent, mix the moulding of pinching bar, obtained the cloverleaf pattern carrier that diameter is 1.2mm in 4 hours through 110 ℃ of dryings 8 hours and 650 ℃ of roastings, length is 3mm～8mm, and the specific surface area of carrier is 248m
2/ g, pore volume are 0.62ml/g, and intensity is 108N/cm.Get 100 gram carriers with containing of saturated extent of adsorption an amount of molybdic oxide, cobaltous carbonate, citric acid and the steeping fluid of phosphoric acid flood, following dry 10 hours at 110 ℃ then, 500 ℃ of roastings are 4 hours in air atmosphere, obtaining molybdenum oxide content is 24wt%, cobalt oxide content is that 5wt% and phosphorus oxide content are that the catalyzer of 6wt% is numbered C-1, and the loss on ignition of catalyzer is 0.01wt%.The composition and the evaluation result of catalyzer see Table 3.
Comparative example 2
The preparation of carrier is with comparative example 1.Getting 100 gram carriers floods with the steeping fluid that contains an amount of molybdic oxide, cobaltous carbonate, phosphoric acid, citric acid and glycol ether (mass ratio of citric acid and glycol ether is 1: 1), following dry 10 hours at 110 ℃ then, obtaining molybdic oxide content is 22wt%, cobalt oxide content is that 4wt% and phosphorus oxide content are that the catalyzer of 5wt% is numbered C-2, and the loss on ignition of catalyzer is 7.5wt%.The composition and the evaluation result of catalyzer see Table 3.
Embodiment 1
Modified aluminas according to method preparation provided by the invention.
Adding 10L concentration in 100 liters of one-tenth glue jars is 40g Al
2O
3The sodium aluminate solution of/L and 2L concentration are 15g SiO
2/ L sodium silicate solution, thorough mixing, temperature is elevated to 75 ℃, and adding concentration then gradually is 20g Al
2O
3/ L, temperature is 75 ℃ a alum liquor, stops to add alum liquor when the pH of slurries value is 8.0, continues constant temperature and stirs 5 minutes, add the dilute nitric acid solution that concentration is 5wt% then, the pH value of adjusting slurries is 2.5, and constant temperature stirred 5 minutes, then adds the sodium aluminate solution of above-mentioned character, adjusting slurry pH value is 9.0, continue constant temperature and stirred 5 minutes, repeat to swing pH value twice, adding 2L concentration then is 8g TiO
2The titanium sulfate solution of/L, and control adding speed finishes adding in 10 minutes, keeping temperature to be 75 ℃ wore out 3 hours, isolate solid product, solid product is through after washing, and drying is 8 hours under 100 ℃, obtain the aluminum hydroxide solid elastomer of titaniferous and silicon, have following feature: (1) dioxide-containing silica is 4.2wt%, and (2) content of titanium dioxide is 2.7wt%, and (3) specific surface area is 337m
2/ g, (4) pore volume is 0.92ml/g, and (5) aperture is that the pore volume of 8nm～15nm accounts for 81% of total pore volume, and the meleic acid amount of (6) 〉=350 ℃ is 0.05mmol/g, and wherein B acid accounts for 48% of total acid.
Embodiment 2
Modified aluminas according to method preparation provided by the invention.
Compare with embodiment 1, the amount that difference is to add the amount of sodium silicate solution and titanium sulfate solution is different, and all the other are with embodiment 1, obtain modified aluminas, have following feature: (1) dioxide-containing silica is 0.2wt%, and (2) content of titanium dioxide is 20wt%, and (3) specific surface area is 310m
2/ g, (4) pore volume is 0.80ml/g, and (5) aperture is that the pore volume of 8nm～15nm accounts for 75% of total pore volume, and the meleic acid amount of (6) 〉=350 ℃ is 0.04mmol/g, and wherein B acid accounts for 42% of total acid.
Embodiment 3
Modified aluminas according to method preparation provided by the invention.
Compare with embodiment 1, the amount that difference is to add the amount of sodium silicate solution and titanium sulfate solution is different, and all the other are with embodiment 1, obtain modified aluminas, have following feature: (1) dioxide-containing silica is 19.6wt%, and (2) content of titanium dioxide is 0.4wt%, and (3) specific surface area is 366m
2/ g, (4) pore volume is 1.04ml/g, and (5) aperture is that the pore volume of 8nm～15nm accounts for 85% of total pore volume, and the meleic acid amount of (6) 〉=350 ℃ is 0.10mmol/g, and wherein B acid accounts for 54% of total acid.
Embodiment 4
Catalyzer E-4 according to method preparation provided by the invention.
Compare with comparative example 2, difference is that all the other are with comparative example 2 with the modified oxidized aluminium substitution pseudo-boehmite of embodiment 1 preparation, and the catalyzer that obtains is numbered E-4, and it is formed and evaluation result sees Table 3.
Catalyzer E-5 according to method preparation provided by the invention.
Compare with embodiment 4, difference is that all the other are with embodiment 4 with the modified aluminas of modified oxidized aluminium substitution embodiment 1 preparation of embodiment 2 preparations, and the catalyzer that obtains is numbered E-5, and it is formed and evaluation result sees Table 3.
Embodiment 6～8
Catalyzer E-6～E-8 according to method preparation provided by the invention.
Except that the active ingredient kind with content is different, all the other are with embodiment 4, the catalyzer that obtains is numbered E-6～E-8, it is formed and evaluation result sees Table 3.
Table 3 catalyst property and test-results
| Catalyzer | MoO 3 wt％ | WO 3 wt％ | NiO wt％ | CoO wt％ | P 2O 5 wt％ | Auxiliary agent wt% | Loss on ignition wt% | The HDS activity | The HDN activity |
| C-1 | 24 | - | - | 5 | 6 | - | 0.01 | 89 | 94 |
| C-2 | 22 | - | - | 4 | 5 | 10 | 7.5 | 100 | 100 |
| E-4 | 22 | - | - | 4 | 5 | 10 | 8 | 165 | 142 |
| E-5 | 20 | - | 5 | - | 4 | 8 | 7.5 | 158 | 156 |
| E-6 | 18 | - | 2 | 3 | 5 | 12 | 10 | 172 | 150 |
| E-7 | - | 26 | 4 | - | 6 | 6 | 5 | 140 | 144 |
| E-8 | - | 22 | 6 | 2 | 3 | 2 | 3.1 | 133 | 152 |
As can be seen from Table 2, activity of such catalysts of the present invention is apparently higher than the comparative catalyst.
Embodiment 9～16
Except that modified aluminas, reactive metal kind and content, the organic additive kind of modified oxidized aluminium substitution embodiment 1 preparation of using embodiment 3 preparations with content is different, all the other are with embodiment 4, catalyzer is numbered E-9～E-16, and it is formed and test-results sees Table 4.
Table 4 catalyst property and test-results
| Catalyzer | MoO 3 wt％ | WO 3 wt％ | NiO wt％ | CoO wt％ | P 2O 5 Wt％ | Auxiliary agent wt% | Loss on ignition wt% | The HDS activity | The HDN activity |
| C-1 C-2 E-9 E-10 E-11 E-12 E-13 E-14 E-15 E-16 | 24 22 22 20 18 - - 21 24 25 | - - - - - 26 22 - - - | - - - 5 2 4 6 - 3.2 2.4 | 5 4 4 - 3 - 2 6 - - | 6 5 5 4 5 6 3 4.1 2.7 3.1 | - 10.0 10.0① 10.0② 15.0③ 15.0④ 20.0⑤ 1.5⑥ 5.0⑦ 11⑧ | 0.01 0.01 9.4 8.8 13.7 13.5 17.2 2.7 6.1 10.9 | 89 100 177 160 148 142 126 133 150 161 | 94 100 130 161 156 181 168 108 122 144 |
Annotate: 1. diethyl enol, 2. glycerol mono acetate bulk, 3. vinyl alcohol butyl ether, 4. glycol ether+Succinic Acid (weight ratio is 1: 1), 5. polyvinyl alcohol (MW=200), 6. citric acid, 7. glucose, 8. ethyl acetate+methyl tertiary butyl ether (weight ratio is 5: 1).
From table 4 result equally as can be seen, activity of such catalysts of the present invention is apparently higher than the comparative catalyst, and different organic additives has different optimum contents in catalyzer, in general, the organic additive molecular weight is big more, and the content that needs is also high more, but general should exceed 20wt% not.
Claims (14)
1, a kind of hydrotreating catalyst is an active metal component with in group vib and the group VIII metal one or more, it is characterized in that this catalyzer is is carrier with the aluminum oxide through silicon and titanium modification, is benchmark with the weight of carrier, SiO
2Content is 0.1wt%～20.0wt%, TiO
2Content is 0.1wt%～20.0wt%, weight with catalyzer is benchmark, the content of modified aluminas is 30.0wt%～95.0wt%, and the content of active metal component is counted 0.1wt%～50.0wt% with oxide compound, and the content of organic additive is 1.0wt%～20.0wt%.
2, catalyzer according to claim 1 is characterized in that containing in the described catalyzer auxiliary agent phosphorus, is benchmark with the weight of catalyzer, and the content of Vanadium Pentoxide in FLAKES is 1.0wt%～10.0wt%.
3, catalyzer according to claim 1, it is characterized in that the weight with catalyzer is benchmark, the content of modified aluminas is 50.0wt%～80.0wt%, and the content of active metal component is counted 2wt%～40.0wt% with oxide compound, and organic additive content is 2.0wt%～10.0wt%.
4, catalyzer according to claim 1 is characterized in that described aluminum oxide through silicon and titanium modification, and have following feature: specific surface area is 310m
2/ g～380m
2/ g, pore volume are 0.8cm
3/ g～1.2cm
3/ g, the aperture is that 75%～85%, 〉=350 ℃ the meleic acid amount that the pore volume of 8nm～15nm accounts for total pore volume is 0.04mmol/g～0.10mmol/g, wherein B acid accounts for 40%～60% of total acid.
5, according to claim 1,2,3 or 4 described catalyzer, the loss on ignition that it is characterized in that described catalyzer is 1wt%～20wt%; In XRD figure, be that 8 °～10 ° positions have a strong diffraction peak at 2 θ.
6, catalyzer according to claim 1 is characterized in that, described organic additive is to be selected from organic carboxyl acid, alcohols, ethers and the ester compound one or more.
7, catalyzer according to claim 6 is characterized in that described carboxylic acid compound is one or more in acetate, propionic acid, oxalic acid, hexanodioic acid, tartrate and the citric acid; Alcohol compound is one or more in vinyl alcohol, vinylcarbinol, glycerol, diethyl enol, two vinylcarbinols, trimethylammonium glycerine, glycol ether, triethyl glycerine, tripropyl glycerine and the polyvinyl alcohol; Ether compound is one or more in vinyl alcohol butyl ether, methyl tertiary butyl ether, diethyl enol methyl ether, diethyl enol ether, diethyl enol propyl ether and the diethyl enol butyl ether; The saccharide compound that has a plurality of hydroxyls is one or more in glucose, fructose, lactose, maltose and the sucrose; Ester compound is one or both in ethyl acetate and the glycerol mono acetate bulk.
8, catalyzer according to claim 1, the metal that it is characterized in that described group vib is selected from molybdenum and/or tungsten, the metal of group VIII is selected from cobalt and/or nickel, weight with catalyzer is benchmark, the group vib metal oxide content is 5.0wt%～35.0wt%, and the group VIII metal oxide content is 1.0wt%～15.0wt%.
9, the arbitrary described Preparation of catalysts method of claim 1～8, comprise the steps: that preparation is through the alumina supporter of silicon and titanium modification earlier, adopt the mode of soaking altogether or soaking step by step to flood again and contain active ingredient and organic additive solution, after the dipping, ℃ following drying obtains hydrotreating catalyst in room temperature～200; Wherein dried catalyzer loss on ignition is controlled at 1wt%～20wt%, contains to contain in active ingredient and the organic additive solution or not phosphorous.
10, method according to claim 9 is characterized in that may further comprise the steps the preparation method of described modified aluminas:
(1) prepares aluminum contained compound solution, silicon-containing compound solution and titanium-containing compound solution respectively;
(2) under agitation condition, aluminum contained compound solution and silicon-containing compound solution are mixed, add the precipitation agent aqueous solution then and be reacted into glue;
(3) after the cemented into bundles, adding acid reagent in the mixed serum that obtains in step (2), to regulate the pH value of slurries be 2～4, adds the pH value 9.0～10.5 of alkaline reagents adjusting slurries again, repeats above-mentioned adjusting pH value step 1～3 times then;
(4) add titanium-containing compound solution in the mixed serum of step (3), constant temperature is aging then;
(5) with step (4) mixed serum after aging filter, washing, 80～120 ℃ dry 2～20 hours down, again 400～800 ℃ of roastings 0.5～8 hour, just can obtain described modified aluminas.
11, method according to claim 10 is characterized in that the silicon-containing compound described in the step (1) is water glass or silicon sol solution, and dioxide-containing silica is 5～40gSiO in the silicon-containing compound solution
2/ l; Described aluminum contained compound is sodium metaaluminate or Tai-Ace S 150, and alumina content is 20～80gAl in the sodium aluminate solution
2O
3/ l, alumina content is 5～40gAl in the alum liquor
2O
3/ l; Described titanium-containing compound is titanium sulfate or titanium tetrachloride, and the content of titanium oxide is 1～50gTiO in the solution
2/ l.
12, method according to claim 10 is characterized in that being controlled to the glue temperature in the step (2) is 50～95 ℃, stops to add the precipitation agent aqueous solution when the pH of mixed serum value reaches 7.5～8.5, and the control gelation time was at 0.5～1.0 hour.
13, method according to claim 10 is characterized in that the joining day of the described titanium-containing compound solution of step (4) was controlled at 5～30 minutes, and aging temperature is 50～95 ℃, and digestion time is 1～3 hour.
14, method according to claim 9, when it is characterized in that adopting substep to soak method impregnation catalyst agent carrier, dipping contains the solution of active metal component and phosphorus earlier, is impregnated with the machine aided agent solution again; Perhaps be impregnated with the machine aided agent solution earlier, dipping contains the solution of active metal component and phosphorus again; After wherein per step dipping, all will be ℃ dry down in room temperature～200.
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