CN100340338C - Hydrotreatment catalyst and its preparation method - Google Patents
Hydrotreatment catalyst and its preparation method Download PDFInfo
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- CN100340338C CN100340338C CNB2004100507135A CN200410050713A CN100340338C CN 100340338 C CN100340338 C CN 100340338C CN B2004100507135 A CNB2004100507135 A CN B2004100507135A CN 200410050713 A CN200410050713 A CN 200410050713A CN 100340338 C CN100340338 C CN 100340338C
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Abstract
The present invention discloses a hydrotreating catalyst and a preparation method thereof. The catalyst uses alumina modified by titanium and silicon as a carrier and metal of the VIB group and the VIII group as active metal components, and also contains 1 wt% to 20 wt% of organic auxiliary agents. In the process of preparing the catalyst, the purpose-made modified alumina is used as the carrier, the catalyst carrier is dried at the temperature lower than 200 DEG C after the catalyst carrier is immersed in active metal and the organic auxiliary agents by the method of co-immersion or step-by-step immersion, and the catalyst of the present invention is obtained without calcining. The catalyst can be widely used for the hydrotreating process of petroleum fraction, and is particularly suitable for the processes of the hydrodesulfurization and the hydrodenitrogenation of middle distillate oil.
Description
Technical field
The present invention relates to a kind of hydrotreating catalyst, be specially adapted to the hydrodesulfurization and the hydrodenitrogeneration 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 sulfur content in the oil product, diesel oil distillate particularly, sulfur content in the diesel oil distillate is that 0.05wt%～0.1wt% is an acceptable at present, but will soon require sulfur content less than 0.05wt%, and foreseeable future will require sulfur 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 sulfur-containing compound that removes in the raw material, the content of 6-dimethyl Dibenzothiophene etc. how much, and can under the condition that relatively relaxes, effectively it be removed 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 catalyst poisoning, 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 is contacted under the condition of hydrogen and high temperature with catalyst.Under this condition, sulfur-bearing in the raw material and nitrogen-containing 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 catalyst, 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, catalyst makes it to be transformed into sulphided state through presulfurization.
Because environmental regulation is more and more stricter to the requirement of sulphur in the oil product 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 catalyst can be under the operating condition that more relaxes operation or make catalyst 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 catalyst, introduce auxiliary agent F, P and B, adopted two sections dipping preparation catalyst.The introducing of auxiliary agent not only activity of such catalysts is significantly improved, and the stability of catalyst has also obtained improvement to a certain degree.
CN85104438 discloses a kind of method for preparing catalyst, and this catalyst action carrier is the high purity aluminium oxide carrier with the fluorine modification, and active metal component is W-Ni, catalyst consist of 1wt%～9wt%F, 1wt%～5wt%NiO, 15wt%～38wt%WO
3With the aluminium oxide of surplus, compare with catalyst in the past, improved the acidity of catalyst, the hydrogenation performance of catalyst 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, catalyst consist of 1wt%～9wt%F, 1wt%～5wt%NiO, 15wt%～38wt%WO
3Aluminium oxide with surplus.The pore structure and the specific surface of the catalyst 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, sulfur 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 component is that Co and/or Ni-Mo load on the alumina support 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 catalyst carrier load and the organic volatile component, make the precursor of catalyst without roasting, reduce volatile component when in the presence of at least a sulfur-containing compound, vulcanizing then, 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 catalyst in this patent without roasting, make catalyst desulfurizing and denitrification activity aspect obtain certain raising, but because this catalyst carrier 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 catalyst carrier dipping contains reactive metal, preferred phosphorous maceration extract, 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 catalyst, is difficult to reach the requirement of deep desulfuration and denitrogenation.
Although the catalyst that the top is mentioned is compared with catalyst 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 sulfur-containing compound and dibenzothiophenes, but sulfur-containing compound 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 product quality 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 catalyst is specially adapted to hydrodesulfurization, the denitrification process of intermediate oil, has higher HDS, HDN activity under identical process conditions.
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 aluminium 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 catalyst 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, be preferably 2wt%～40wt%, more preferably 2wt%～30wt%.Also contain organic additive in this catalyst, its content is 1wt%～20wt%, is preferably 2wt%～10wt%.This catalyst 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 catalyst XRD figure is that 8 °～10 ° positions have a strong diffraction maximum at 2 θ.
Described aluminium 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 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 aluminium oxide thing can be θ-aluminium oxide, gama-alumina or η-aluminium 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 stirring condition, aluminum contained compound solution and silicon-containing compound solution are mixed, add the precipitating reagent 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 reagent 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, adipic acid, tartaric acid and citric acid etc., preferred adipic acid, tartaric acid and citric acid, more preferably citric acid; Alcohol compound is vinyl alcohol, propenyl, glycerine, diethyl enol, two propenyls, trimethyl glycerine, diethylene glycol (DEG), triethyl group glycerine, tripropyl glycerine and polyvinyl alcohol etc., is preferably diethyl enol, two propenyls, diethylene glycol (DEG) and mean molecule quantity and is 150～300 polyvinyl alcohol; Ether compound is vinyl alcohol butyl ether, methyl tertiary butyl ether(MTBE), 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 type compound is ethyl acetate, acetoglyceride 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 support at first according to the method described above, then with required component in the impregnation method load, comprising active component 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 catalyst 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 catalyst of the present invention, the content of organic additive will suit, and general content (with respect to catalyst) 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 organic matters to cause taking place coking on the catalyst in application process.
Compare with the preparation process of the hydrogenation catalyst of routine, catalyst 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 catalyst of the present invention, and do not contain similar compounds on the conventional catalyst.Catalyst 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 catalyst in sulfuration, thereby make have in the catalyst more active mutually or actively have higher decentralization mutually, improved the catalytic activity of catalyst.
It is carrier that the present invention adopts the aluminium oxide through titanium and silicon modification, because its pore structure and acid matter are more suitable for the hydrogenation reaction of petroleum distillate, prepared catalyst has higher HDS and HDN activity under the process conditions close with comparing catalyst.
Catalyst of the present invention can be widely used in the hydrotreatment process of petroleum distillate, and the hydrotreatment process of diesel oil, kerosene, naphtha, vacuum gas oil (VGO) and heavy gas oil for example is particularly suitable for hydrodesulfurization, the hydrodenitrogeneration process of diesel oil.
Catalyst of the present invention is used for the hydrotreatment process, and its operating condition can be with conventional hydrotreatment operating 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 catalyst.
Fig. 2 is the XRD figure of embodiment 1 catalyst.
Fig. 3 is the XRD figure of embodiment 5 catalyst.
Fig. 4 is the XRD figure of embodiment 9 catalyst.
From these XRD figures as can be seen, be that 8～10 ° position has a strong diffraction maximum (Fig. 2,3 and 4) at 2 θ on the XRD figure of catalyst of the present invention, and through the comparative catalyst of high-temperature roasting, then this diffraction maximum weaken (Fig. 1) greatly.
The specific 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 organic matter or inorganic matter, be preferably inorganic matter, more preferably sodium metasilicate or silicon sol solution, silica in the silicon-containing compound solution (in silica) 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 aluminum sulfate, 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 aluminum sulfate solution
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 addition of silicon-containing compound solution is according to the requirement decision of product, in dioxide-containing silica in the final products, be warmed up to 50～95 ℃ of constant temperature, under stirring condition, neutralize with containing the precipitating reagent 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 precipitating reagent is can react with aluminum contained compound to generate all substances of aluminium hydroxide gel, for example aluminum contained compound is a sodium metaaluminate, precipitating reagent can be selected from hydrolysis can produce hydrionic all compounds, is preferably carbon dioxide or aluminum sulfate, more preferably aluminum sulfate.When being aluminum sulfate as aluminum contained compound, precipitating reagent can be selected from all compounds that hydrolysis can produce hydroxide ion, is preferably potassium hydroxide, NaOH, sodium carbonate, 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 reagent 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, inorganic acid and the dissolving, be preferably in inorganic 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 reagent can be selected from one or more of compound that dissolving back generates hydroxide ion, is preferably one or more of inorganic compound, more preferably one or more in sodium metaaluminate, NaOH and the ammoniacal liquor.
The described method of step (4) adds titanium-containing compound solution in the solution after the cemented into bundles, addition is adjusted as required, and adding speed is controlled to add in 5～30 minutes and finishes, 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 catalyst 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) in catalyst 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 catalyst, and the content of phosphorus pentoxide is 1wt%～10wt%, be preferably 2wt%～6wt%, the adding of phosphorus can improve hydrodesulfurization, denitrogenation and the Tuo Fang performance of catalyst.
In carrier loaded active component and organic additive process, organic additive can together load on the catalyst with other active component, also can step load to catalyst, 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 catalyst, and then the load organic additive.If adding assistant phosphorus can together load on the catalyst carrier 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 maceration extract that is about to saturated extent of adsorption joins in the carrier, is adsorbed fully until it.After impregnation steps is finished, catalyst will carry out dry to remove solvent wherein, in dry run, want strict control 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 catalyst 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 radiation source is the copper target, the filtering of graphite monocrystalline, operation tube voltage 35KV, tube current 30～50mA, sweep speed (2 θ) be 4 degree/minute, sweep limits is 4～35 degree.The specific area of carrier and catalyst 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 adsorbent that uses is pyridine.SiO
2And TiO
2Content adopt gravimetric method and AAS to record respectively.
The embodiment of the invention is to adopt 100 milliliters of fixed bed reactors, and employed raw material is grand celebration catalytic diesel oil (character sees Table 1).Catalyst carries out presulfurization by following conditions before use to be handled, sulfurized oil adopts and adds the virgin kerosene (character sees Table 1) that contains 1.5wt% sulphur (vulcanizing agent is a carbon disulfide), directly carry out catalytic test after the presulfurization, the condition of presulfurization and test sees Table 2.
The character of table 1 virgin kerosene and catalytic diesel oil
| The feedstock oil title | Virgin kerosene | Catalytic diesel oil |
| Density (20 ℃), g/cm 3 | 0.8044 | 0.8643 |
| Sulfur 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 presulfurization and experimental condition
| The presulfurization condition | Experimental condition | |
| Temperature, ℃ | 320 | 330 |
| The hydrogen dividing potential drop, Mpa | 6.0 | 6.0 |
| LHSV， | 1 | 2 |
| Hydrogen to oil volume ratio | 300 | 300 |
| Time, h | 8 | 160 |
The desulphurization reaction speed K of each catalyst
nComputing formula by bottom calculates:
K
n＝LHSV*1/(n-1)*(1/S
n-1*1/S
0 n-1)
Here the sulfur content in the S representative products, S
0Represent the sulfur content in the raw material, n represents the order of reaction of hydrodesulfurization, 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 catalyst is relative value.
The denitrogenation speed constant K of catalyst
nComputing formula by bottom calculates:
K
n=LHSV*ln (N
0* the nitrogen content in the N representative products here N), 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 catalyst 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 area is 278m with 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 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 molybdenum trioxide, cobalt carbonate, citric acid and the maceration extract 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 phosphorous oxide content are that the catalyst of 6wt% is numbered C-1, and the loss on ignition of catalyst is 0.01wt%.The composition and the evaluation result of catalyst see Table 3.
Comparative example 2
The preparation of carrier is with comparative example 1.Getting 100 gram carriers floods with the maceration extract that contains an amount of molybdenum trioxide, cobalt carbonate, phosphoric acid, citric acid and diethylene glycol (DEG) (mass ratio of citric acid and diethylene glycol (DEG) is 1: 1), following dry 10 hours at 110 ℃ then, obtaining molybdenum trioxide content is 22wt%, cobalt oxide content is that 4wt% and phosphorous oxide content are that the catalyst of 5wt% is numbered C-2, and the loss on ignition of catalyst is 7.5wt%.The composition and the evaluation result of catalyst see Table 3.
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 fully mixes, and temperature is elevated to 75 ℃, and adding concentration then gradually is 20g Al
2O
3/ L, temperature is 75 ℃ a aluminum sulfate solution, stops to add aluminum sulfate solution 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 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.
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 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.
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 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.
Catalyst 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 boehmite of embodiment 1 preparation, and the catalyst that obtains is numbered E-4, and it is formed and evaluation result sees Table 3.
Catalyst 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 catalyst that obtains is numbered E-5, and it is formed and evaluation result sees Table 3.
Embodiment 6～8
Catalyst E-6～E-8 according to method preparation provided by the invention.
Except that the active component kind with content is different, all the other are with embodiment 4, the catalyst that obtains is numbered E-6～E-8, it is formed and evaluation result sees Table 3.
Table 3 catalyst property and result of the test
| Catalyst | 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, catalyst is numbered E-9～E-16, and it is formed and result of the test sees Table 4.
Table 4 catalyst property and result of the test
| Catalyst | 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 | 10.0 | 0.01 | 100 | 100 |
| E-9 | 22 | - | - | 4 | 5 | 10.0① | 9.4 | 177 | 130 |
| E-10 | 20 | - | 5 | - | 4 | 10.0② | 8.8 | 160 | 161 |
| E-11 | 18 | - | 2 | 3 | 5 | 15.0③ | 13.7 | 148 | 156 |
| E-12 | - | 26 | 4 | - | 6 | 15.0④ | 13.5 | 142 | 181 |
| E-13 | - | 22 | 6 | 2 | 3 | 20.0⑤ | 17.2 | 126 | 168 |
| E-14 | 21 | - | - | 6 | 4.1 | 1.5⑥ | 2.7 | 133 | 108 |
| E-15 | 24 | - | 3.2 | - | 2.7 | 5.0⑦ | 6.1 | 150 | 122 |
| E-16 | 25 | - | 2.4 | - | 3.1 | 11⑧ | 10.9 | 161 | 144 |
Annotate: 1. diethyl enol, 2. acetoglyceride, 3. vinyl alcohol butyl ether, 4. diethylene glycol (DEG)+succinic acid (weight ratio is 1: 1), 5. polyvinyl alcohol (MW=200), 6. citric acid, 7. glucose, 8. ethyl acetate+methyl tertiary butyl ether(MTBE) (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 catalyst, in general, the organic additive molecular weight is big more, and the content that needs is also high more, but generally should not surpass 20wt%.
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 catalyst is is carrier with the aluminium 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 catalyst 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, and the content of organic additive is 1.0wt%～20.0wt%; The metal of described group vib is selected from molybdenum and/or tungsten, and the metal of group VIII is selected from cobalt and/or nickel.
2, catalyst according to claim 1 is characterized in that containing in the described catalyst auxiliary agent phosphorus, is benchmark with the weight of catalyst, and the content of phosphorus pentoxide is 1.0wt%～10.0wt%.
3, catalyst according to claim 1, it is characterized in that the weight with catalyst 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, and organic additive content is 2.0wt%～10.0wt%.
4, catalyst according to claim 1 is characterized in that described aluminium oxide through silicon and titanium modification, and have following feature: specific 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 catalyst, the loss on ignition that it is characterized in that described catalyst is 1wt%～20wt%; In XRD figure, be that 8 °～10 ° positions have a strong diffraction maximum at 2 θ.
6, catalyst according to claim 1 is characterized in that, described organic additive is to be selected from organic carboxyl acid, alcohols, ethers and the ester type compound one or more.
7, catalyst according to claim 6 is characterized in that described carboxylic acid compound is one or more in acetate, propionic acid, oxalic acid, adipic acid, tartaric acid and the citric acid; Alcohol compound is one or more in vinyl alcohol, propenyl, glycerine, diethyl enol, two propenyls, trimethyl glycerine, diethylene glycol (DEG), triethyl group glycerine, tripropyl glycerine and the polyvinyl alcohol; Ether compound is one or more in vinyl alcohol butyl ether, methyl tertiary butyl ether(MTBE), 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 type compound is one or both in ethyl acetate and the acetoglyceride.
8, catalyst according to claim 1 is characterized in that the weight with catalyst is benchmark, and 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 support of silicon and titanium modification earlier, adopt the mode of soaking altogether or soaking step by step to flood again and contain active component and organic additive solution, after the dipping, ℃ following drying obtains hydrotreating catalyst in room temperature～200; Wherein dried catalyst loss on ignition is controlled at 1wt%～20wt%, contains to contain in active component 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 stirring condition, aluminum contained compound solution and silicon-containing compound solution are mixed, add the precipitating reagent 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 reagent 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 sodium metasilicate 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 aluminum sulfate, and alumina content is 20～80gAl in the sodium aluminate solution
2O
3/ l, alumina content is 5～40gAl in the aluminum sulfate solution
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 precipitating reagent 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 ageing 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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| CN113398933B (en) * | 2020-03-16 | 2024-03-29 | 中国石油化工股份有限公司 | Catalyst for preparing diamine by hydrogenation of dinitrile, preparation method and application thereof |
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