CN1952055A - Preparation method of hydrogenation catalyst of hydrocarbon - Google Patents
Preparation method of hydrogenation catalyst of hydrocarbon Download PDFInfo
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- CN1952055A CN1952055A CN 200510047527 CN200510047527A CN1952055A CN 1952055 A CN1952055 A CN 1952055A CN 200510047527 CN200510047527 CN 200510047527 CN 200510047527 A CN200510047527 A CN 200510047527A CN 1952055 A CN1952055 A CN 1952055A
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Abstract
The invention relates to the preparing method of an alkanes hydrogenating catalyst. The carrier of the catalyst is gamma-Al2O3, the active ingredient is VIB group and VIII group metals and the active accessory ingredient is Ti. Ti is led in the aluminum hydroxide gel. It adopts second-aging in the stage of gel-forming so it can ensure the uniform disperse of Ti on the aluminum hydroxide surface and larger bore volume, larger specific surface area and larger aperture. The invention adopts complete mix-and-pinch method to prepare the catalyst. The processing procedure comprises the following steps: adding alkaline solution that contains Mo and/or W to the second-aging aluminum hydroxide dry gel powder which contains Ti; mixing and pinching fully until the aluminium hydrate powder is totally sodden by alkaline solution; adding acid solution that contains Co and/or Ni, mixing and pinching until the material is able to be molded; squeezing the materials to be strips; drying and calcinating. Ti spreads more uniformly on the catalyst made in the invention; the function of the catalyst also improves substantially.
Description
Technical field
The present invention relates to a kind of preparation method's of hydrocarbon hydrogenizing treamtent catalyst, particularly Hydrodevulcanizing catalyst for hydro-carbons preparation method.
Background technology
Hydrotreatment is the important process technology in the hydro carbons processing, mainly comprise hydrogenating desulfurization, hydrodenitrification, hydrocracking etc., the key of hydrotreatment technology is catalyzer, and at present hydrocarbon hydrogenizing treamtent catalyst is many is carrier with the aluminum oxide, is active ingredient with Mo and/or W and Ni and/or Co.In order to reach maximum economic benefits, improving catalyst performance and reducing cost is the target that pursue this area.
Usually, the simplification catalyst preparation process can reduce the Catalyst Production cost greatly, and as United States Patent (USP) 4,443,558, its adopts and mixes the method that the method for pinching substitutes " pickling process " or " mix and soak combination " fully, and one-step moulding prepares catalyzer, and preparation cost is low.But do not introduce any auxiliary agent in its catalyzer, simultaneously, Preparation of catalysts adopts and to add the method that adds alkali after the acid earlier, and this method is because strong acid and the aluminum oxide effect that adds earlier is stronger, make pore volume, the specific surface loss of aluminum oxide powder serious, make the performance of final catalyzer unsatisfactory.Improve catalyst activity and usually adopt the method for adding auxiliary agent, as Ti, Zr, P, B, F etc.But this is because introduce the acid of auxiliary agent regulating catalyst and/or improve interaction between active ingredient and carrier.United States Patent (USP) 5,089,453 have introduced auxiliary agent Ti in Hydrobon catalyst, activity of such catalysts is improved, but this catalyzer also adopts and add acid earlier, add alkali neutral method again, cause pore volume, the specific surface of final catalyzer to reduce greatly, catalyst performance is affected.EP0339640 discloses the method that a kind of coprecipitation method prepares titanium-contained aluminum oxide, mixes with aluminum soluble salts such as aluminum chloride with solubility titanium salts such as titanous chlorides, regulates pH value with basic solution then, and titanium and aluminium are precipitated simultaneously.This method can not be applicable in the carborization production alumina process, because, the aluminum salt solution that carborization is produced the aluminum oxide use is the sodium aluminate solution of alkalescence, if with tart titaniferous salt solution mix precipitin reaction takes place at first then, and this reaction process obtains product titanium skewness.In kneading method and " mix soak in conjunction with " method (as CN 1098433A, US5,089,453, CN 1289822A etc.), because active ingredient and auxiliary agent titanium add simultaneously, each material particularly solution metal ion and the aluminium hydroxide competition when interacting is that inevitably this will weaken TiO
2To the promoter action of catalyst performance, this is to add the deficiency that auxiliary agent titanium or zirconium exist with the solution form, otherwise the performance that obtains catalyzer can further improve.CN 1289636A has announced a kind of method that titanium salt prepares Ti-contained aluminium hydroxide that precipitates in aluminum hydroxide slurry, can prepare and disperse Ti-contained aluminium hydroxide preferably, but owing to contain Cl in the titanium salt solution
-And SO
4 2-Plasma, etching apparatus, and become γ-Al at Aluminium hydroxide roasting
2O
3The time can produce gas contamination environment such as chlorine and sulfurous gas; CN 1324687A has announced that a kind of carborization adds levigate metatitanic acid, TiO for this reason
2Prepare the method for Ti-contained aluminium hydroxide, reduced environmental pollution, but the pore volume of this titanium-contained aluminum oxide and specific surface are lower, use is restricted; CN 03133554.3 discloses a kind of pore volume and big Ti-contained aluminium hydroxide method of specific surface area of preparing, but it becomes in the glue process to use ultrasonic wave at aluminium hydroxide, owing to need special equipment and have noise pollution, use is restricted.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of auxiliary agent titanium of in the one-tenth glue process of Carbonization Preparation aluminium hydroxide, introducing, and become the glue aging step to adopt secondary aging at it, both can guarantee the homodisperse of auxiliary agent titanium in surface of aluminum hydroxide; Simultaneously can make Ti-contained aluminium hydroxide particle pore volume and specific surface area bigger again, the aperture is also big.Cooperate suitable catalyst preparation process, can further improve the use properties of catalyzer.
The preparation process of hydrocarbon hydrogenizing treamtent catalyst of the present invention is as follows:
The Preparation of catalysts method is to adopt complete kneading method, the Ti-contained aluminium hydroxide dry glue powder is added the basic solution that is dissolved with the group vib reactive metal, fully mix and pinch, add the acidic solution that is dissolved with VIII family metal again, mix and pinch into after the plastic, material is made final catalyzer through extrusion, drying and roasting; Wherein the auxiliary agent titanium in the Ti-contained aluminium hydroxide dry glue powder is to become in the glue to introduce at aluminium hydroxide, and carries out secondary after the aging step again at its one-tenth glue and wear out.The group vib metal is generally Mo and/or W, and VIII family metal is generally Ni and/or Co.
The preparation process of Ti-contained aluminium hydroxide is as follows: sodium aluminate solution, titanium-containing compound slurries and carbon dioxide are reacted into glue under agitation condition, slurries are aging, filter, and filter cake carries out wearing out second time more then, filtration, washing, drying promptly make final Ti-contained aluminium hydroxide product.Have after this Ti-contained aluminium hydroxide roasting that titanium is evenly distributed, characteristics such as specific surface area and pore volume are big.Temperature when wherein the aged temperature is into the glue termination for the first time, digestion time is 0.5～3 hour; The aged temperature is 70～95 ℃ for the second time, and digestion time is 0.5～3 hour.Because passed through filtration, so the pH value when for the second time aging also is lower than the pH value when wearing out for the first time.This Ti-contained aluminium hydroxide after 300～750 ℃ of following roastings roasting in 0.5～10 hour, product has following character: contain titanium dioxide 1w%～20w%, be preferably 5w%～15w%, pore volume is 1.2～1.6ml/g, and specific surface is 380～480m
2/ g, the dispersity I of titanium on aluminum oxide
Ti/ I
AlBe more than 0.3, to be generally 0.3～0.4.
Various raw materials are formed definite add-on: MoO by following final catalyst weight
3(and/or WO
3) 8.0～24.0%, be preferably 16.0～20.0w%; CoO and/or NiO 1.0～15.0w% are preferably 4.0～12.0%, and preferred two kinds of group VIII metals exist simultaneously; TiO
24.0～12.0%, be preferably 5.0～10.0%; Surplus is γ-Al
2O
3The catalyzer pore volume is 0.30～0.65ml/g, and specific surface is 120～300m
2/ g, mean pore size is 6.0～15.0nm.Bulk density is 0.75～0.85g/ml.
Introduce cheap titanium compound in the process of Ti-contained aluminium hydroxide employing Carbonization Preparation aluminium hydroxide of the present invention.Preparation process does not have the discharge of pollutent, non-environmental-pollution; In addition and since high temperature (with relatively low pH value) down secondary wear out, changed size, shape and accumulation mode that aluminium hydroxide becomes primary particle in the glue reaction process, make the finished product have bigger pore volume and specific surface area, character is more even.The present invention adds basic solution earlier in the Ti-contained aluminium hydroxide dry glue powder; adsorb and be covered in surfaces externally and internally formation one deck " protective membrane " of aluminium hydroxide; can slow down the strong interaction of acid and aluminium hydroxide when adding the acidic solution peptization more greatly; reduced the loss of aluminum oxide pore volume and specific surface, made final catalyzer have higher pore volume and specific surface.The inventive method has been taken all factors into consideration influence and the protection carrier hole structure two aspect factors of the adding mode of metal and auxiliary agent to catalyst performance, makes the metal dispersion and the pore structure of catalyzer reach the ideal state simultaneously, and catalyst performance improves greatly.The inventive method is simple, does not have special environmental protection problem, does not need Special Equipment, can produce in existing Catalyst Production device.Because Ti-contained aluminium hydroxide of the present invention has bigger pore volume and specific surface area, so can adopt the simple full kneading method of process to prepare the catalyzer of excellent property.
Embodiment
The concrete preparation process of catalyzer of the present invention is:
(1) preparation sodium aluminate solution, titanium-containing compound slurries;
(2) sodium aluminate solution, titanium-containing compound slurries are become glue with carbon dioxide stirring reaction under the certain temperature condition, material solution or slurries mix the back and feed carbon dioxide and become glue or wherein one or both to add into glue continuously when feeding carbon dioxide, when slurry pH value stops logical carbonic acid gas during for certain value;
(3) (2) step gained slurries are aging under the temperature after the cemented into bundles, filtration;
(4) (3) step gained filter cake is put back in the glue jar, added that hot water with the close volume of former sodium aluminate solution is aging once more, filtration, washing, drying promptly make final Ti-contained aluminium hydroxide product.
(5) take by weighing a certain amount of above-mentioned Ti-contained aluminium hydroxide dry glue powder, add basic solution and (contain NH
34.0～12.0wt%, MoO
3And/or WO
328.0～48.0wt%), thorough mixing, treat that the aluminum hydroxide solid elastomer powder is all wetted after, add an amount of acidic solution again and (contain NiO 3.0～9.0wt%, and/or CoO 3.0～9.0wt%), mix again and pinch into plastic, (can add nitric acid or acetic acid solution in case of necessity, as containing acetate 12.0～30.0wt%), extruded moulding on banded extruder, drying, roasting promptly obtains catalyzer.
The concentration of above-mentioned sodium aluminate solution is 5～60g Al
2O
3/ l.Above-mentioned titanium-containing compound slurries become granularity less than 65 μ m slurry like material by titanium-containing compounds such as metatitanic acid, titanium dioxide through adding water mill, and thin up is 5～40g TiO then
2/ l, its pH value is adjusted to 7～11, is preferably 7～8, and carries out under agitation condition, and its pH value is suitable regulates with ammoniacal liquor, and ammonia concn is preferably 0.1～20w%.The add-on of titanium-containing compound slurries is benchmark with the finished product, and wherein containing titanium dioxide is 0.1～20w%, is preferably 4～15w%.Become the glue temperature to be controlled at 10～45 ℃ according to the porous of needed Ti-contained aluminium hydroxide, concentration of carbon dioxide is controlled at 10～50v%.Be controlled to the glue slurry pH value and be at 9～12 o'clock and stop logical carbonic acid gas.Temperature when one time the aged temperature is into the glue termination, digestion time is 0.5～3 hour; Secondary aged temperature is 70～95 ℃, and digestion time is 0.5～3 hour.The filter cake that obtains behind dope filtration deionized water wash 1～5 time contains Na in the aluminium hydroxide of preparation
+By weight＜0.05%, following dry 2～12 hours 80～180 ℃ of temperature then.Above-mentioned steps (4) basic solution add-on is Ti-contained aluminium hydroxide dry glue powder 20～80wt%, mixes and pinches 10～50 minutes, and the acidic solution add-on is 20～80w% of Ti-contained aluminium hydroxide dry glue powder, mixes and pinches 30～80 minutes.Catalyst shape can be cylinder or three (four) leaf grass, and dry and roasting can be adopted normal condition.As drying temperature is 80～140 ℃, and the time is 1～30 hour.During roasting, 400 ℃～750 ℃ roastings 1～15 hour.
Catalyzer of the present invention can be used for the various hydrotreatment processes of various hydro carbons, raw material can be various distillates, secondary processing oil, heavy oil, residual oil and the hydro carbons that derives from coal etc., the hydrotreatment process comprises hydrogenating desulfurization, hydrodenitrification, hydrocracking etc., is specially adapted to the hydrodesulfurization process of weight, residual oil.For different raw materials and different hydrogenation process, can adjust the component and the content of catalyzer according to this area general knowledge, can substitute with W as Mo, or Mo and W use simultaneously, as adding auxiliary agents such as other Si, P, B, F in the catalyzer, handling light hydrocarbons activity of such catalysts metal and auxiliary dosage can suitably reduce, and treatment of heavy hydrocarbon class activity of such catalysts metal and auxiliary dosage can suitably increase, and adopt the inventive method to prepare corresponding catalyst then.
Further describe technical characterictic of the present invention below by comparative example and embodiment, but be not limited to embodiment.
Embodiment 1
With concentration is 30g Al
2O
3The sodium aluminate solution 500mL of/l places in the glue jar, is controlled to 25 ℃ of glue temperature, and feeding concentration is the carbon dioxide of 40v%, and the concentration that adds pulp under continuous whipped state is 20g TiO
2/ l metatitanic acid slurries (the pH value is 8.0, and granularity is less than 40 μ m) make carrier contain TiO
2Being 10% by weight, continue feeding carbon dioxide, is to stop logical carbon dioxide at 10 o'clock until slurry pH value, aging 1.0 hours of slurries filter, and filter cake is put back in the glue jar again, adding the 500mL temperature is 75 ℃ of deionized waters, and controlled temperature wore out 1.0 hours at 75 ℃.Filter then, use deionized water wash, in carrier, contain Na
+By weight＜during 0.05w% till, dry (120 ℃) 4 hours are crushed to 180 orders again.Take by weighing this Ti-contained aluminium hydroxide dry glue powder 50g, add molybdenum acid ammonia solution 35g, wherein MoO
3Concentration is 30.0wt%, and solution contains NH
3Be 10wt%, it is wetting with aluminium hydrate powder to be fully mixed to alkali lye, adds the 36g acidic solution then, contains Ni (NO in the acid liquid
3)
216.2wt%, Co (NO
3)
216.2wt%, solution contain acetate 17wt%, fully mix and pinch to plastic, and to become diameter be the Herba Galii Bungei bar of 1.1 * 1.2mm to extrusion on preceding crowded formula twin screw banded extruder, and the gained catalyzer was 100 ℃ of dryings 4 hours; 490 ℃ of roastings 3 hours, catalyst A, its character sees Table 1.
Embodiment 2
Compare with embodiment 1, the secondary aging temperature is controlled at 85 ℃, MoO
3Concentration changes 46.0% into, Ni (NO
3)
2Concentration change 24.8% into, Co (NO
3)
2Concentration change 24.8% into, other implementation conditions are constant, both cost example catalyst B, its character sees Table 1.
Embodiment 3
Compare with embodiment 1, the secondary aging temperature is controlled at 95 ℃, and other implementation conditions are constant, both cost example catalyzer C, and its character sees Table 1.
Embodiment 4
Catalyzer maturing temperature among the embodiment 1 is become 550 ℃, and other implementation conditions are constant, both cost example catalyzer D, and its character sees Table 1.
Comparative example 1
This comparison example is to prepare carrier by the method that CN 03133554.3 describes.
With concentration is 30g Al
2O
3The sodium aluminate solution 500mL of/l places ultrasonic transducer, and control ultrasonic transducer transmitted power is 25kHz for the 200W frequency, and cemented into bundles is closed ultrasonic transducer.The unclassified stores consumption is identical with embodiment 1 with operational condition, gets catalyzer E.
Comparative example 2
This comparison example is to prepare carrier by the method that CN1324687A describes.
Compare with embodiment 1, save the aging step of secondary, the unclassified stores consumption is identical with embodiment 1 with operational condition, gets catalyzer F.
Embodiment 5
Under the same process condition, desulfurization, the denitrogenation that comparative catalyst A, B, C, D, E show when handling Middle East residual oil and take off the carbon residue performance.Estimate stock oil character and estimate processing condition and see Table 2 and table 3 respectively, wherein Hydrobon catalyst is the catalyzer that various embodiments of the present invention make, hydrodenitrogenation catalyst is the same industry catalyzer, is the FZC-41 residual hydrogenation denitrification catalyst of development Qilu Petrochemical company of Fushun Petrochemical Research Institute catalyst plant production.Evaluation result sees Table 4.
Table 1 catalyzer physico-chemical property
| Catalyzer | A | B | C | D | E | F |
| Dispersity *I Ti/I AlPore volume, ml/g specific surface, m 2/ g piles ratio, g/ml MoO 3，wt％ NiO，wt％ CoO，wt％ TiO 2，wt％ | 0.28 0.48 182 0.82 18.2 4.2 4.3 7.3 | 0.29 0.49 195 0.82 23.2 5.4 5.0 6.8 | 0.29 0.51 204 0.80 18.4 4.1 4.1 7.2 | 0.26 0.48 183 0.81 18.4 4.0 4.2 7.3 | 0.27 0.47 176 0.81 18.1 4.0 4.2 7.2 | 0.19 0.42 175 0.82 18.2 4.2 4.1 7.3 |
Table 2 stock oil character
| Density (20 ℃) g/cm 3 S，wt％ N，wt％ CCR，wt％ | 1.013 3.56 0.56 11.6 |
CCR is a carbon residue.
Table 3 is estimated processing condition
| Catalyst loading ml | One anti-two is anti- | HDS HDN | 120 180 |
| Pressure, MPa air speed, h -1Temperature, ℃ hydrogen-oil ratio, (v) | 14.7 0.33 400 1000 | ||
Table 4 activity rating result
*
| Catalyzer | A | B | C | D | E | F |
| Desulfurization degree, the wt% denitrification percent, wt% takes off carbon yield, wt% | 92.1 63.1 61.4 | 92.7 63.8 62.4 | 93.0 64.9 64.8 | 92.2 63.6 61.7 | 91.5 63.0 61.5 | 89.2 60.6 58.7 |
*Sampling analysis result after turning round 300 hours
From table 1 catalyzer physico-chemical property as seen, in the process of Carbonization Preparation aluminium hydroxide, introduce auxiliary agent Ti, and adopt secondary aging, prepared catalyst metal dispersity I
Ti/ I
AlBe better than the comparative catalyst with specific surface, pore volume; And as seen from Table 4, the use properties of catalyzer of the present invention is better than the comparative catalyst.
The measuring method of metal dispersity is an X-ray photoelectron spectroscopy among the present invention, and dispersity numerical value is big more, illustrates that the dispersion of metal in aluminum oxide is even more.Specific surface area is measured for the BET method, and pore volume is that low-temperature nitrogen adsorption method is measured.
Claims (10)
1, a kind of preparation method of hydrocarbon hydrogenizing treamtent catalyst, adopt complete kneading method, the Ti-contained aluminium hydroxide dry glue powder is added the basic solution that is dissolved with the group vib metal, fully mix and pinch, add the acidic solution that is dissolved with VIII family metal again, mix and pinch into after the plastic, material is made final catalyzer through extrusion, drying and roasting; It is characterized in that the auxiliary agent titanium in the Ti-contained aluminium hydroxide dry glue powder wherein is to become in the glue to introduce at aluminium hydroxide, and it is aging to carry out second time after it becomes glue aging again, the second time, the aged temperature was 70～95 ℃, and digestion time is 0.5～3 hour.
2, in accordance with the method for claim 1, the preparation process that it is characterized in that described Ti-contained aluminium hydroxide is as follows: sodium aluminate solution, titanium-containing compound slurries and carbon dioxide are reacted into glue under agitation condition, slurries are aging, filter, and filter cake carries out wearing out second time then, filtration, washing, drying promptly make final Ti-contained aluminium hydroxide product.
3, in accordance with the method for claim 1, it is characterized in that described group vib metal is Mo and/or W, consumption is for being 8.0%～24.0% in oxide compound at final catalyst weight content, VIII family metal is Co and/or Ni, consumption is for being 1.0%～15.0% in oxide compound at final catalyst weight content, and TiO2 weight content in final catalyzer is 4.0%～12.0%.
4, in accordance with the method for claim 1, it is characterized in that described Ti-contained aluminium hydroxide preparation process is:
(1) preparation sodium aluminate solution, titanium-containing compound slurries;
(2) sodium aluminate solution, titanium-containing compound slurries are become glue with carbon dioxide stirring reaction under the certain temperature condition, when slurry pH value stops logical carbonic acid gas during for certain value;
(3) (2) step gained slurries are aging under the temperature after the cemented into bundles, filtration;
(4) (3) step gained filter cake is put back in the glue jar, carried out aging, the filtration second time, washing, drying and promptly make final Ti-contained aluminium hydroxide product.
5, in accordance with the method for claim 4, the concentration that it is characterized in that described sodium aluminate solution is 5～60g Al
2O
3/ l, the titanium-containing compound slurries become granularity less than 65 μ m slurry like material by titanium-containing compounds such as metatitanic acid, titanium dioxide through adding water mill, and thin up is 5～40g TiO then
2/ l, the add-on of titanium-containing compound slurries is benchmark with the finished product, wherein containing titanium dioxide is 0.1～20w%.
6, in accordance with the method for claim 4, it is characterized in that described one-tenth glue temperature is controlled at 10～45 ℃, concentration of carbon dioxide is controlled at 10～50V%, and becoming the glue slurry pH value is to stop logical carbonic acid gas at 9～12 o'clock.
7, in accordance with the method for claim 4, it is characterized in that the temperature when the aged temperature described in the step (3) is into the glue termination, digestion time is 0.5～3 hour, and the drying process described in the step (4) is following dry 2～12 hours at 80～180 ℃.
8,, it is characterized in that described titanium-containing compound slurries regulate its pH value to 7～11 with ammoniacal liquor according to claim 4 or 5 described methods.
9, in accordance with the method for claim 1, it is characterized in that described basic solution is the basic solution that contains NH3 4.0～12.0wt%, acidic solution is the acidic solution that contains nitric acid or acetate; The basic solution add-on is 20%～80% of a Ti-contained aluminium hydroxide dry glue powder weight, mixes and pinches 10～50 minutes; The acidic solution add-on is 20%～80% of a Ti-contained aluminium hydroxide dry glue powder weight, mixes and pinches 30～80 minutes.
10, in accordance with the method for claim 1, it is characterized in that described catalyzer drying conditions for 80～140 ℃ of dryings 1～30 hour, the catalyzer roasting condition is 400～750 ℃ of roastings 1～15 hour.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115518663A (en) * | 2021-06-25 | 2022-12-27 | 中国石油化工股份有限公司 | Preparation method of residual oil hydrocracking catalyst |
| CN115518644A (en) * | 2021-06-25 | 2022-12-27 | 中国石油化工股份有限公司 | Preparation method of residual oil hydrodemetallization catalyst |
-
2005
- 2005-10-19 CN CNB2005100475270A patent/CN100467570C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115518663A (en) * | 2021-06-25 | 2022-12-27 | 中国石油化工股份有限公司 | Preparation method of residual oil hydrocracking catalyst |
| CN115518644A (en) * | 2021-06-25 | 2022-12-27 | 中国石油化工股份有限公司 | Preparation method of residual oil hydrodemetallization catalyst |
| CN115518644B (en) * | 2021-06-25 | 2024-01-09 | 中国石油化工股份有限公司 | Preparation method of residual oil hydrodemetallization catalyst |
| CN115518663B (en) * | 2021-06-25 | 2024-01-09 | 中国石油化工股份有限公司 | Preparation method of residual oil hydrocracking catalyst |
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