CN1766048A - Preparation method of hydrocarbon hydrotreatment catalyst - Google Patents
Preparation method of hydrocarbon hydrotreatment catalyst Download PDFInfo
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- CN1766048A CN1766048A CN 200410050746 CN200410050746A CN1766048A CN 1766048 A CN1766048 A CN 1766048A CN 200410050746 CN200410050746 CN 200410050746 CN 200410050746 A CN200410050746 A CN 200410050746A CN 1766048 A CN1766048 A CN 1766048A
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Abstract
The invention relates to a preparation method for a catalyst to hydrotreat hydrocarbons, which comprises gama- Al2O3 as carrier, metal from VIB group and VIII group as active constituents, and Ti as active adjuvant. The prepraration method comprises: adding titanate solution to bring said Ti during the gelatinization for preparing aluminum hydroxide; adding basic solution contained Mo or W into the dried aluminum hydroxide powder, mixing till the powder wet fully by solution; adding acid solution contained Co or Ni, mixing till plastic, extruding to form, drying, baking, and obtaining the catalyst. This invention improves the catalyst property obviously.
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 the deficiency that exists with solution form adding auxiliary agent titanium or zirconium, and the performance that obtains catalyzer can further improve.CN 1324687A has announced that a kind of carborization adds the method for levigate metatitanic acid and silicon-containing compound formulations prepared from solutions titaniferous, silicon aluminium hydroxide, although reduced environmental pollution, but when becoming glue with carbon dioxide reaction, sodium aluminate solution can produce aggregate owing to add solid particulate (although its granularity is extremely less than 65 μ m), influence the granularity of aluminium hydroxide, and titanium and the distribution of silicon in aluminium hydroxide also can be uneven, can cause its use properties to reduce.
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, guaranteeing under the prerequisite that the auxiliary agent titanium is evenly distributed, further improve the performance of titanium-contained aluminum oxide, 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; It is characterized in that auxiliary agent titanium in the described Ti-contained aluminium hydroxide dry glue powder be in the one-tenth glue process of Carbonization Preparation aluminium hydroxide, titanium salt solution is dripped, stream adds or spray pattern is introduced.
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.
Ti-contained aluminium hydroxide of the present invention adopt in the process of Carbonization Preparation aluminium hydroxide with titanium salt solution by drip, stream adds or mode such as spraying is introduced, method is simple; Add with ionic species owing to titanium simultaneously, titanium distributes more even in surface of aluminum hydroxide after becoming glue, with this raw material is the competition that the preparing carriers catalyzer will weaken titanium and reactive metal dramatically, improved the utilization ratio of reactive metal, thereby catalyst activity is higher.In the Ti-contained aluminium hydroxide dry glue powder, add basic solution earlier; 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.
Embodiment
The concrete preparation process of catalyzer of the present invention is:
(1) preparation sodium metaaluminate and titanium salt solution;
(2) sodium aluminate solution for preparing and carbon dioxide are reacted into glue on one side under agitation condition, on one side by drip, stream adds or form such as spraying is introduced titanium salt solution.
(3) solution filtration, washing, drying promptly make final Ti-contained aluminium hydroxide product after the cemented into bundles.
(4) 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, Na and Al atomic ratio are 1.2～2.0.Above-mentioned titanium salt solution is selected from titanium trichloride aqueous solution, titanium sulfate aqueous solution, aqueous solution of titanyle sulfate, the oxychlorination titanium aqueous solution or its mixing solutions, and titanium salt solution concentration is in titanium dioxide weight 10～100g/l.The add-on of titanium salt solution is benchmark with the finished product, and wherein containing titanium dioxide is 0.1～20w%, is preferably 5～15w%.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 7.5～12 o'clock and stop logical carbonic acid gas, the control slurry pH value is higher than the titanium salt solution interpolation in 0～3 o'clock of final one-tenth glue rear slurry pH value and finishes.Stop can to wear out behind the logical carbonic acid gas and also can not wear out, digestion time is no more than 2 hours at most.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.Drip and to add and can add above becoming the glue jar with stream, the titanium salt solution after spray pattern preferably will atomize is dispersed in in the glue usefulness carbon dioxide containing gas, and the titanium salt solution after the atomizing becomes glue to react with carbonic acid gas with sodium aluminate solution in becoming the glue jar.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 drying temperature is 80～140 ℃, and the time is 3～6 hours.During roasting, the heating-up time is 4～6 hours, and constant temperature 2～4 hours, thermostat temperature are 450 ℃～700 ℃.
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
3/ l, Na and Al atomic ratio are that 1.4 sodium aluminate solution 2000mL places reactor, 25 ℃ of temperature, and feeding concentration is the carbon dioxide of 40v%, in logical carbonic acid gas, dripping concentration under whipped state is 50g TiO
2The Titanium Trichloride Solution 140ml of/l is that 11 o'clock Titanium Trichloride Solutions dropwise at slurry pH value, is to stop logical carbon dioxide at 10 o'clock to slurry pH value.Aging 1.0 hours of slurries.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, sodium aluminate solution concentration is become 20g Al
2O
3/ l, the titanium salt solution 92ml of dropping same concentrations, 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
Titanium Trichloride Solution among the embodiment 1 is added with spray pattern, 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 the dried glue of Ti-contained aluminium hydroxide by the method that CN1324687A describes.
With concentration is 30g Al
2O
3The sodium aluminate solution 500mL of/l places reactor, 25 ℃ of temperature, and feeding concentration is the carbon dioxide of 40v%, the concentration that adds pulp under continuous whipped state is 20gTiO
2/ l metatitanic acid slurries (the pH value is 8.0, and granularity is less than 40 μ m) make carrier contain TiO
2Be 10% by weight.The unclassified stores consumption is identical with embodiment 1 with operational condition and method for preparing catalyst, gets catalyzer E.
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 Qilu Petrochemical company catalyst plant production.Evaluation result sees Table 4.
Table 1 catalyzer physico-chemical property
| Catalyzer | A | B | C | D | E |
| 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％ | 0.27 0.49 279 0.82 18.4 4.1 4.1 7.4 | 0.29 0.48 269 0.82 23.4 5.5 5.1 6.8 | 0.24 0.46 259 0.80 18.3 4.2 4.2 7.3 | 0.26 0.52 263 0.81 18.4 4.2 4.1 7.4 | 0.19 0.42 245 0.82 18.2 4.1 4.1 7.2 |
*Annotate: the dispersivity test method is an X-ray photoelectron spectroscopy, and the dispersity value is big more, illustrates that the dispersion of metal in aluminum oxide is even more.
Table 2 stock oil property list 3 is estimated processing condition
| Density (20 ℃) g/cm 3 S，wt％ N，wt％ CCR，wt％ | 1.013 3.56 0.56 11.6 |
| 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 |
| Desulfurization degree, the wt% denitrification percent, wt% takes off carbon yield, wt% | 91.8 63.2 60.4 | 92.1 63.7 61.4 | 90.9 60.9 59.8 | 91.5 62.6 62.3 | 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, drip mode such as titanium salt solution and introduce titanium, 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.
Claims (14)
1, a kind of preparation method of hydrocarbon hydrogenizing treamtent catalyst, 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; It is characterized in that auxiliary agent titanium in the described Ti-contained aluminium hydroxide dry glue powder be in the one-tenth glue process of Carbonization Preparation aluminium hydroxide, titanium salt solution is dripped, stream adds or spray pattern is introduced.
2, in accordance with the method for claim 1, it is characterized in that the various raw materials of catalyzer are by definite add-on: the MoO of following final catalyst weight composition
3And/or WO
38.0～24.0%, CoO and/or NiO1.0～15.0w%, TiO
24.0～12.0w%, surplus is γ-Al
2O
3Carrier.
3, in accordance with the method for claim 2, it is characterized in that the various raw materials of catalyzer are by definite add-on: the MoO of following final catalyst weight composition
3And/or WO
316.0～20.0w%, CoO and/or NiO4.0～12.0w%, TiO
25.0～10.0w%.
4, in accordance with the method for claim 1, the process that it is characterized in that described Carbonization Preparation Ti-contained aluminium hydroxide dry glue powder is: prepare sodium aluminate solution and titanium salt solution earlier, then sodium aluminate solution and the carbon dioxide for preparing is reacted into glue under agitation condition, solution filtration, washing, drying promptly make final Ti-contained aluminium hydroxide product after the cemented into bundles, it is characterized in that sodium aluminate solution becomes glue reaction with carbon dioxide when, with titanium salt solution with drip, stream adds or Sprayable adds.
5, in accordance with the method for claim 4, the concentration that it is characterized in that described sodium aluminate solution is 5～60gAl
2O
3/ l, Na and Al atomic ratio are 1.2～2.0.
6, in accordance with the method for claim 4, it is characterized in that described titanium salt solution is selected from titanium trichloride aqueous solution, titanium sulfate aqueous solution, aqueous solution of titanyle sulfate, the oxychlorination titanium aqueous solution or its mixing solutions.
7,, it is characterized in that the concentration of described titanium salt solution is counted 10～100g/l with titanium dioxide weight according to claim 4 and 6 described methods.The add-on of titanium salt solution is benchmark with the finished product, and wherein containing titanium dioxide is 0.1～20w%.
8, ask 4 described methods according to right, it is characterized in that described one-tenth glue temperature is 10～45 ℃, concentration of carbon dioxide is controlled at 10～50v%, is controlled to the glue slurry pH value and is at 9～12 o'clock and stop logical carbonic acid gas.
9, in accordance with the method for claim 4, it is characterized in that described washing for using deionized water wash 1～5 time, contains Na to the aluminium hydroxide of preparation
+By weight＜0.05%, drying is following dry 2～12 hours at 80～180 ℃.
10, in accordance with the method for claim 1, it is characterized in that the described basic solution that is dissolved with the group vib reactive metal contains NH
34.0～12.0wt%, MoO
3And/or WO
328.0～48.0wt%, the acidic solution of the described VIII of being dissolved with family metal contains NiO 3.0～9.0wt% and/or CoO 3.0～9.0wt%, acetate 12.0～30.0wt%.
11, in accordance with the method for claim 1, it is characterized in that described basic solution add-on is 20～80wt% of Ti-contained aluminium hydroxide dry glue powder, mix and pinched 10～50 minutes, the acidic solution add-on is 20～80w% of Ti-contained aluminium hydroxide dry glue powder, mixes and pinches 30～80 minutes.
12, in accordance with the method for claim 1, it is characterized in that described drying temperature is 80～140 ℃, the time is 3～6 hours, and maturing temperature is 450 ℃～700 ℃, and roasting time is 2～4 hours.
13, in accordance with the method for claim 1, it is characterized in that described hydrocarbon hydrogenizing treamtent catalyst is heavy, residuum hydrodesulfurization catalyzer.
14, in accordance with the method for claim 1, the pore volume that it is characterized in that described hydrotreating catalyst is 0.30～0.65ml/g, and specific surface is 120～300m
2/ g.
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|---|---|---|---|
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| CN100340638C CN100340638C (en) | 2007-10-03 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989493A (en) * | 2011-09-15 | 2013-03-27 | 中国石油天然气股份有限公司 | Heavy oil hydrotreating composite catalyst preparation method |
| CN103282118A (en) * | 2010-09-01 | 2013-09-04 | 中国石油化工股份有限公司 | Method for treating sulfur-ontaining gas and hydrogenation catalyst used in the method |
| CN107297209A (en) * | 2016-04-16 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of hydrotreating catalyst and preparation method thereof |
| US10563130B2 (en) | 2014-07-17 | 2020-02-18 | Sabic Global Technologies B.V. | Upgrading hydrogen deficient streams using hydrogen donor streams in a hydropyrolysis process |
| CN110871081A (en) * | 2018-08-30 | 2020-03-10 | 中国石油化工股份有限公司 | Catalyst for high-selectivity hydrogenation of methyl isobutyl ketone, preparation method and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5089453A (en) * | 1990-06-25 | 1992-02-18 | Chevron Research And Technology Company | Hydroconversion catalyst and method for making the catalyst |
| CN1107534C (en) * | 2000-05-19 | 2003-05-07 | 中国石油化工集团公司 | Prepn. of titanium-containing aluminium bydroxide |
-
2004
- 2004-10-29 CN CNB200410050746XA patent/CN100340638C/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103282118A (en) * | 2010-09-01 | 2013-09-04 | 中国石油化工股份有限公司 | Method for treating sulfur-ontaining gas and hydrogenation catalyst used in the method |
| CN103282118B (en) * | 2010-09-01 | 2015-03-25 | 中国石油化工股份有限公司 | Method for treating sulfur-ontaining gas and hydrogenation catalyst used in the method |
| CN102989493A (en) * | 2011-09-15 | 2013-03-27 | 中国石油天然气股份有限公司 | Heavy oil hydrotreating composite catalyst preparation method |
| CN102989493B (en) * | 2011-09-15 | 2015-05-20 | 中国石油天然气股份有限公司 | Heavy oil hydrotreating composite catalyst preparation method |
| US10563130B2 (en) | 2014-07-17 | 2020-02-18 | Sabic Global Technologies B.V. | Upgrading hydrogen deficient streams using hydrogen donor streams in a hydropyrolysis process |
| CN107297209A (en) * | 2016-04-16 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of hydrotreating catalyst and preparation method thereof |
| CN107297209B (en) * | 2016-04-16 | 2019-08-06 | 中国石油化工股份有限公司 | A kind of hydrotreating catalyst and preparation method thereof |
| CN110871081A (en) * | 2018-08-30 | 2020-03-10 | 中国石油化工股份有限公司 | Catalyst for high-selectivity hydrogenation of methyl isobutyl ketone, preparation method and application |
| CN110871081B (en) * | 2018-08-30 | 2022-08-09 | 中国石油化工股份有限公司 | Catalyst for high-selectivity hydrogenation of methyl isobutyl ketone, preparation method and application |
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|---|---|
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