CN1211461C - Preparation method of hydrotreatment catalyst - Google Patents
Preparation method of hydrotreatment catalyst Download PDFInfo
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- CN1211461C CN1211461C CN 02144544 CN02144544A CN1211461C CN 1211461 C CN1211461 C CN 1211461C CN 02144544 CN02144544 CN 02144544 CN 02144544 A CN02144544 A CN 02144544A CN 1211461 C CN1211461 C CN 1211461C
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Abstract
The present invention discloses a method for preparing a hydrotreating catalyst, particularly a method for preparing a hydrotreating catalyst containing fluorine. The method is characterized in that in the method for adding fluorine as an assistant agent, pseudo-boehmite and/or alumina and ammonium salts of fluorine compounds or aqueous solutions thereof are thoroughly mixed for a period of time to obtain a fluorine-aluminium material, wherein the mixing time is more than 5 minutes; the fluorine-aluminium material is prepared into the hydrotreating catalyst by a kneading method or a dipping method. Compared with the prior art, the method has the advantages of simple fluorine adding method, uniform fluorine distribution, easy catalyst shaping, high catalyst intensity, little loss of the specific surface area and high hydrogenating and impurity-eliminating activity. The hydrotreating catalyst prepared by the method can be used for the hydrotreating process of hydrocarbons, particularly for the hydrofining process of heavy distillate oil.
Description
1, technical field
The present invention relates to the preparation method of a kind of preparation method of hydrotreatment catalyst, particularly fluorine-containing catalyst for hydro-processing heavy distillate.
2, background technology
Contain sulphur, nitrogen, oxygen and metal impurities in crude oil and the distillate that from crude oil, obtains.The existence of these impurity not only influences the stability of oil product, and in use also can discharge SO
X, NO
XDeng the obnoxious flavour contaminate environment.In the secondary processing process of oil product, the existence of sulphur, nitrogen, oxygen and metal impurities can make poisoning of catalyst.Distillate hydrogenation is handled and is meant that under certain temperature and pressure stock oil contacts with catalyzer with hydrogen, removes impurity, and the saturated process of aromatic hydrocarbons.
The hydrotreating catalyst of excellent property at first must have good hydrogenation activity and certain cracking activity, in addition, and from considering that economically Preparation of catalysts technology should be tried one's best simply.
Oxide compound or sulfide that typical hydrotreating catalyst is VIII family and group vib metal are supported on γ-Al
2O
3Or low SiO
2Stable Al
2O
3On the carrier.In order to improve metal and carrier interactions, improve the acidity of catalyzer, the adding auxiliary agent of still needing sometimes.Fluorine is one of hydrotreating catalyst auxiliary agent commonly used.Add the auxiliary agent fluorine in the hydrotreating catalyst and can improve metal and carrier interactions, improve the acidity of catalyzer, improve the ability that the anti-organic basic nitride of catalyzer is poisoned.
Adding method about auxiliary agent fluorine in the hydrotreating catalyst mainly contains pickling process, original position (in-situ) fluorination method, aluminum oxide fluorination method and kneading method, the fluorine cpd that add mainly contain ammonium salt, the fluorochemical (for example, hydrogen fluoride, aluminum fluoride etc.) of fluorine cpd.
Chinese patent CN85104438 describes the method for preparing catalyst that a kind of pickling process is added the auxiliary agent fluorine, this method be the support of the catalyst of rafifinal preparation after high-temperature roasting with ammonium fluoride solution dipping, dry, roasting, make catalyzer with tungsten nickel solution dipping, drying, roasting again.U.S. Pat 4,285,836 have described the method for preparing catalyst that another kind of pickling process is added the auxiliary agent fluorine, and this method is that catalyzer is made in drying, roasting with the basic solution impregnation catalyst agent carrier that contains molybdenum ion, nickel ion, fluorion and ammonium radical ion.U.S. Pat 4,220,557 have also described the method for preparing catalyst that a kind of pickling process is added the auxiliary agent fluorine, and this method is with containing molybdate solution impregnation catalyst agent carrier, use the nickelous fluosilicate solution impregnation after drying, the roasting again, catalyzer is made in dry, roasting.
U.S. Pat 4,582,592, US4,420,388, US4,330,395 have described original position (in-situ) fluoridizes the method for adding the auxiliary agent fluorine, this method is that the stock oil that will contain organic fluoride is injected in the reactor that catalyzer is housed fluorination catalyst under certain temperature, pressure and hydrogen atmosphere condition.
U.S. Pat 3,434,964 have described a kind of aluminum oxide fluoridizes the method for preparing catalyst that adds the auxiliary agent fluorine, this method is the aluminum oxide that the aluminium alcoholates hydrolysis method prepares to be added entry form suspension liquid, add the aqueous hydrogen fluoride solution after drying again, the preparation carrier, catalyzer is made in drying, roasting behind the carrier impregnation metal component.The aluminum oxide suspension liquid also can earlier and add aqueous hydrogen fluoride solution again behind the silicon sol uniform mixing.
Step impregnation method adds the auxiliary agent fluorine and prepares catalyzer needs repeatedly drying, roasting, catalyst preparation process complexity, cost height.Though adding the auxiliary agent fluorine, the single-steeping method prepares catalyzer Preparation of Catalyst flow process weak point,, the catalyst metal content of preparation is low, and metal impregnation liquid instability.
Original position (in-situ) is fluoridized the method for adding the auxiliary agent fluorine and is existed catalyzer to fluoridize more problems such as inhomogeneous, cost height, yet there are no application report on the hydrotreater of countries in the world.
Aluminum oxide is fluoridized the method for preparing catalyst complicated process of preparation of adding the auxiliary agent fluorine, and the specific surface area of fluorided alumina is low simultaneously, pore structure is unreasonable.The fluorine cpd that add are hydrogen fluoride, because of hydrogen fluoride corrosion is strong, bring disadvantageous effect for the catalyzer industrial production.
The method for preparing catalyst that kneading method adds the auxiliary agent fluorine is meant that with pseudo-boehmite and/or aluminum oxide, fluorochemicals through mixing, kneading, moulding, carrier is made in drying, roasting then, and carrier is made catalyzer through metallic solution dipping, dry, roasting; Perhaps pseudo-boehmite and/or aluminum oxide, fluorochemicals, metal component together, through mixing, kneading, moulding, catalyzer is made in drying, roasting then.Kneading method adds the method for preparing catalyst advantages of simple technological process of auxiliary agent fluorine, overcome the shortcoming of pickling process, aluminum oxide fluorination method.But in the prior art, if when adopting the ammonium salt of fluorine cpd, owing to brought ammonium into, the shaping of catalyst difficulty, carrier that makes or specific surface area of catalyst lose greatly, intensity is low, therefore to add the fluorine source that the auxiliary agent fluorine adopted all be stable fluorine cpd to kneading method, so the auxiliary agent fluorine can not be fully played the modifying function of catalyzer.Chinese patent CN98114342 has described the method for preparing catalyst that a kind of kneading method adds the auxiliary agent fluorine, the fluorine source that this method adopts is an aluminum fluoride, because aluminum fluoride is stable compound, so the auxiliary agent fluorine can not be fully played the modifying function of catalyzer, has influenced the use properties of catalyzer; In addition, kneading method adds the auxiliary agent fluorine because fluorine cpd and pseudo-boehmite, tackiness agent (or acid solution) and deionized water are mixed together, and mixture lumps rapidly, so auxiliary agent fluorine skewness in catalyzer.
3, summary of the invention
At the deficiencies in the prior art, the purpose of this invention is to provide the hydrotreating catalyst preparation method that a kind of fluorine adding method is simple, be evenly distributed, the catalyzer of this method preparation has that moulding is easy, catalyst strength is high, the specific surface area loss is little, hydrogenation takes off characteristics such as impurity activity height.
Method for preparing catalyst of the present invention is: with ammonium salt (or the ammonium salt aqueous solution of fluorine cpd is an ammonium fluoride solution) thorough mixing for some time of pseudo-boehmite and/or aluminum oxide and fluorine cpd, mixing time makes fluoro-aluminium material more than 5 minutes.Above-mentioned fluoro-aluminium material is made carrier through kneading, moulding, drying, roasting, carrier is made catalyzer through reactive metal solution impregnation, drying, roasting, or, make catalyzer through mixing, kneading, moulding, drying, roasting with above-mentioned fluoro-aluminium material adding active metal component.
Key of the present invention at first is first thorough mixing for some time of ammonium salt (or ammonium salt aqueous solution of fluorine cpd) of pseudo-boehmite and/or aluminum oxide and fluorine cpd, then kneading, moulding again; Next is when adding the ammonium salt aqueous solution of fluorine cpd, guarantee that pseudo-boehmite and/or aluminum oxide remain meal, can not produce bigger caking.
Through studies show that in a large number, the ammonium salt of pseudo-boehmite and/or aluminum oxide and fluorine cpd (or ammonium salt aqueous solution of fluorine cpd) thorough mixing is after for some time, fluorochemical and pseudo-boehmite and/or aluminum oxide react, ammonium ion in the ammonium salt of fluorine cpd will discharge with the form of ammonia, solved the shaping of catalyst difficulty, the problem that the loss of the carrier that makes or specific surface area of catalyst is big, intensity is low, and fluorine content wherein can be in very large range regulated at will on demand.In addition, pseudo-boehmite and/or aluminum oxide remain meal with the ammonium salt (or ammonium salt aqueous solution of fluorine cpd) of fluorine cpd when mixing, the auxiliary agent fluorine is evenly distributed in catalyzer.Ammonium ion in the ammonium salt of fluorine cpd discharges with the form of ammonia, and the auxiliary agent fluorine is fully combined with aluminum oxide with the fluorion form, can bring into play the effect of auxiliary agent fluorine to greatest extent, thereby improves activity of such catalysts and stability.
4, embodiment
Hydrotreating catalyst preparation of the present invention comprises the preparation of fluoro-aluminium material and is used for preparing catalyzer.The preparation method of fluoro-aluminium material is: ammonium salt (or ammonium salt aqueous solution of fluorine cpd) thorough mixing for some time of pseudo-boehmite and/or aluminum oxide elder generation and fluorine cpd, ammonium salt (or ammonium salt aqueous solution of the fluorine cpd) mixing time of pseudo-boehmite and/or aluminum oxide elder generation and fluorine cpd was greater than 5 minutes, the suitable time is greater than 15 minutes, the optimum time is greater than 30 minutes, prolong the favourable two kinds of materials of mixing time and fully contact, discharge the ammonia that produces.When the auxiliary agent fluorine adds fashionablely with the ammonium salt aqueous solution form of fluorine cpd, strength of solution will be regulated according to the add-on and the material properties of auxiliary agent fluorine, and key will guarantee that pseudo-boehmite and/or aluminum oxide remain meal, can not produce bigger caking.The solution add-on is generally 5ml～80ml/100g pressed powder.Mixing process is for making two kinds of uniform dynamic operations of mixing of materials, generally can adopt mixing equipment such as solid mixer, agitator, rolling machine, kneading machine, when adding the ammonium salt aqueous solution of fluorochemicals, preferably in mixing process, solution is evenly sprayed in the pressed powder.The fluorine content of fluoro-aluminium material is 0.3w%～10.0w%.By ammonium salt (or ammonium salt aqueous solution of the fluorine cpd) thorough mixing of pseudo-boehmite that the present invention narrates and/or aluminum oxide and fluorine cpd after for some time, also can continue dry for some time at 30 ℃～120 ℃, as more than 5 minutes, best 5～120 minutes, drying can further promote to react and the ammonia that produces is discharged.
Above-mentioned fluoro-aluminium material and appropriate amount of deionized water, mineral acid and extrusion aid kneading, moulding, drying, roasting are made carrier, carrier is made catalyzer through reactive metal solution impregnation, drying, roasting, or above-mentioned fluoro-aluminium material added active metal component, mix with appropriate amount of deionized water, mineral acid and extrusion aid, kneading, moulding, drying, roasting make catalyzer.
The used fluorochemical of catalyzer of the present invention is the ammonium salt of fluorine cpd, preferably Neutral ammonium fluoride.Fluorine content is 0.2w%～7.0w% in the catalyzer, is preferably 0.5w%～5.0w%.The aluminum oxide that uses among the present invention can be the aluminum oxide that contains auxiliary agents of silicon.
The forming method of catalyzer of the present invention can be to drip ball forming, extrusion molding, compression molding, is best with extrusion molding.The shape of catalyzer can be spherical, bar shaped special-shaped bars such as (comprise cylindrical or) trifolium, sheet shape, is best with bar shaped.
The active metal component that is added in the catalyst preparation process of the present invention is group vib metal (as molybdenum or tungsten) and VIII family metal (as nickel or cobalt), the content of active metal component is group vib metal 15w%-35w% (in oxide compound), be preferably 20w%-30w% (in oxide compound), the metal 1w%-9w% of VIII family (in oxide compound) is preferably 2w%-6w% (in oxide compound).Catalyzer can also contain auxiliary agent phosphorus, and phosphorus can adopt dipping method to add, and also can adopt kneading method to add, and is generally 0.5～5% in the element wt phosphorus content.
The adding mode of activity of such catalysts metal component of the present invention can be pickling process (comprising saturated dipping, spray dipping and excessive dipping), kneading method, is preferably pickling process.
The maturing temperature of catalyzer of the present invention is 350 ℃～650 ℃, is preferably 400 ℃～600 ℃.
Catalyzer of the present invention is the same with general hydrofining, hydrotreating catalyst, need pass through prevulcanized before use.The mode of hydrogen sulfide or other organic or inorganic sulfide of can injecting in hydrogen stream is carried out.
Catalyzer of the present invention is applicable to the hydrotreatment of petroleum fractions.
The feature that the invention is further illustrated by the following examples, but these embodiment can not limit the present invention.
Embodiment 1
Catalyzer cat A of the present invention.
(1) with 220g pseudo-boehmite powder (production of Fushun Petrochemical Company catalyst plant) and 220g SB-aluminum oxide powder (Germany produces) thorough mixing 3 minutes.
(2) the 30g Neutral ammonium fluoride was joined in the above-mentioned aluminum oxide powder remix 45 minutes.
(3) after adding 25ml concentration is the salpeter solution of 30 (m) %, an amount of extrusion aid and deionized water in the fluoro-containing alumina powder that step (2) obtains, mix, mediated 20 minutes, material after mixing, mediating is extruded into the trifolium bar that diameter is φ 1.1mm, wet bar was 120 ℃ of dryings 4 hours, and dried carrier strip was made carrier in 4 hours 500 ℃ of roastings.
(4) carrier of step (3) being made contains molybdenum oxide 42g/100ml in this nickel-molybdenum-phosphorus steeping fluid, nickel oxide 3.8g/100ml, phosphorus 2.1g/100ml with nickel-molybdenum-phosphorus steeping fluid dipping.Moist catalysis bar behind the dipping was 120 ℃ of dryings 4 hours, and dried catalyzer bar was 480 ℃ of roastings 4 hours
Embodiment 2
Catalyzer catB of the present invention.
(1) with 220g pseudo-boehmite powder (production of Fushun Petrochemical Company catalyst plant) and 220g SB-aluminum oxide powder (Germany produces) thorough mixing 3 minutes.
(2) the 30g Neutral ammonium fluoride is added fully dissolving in the 90ml deionized water.
(3) add the fluorinated water solution that step (2) obtains in the mixed powder of the aluminum oxide that step (1) obtains, thorough mixing is 45 minutes again.
(4) with embodiment 1 step (3).
(5) with embodiment 1 step (4).
Embodiment 3
Catalyzer cat C of the present invention.
(1) with 220g pseudo-boehmite powder (production of Fushun Petrochemical Company catalyst plant) and 220g SB-aluminum oxide powder (Germany produces) thorough mixing 3 minutes.
(2) the 30g Neutral ammonium fluoride was joined in the above-mentioned aluminum oxide powder remix 15 minutes.
(3) the fluoro-containing alumina powder that step (2) is obtained is under 80 ℃ of conditions dry 30 minutes.
(4) with embodiment 1 step (3).
(5) with embodiment 1 step (4).
Comparative example 1
Reference catalyst cat D.
(1) with 220g pseudo-boehmite powder (production of Fushun Petrochemical Company catalyst plant) and 220g SB-aluminum oxide powder (Germany produces) thorough mixing 3 minutes.
(2) after adding 20ml concentration is the salpeter solution of 30 (m) %, an amount of extrusion aid and deionized water in the mixed powder of the aluminum oxide that step (2) obtains, mix, mediated 20 minutes, material after mixing, mediating is extruded into the trifolium bar that diameter is φ 1.1mm, wet bar was 120 ℃ of dryings 4 hours, and dried carrier strip was made carrier in 4 hours 500 ℃ of roastings.
(3) with embodiment 1 step (4).
Comparative example 2
Reference catalyst catE.
(1) with 220g pseudo-boehmite powder (production of Fushun Petrochemical Company catalyst plant) and 220g SB-aluminum oxide powder (Germany produces) thorough mixing 3 minutes.
(2) mix to aluminum oxide that step (2) obtains and add simultaneously in the powder after 30g Neutral ammonium fluoride, 30ml concentration be the salpeter solution of 30 (m) %, an amount of extrusion aid and deionized water, mix, mediated 20 minutes, material after mixing, mediating is extruded into the trifolium bar that diameter is φ 1.1mm, wet bar was 120 ℃ of dryings 4 hours, and dried carrier strip was made carrier in 4 hours 500 ℃ of roastings.
(3) with embodiment 1 step (4).
Comparative example 3
Reference catalyst cat F.
(1) with 220g pseudo-boehmite powder (production of Fushun Petrochemical Company catalyst plant) and 220g SB-aluminum oxide powder (Germany produces) thorough mixing 3 minutes.
(2) mix to aluminum oxide that step (2) obtains and add simultaneously in the powder after 22g aluminum fluoride, 20ml concentration be the salpeter solution of 30 (m) %, an amount of extrusion aid and deionized water, mix, mediated 20 minutes, material after mixing, mediating is extruded into the trifolium bar that diameter is φ 1.1mm, wet bar was 120 ℃ of dryings 4 hours, and dried carrier strip was made carrier in 4 hours 500 ℃ of roastings.
(3) with embodiment 1 step (4).
The physico-chemical property of cat A, cat B, cat C, cat D, cat E, six kinds of catalyzer of cat F sees Table 1.From the data of table 1 as can be seen, compare, adopt the present invention to add cat A, the cat B of auxiliary agent fluorine preparation, specific surface area, intensity and the bulk density of three kinds of catalyzer of cat C do not have evident difference with the catalyzer that does not add the auxiliary agent fluorine.And the specific surface area of cat E, intensity and bulk density are starkly lower than cat A, cat B, cat C.
Embodiment 4
Present embodiment is the activity rating of catalyst test.
The catalyst activity evaluation test is carried out on the 200ml small hydrogenation device, before the activity rating catalyzer is carried out prevulcanized.Active evaluation test sees Table 2 with stock oil character, and active evaluation test the results are shown in Table 3.From the data of table 3 as can be seen, adopt identical stock oil, under identical processing condition, the denitrification activity that adopts the inventive method to add cat A, the cat B of the preparation of auxiliary agent fluorine, three kinds of catalyzer of cat C obviously is better than adopting prior art to add the catalyzer of auxiliary agent fluorine preparation.
This shows, the catalyzer of employing the present invention preparation, auxiliary agent fluorine add mode simply, rationally, when having overcome the ammonium salt of kneading method interpolation fluorine cpd, carrier or shaping of catalyst difficulty, carrier that makes or specific surface area of catalyst lose problems such as big, that intensity is low; The catalyzer of the present invention's preparation, the auxiliary agent fluorine is evenly distributed in catalyzer, and fully combines with aluminum oxide with the fluorion form, can bring into play the effect of auxiliary agent fluorine to greatest extent, thereby improves activity of such catalysts and stability.
Table 1 catalyzer physico-chemical property
Project cat A cat B cat C cat D cat E cat F
Chemical constitution, m%
MoO
3 25.0 24.5 25.3 24.5 24.8 24.6
NiO 3.45 3.53 3.47 3.56 3.60 3.39
P 1.85 1.91 1.93 1.89 1.96 1.87
F 3.18 3.15 3.09 - 3.11 3.21
Al
2O
3Surplus surplus surplus surplus surplus surplus
Physico-chemical property
Pore volume, ml/g 0.362 0.361 0.357 0.353 0.378 0.356
Specific surface area, m
2/ g 175 179 182 185 154 181
Tap density, g/100ml 88.5 88.2 89.1 90.2 79.1 88.7
Crushing strength, N/mm 16.1 16.5 16.2 17.5 11.5 15.8
Table 2 stock oil character
Stock oil SLVGO
Density (20 ℃), g/cm
30.8993
Boiling range, ℃
IBP 322
50％ 441
EBP 533
Carbon residue, % 0.53
S，m％ 4900
N，μg/g 1552
Table 3 activity rating of catalyst result
Catalyzer numbering cat A cat B cat C catD catE cat F
Stock oil SLVGO SLVGO SLVGO SLVGO SLVGO SLVGO
Processing condition
The reaction hydrogen pressure, MPa 14.7 14.7 14.7 14.7 14.7 14.7
Volume space velocity, h-1 1.0 1.0 1.0 1.0 1.0 1.0
Hydrogen to oil volume ratio 1000: 1 1000: 1 1000: 1 1000: 1 1000: 1 1000: 1
Temperature of reaction, ℃ 374 374 374 374 374 374
Generate oily N content, μ g/g 4.3 3.8 4.1 27.6 24.4 20.5
Claims (9)
1, a kind of preparation method of hydrotreatment catalyst, with the fluoro-containing alumina is carrier, with group vib metal and VIII family metal is active ingredient, the addition means that it is characterized in that fluorine is as follows: ammonium salt aqueous solution thorough mixing for some time of the ammonium salt of pseudo-boehmite and/or aluminum oxide and fluorine cpd or fluorine cpd, mixing time is more than 5 minutes, make fluoro-aluminium material, further adopt kneading method or immersion process for preparing hydrotreating catalyst with this fluoro-aluminium material; When adding the ammonium salt aqueous solution of fluorine cpd, its add-on is 5ml～80ml/100g pressed powder.
2, in accordance with the method for claim 1, it is characterized in that fluorine content is 0.2w%～7.0w% in the described hydrotreating catalyst.
3, in accordance with the method for claim 1, it is characterized in that fluorine content is 0.5w%～5.0w% in the described hydrotreating catalyst.
4, in accordance with the method for claim 1, it is characterized in that described mixing time is more than 30 minutes.
5, in accordance with the method for claim 1, it is characterized in that described aluminum oxide contains silicon additive.
6, in accordance with the method for claim 1, it is characterized in that the ammonium salt or fluorine cpd ammonium salt aqueous solution thorough mixing of described pseudo-boehmite and/or aluminum oxide and fluorine cpd after, continue dry more than 5 minutes at 30 ℃～120 ℃.
7, in accordance with the method for claim 6, it is characterized in that be 5～120 minutes described time of drying.
8, in accordance with the method for claim 1, it is characterized in that described group vib metal is molybdenum or tungsten, VIII family metal is nickel or cobalt, contains group vib metal 15w%-35w% in oxide compound, contains the metal 1w%-9w% of VIII family.
9, in accordance with the method for claim 1, it is characterized in that adopting pickling process or kneading method to add auxiliary agent phosphorus.
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|---|---|---|---|
| CN 02144544 CN1211461C (en) | 2002-11-02 | 2002-11-02 | Preparation method of hydrotreatment catalyst |
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|---|---|---|---|
| CN 02144544 CN1211461C (en) | 2002-11-02 | 2002-11-02 | Preparation method of hydrotreatment catalyst |
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| CN1211461C true CN1211461C (en) | 2005-07-20 |
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| CN101927197B (en) * | 2009-06-26 | 2012-05-30 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with gradient decreasing distribution of active metal and acid additive concentration and preparation method thereof |
| CN101927192B (en) * | 2009-06-26 | 2012-05-30 | 中国石油天然气股份有限公司 | Hydrogenation catalyst carrier with gradient-reduced concentration distribution of acid auxiliary agent and preparation method thereof |
| CN102861601B (en) * | 2011-07-07 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of fluorine-containing hydrogenation catalyst and preparation thereof |
| CN103787389B (en) * | 2012-11-01 | 2016-06-22 | 中国石油化工股份有限公司 | A kind of production method of alumina support |
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