CN101255357B - Catalyst used for distillate oil deep hydrofinishing and preparation method thereof - Google Patents
Catalyst used for distillate oil deep hydrofinishing and preparation method thereof Download PDFInfo
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- CN101255357B CN101255357B CN2008101043051A CN200810104305A CN101255357B CN 101255357 B CN101255357 B CN 101255357B CN 2008101043051 A CN2008101043051 A CN 2008101043051A CN 200810104305 A CN200810104305 A CN 200810104305A CN 101255357 B CN101255357 B CN 101255357B
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Abstract
A catalyst for deeply hydrofinishing fraction and preparation thereof are disclosed. The process is mixing precursor of several metal component with urea to carry out solid-phase reaction, and obtaining a catalyst particle with nanometer pole and relatively high specific surface area. The most outstanding technical characteristic is that by adopting synthesis technique of urea solid phase reaction, metal is free of loss, prepared metal composite has nanometer pore and relatively high specific surface area, and could provide abundant catalytic hydrogenation activity bits, and the inventive catalyst has much higher catalytic hydrogenation activity comparing with conventional supported catalyst because of this. Meanwhile, the invention is simple in process, easy to operate, suitable for industrial production.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method of distillate oil deep hydrofinishing.It is the improvement that belongs to hydrogenization catalyst preparation method, mainly is metal component and urea are mixed and carries out solid state reaction, obtains a kind of catalyzer that self has nano pore and high specific surface area.
Background technology
As everyone knows, hydrogenation technique is to improve the most effectively one of process means of oil quality, and hydrogenation catalyst is a technology the most important and crucial in the hydrogenation technique.Traditional Hydrobon catalyst generally is made up of the metal with hydrogenating function or MOX and carrier; Metal component commonly used is group vib and VIII metal; For example cobalt, molybdenum, nickel, tungsten etc.; This type catalyzer generally is carried on the carrier metal active component through pickling process, owing to receive metal load quantitative limitation (general active metal oxide charge capacity is less than 30%), its catalytic activity is restricted.Certainly the character through optimization of preparation and change carrier improves activity of such catalysts and selectivity.Therefore, domestic and international many oil and petro-chemical corporation all are devoted to the improvement to existing hydrogenation catalyst at present, in the hope of continually developing out the better hydrotreating catalyst of performance.This type of technology is such as USP 4,113, and 605 introduced a kind of hydrogenation catalyst preparation, is reactions such as nickelous carbonate and molybdic oxide are formed the crystallization nickel molybdate, then with alumina mixing extruded moulding; US4, having introduced a kind of in 188,281 is active constituent with VIB, VIIB, VIII family metal, is the hydrotreating catalyst of carrier with faujusite (adding small amounts aluminium is caking agent), this catalyzer can be used for BO hydrotreatment process; US3, the dry and roasting with alumina sol makes the carrier that pore volume is 0.15-0.45ml/g in 779,903, floods nickel, tungsten then and makes catalyzer through dry, roasting; US4,330,395 to disclose a kind of be raw material with tungsten compound and aluminum compound, through evaporate to dryness, roasting, with the nickel compound dipping, vulcanizes and fluoridize with sulfide and fluorochemical then and prepare a kind of middle runnings oil hydrogenating treatment catalyst; CN1; 105; 053 discloses a kind of catalyzer that is applicable to the heavy distillate hydrotreatment, this catalyzer consist of the heavy % of nickel oxide 1-5, the heavy % of Tungsten oxide 99.999 15-38, the heavy % of fluorine 1-9, its carrier is a kind ofly at high temperature to handle the modified aluminas that obtains with air and water vapour.
Can find out that though above-mentioned catalyzer has carried out modification to carrier character, its hydrogenation activity is still very gentle, can not satisfy the requirement that distillate is surpassed deep hydrofinishing.In order to improve activity of hydrocatalyst, some new catalyst technologies of preparing begin to be used for to produce in recent years, such as, US 6; 652,738 with US 6,534; 437 grades disclose a kind of preparation method of body catalyst, adopt hydro-thermal synthetic method, obtain a kind of mixed metal compositions; Be used to prepare hydrogenation catalyst, the shortcoming that this kind method exists mainly is: (1) hydrothermal synthesis method can cause the part metals loss, and metal recovery rate is low; (2) resulting mixed metal compositions pore structure specific surface area is little, and the using rate of metal of catalyzer is not high, causes the catalyzer cost to increase.
Summary of the invention
The Catalysts and its preparation method that the object of the invention has proposed a kind of distillate oil deep hydrofinishing with regard to being to avoid the weak point of prior art.This method can overcome the shortcoming of hydro-thermal reaction method, improves metal recovery rate, increases the specific surface area of catalyzer, thereby can improve the hydrogenation activity of catalyzer greatly.
The present invention's this catalyzer that propose with high hydrogenation activity more, its active constituent is by comprising that one or both and the Mo among Co, the Ni, one or both metal ingredients among the W constitute, its active metal oxide content is at 30-100wt%.The concrete preparation process of catalyzer according to the invention is following:
(1) metal component precursor
The catalyzer of high hydrogenation activity provided by the present invention, its VIII family metal is generally metals such as Fe, Co, Ni, is preferably Ni and Co; Its metal oxide content is generally 10-90%; Be preferably 20-80%, its group vib metal is generally metals such as Mo, W, Cr, is preferably Mo and W; Its metal oxide content is generally 1-90%, is preferably 20-80%.Used metal precursor can be one or both of VIII family metal, adds one or both of group vib metal, such as Co-Mo, and Ni-Mo, Ni-W, Co-Ni-W, Ni-Mo-W, Co-Mo-W and Co-Mo-Ni-W etc.According to this Preparation of catalysts method provided by the invention; Said reactive metal precursor is salt, oxide compound and the acids etc. that comprise reactive metal; Metallic salt such as, the carbonate of Co, Mo, Ni, W, nitrate salt, phosphoric acid salt, Citrate trianion, tungstate, molybdate etc.
(2) urea solid state reaction
The method for preparing catalyst of high hydrogenation activity provided by the present invention is with the above metal component precursor and urea mixes and reaction, obtains a kind of catalyst particles that self has nano pore and high specific surface area; The amount of its used urea and the mass ratio of metallics are 0.3-5/1, are preferably 0.5-2/1, its said hybrid reaction method; Can be domestic methods such as grinding, stirring, ultrasonic, compressing tablet; Its said temperature of reaction is generally 30-200 ℃, is preferably 70-150 ℃; Reaction times is 2-50 hour, is preferably 20-30 hour.Its said a kind of catalyst particles that self has nano pore and high specific surface area, its channel diameter is 3～6nm, its BET method specific surface area is 50-400m
2/ g is generally 100-300m
2/ g.
The most outstanding technical characterictic of the present invention is owing to adopted urea solid state reaction synthetic technology; Make prepared metal compound particles self have flourishing duct and bigger specific surface area, himself just can provide abundant catalytic hydrogenation activity position.Just for this reason, make catalyzer of the present invention have the catalytic hydrogenation activity more much higher than conventional negative supported catalyst.
(3) shaping of catalyst
According to this Preparation of catalysts method provided by the invention; Catalyzer can be a powder type, also can carry out moulding, and its moulding process can add certain sticker; Its add-on is 0-50%; Be preferably 10-30%, sticker can select for use industry to go up kind commonly used, such as silicon sol, aluminium colloidal sol etc.Wherein said forming method comprises methods such as compressing tablet, balling-up or extrusion, preferably adopts the method for extruded moulding.
(4) catalyzer roasting
According to this Preparation of catalysts method provided by the invention, its said catalyzer can be through calcination process, and maturing temperature is that 200-500 ℃, time are 2-8 hour; Preferably maturing temperature is that 250-450 ℃, time are 4-6 hour.
That catalyzer provided by the invention can be used for comprising is light,, the oil product of last running wet goods surpasses Deep Hydrotreating; And other suitable hydrotreatment occasions; Such as: the hydrogenation of hydrogenating desulfurization, hydrodenitrification, HDM, alkene and aromatic hydrocarbons is saturated etc., and the processing condition that are suitable for are conventional hydrogenation technique condition.This catalyzer can be regulated as required and process dissimilar solid particulate matters, such as being used for fixing hydrogenation technique processes such as bed, fluidized-bed and suspension bed.
Embodiment
Embodiment 1
Present embodiment is explained Preparation of catalysts method according to the invention.
Take by weighing the molybdic oxide (0.1 mole of Mo) of 14.2 grams, the wolframic acid (0.1 mole of W) of 25.0 grams, the basic nickel carbonate (0.3 mole of Ni) of 41.5 grams; 80.7 gram urea joins in the mortar and ground 30 minutes, places encloses container, puts into 120 ℃ of reactions of baking oven 24 hours; Open container; Continue oven dry, make unnecessary urea decomposition, cool off solid powder substance.Taking by weighing pressed powder 30% heavy pseudo-boehmite adds 10% dilute nitric acid solution and processes aluminium colloidal sol; Join pressed powder in the aluminium colloidal sol, and become pasty state, pinch through mixing, extrusion; Process the bar of diameter 1.6mm; Under ir lamp, behind the dry 5h, put in the baking oven to descend dry 10 hours at 110 ℃, 400 ℃ of roasting 5h make catalyzer G1 in muffle furnace.The BET surface-area of this catalyzer is 212.5m
2/ g, pore volume 0.31cm
3/ g, mean pore size 5.5nm.
Embodiment 2
Present embodiment is explained Preparation of catalysts method according to the invention.
Get the ammonium molybdate (0.1 mole of Mo) of 17.6 grams, the ammonium metawolframate (0.1 mole of W) of 26.4 grams, the basic nickel carbonate (0.3 mole of Ni) of 41.5 grams, 85.5 gram urea join in the mortar and ground 30 minutes, place encloses container; Put into 120 ℃ of reactions of baking oven 24 hours, open container, continue oven dry; Make unnecessary urea decomposition, cool off solid powder substance, taking by weighing the heavy pseudo-boehmite of pressed powder 30%, to add concentration be that the dilute nitric acid solution of 10wt% is processed aluminium colloidal sol; Join pressed powder in the aluminium colloidal sol, and become pasty state, pinch through mixing, extrusion; Process the bar of diameter 1.6mm; Under ir lamp, behind the dry 5h, put in the baking oven to descend dry 10 hours at 110 ℃, 400 ℃ of roasting 5h make catalyzer G2 in muffle furnace.The BET surface-area of this catalyzer is 230.7m
2/ g, pore volume 0.3cm
3/ g, mean pore size 4.5nm.
Embodiment 3
Present embodiment is explained Preparation of catalysts method according to the invention.
Take by weighing the molybdic oxide (0.1 mole of Mo) of 14.2 grams, the wolframic acid (0.1 mole of W) of 25.0 grams, the basic nickel carbonate (0.2 mole of Ni) of 27.6 grams; 66.8 gram urea joins in the mortar and ground 30 minutes, places encloses container, puts into 120 ℃ of reactions of baking oven 24 hours; Open container; Continue oven dry, make unnecessary urea decomposition, cool off solid powder substance.Taking by weighing the heavy pseudo-boehmite of pressed powder 30%, to add concentration be that the dilute nitric acid solution of 10wt% is processed aluminium colloidal sol; Join pressed powder in the aluminium colloidal sol, and become pasty state, pinch through mixing, extrusion; Process the bar of diameter 1.6mm; Under ir lamp, behind the dry 5h, put in the baking oven to descend dry 10 hours at 110 ℃, 400 ℃ of roasting 5h make catalyzer G3 in muffle furnace.The BET surface-area of catalyzer is 182.6m
2/ g, pore volume 0.29cm
3/ g, mean pore size 5.8nm.
Comparative Examples
Take by weighing the molybdic oxide (0.1 mole of Mo) of 14.2 grams, the wolframic acid (0.1 mole of W) of 25.0 grams, the basic carbonate nickel by powder (0.2 mole of Ni) of 27.6 grams; Add 20 gram pseudo-boehmites and mix, the dilute nitric acid solution that adds concentration then and be 10wt% with becomes pasty state, warp is mixed to be pinched, extrusion; Process the bar of diameter 1.6mm; Under ir lamp, behind the dry 5h, put in the baking oven to descend dry 10 hours at 110 ℃, 400 ℃ of roasting 5h make the comparative catalyst in muffle furnace.
Embodiment 4
Present embodiment is explained the evaluation method of catalyzer according to the invention
The catalyst activity evaluation is to carry out in anti-in that the 10mL high pressure is little.The model compound raw material consists of: 10% naphthalene, 2% dibenzothiophene (DBT) (about 3630ppm sulphur), 2% quinoline (about 2170ppm nitrogen), 86% toluene.Raw material adopts rampump to pump into, and hydrogenation products is after HP separator (cold high score) and light pressure separator are isolated liquids and gases, and product liquid flows into and connects an appearance jar.In the time of 120 ℃, begin to pump into and contain CS
2Hexanaphthene (3wt%) carries out prevulcanized, is warmed up to 360 ℃, vulcanizes 10 hours, and liquid hourly space velocity is 2.0h
-1Be cooled to temperature of reaction then, begin into raw material (model compound), stable reaction was taken a sample after 5 hours, analyzed with gas chromatograph (Varian3800 capillary chromatograph, fid detector).Reaction conditions: 340 ℃, liquid hourly space velocity is 2.0h
-1, hydrogen-oil ratio: 300/1, reaction pressure: 2.0MPa.The reaction evaluating result of several kinds of catalyzer is as shown in table 1.
Hydrogenating desulfurization, hydrodenitrification and the aromatic hydrogenation activity of the hydrogenation catalyst that presentation of results the present invention of table 1 is prepared is significantly higher than the catalyzer of traditional method preparation.
Table 1 catalyst activity evaluation result of the present invention
| Catalyzer | HDS，％ | HDN，％ | HDAr，％ |
| G1 | 100.0 | 93.4 | 68.8 |
| G2 | 100.0 | 94.0 | 70.4 |
| G3 | 100.0 | 95.6 | 67.8 |
| The comparative catalyst | 95.8 | 63.5 | 39.1 |
The invention effect
Compared with prior art; The most outstanding technical characterictic of the present invention is to have adopted urea solid state reaction synthetic technology; Metal free of losses, prepared metallic combination composition granule self have flourishing duct and bigger specific surface area, and himself just can provide abundant catalytic hydrogenation activity position; Just for this reason, make catalyzer of the present invention have the catalytic hydrogenation activity more much higher than conventional negative supported catalyst.Simultaneously, the inventive method is simple, and operation easily is fit to industrialized mass production.
Claims (3)
1. catalyzer that is used for distillate oil deep hydrofinishing; This catalyzer is with metal component and urea mixing and carries out solid state reaction; Obtain a kind of PM for particulate matter that self has nano pore and high specific surface area, it is characterized in that its metal component is that one or both and the Mo among Co, the Ni, one or both metal ingredients among the W constitute, these metal components use its MOXs; Salt, sour metal precursor; Its solid phase reaction method is meant that in temperature of reaction be 30-200 ℃, and the reaction times is under 2-50 hour the condition, through the method for grinding, stirring, ultrasonic and compressing tablet; In MOX, the mass ratio of the amount of its used urea and the total material of metal is 0.3～5/1.
2. the catalyzer that is used for distillate oil deep hydrofinishing according to claim 1 is characterized in that described catalyzer is a powder type, also can carry out forming processes; Its moulding process is the sticker of adding 10～30%, and sticker is silicon sol, aluminium colloidal sol, and its forming method comprises the method for compressing tablet, balling-up or extrusion.
3. the catalyzer that is used for distillate oil deep hydrofinishing according to claim 1 is characterized in that described catalyzer carries out calcination process, and its maturing temperature is that 200～500 ℃, time are 2～8 hours; When catalyzer is used for hydrogenation, carry out prevulcanized and handle, its curing temperature is 200～450 ℃, and curing time is 8～48 hours, and hydrogen to oil volume ratio is 100～500.
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| CN2008101043051A CN101255357B (en) | 2008-04-17 | 2008-04-17 | Catalyst used for distillate oil deep hydrofinishing and preparation method thereof |
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| CN101255357B true CN101255357B (en) | 2012-02-29 |
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| CN102836726A (en) * | 2011-06-23 | 2012-12-26 | 中国石油天然气集团公司 | Preparation method and application of hydrogenation catalyst composition |
| CN102989526A (en) * | 2012-12-25 | 2013-03-27 | 东北石油大学 | Method of preparing body catalyst for distillate oil depth hydrofining by utilizing microwave method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958457A (en) * | 2006-10-27 | 2007-05-09 | 北京化工大学 | Round alumina of containing silicon, and preparation method |
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| CN1958457A (en) * | 2006-10-27 | 2007-05-09 | 北京化工大学 | Round alumina of containing silicon, and preparation method |
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