CN101255356B - Unsupported catalyst and preparation method thereof - Google Patents
Unsupported catalyst and preparation method thereof Download PDFInfo
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- CN101255356B CN101255356B CN2008101043028A CN200810104302A CN101255356B CN 101255356 B CN101255356 B CN 101255356B CN 2008101043028 A CN2008101043028 A CN 2008101043028A CN 200810104302 A CN200810104302 A CN 200810104302A CN 101255356 B CN101255356 B CN 101255356B
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Abstract
Disclosed are a unsupported catalyst for deeply hydrofinishing of intermediate distillate and method for making the same, particularly a catalyst particle with nanometer pore and relatively high specific surface area obtained by urea melt reaction. The most outstanding technical feature of the invention is that by adopting synthesis technique of urea melt 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, fast in reaction, suitable for industrial production.
Description
Technical field
The present invention relates to the unsupported catalyst and the preparation thereof of the ultra deep hydrofinishing of a kind of intermediate oil.It is the improvement that belongs to hydrogenization catalyst preparation method; Specifically through the urea melting reaction; Obtain a kind of catalyst particles that self has nano pore and high specific surface area; Extruded moulding obtains a kind of so-called unsupported catalyst that is different from the conventional negative supported catalyst then, compares with the conventional negative supported catalyst, and unsupported catalyst has higher catalytic activity.
Background technology
In recent years, crude oil poor qualityization tendency is obvious day by day in the world wide, and sulphur, nitrogen and arene content increase day by day in the oil product, and more and more stricter environmental requirement and the contradiction between this reality are more sharp-pointed.The China's oil product particularly diesel product to have more than 1/3rd be by catalytic cracking process production; Widespread usage along with the RFCC technology; Catalytically cracked material becomes gradually heavily, becomes bad; The character that makes catalytic cracking diesel oil is variation day by day, and sulphur, nitrogen and arene content increase day by day in the diesel oil, and Cetane number significantly reduces.At present, for slowing down atmosphere pollution, countries in the world have proposed more strict requirement to the quality index of vehicle fuel, and the sulphur in the derv fuel index, nitrogen and arene content reduce greatly, and Cetane number requires to significantly improve.At present; To the diesel oil standard sulfur content; The America and Europe is limited in 150～350ug/g; To be limited in 50ug/g to 2005, European Union, the U.S., Japan and other countries are advocated energetically recently and are carried out in the near future implementing ultralow diesel oil standard (ULSD), require the sulfur content in the derv fuel to be limited on 10～15ppm level exactly.
As everyone knows; Hydrogenation technique is to improve the most effectively one of process means of oil quality; Hydrogenation catalyst is a technology the most important and crucial in the hydrogenation technique; 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.In conjunction with the state of the art both domestic and external; Poor ignition quality fuel (for example: the mixed diesel of high-sulfur cycloalkyl straight-run diesel oil, coker gas oil, catalytic cracking diesel oil or above raw material) have only through could be as the blend component of derv fuel behind the deep hydrofinishing (desulfurization, denitrogenation, rare hydrocarbon, aromatic hydrocarbons are saturated); So the hydrotreating catalyst that is specially adapted to the ultra deep hydrofinishing of poor ignition quality fuel is one of catalizer variety of being badly in need of of present petroleum refining industry.
Traditional Hydrobon catalyst generally is made up of the metal with hydrogenating function or metal oxide and carrier; Metal component commonly used is group vib and VIII metal; For example cobalt, molybdenum, nickel, tungsten etc.; This type catalyst generally is carried on the carrier metal active component through infusion process, owing to receive the restriction (general reactive metal oxides load capacity is less than 30%) of content of metal, its catalytic activity is comparatively gentle.Certainly the character through optimization of preparation and change carrier improves activity of such catalysts and selectivity, make it more appropriate to the deep hydrofinishing of poor-quality diesel-oil by cut fraction.This type of technology is such as US4; 188; Having introduced a kind of in 281 is active constituent with VIB, VIIB, VIII family metal, is the hydrotreating catalyst of carrier with faujasite (adding small amounts aluminium is bonding agent), and this catalyst can be used for mink cell focus hydrotreatment process; Tail oil after the hydrotreatment is as the raw material of steam cracking production ethene, and ethylene yield has raising by a relatively large margin; 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 the catalyst that contains nickel oxide 10～18 heavy %, tungsten oxide 25～40 heavy % and fluorine 1～9 heavy % through dry, roasting; US4,330,395 to disclose a kind of be raw material with tungsten compound and aluminium compound, through evaporate to dryness, roasting, with the nickel compound dipping, vulcanizes and fluoridize with sulphur compound and fluorine compounds then, prepares a kind of midbarrel oil hydrogenating treatment catalyst; CN85,104, the high single diaspore of the method preparation of 438B employing aluminum alkoxide or alkyl aluminum hydrolysis is prepared a kind of hydrotreating catalyst that contains nickel oxide 1～5 heavy %, tungsten oxide 12～35 heavy %, fluorine 1～9 heavy % as the precursor of catalyst carrier; CN1; 105; 053 discloses a kind of catalyst that is applicable to the heavy distillate hydrotreatment, this catalyst consist of nickel oxide 1～5 heavy %, tungsten oxide 15～38 heavy %, fluorine 1～9 heavy %, its carrier is a kind ofly at high temperature to handle the modified aluminas that obtains with air and steam; CN1; 169; 336A discloses the catalyst that a kind of distillate hydrogenation is handled; This catalyst consist of nickel oxide 1～5 heavy %, tungsten oxide 15～38 heavy %, fluorine 1～9 heavy %, all the other are aluminium oxide, this alumina support is to be composited by one or more little porous aluminum oxides and one or more macroporous aluminium oxides weight ratio according to 75: 25～50: 50; Wherein aperture aluminium oxide micro-pore diameter accounts for the aluminium oxide of total pore volume more than 95% less than the pore volume in the hole of 8nm, and the pore volume in macroporous aluminium oxide micro-pore diameter 6～60nm hole accounts for the aluminium oxide of total pore volume more than 70%.
Can find out that though above-mentioned catalyst has carried out modification to carrier character, its hydrogenation activity still can not satisfy the requirement to the ultra deep hydrofinishing of the special poor ignition quality fuel of middle distillate.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 disclose a kind of preparation method of body catalyst with US 6,534,437 grades; Adopt the synthetic method of hydro-thermal, obtain a kind of mixed metal compositions, be used to prepare hydrogenation catalyst; US 4,596, and 785 disclose a kind of method of using the metal sulfide coprecipitation to prepare hydrogenation catalyst.Though the prepared catalyst of these methods can improve hydrogenation activity, the shortcoming that these methods exist mainly is: (1) hydrothermal synthesis method or coprecipitation can cause the part metals loss, and metal recovery rate is low; (2) resulting mixed metal compositions pore structure specific area is little, and the using rate of metal of catalyst is not high, causes the catalyst cost to increase.
Summary of the invention
The unsupported catalyst that the object of the invention proposes the ultra deep hydrofinishing of a kind of intermediate oil with regard to being to avoid the weak point of prior art, this catalyst are that several kinds of metal component precursor and mixed being incorporated in of urea are reacted resultant a kind of catalyst particles that self has nano pore and high specific surface area under the molten condition.The method can overcome the shortcoming of hydro-thermal reaction and coprecipitation reaction method, improves metal recovery rate, increases the specific area of catalyst, thereby can improve the hydrogenation activity of catalyst greatly.This has the catalyst of high hydrogenation activity, and 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, and its reactive metal oxides content is at 30～100wt%.The concrete preparation process of catalyst according to the invention is following:
(1) metal component precursor
The catalyst 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 VI I I 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 and the acids etc. that comprise reactive metal; Metallic salt such as, the carbonate of Co, Mo, Ni, W, nitrate, phosphate, citrate, tungstates, molybdate etc.
(2) urea melting reaction
The method for preparing catalyst of high hydrogenation activity provided by the present invention is that the above metal component precursor and mixed being incorporated under the urea melting state of urea are reacted, and removes unnecessary urea; Obtain 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 1～5/1, are preferably 2～3/1; Its said hybrid reaction method can be common methods such as grinding, stirring, ultrasonic dispersion, its said reaction temperature; Be generally 100～200 ℃; Be preferably 120～150 ℃, the reaction time is 2～10 hours, is preferably 4～6 hours.Its reactant is dispersed in molten state urea the inside; With the metal oxide timing, self have the catalyst particles of nano pore and high specific surface area, its channel diameter is 3～10nm, its BET method specific area is 100～450m
2/ g is generally 150～350m
2/ g.
The most outstanding technical characterictic of the present invention is owing to adopted the urea melting reactive synthesis technique; Reaction speed is fast; Make prepared metal compound particles self have flourishing duct and bigger specific area, himself just can provide abundant catalytic hydrogenation activity position.Just for this reason, make catalyst 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; Catalyst can be a powder type, also can carry out moulding, and its forming process can add certain binding agent; Its addition is 0～50%; Be preferably 10～30%, binding agent can select for use industry to go up kind commonly used, such as Ludox, 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) activation of catalyst
According to this Preparation of catalysts method provided by the invention, its said catalyst can be through calcination process, and sintering temperature is that 200～500 ℃, time are 2～8 hours; Preferably sintering temperature is that 250-400 ℃, time are 4～6 hours.
According to this Preparation of catalysts method provided by the invention, its said catalyst must be handled through presulfurization, and curing temperature is 200～450 ℃; Be preferably 300～400 ℃, cure time is 8～48 hours, is preferably 10～25 hours; Hydrogen to oil volume ratio is 100-800, is preferably 300～500.
That catalyst provided by the invention can be used for comprising is light,, the oil product of heavy distillat wet goods surpasses Deep Hydrotreating; And other suitable hydrotreatment occasions; Such as: the hydrogenation of hydrodesulfurization, hydrodenitrogeneration, HDM, alkene and aromatic hydrocarbons is saturated etc., and the process conditions that are suitable for are conventional hydrogenation technique condition.This catalyst can be regulated as required and process dissimilar solid particulate matters, such as being used for fixing hydrogenation technique processes such as bed, fluid bed and suspension bed.
The specific embodiment
To combine embodiment to come enumeration technical characterstic of the present invention below.
Embodiment 1
Present embodiment is explained Preparation of catalysts method according to the invention.
Take by weighing the molybdenum trioxide (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; 161.4 gram urea joins in the there-necked flask, and adds low amounts of water it is uniformly dispersed, and places oil bath in 130 ℃ of stirring reactions 4 hours; Pour reactant in the pallet into while hot and cool off; With pulverizer cooled product is pulverized, placed 150 degree baking ovens to dry, make unnecessary urea decomposition.Taking by weighing pressed powder 30% heavy 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 infrared lamp, behind the dry 5h, put in the baking oven to descend dry 10 hours at 110 ℃, 400 ℃ of roasting 5h make unsupported catalyst F1 in muffle furnace.The BET surface area of this catalyst is 232.0m
2/ g, pore volume 0.35cm
3/ g, average pore size 5.8nm.
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 metatungstate (0.1 mole of W) of 26.4 grams, the basic nickel carbonate (0.3 mole of Ni) of 41.5 grams; 171.0 gram urea joins in the there-necked flask, and adds low amounts of water it is uniformly dispersed, and places oil bath in 130 ℃ of stirring reactions 4 hours; Pour reactant in the pallet into while hot and cool off; With pulverizer cooled product is pulverized, placed 150 degree baking ovens to dry, make unnecessary urea decomposition.Taking by weighing the heavy 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 infrared lamp, behind the dry 5h, put in the baking oven to descend dry 10 hours at 110 ℃, 400 ℃ of roasting 5h make catalyst F2 in muffle furnace.The BET surface area of this catalyst is 240.6m
2/ g, pore volume 0.31cm
3/ g, average pore size 5.5nm.
Embodiment 3
Present embodiment is explained Preparation of catalysts method according to the invention.
Take by weighing the molybdenum trioxide (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; 133.6 gram urea joins in the there-necked flask, and adds low amounts of water it is uniformly dispersed, and places oil bath in 130 ℃ of stirring reactions 4 hours; Pour reactant in the pallet into while hot and cool off; With pulverizer cooled product is pulverized, placed 150 degree baking ovens to dry, make unnecessary urea decomposition.Taking by weighing the heavy 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 infrared lamp, behind the dry 5h, put in the baking oven to descend dry 10 hours at 110 ℃, 400 ℃ of roasting 5h make catalyst F3 in muffle furnace.The BET surface area of catalyst is 200.5m
2/ g, pore volume 0.30cm
3/ g, average pore size 6.8nm.
Embodiment 4
Present embodiment explanation comparative catalyst's preparation method.
Take by weighing the molybdenum trioxide (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 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 infrared 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 5
Present embodiment is explained the evaluation method of catalyst 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% dibenzothiophenes (DBT) (about 3630ppm sulphur), 2% quinoline (about 2170ppm nitrogen), 86% toluene.Raw material adopts plunger displacement pump to pump into, and hydrogenation products is after high-pressure separator (cold high score) and low 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
2Cyclohexane (3wt%) carries out presulfurization, is warmed up to 360 ℃, vulcanizes 10 hours, and liquid hourly space velocity (LHSV) is 2.0h
-1Be cooled to reaction temperature 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 condition: 340 ℃, liquid hourly space velocity (LHSV) is 2.0h
-1, hydrogen-oil ratio: 300/1, reaction pressure: 2.0MPa.The reaction evaluating of several kinds of catalyst is as a result shown in the table 1.
Hydrodesulfurization, hydrodenitrogeneration 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 comparative catalyst of traditional kneading method preparation.
Table 1 catalyst activity evaluation result of the present invention
| Catalyst | HDS，％ | HDN，％ | HDAr，％ |
| F1 | 99.0 | 87.9 | 55.9 |
| F2 | 100.0 | 86.0 | 52.1 |
| F3 | 99.6 | 88.2 | 54.1 |
| 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 the urea melting reactive synthesis technique; Metal free of losses, prepared metallic combination composition granule self have flourishing duct and bigger specific area, and himself just can provide abundant catalytic hydrogenation activity position; Just for this reason, make catalyst of the present invention have the catalytic hydrogenation activity more much higher than conventional negative supported catalyst.Simultaneously, the inventive method is simple, operation easily, and reaction speed is fast, is fit to industrialized mass production.That catalyst provided by the invention can be used for comprising is light,, the oil product of heavy distillat wet goods surpasses Deep Hydrotreating; And other suitable hydrotreatment occasions; Such as: the hydrogenation of hydrodesulfurization, hydrodenitrogeneration, HDM, alkene and aromatic hydrocarbons is saturated etc., and the process conditions that are suitable for are conventional hydrogenation technique condition.This catalyst can be regulated as required and process dissimilar solid particulate matters, such as being used for fixing hydrogenation technique processes such as bed, fluid bed and suspension bed.
Claims (3)
1. the preparation method of a unsupported catalyst; This catalyst is that several kinds of metal component precursor and mixed being incorporated in of urea are reacted resultant a kind of catalyst particles that self has nano pore and high specific surface area under the molten condition; 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 metal oxide, salt, sour metal precursor; It reacts under molten condition, is meant that in reaction temperature be 100～200 ℃, and the reaction time is to react in 2～10 hours, and its reactant is dispersed in molten state urea the inside; With the metal oxide timing, the mass ratio of the amount of its urea and the total material of metal is 1～5/1; Resulting catalyst is measured through the BET method, himself has the catalyst particles of nano pore and high specific surface area, and its channel diameter is 3～10nm, and specific area is 100～450m
2/ g.
2. the preparation method of a kind of unsupported catalyst according to claim 1; It is characterized in that described catalyst is a powder type; Also can carry out forming processes; Its forming process is the binding agent of adding 10～30%, and binding agent is Ludox, aluminium colloidal sol, and its forming method comprises compressing tablet, balling-up or extrusion method.
3. the preparation method of a kind of unsupported catalyst according to claim 1 is characterized in that catalyst carries out calcination process, and its sintering temperature is that 200～500 ℃, time are 2～8 hours; When catalyst is used for hydrogenation, carry out presulfurization and handle, its curing temperature is 200～450 ℃, and cure time is 8～48 hours, and hydrogen to oil volume ratio is 300～500.
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| CN2008101043028A CN101255356B (en) | 2008-04-17 | 2008-04-17 | Unsupported catalyst and preparation method thereof |
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| CN101255356B true CN101255356B (en) | 2012-07-18 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103285886B (en) * | 2013-03-07 | 2016-02-10 | 中国石油大学(华东) | The catalyst of naphthalene one step hydrogenation synthesis decahydronaphthalene and method thereof |
| WO2015007230A1 (en) | 2013-07-18 | 2015-01-22 | 中国石油大学(北京) | Iron-based hydrogenation catalyst and applications thereof |
| CN109847793B (en) * | 2019-01-11 | 2021-12-10 | 中国石油大学(华东) | Method for synthesizing ZSM-5 molecular sieve based non-supported hydrogenation catalyst by eutectic method |
Citations (3)
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| CN1045414A (en) * | 1985-12-05 | 1990-09-19 | 东北师范大学 | Process for synthesizing cobalt phthalocyanine desulfating catalyst |
| US6652738B2 (en) * | 1999-01-15 | 2003-11-25 | Akzo Nobel N.V. | Process for preparing a mixed metal catalyst composition |
| CN1609173A (en) * | 2003-10-24 | 2005-04-27 | 中国石油化工股份有限公司 | Prepn process of hydroprocessing catalyst |
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2008
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045414A (en) * | 1985-12-05 | 1990-09-19 | 东北师范大学 | Process for synthesizing cobalt phthalocyanine desulfating catalyst |
| US6652738B2 (en) * | 1999-01-15 | 2003-11-25 | Akzo Nobel N.V. | Process for preparing a mixed metal catalyst composition |
| CN1609173A (en) * | 2003-10-24 | 2005-04-27 | 中国石油化工股份有限公司 | Prepn process of hydroprocessing catalyst |
Non-Patent Citations (1)
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