CN103055885B - A kind of Catalysts and its preparation method of low-carbon alkene hydrotreated lube base oil and application - Google Patents
A kind of Catalysts and its preparation method of low-carbon alkene hydrotreated lube base oil and application Download PDFInfo
- Publication number
- CN103055885B CN103055885B CN201110317650.5A CN201110317650A CN103055885B CN 103055885 B CN103055885 B CN 103055885B CN 201110317650 A CN201110317650 A CN 201110317650A CN 103055885 B CN103055885 B CN 103055885B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- oxide
- auxiliary agent
- hours
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a kind of Catalysts and its preparation method and application of tooth ball-type low-carbon alkene hydrotreated lube base oil.Catalyst is in gross weight 100%, and wherein tungsten oxide content is 0 ~ 30%, and molybdenum oxide content is 5 ~ 40%, and nickel oxide is 1 ~ 20%, and cobalt oxide is 0 ~ 10%, auxiliary agent X
1content is 0 ~ 6%, and surplus is tooth spherical alumina support.Wherein auxiliary agent X
1can be one or more in Y, La, Sc, Ce.The specific area of catalyst is 100 ~ 250m
2/ g, pore volume is 0.3 ~ 0.5ml/g.Catalyst of the present invention have active high, good stability, high-speed and sulfur resistive toxicity good etc. feature, and in hydrogenation process, bed pressure drop is low, and reacting fluid resistance is little, and energy consumption is low.This catalyst is mainly applicable to C
4~ C
8olefins hydrogenation.
Description
Technical field
The present invention relates to a kind of low-carbon alkene hydrogenation catalyst and its preparation method and application, specifically one is applied to C
4~ C
8the Catalysts and its preparation method of middle olefins hydrogenation and application, be particularly useful for C
4olefins hydrogenation.
Background technology
Along with domestic and international petroleum refining industry develops, especially the improving constantly of catalytic cracking technology, secondary operations device proportion in Crude Oil Processing is increasing, and refinery gas resource is also thereupon abundanter, and the deep processing of refinery gas is subject to people's attention gradually.Many refining & chemical industry integration enterprises of China ubiquity C
4the problem that cut is superfluous, utilization rate is low.The C of current refinery by-product
4produced except high-knock rating gasoline blend component by etherificate, alkylation except a small amount of, all the other major parts are sold as oil liquefied gas product.Due to rising steadily of crude oil price, C
4the economy of selling as conventional fuel is worthy of consideration.In addition, natural gas widely uses civilian and automobile-used market, and the sale of refinery's liquefied gas will face huge challenge.Therefore, refinery by-product C how is utilized
4the downstream product of production high added value, is subject to the common concern of vast Petrochemical Enterprises.
By C
4cut is a comparatively feasible approach as preparing ethylene by steam cracking raw material, but these C
4in cut, olefin(e) centent is general higher, and alkene can be polymerized in pyrolysis furnace, cyclisation, condensation and coking reaction, therefore alkene must be removed, could by C
4cut is as the raw material of preparing ethylene by steam cracking.
USP4059504 discloses and is mixed with co-impregnated solution a kind of being added in nickel nitrate aqueous solution by tungsten oxide, and load is greater than 150m in specific area
2on/g aluminium oxide, through air oxygen detrition, 457 DEG C of roastings 3 hours, obtain cobalt 2.5%, tungsten 8.0%.The specific area of this catalyst is low, and to cause catalyst activity low, and therefore, when processing drippolene, colloid is easily adhered on a catalyst, and easy coking, catalyst life is shorter.
A kind of in CN200810238973.3 is carrier with aluminium oxide, and active component is the hydrogenation catalyst of precious metal palladium, selects auxiliary agent B, one or more and Ag, Pb in P, Si, Au, Co, Cu, Bi, one or more in Ni, Pt, Ti, add alkali metal and/or alkaline-earth metal, catalyst is applicable to catalytic cracking process and preparing ethylene by steam cracking byproduct in process C simultaneously
4the hydrotreated lube base oil of cut, but thus this type of catalyst preparation process is comparatively complicated, and cost is also higher, is very easy to poisoning as noble metal catalyst simultaneously, and the liquid air speed of hydrogenation reaction also lower (0.5 ~ 3.0h
-1).
Summary of the invention
Object of the present invention is exactly the defect overcoming prior art, there is provided that a kind of hydrotreated lube base oil activity is high, good stability, high-speed and the good tooth ball shape catalyst of sulfur resistive toxicity and preparation method thereof, present invention also offers the application of this catalyst, this catalyst can be used in C
4~ C
8olefins hydrogenation, is specially adapted to the mixed C containing normal butane, suitable anti-butylene and part iso-butane
4ethylene cracking material is produced in olefin saturated and desulfurization.
Catalyst of the present invention with tooth ball-aluminium oxide for carrier, active component is: tungsten oxide, molybdenum oxide, nickel oxide and cobalt oxide, catalyst is in gross weight 100%, wherein tungsten oxide content is 0 ~ 30wt%, molybdenum oxide content is 5 ~ 40wt%, nickel oxide on a catalyst content is 1 ~ 20wt%, and cobalt oxide content is 0 ~ 10wt%, auxiliary agent X
1content is 0 ~ 6wt%, and surplus is tooth spherical alumina support.The specific area of catalyst is 100 ~ 250m
2/ g, pore volume is 0.3 ~ 0.5ml/g.
First object of the present invention can also realize with such prioritization scheme: tungsten oxide is 1 ~ 20wt%, and molybdenum oxide is 10 ~ 21wt%, and nickel oxide is 1 ~ 11wt%, and cobalt oxide is 1 ~ 10wt%, X
1be 0.1 ~ 3wt%, surplus is tooth spherical alumina support.
Auxiliary agent X described in the present invention
1can be one or more mixtures in Y, La, Sc, Ce.One or more in preferred La, Sc, Ce.
The preparation method of catalyst of the present invention is:
(1) in catalyst of the present invention, alumina support is that tooth is spherical, and existing method can be adopted to prepare, as the method etc. as described in see CN200910079772.8.The alumina support obtained be impregnated in the salting liquid of auxiliary agent, in the carrier that will be shaped roasting 2 ~ 8 hours at dry 2 ~ 14 hours, 400 ~ 700 DEG C in air atmosphere, obtain the carrier containing auxiliary agent.
(2) preparation of catalyst impregnating solution: mix containing active constituent compound and ammonia spirit and be configured to active component solution, obtained catalyst impregnating solution.
(3) preparation of catalyst: the tooth ball type carrier that step (1) is obtained is placed in dipping tank, add the obtained impregnation fluid of step (2), obtain wet bulb carrier, health 0.5 ~ 3 hour after taking out (health and normal temperature cool place place place), then at 100 ~ 180 DEG C of temperature dry 4 ~ 8 hours.By roasting in product 350 ~ 550 DEG C of air atmospheres 2 ~ 6 hours, catalyst of the present invention can be obtained.
Catalyst of the present invention also can adopt unsaturated infusion process or the preparation of saturated infusion process.
Present invention also offers a kind of application process of this catalyst, hydrogenation of liquefied petroleum gas process is used for catalyst of the present invention, good process conditions are: Hydrogen Vapor Pressure 1.5 ~ 3.0MPa, hydrogen to oil volume ratio is 100: 1 ~ 400: 1, reaction temperature is 30 ~ 150 DEG C, and during the liquid of liquefied petroleum gas, volume space velocity is 2 ~ 10h
-1.This catalyst needs under hydrogen before use, at 150 ~ 450 DEG C, preferably at 200 ~ 380 DEG C, reduces 4 ~ 10 hours.Catalyst of the present invention can also be applied to C
4~ C
8in olefins hydrogenation reaction.
Hydrogenation catalyst of the present invention adopts the low acid tooth ball-aluminium oxide of rare earth and other additive modifications to be carrier, and for active component, and add rare earth metal with oxidation state tungsten, molybdenum, nickel, cobalt, adding of this rare earth metal preferentially can be anchored on Al
2o
3in the surface of carrier and the defect of body phase, occupy Adsorption, reduce surface energy, improve Al
2o
3heat endurance, and increase the decentralization of active metal.Compared with simple nickel-loaded catalyst, activity is higher; Compared with the noble metal catalysts such as supported palladium, sulfur resistive toxicity is better.This invention catalyst is adopted to be applicable to C
4~ C
8olefins hydrogenation course of reaction, especially for the C of process catalytic cracking unit
4the C of cut and preparing ethylene by steam cracking device
4cut, hydrotreated lube base oil activity is higher, can obtain the purified product of olefin(e) centent < 0.5 volume %.
Detailed description of the invention
Below by embodiment, the present invention is further described, but therefore do not limit the present invention.Catalyst adopts one section of fixed bed hydrogenation reactor to carry out catalyst activity and estimation of stability, and reactor adopts stainless steel axial flow reactor, and internal diameter is 16mm, is highly 80cm, and reactor exterior circumferential adopts electrical heating constant temperature.Being mixed with inert carrier (volume 1: 1) by the catalyst prepared loads in reaction tube, heats up slowly and carries out selective hydrogenation reaction.
Embodiment 1
(1) preparation of catalyst: prepare tooth spherical alumina support; Alumina support be impregnated in the salting liquid of auxiliary agent, in the carrier that will be shaped roasting 4 hours at dry 6 hours, 650 DEG C in air atmosphere, obtain the carrier containing auxiliary agent; Tooth spherical alumina support is placed in dipping tank, the preparation of catalyst impregnating solution: the ammonia spirit containing molybdenum, cobalt, nickel and tungsten mixes and is mixed with active component solution, obtained catalyst impregnating solution.Add obtained impregnation fluid, obtain wet bulb carrier, health 2 hours after taking out, then at 160 DEG C of temperature dry 6 hours.By roasting in product 480 DEG C of air atmospheres 4 hours, catalyst of the present invention can be obtained.
(2) be 15wt% by preparing molybdenum oxide in (1), nickel oxide is 3wt%, the catalyst of cobalt oxide to be 2wt%, La be 0.5wt%.Catalyst is used for hydrogenation of liquefied petroleum gas reaction, and reaction condition and effect are in table 1.
Embodiment 2
(1) preparation of catalyst: prepare tooth spherical alumina support; Alumina support be impregnated in the salting liquid of auxiliary agent, in the carrier that will be shaped roasting 4 hours at dry 6 hours, 650 DEG C in air atmosphere, obtain the carrier containing auxiliary agent; Tooth spherical alumina support is placed in dipping tank, the preparation of catalyst impregnating solution: the ammonia spirit containing molybdenum, cobalt, nickel and tungsten mixes and is mixed with active component solution, obtained catalyst impregnating solution.Add obtained impregnation fluid, obtain wet bulb carrier, health 2 hours after taking out, then at 160 DEG C of temperature dry 6 hours.By roasting in product 480 DEG C of air atmospheres 4 hours, catalyst of the present invention can be obtained.
(2) be 6wt% by preparing tungsten oxide in (1), molybdenum oxide is 9wt%, and nickel oxide is 3wt%, the catalyst of cobalt oxide is 3wt%, La to be 0.9wt%, Sc be 0.4wt%.Catalyst is used for hydrogenation of liquefied petroleum gas reaction, and reaction condition and effect are in table 1.
Embodiment 3
(1) preparation of catalyst: prepare tooth spherical alumina support; Alumina support be impregnated in the salting liquid of auxiliary agent, in the carrier that will be shaped roasting 4 hours at dry 6 hours, 650 DEG C in air atmosphere, obtain the carrier containing auxiliary agent; Tooth spherical alumina support is placed in dipping tank, the preparation of catalyst impregnating solution: the ammonia spirit containing molybdenum, cobalt, nickel and tungsten mixes and is mixed with active component solution, obtained catalyst impregnating solution.Add obtained impregnation fluid, obtain wet bulb carrier, health 2 hours after taking out, then at 160 DEG C of temperature dry 6 hours.By roasting in product 480 DEG C of air atmospheres 4 hours, catalyst of the present invention can be obtained.(2) be 5wt% by preparing tungsten oxide in (1), molybdenum oxide is 10wt%, and nickel oxide is 3wt%, the catalyst of cobalt oxide to be 2wt%, Ce be 2wt%.Catalyst is used for hydrogenation of liquefied petroleum gas reaction, and reaction condition and effect are in table 1.
Table 1 hydrogenation reaction raw material, product characteristics and reaction condition
Table 1 (Continued)
Note: sulfur content 130ppm; Arsenic content 35ppb.
Claims (4)
1. the method for a hydrogenation of liquefied petroleum gas process, it is characterized in that: adopt following low-carbon alkene hydrogenation catalyst, with tooth ball-aluminium oxide for carrier, active component is: tungsten oxide, molybdenum oxide, nickel oxide and cobalt oxide, and catalyst is in gross weight 100%, and wherein the content of tungsten oxide is 1 ~ 20wt%, the content of molybdenum oxide is 10 ~ 21wt%, the content of nickel oxide is 1 ~ 11wt%, and the content of cobalt oxide is 1 ~ 10wt%, X
1content be 0.1 ~ 3wt%, surplus is tooth spherical alumina support; Auxiliary agent X
1one or more mixtures in Y, La, Sc, Ce; The specific area of catalyst is 100 ~ 250m
2/ g, pore volume is 0.3 ~ 0.5ml/g;
The preparation method of described hydrogenation catalyst, comprises the steps:
(1) tooth spherical alumina support is prepared; Alumina support be impregnated in the salting liquid of auxiliary agent, by the roasting 2 ~ 8 hours at dry 2 ~ 14 hours, 400 ~ 700 DEG C in air atmosphere of the carrier that is shaped, obtain the carrier containing auxiliary agent;
(2) preparation of catalyst impregnating solution: active component and ammonia spirit mix and be configured to active component solution, obtained catalyst impregnating solution;
(3) preparation of catalyst: the tooth ball type carrier containing auxiliary agent obtained for step (1) is placed in dipping tank, add the obtained impregnation fluid of step (2), obtain wet bulb carrier, health 0.5 ~ 3 hour after taking out, then at 100 ~ 180 DEG C of temperature dry 4 ~ 8 hours; By roasting in product 350 ~ 550 DEG C of air atmospheres 2 ~ 6 hours, namely obtain catalyst;
The process conditions of described hydrotreatment are: Hydrogen Vapor Pressure 1.5 ~ 3.0MPa, and hydrogen to oil volume ratio is 100: 1 ~ 400: 1, and reaction temperature is 30 ~ 150 DEG C, and during liquid, volume space velocity is 2 ~ 10h
-1.
2. method according to claim 1, is characterized in that: auxiliary agent X1 can be one or more in La, Sc, Ce.
3. method according to claim 1, is characterized in that: catalyst needs under hydrogen before use, at 150 ~ 450 DEG C, reduces 4 ~ 10 hours.
4. method according to claim 3, is characterized in that: the reduction temperature before catalyst uses is 200 ~ 380 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110317650.5A CN103055885B (en) | 2011-10-19 | 2011-10-19 | A kind of Catalysts and its preparation method of low-carbon alkene hydrotreated lube base oil and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110317650.5A CN103055885B (en) | 2011-10-19 | 2011-10-19 | A kind of Catalysts and its preparation method of low-carbon alkene hydrotreated lube base oil and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103055885A CN103055885A (en) | 2013-04-24 |
| CN103055885B true CN103055885B (en) | 2015-12-02 |
Family
ID=48098952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110317650.5A Active CN103055885B (en) | 2011-10-19 | 2011-10-19 | A kind of Catalysts and its preparation method of low-carbon alkene hydrotreated lube base oil and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103055885B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105536808B (en) * | 2015-12-28 | 2018-09-21 | 北京高新利华科技股份有限公司 | A kind of hydrogenation catalyst and its preparation method and application |
| CN106563441A (en) * | 2016-10-20 | 2017-04-19 | 中国石油化工股份有限公司 | A method of preparing an anoxic tungsten oxide hydrogenation catalyst |
| CN112547114A (en) * | 2019-09-10 | 2021-03-26 | 中石化南京化工研究院有限公司 | Olefin hydrogenation catalyst, preparation method and application thereof |
| CN112479862A (en) * | 2019-09-11 | 2021-03-12 | 王宏涛 | Low-cost method for synthesizing succinic acid by continuous aqueous phase catalytic hydrogenation |
| GB2600690A (en) * | 2020-10-30 | 2022-05-11 | Jemmtec Ltd | Catalyst support |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113126B (en) * | 2006-07-26 | 2010-05-12 | 李莉 | Olefin-containing lighter hydrocarbons catalytic hydrogenation method |
| CN101497044B (en) * | 2009-03-10 | 2011-05-11 | 北京高新利华催化材料制造有限公司 | Teeth spherical heavy oil hydrotreating catalyst and preparation method thereof |
-
2011
- 2011-10-19 CN CN201110317650.5A patent/CN103055885B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103055885A (en) | 2013-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103055885B (en) | A kind of Catalysts and its preparation method of low-carbon alkene hydrotreated lube base oil and application | |
| CN101423775B (en) | Selective nickle series hydrocatalyst and its preparing process | |
| CN102247852B (en) | Cu-Fe-Co base catalyst used for synthesizing low carbon alcohol by utilizing synthesis gas as well as preparation method and application thereof in low carbon alcohol synthesizing process by virtue of synthesis gas | |
| CN105921148A (en) | Catalyst for preparing olefins from saturated alkanes through dehydrogenation and preparing method and application thereof | |
| CN102247876B (en) | Method for preparing ethylene with acetylene selective catalytic hydrogenation | |
| CN103934040B (en) | The preparation method of the metallic catalyst of a kind of high selectivity, high dispersive | |
| CN106861691A (en) | A kind of preparation of hydrogenation catalyst and hydrogenation catalyst and application | |
| CN106582706B (en) | Selective hydrogenation of butadiene catalyst | |
| CN103203238A (en) | Fischer-Tropsch synthesis catalyst, its preparation and application | |
| CN101429454B (en) | Full-cut fraction pyrolysis gasoline diolefin selective hydrogenation method | |
| CN102500409A (en) | Gasoline aromatization and isomerization reforming catalyst and preparation method and applications thereof | |
| CN101745389A (en) | A kind of egg-shell catalyst that is used for preparation of ethylene through selective hydrogenation of acetylene | |
| CN104588011A (en) | Alkane dehydrogenation catalyst and preparation method thereof | |
| CN110523433A (en) | A kind of nickel-base catalyst and the preparation method and application thereof | |
| CN105642324A (en) | Non-noble metal selective hydrogenation catalyst, preparation method and application thereof | |
| CN105536808A (en) | Hydrogenation catalyst and preparation method and application thereof | |
| CN105312058B (en) | diacetylene hydrogenation catalyst | |
| CN105582920B (en) | Catalyst for dehydrogenation of low-carbon paraffin and its application | |
| CN102908957A (en) | Method for Fischer-Tropsch synthesis | |
| CN105435801B (en) | Load typed iron catalyst and its preparation method and application | |
| CN107970929B (en) | A kind of alkynes and alkadienes liquid phase selective hydrogenation catalyst, preparation method and application | |
| CN100417713C (en) | Hydrocracking catalyst for Tscher-Topsch synthesis of heavy wax, its preparation method and application thereof | |
| CN106607048B (en) | The method of fixed bed production low-carbon alkene | |
| CN103566933A (en) | Catalyst for preparing alcohol by acetate hydrogenation as well as preparation method thereof | |
| CN102794178A (en) | Selective hydrogenation catalyst and preparation thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 101111, Beijing Tongzhou light mechanical and electrical integration industry base, No. Patentee after: BEIJING GAOXIN LIHUA TECHNOLOGY CO., LTD. Address before: 101111, Beijing Tongzhou light mechanical and electrical integration industry base, No. Patentee before: Beijing Gaoxin Lihua Catalytic Materials Manufacture Co., Ltd. |