CN101757917A - Low nickel-content benzene hydrogenation catalyst and preparation method thereof - Google Patents
Low nickel-content benzene hydrogenation catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN101757917A CN101757917A CN200810244197A CN200810244197A CN101757917A CN 101757917 A CN101757917 A CN 101757917A CN 200810244197 A CN200810244197 A CN 200810244197A CN 200810244197 A CN200810244197 A CN 200810244197A CN 101757917 A CN101757917 A CN 101757917A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- nickel
- carrier
- auxiliary agent
- oxide
- 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.)
- Pending
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention provides a low nickel-content benzene hydrogenation catalyst and a preparation method thereof. Nickel oxide is adopted as a main active component of the catalyst, and aluminum oxide is adopted as a carrier. One or more of carbonate and rare earth oxide are added as an assistant. The composition of the catalyst is as follows: the nickel oxide (5 to 30wt %), the Al2O3 (50 to 90wt %), and the assistant (0.1 to 4.0wt %). The catalyst adopts the immersion method and utilizes the Al2O3 as raw materials, the assistant is added, the carrier is obtained through mixing, grinding, granulating, sheeting and high-temperature roasting, and the active component is immersed by the carrier through the immersion method. Compared with the present benzene hydrogenation catalyst, the nickel content of the benzene hydrogenation catalyst in the invention is greatly lowered; moreover, the benzene hydrogenation catalyst in the invention has the characteristics of high intensity, low stacking density, wide operating temperature zone, good heat enduring activity and high selectivity of cyclohexane under the same reaction conditions.
Description
Technical field: the invention belongs to catalyst technical field, relating to a kind of active constituent is the prepared from benzene and hydrogen cyclohexane Catalysts and its preparation method of nickel.
Background technology: cyclohexane is a kind of important Organic Chemicals.It is colourless, easily flow, have penetrating odor, and is main as producing products such as cyclohexanol, cyclohexanone, caprolactam, is the fine solvent of cellulose ether, resin, wax, grease and pitch and rubber.Cyclohexane more than 90% is by benzene hydrogenation, and its production Technology is comparative maturity, and catalyst commonly used has nickel, platinum, palladium etc., and wherein nickel aluminium System Catalyst is because of having preferably active and relatively low price is widely used on commercial plant.US4490480 introduces as patent.But the active temperature of the nickel aluminium System Catalyst of present industrial use narrow (being generally 130～180 ℃), because benzene hydrogenation is exothermic reaction, when can not transferring out very soon, heat just causes overtemperature easily, be prone to " temperature runaway " phenomenon, cause accessory substance to increase, be difficult to control in the operation, poison resistance to sulfide is also relatively poor, these shortcomings it is generally acknowledged it is because nickel content is higher to a great extent, nickel is piled up at carrier surface, decentralization is not high, and the effective rate of utilization of nickel is low, and nickel and alumina catalyst support interaction formation nickel aluminate, make catalyst be difficult to reduce and lose catalytic activity, so reduce nickel content, improve the effective rate of utilization of nickel, just seem particularly important.
Patent No. CN1546230 has told about people such as Liu Biwu and has adopted a kind of nickel oxide that coprecipitation makes and the mixture benzene hydrogenating catalyst of rare earth oxide.The Linxi equality that patent No. CN1210759 has told about the petroleum institute, Jiangsu is benzene hydrogenating catalyst with the nickel that sol-gel process prepares.Employing quenching legal systems such as the Deng Jing of Fudan University sends out are equipped with the Ni-Al-P amorphous alloy catalyst, and experimental result shows, this catalyst performance obviously is better than the Raney Ni catalyst used always and better heat stability.The nano metal nickel cerium particle hydrogenation catalyst of Nanometer Material Inst., Qingdao Chemical Engineering College's preparation because of its superior performance, also is expected to become a kind of new and effective benzene hydrogenating catalyst.
Domestic cyclohexane manufacturer is as Ba Ling petrochemical industry and Yanshan Petrochemical.Used catalyst is a traditional nickel aluminium system, NCG series as former southization catalyst plant production, it has active preferably and fine selectivity, but since in this class catalyst Ni content generally up to 30～50% (production application often be about 40%), because nickel content height, during reduction, catalyst must reduction for a long time under 400～500 ℃, hydrogen atmosphere, and NiO just can be reduced into metallic nickel.So not only consume a large amount of energy in the reduction process, equipment investment is increased, and also will be reduced to the low temperature use behind the catalyst high temperature reduction, make troubles to industrial production.
Summary of the invention: the object of the invention provides a kind of benzene hydrogenating catalyst of low nickel-content, adopts infusion process, reduces nickel content, improves the service efficiency of nickel.
The present invention realizes by following approach:
Catalyst of the present invention is with NiO
2Be active constituent, Al
2O
3Being carrier, is auxiliary agent with in carbonate, the rare earth oxide one or more, is benchmark with the gross weight of catalyst, and it consists of: NiO
2Be 5～30wt%, Al
2O
3Be 50～90wt%, auxiliary agent is 0.1～4.0wt%..
The optimum weight ratio of alumina catalyst usually of the present invention and auxiliary agent is Al
2O
3: auxiliary agent=100: (0.1～4.0).
Auxiliary agent is one or more compositions in Na, K, Mg, Ca carbonate or La, the Ce oxide; The most frequently used is sodium carbonate or potash.
Preparation of catalysts method of the present invention mainly comprises preparing carriers and dipping active constituent two parts.
Preparing carriers: at room temperature aluminium oxide and auxiliary agent are mixed the adding ionized water by required weight,, make carrier through mixed grind, granulation, compressing tablet, calcining.The calcining heat of carrier is 400～800 ℃, and the time is 1～10 hour.
Dipping process may further comprise the steps:
1) gets the nickel nitrate crystal, place 80-100 ℃ of temperature water-bath heating, dissolve fully to nickel nitrate;
2) with the carrier for preparing, immerse in 80-100 ℃ of nickel nitrate solution of constant temperature, flooded 10～100 minutes, take out, drain and place 80-100 ℃ of temperature constant temperature water bath slaking 1～10 hour;
3) catalyst Precursors that passes through the slaking of dipping constant temperature descended dry 2～12 hours at 80～200 ℃;
4) dry rear catalyst parent was calcined 2～10 hours down at 200～600 ℃, promptly got catalyst.
The distinguishing feature of catalyst of the present invention is to add auxiliary agent in the catalyst carrier, can effectively improve the decentralization of nickel, reduces catalyst nickel content, improves the service efficiency of nickel.
The specific embodiment: can do to describe in further detail to the present invention by following examples:
Comparative example:
Get the NCG-6 type benzene hydrogenating catalyst that former southization group catalyst plant is produced, this catalyst is main active constituent with nickel, adopts coprecipitation method, and wherein nickel oxide content is about 50% (wt).
Embodiment 1:
Get commercially available high purity aluminium oxide 100g, add the 1.2g auxiliary agent, get that an amount of sodium carbonate is soluble in water to be made into certain density sodium carbonate liquor, sodium carbonate liquor was added in the aluminium oxide mixed grind 50 minutes, granulation then, compressing tablet, calcining, calcining heat is 400～800 ℃, and the time is to make carrier 1 in 1～10 hour.
Get Ni (NO
3)
26H
2O places 90 ℃ of temperature water-baths heating, dissolves fully to nickel nitrate;
With carrier I, immerse in 90 ℃ of nickel nitrate solutions of constant temperature, flood 10～100 minutes, taking-up drains and places another beaker to place 90 ℃ of temperature constant temperature water baths slaking 1～10 hour; The catalyst Precursors that passes through the slaking of dipping constant temperature is following dry 2～12 hours at 80～200 ℃; Dry rear catalyst parent was calcined 2～10 hours down at 200～600 ℃, promptly got catalyst 1.
Embodiment 2～5:
Change auxiliary dosage, change dip time, obtain the catalyst of different Ni contents and different auxiliary agent/aluminium oxide.Make embodiment 2～5 catalyst 2～5.
Embodiment 1～5 gained catalyst sees Table 1.
Table 1
| Nickel oxide content (wt) | Auxiliary agent/aluminium oxide (wt) | |
| Embodiment 1 | ??14.0 | ??0.15 |
| Embodiment 2 | ??14.4 | ??0.20 |
| Embodiment 3 | ??14.6 | ??1.0 |
| Embodiment 4 | ??16.0 | ??0.22 |
| Embodiment 5 | ??19.6 | ??0.21 |
Above-mentioned catalyst simulation technical benzene hydroconversion condition on original catalyst particle size pressurization evaluating apparatus carries out activity rating.
Appreciation condition is as follows:
1. catalyst reduces with following condition:
Reducing gases: high-purity hydrogen
Reduction pressure: normal pressure
Reduction temperature: 400 ℃
Catalyst loading amount: former granularity 30ml
Air speed: 400～500h
-1
Time: 24h
2. catalyst carries out activity rating with following condition:
Pressure: 0.6MPa
Reaction temperature: 140～260 ℃
Catalyst loading amount: former granularity 30ml
Hydrogen/benzene (mol): 6.0
Liquid benzene air speed: 1.0h
-1
3. benzene conversion ratio % under these conditions and cyclohexane selectivity % such as table 2:
Table 2
4. benzene conversion ratio and cyclohexane selectivity definition
Claims (6)
1. the benzene hydrogenating catalyst of a low nickel-content is characterized in that it mainly is made up of the oxide of nickel and aluminium, with NiO
2Be active constituent, Al
2O
3Being carrier, is auxiliary agent with in carbonate, the rare earth oxide one or more, is benchmark with the gross weight of catalyst, and it consists of: NiO
2Be 5～30wt%, Al
2O
3Be 50～90wt%, auxiliary agent is 0.1～4.0wt%.
2. catalyst as claimed in claim 1 is characterized in that the weight ratio Al of aluminium oxide and auxiliary agent
2O
3: auxiliary agent=100: (0.1～4.0).
3. catalyst as claimed in claim 1 is characterized in that described auxiliary agent is one or more compositions in Na, K, Mg, Ca carbonate or La, the Ce oxide.
4. as catalyst as described in claim 1 or 3, it is characterized in that described auxiliary agent is sodium carbonate or potash.
5. Preparation of catalysts method according to claim 1 is characterized in that its adopts impregnation technology preparation, comprises preparing carriers and dipping active constituent two parts; The method for making of carrier comprises following process: at room temperature aluminium oxide and auxiliary agent are mixed the adding ionized water by required weight, through mixed grind, granulation, compressing tablet, calcining, make carrier; Dipping process may further comprise the steps: 1) get the nickel nitrate crystal, place 80-100 ℃ of temperature water-bath heating, dissolve fully to nickel nitrate; 2) carrier for preparing is immersed in 80-100 ℃ of nickel nitrate solution of constant temperature, flooded 10～100 minutes, take out, drain and place 80-100 ℃ of temperature constant temperature water bath slaking 1～10 hour; 3) catalyst Precursors that passes through the slaking of dipping constant temperature descended dry 2～12 hours at 80～200 ℃; 4) dry rear catalyst parent was calcined 2～10 hours down at 200～600 ℃, promptly got catalyst.
6. as Preparation of catalysts method as described in the claim 5, the calcining heat that it is characterized in that carrier is 400～800 ℃, and the time is 1～10 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810244197A CN101757917A (en) | 2008-12-25 | 2008-12-25 | Low nickel-content benzene hydrogenation catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810244197A CN101757917A (en) | 2008-12-25 | 2008-12-25 | Low nickel-content benzene hydrogenation catalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101757917A true CN101757917A (en) | 2010-06-30 |
Family
ID=42489394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810244197A Pending CN101757917A (en) | 2008-12-25 | 2008-12-25 | Low nickel-content benzene hydrogenation catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101757917A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408297A (en) * | 2010-09-21 | 2012-04-11 | 中国石油化工股份有限公司 | Method for preparing cyclohexane by hydrogenating benzene |
| CN102553608A (en) * | 2010-12-24 | 2012-07-11 | 中国石油化工集团公司 | Supported hydrogenation catalyst as well as preparation method and application thereof |
| CN102716748A (en) * | 2012-06-19 | 2012-10-10 | 吉林大学 | Catalyst used in pseudocumene hydrogenation reaction for producing BTX aromatic hydrocarbon and preparation method thereof |
| CN102941093A (en) * | 2012-09-26 | 2013-02-27 | 中国科学院山西煤炭化学研究所 | Catalyst for decahydronaphthalene preparation by naphthalene hydrogenation |
| CN103623827A (en) * | 2012-08-23 | 2014-03-12 | 中国石油化工股份有限公司 | Wide temperature range aromatic hydrocarbon hydrogenation catalyst and preparation method thereof |
| CN104174406A (en) * | 2013-05-22 | 2014-12-03 | 中国石油化工股份有限公司 | Methanation catalyst for preparation of substitute natural gas from coal and preparation method thereof |
| CN105688915A (en) * | 2016-04-13 | 2016-06-22 | 凯凌化工(张家港)有限公司 | Dual-function catalyst for hydrogenating benzene rings and reducing carbonyl, preparation of dual-function catalyst and application thereof |
| CN112552138A (en) * | 2020-12-29 | 2021-03-26 | 阚晓震 | Low-cost synthesis process for producing cyclohexane by benzene hydrogenation |
| CN112827502A (en) * | 2020-12-30 | 2021-05-25 | 西安交通大学 | Composite catalyst body, method and system for in-situ elimination of carbon deposition of methane and carbon dioxide reforming catalyst |
| CN112851458A (en) * | 2019-11-27 | 2021-05-28 | 湖北华科石化工程有限公司 | Device and method for producing cyclohexane by using benzene gas phase hydrogenation |
| CN115555034A (en) * | 2022-10-17 | 2023-01-03 | 湖南科瑞生物制药股份有限公司 | Composite catalyst for converting carbonyl into methylene and preparation method for efficiently catalyzing cholesterol synthesis by using composite catalyst |
-
2008
- 2008-12-25 CN CN200810244197A patent/CN101757917A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408297A (en) * | 2010-09-21 | 2012-04-11 | 中国石油化工股份有限公司 | Method for preparing cyclohexane by hydrogenating benzene |
| CN102408297B (en) * | 2010-09-21 | 2014-02-05 | 中国石油化工股份有限公司 | Method for preparing cyclohexane by hydrogenating benzene |
| CN102553608A (en) * | 2010-12-24 | 2012-07-11 | 中国石油化工集团公司 | Supported hydrogenation catalyst as well as preparation method and application thereof |
| CN102716748A (en) * | 2012-06-19 | 2012-10-10 | 吉林大学 | Catalyst used in pseudocumene hydrogenation reaction for producing BTX aromatic hydrocarbon and preparation method thereof |
| CN103623827A (en) * | 2012-08-23 | 2014-03-12 | 中国石油化工股份有限公司 | Wide temperature range aromatic hydrocarbon hydrogenation catalyst and preparation method thereof |
| CN102941093A (en) * | 2012-09-26 | 2013-02-27 | 中国科学院山西煤炭化学研究所 | Catalyst for decahydronaphthalene preparation by naphthalene hydrogenation |
| CN104174406A (en) * | 2013-05-22 | 2014-12-03 | 中国石油化工股份有限公司 | Methanation catalyst for preparation of substitute natural gas from coal and preparation method thereof |
| CN105688915A (en) * | 2016-04-13 | 2016-06-22 | 凯凌化工(张家港)有限公司 | Dual-function catalyst for hydrogenating benzene rings and reducing carbonyl, preparation of dual-function catalyst and application thereof |
| CN105688915B (en) * | 2016-04-13 | 2017-03-08 | 凯凌化工(张家港)有限公司 | A kind of method for preparing 1,4 cyclohexanedimethanols |
| CN112851458A (en) * | 2019-11-27 | 2021-05-28 | 湖北华科石化工程有限公司 | Device and method for producing cyclohexane by using benzene gas phase hydrogenation |
| CN112552138A (en) * | 2020-12-29 | 2021-03-26 | 阚晓震 | Low-cost synthesis process for producing cyclohexane by benzene hydrogenation |
| CN112827502A (en) * | 2020-12-30 | 2021-05-25 | 西安交通大学 | Composite catalyst body, method and system for in-situ elimination of carbon deposition of methane and carbon dioxide reforming catalyst |
| CN115555034A (en) * | 2022-10-17 | 2023-01-03 | 湖南科瑞生物制药股份有限公司 | Composite catalyst for converting carbonyl into methylene and preparation method for efficiently catalyzing cholesterol synthesis by using composite catalyst |
| CN115555034B (en) * | 2022-10-17 | 2023-08-18 | 湖南科瑞生物制药股份有限公司 | Composite catalyst for converting carbonyl into methylene and preparation method for efficiently catalyzing synthesis of cholesterol by composite catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101757917A (en) | Low nickel-content benzene hydrogenation catalyst and preparation method thereof | |
| CN110743544B (en) | Palladium-carbon catalyst for preparing alpha-phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof | |
| CN101269326B (en) | Integral catalyst for producing cyclohexene with benzene hydrogenation and method for producing the same | |
| CN110327933B (en) | Catalyst for preparing methanol by carbon dioxide hydrogenation, preparation method and application thereof | |
| CN114797912B (en) | Dehydrogenation catalyst and preparation method thereof | |
| CN110947382B (en) | Catalyst for preparing methanol and co-producing ethylene glycol by ethylene carbonate hydrogenation and preparation method thereof | |
| CN105618042A (en) | Bimetallic oxide catalyst for removing hydrogen in CO gas and preparation method of bimetallic oxide catalyst | |
| CN107930635B (en) | Catalyst for co-production of methyl isobutyl ketone and diisobutyl ketone | |
| CN102416325B (en) | Preparation method of isobutyl ketone synthesis catalyst | |
| CN102553608A (en) | Supported hydrogenation catalyst as well as preparation method and application thereof | |
| CN102744085A (en) | Catalytic system containing nanometer Ru catalyst and alkali zinc sulfate salt and method for preparing cyclohexene through catalytic benzene selective hydrogenation | |
| CN110508277A (en) | A kind of high dispersive palladium nanoparticle catalyst and its preparation method and application | |
| CN104028267B (en) | A kind of method for making of benzene selective Hydrogenation cyclohexene noble metal Ru catalyst | |
| CN101733124B (en) | Catalyst for fixed bed hydrogenation for continuous production of fatty alcohol, preparation method thereof and application thereof | |
| CN108067227B (en) | Platinum-based catalyst highly dispersed in carrier aluminum oxide and preparation method and application thereof | |
| CN111530473B (en) | Catalyst for preparing ethanol by ethyl acetate hydrogenation and preparation method and application thereof | |
| CN110508290B (en) | High-dispersion palladium/cobalt hydroxide catalyst and preparation method and application thereof | |
| CN107930657B (en) | Cobalt-based catalyst for synthesizing methyl isobutyl ketone from acetone | |
| CN102319562A (en) | The Preparation of catalysts method of producing cyclohexene with benzene selective hydrogenation and the catalyst for preparing through this method | |
| CN103331160B (en) | Preparation method of high-dispersion copper-based catalyst based on non-precious metal | |
| CN102794178A (en) | Selective hydrogenation catalyst and preparation thereof | |
| CN106902827B (en) | Preparation method and application of catalyst with nickel loaded on attapulgite as carrier | |
| CN103861626B (en) | Cyclohexanone catalyst by cyclohexanol dehydrogenation and application thereof | |
| CN107930634B (en) | Nickel-based catalyst for synthesizing methyl isobutyl ketone and co-producing isopropanol | |
| CN102886269B (en) | Catalyst for synthesizing crotyl alcohol by crotonic aldehyde through gas phase selective hydrogenating and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20100630 |