CN103623827A - Wide temperature range aromatic hydrocarbon hydrogenation catalyst and preparation method thereof - Google Patents
Wide temperature range aromatic hydrocarbon hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN103623827A CN103623827A CN201210301247.8A CN201210301247A CN103623827A CN 103623827 A CN103623827 A CN 103623827A CN 201210301247 A CN201210301247 A CN 201210301247A CN 103623827 A CN103623827 A CN 103623827A
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Abstract
The invention belongs to the technical field of catalyst, and relates to a wide temperature range aromatic hydrocarbon hydrogenation catalyst and a preparation method thereof. The wide temperature range aromatic hydrocarbon hydrogenation catalyst comprises, based on the total weight of the wide temperature range aromatic hydrocarbon hydrogenation catalyst, 5 to 30wt% of NiO, 50 to 90wt% of Al2O3, and the balance an auxiliary agent. The preparation method mainly comprises two steps of carrier preparation, and dipping of active components. Active component content of the wide temperature range aromatic hydrocarbon hydrogenation catalyst is low; utilization ratio is high; applicable temperature range is wide; the applicable temperature still possesses excellent conversion rate and selectivity at high temperatures, and is high in intensity; and efflorescence is not easy to happen.
Description
Technical field
The invention belongs to catalyst technical field, relate to a kind of aromatic hydrocarbon hydrogenation catalyst and preparation method thereof.
Background technology
The active component that aromatic hydrocarbon hydrogenation catalyst is conventional has nickel, platinum, palladium etc., wherein nickel has good aromatic hydrogenation activity, and cheap and easy to get, from the viewpoint of two of the catalytic performance of catalyst and manufacturing costs, metallic nickel is loaded on carrier, catalyst cost can not only be reduced, and its catalytic performance can be improved widely.Therefore nickel aluminium System Catalyst is because having good activity and relatively low price to be widely used on commercial plant.
But the active temperature of the nickel aluminium System Catalyst of current industrial use narrow (being generally 130 ~ 180 ℃), for example benzene hydrogenation is exothermic reaction, when can not transferring out very soon, heat just easily causes overtemperature, be prone to " temperature runaway " phenomenon, cause accessory substance to increase, in operation, be difficult to control, also poor to the poison resistance of sulfide, 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, the effective rate of utilization of nickel is low, and nickel and alumina catalyst support interact and form nickel aluminate, make catalyst be difficult to reduce and lose catalytic activity.The nickel content of catalyst is controlled to a rational scope, Raney nickel can normally be used under wider temperature range, just seem particularly important.
The patent that publication number is 1171429 provides a kind of preparation method of aromatic hydrocarbon hydrogenation catalyst, by aluminium hydrate powder extruded moulding, this catalyst is applicable to aromatic hydrogenation course of reaction, but its molding mode is strip squeezing type, the catalyst strength of the method gained is low, at high temperature reacts easy efflorescence.
The patent that publication number is 1351117 provides a kind of hydrocatalyst for saturating arylhydrocarbon in diesel oil and preparation method thereof, and this catalyst has high resistance to sulphur, resistance to nitrogen characteristic, and its hydrogenation metal component has the noble metal of a kind of Pt of being selected from, Pd, Ir, Rh etc. at least.This catalyst activity component is noble metal, and expensive, cost is high.
Be disclosed as 1836776 patent a kind of aromatic hydrocarbon hydrogenation catalyst and preparation method with higher hydrogenation activity and sulfur poisoning-resistant ability is provided.Composition comprises nickel oxide, boron oxide and tungsten oxide.It adopts coprecipitation method preparation, and NiO:50%～80% is because nickel content is high, and during reduction, catalyst must be in reduction for a long time under 400 ~ 500 ℃, hydrogen atmosphere, and NiO just can be reduced into metallic nickel.So not only in reduction process, consume mass energy, equipment investment is increased, and after catalyst high temperature reduction, also will be reduced to low temperature use, to industrial production, make troubles.
Summary of the invention
The object of the invention is to provide a kind of aromatic hydrocarbon hydrogenation catalyst, and its active component content is low, and utilization rate is high, and Applicable temperature is wide, has good conversion ratio and selective, and intensity is high is difficult for efflorescence.
Catalyst provided by the invention is wide temperature range type aromatic hydrocarbon hydrogenation catalyst, is to take NiO as active constituent, Al
2o
3for carrier, one or more in carbonate, rare earth oxide of take are auxiliary agent; The gross weight of catalyst of take is benchmark, and it consists of: NiO is 5 ~ 30wt%, Al
2o
3be 50 ~ 90wt%, all the other are auxiliary agent.
Described catalyst is cylindrical particle, specification φ 5 * 5 mm, and bulk density 0.9 ~ 1.1 g/mL, radially anti-crushing power is greater than 150 ~ 200N/cm.
Described auxiliary agent is one or more compositions in Na, K, Mg, Ca carbonate or La, Ce oxide; The most frequently used is sodium carbonate or potash.The optimum weight ratio of auxiliary agent and aluminium oxide is auxiliary agent: Al
2o
3=(0.1 ~ 4.0): 100
The preparation method of catalyst of the present invention mainly comprises carrier preparation and dipping active constituent two parts.
Carrier preparation: at room temperature aluminium oxide and auxiliary agent are mixed and add ionized water by required weight, through mixed grind, granulation, compressing tablet, calcining, make carrier.
Usually, the calcining heat of carrier is 400 ~ 800 ℃, and the time is 1 ~ 10 hour.
Dipping process comprises the following steps:
1) get nickel nitrate crystal, be placed in 80 ~ 100 ℃ of temperature heating water baths, dissolve completely to nickel nitrate;
2) by the carrier preparing, immerse in 80 ~ 100 ℃ of nickel nitrate solutions of constant temperature, flood 10 ~ 100 minutes, preferably 50 ~ 80 minutes, take out, drain and be placed in 80 ~ 100 ℃ of temperature constant temperature water baths slaking 1 ~ 10 hour, preferably 5 ~ 8 hours;
3) catalyst Precursors through dipping cooked at constant is dried 2 ~ 12 hours, preferably 10 ~ 12 hours at 80 ~ 200 ℃;
4) dry rear catalyst parent is calcined 2 ~ 10 hours at 200 ~ 600 ℃, preferably 4 ~ 8 hours, obtains catalyst.
The distinguishing feature of catalyst of the present invention is in catalyst carrier, to add auxiliary agent, can effectively improve the decentralization of nickel, reduces catalyst nickel content, improves the service efficiency of nickel.
The specific embodiment
By following examples, can do to describe in further detail to the present invention.
Embodiment 1:
Get that the sodium carbonate of 1.2 g is soluble in water is made into certain density sodium carbonate liquor, sodium carbonate liquor is added in 100g commercial alumina to mixed grind 50 minutes, then granulation, compressing tablet, calcining, calcining heat is 400 ~ 800 ℃, the time is within 1 ~ 10 hour, to make carrier.
Get Ni (NO
3)
26H
2o, is placed in 90 ℃ of temperature heating water baths, dissolves completely to nickel nitrate;
Carrier is immersed in 90 ℃ of nickel nitrate solutions of constant temperature, flood 30 minutes, take out, drain and be placed in another beaker and be placed in 90 ℃ of temperature constant temperature water baths slaking 1 ~ 10 hour; Catalyst Precursors through dipping cooked at constant is dried 2 ~ 12 hours at 80 ~ 200 ℃; Dry rear catalyst parent is calcined 2 ~ 10 hours at 200 ~ 600 ℃, obtains catalyst 1.Its NiO content is 14%, radially anti-crushing power 150N/cm.
Embodiment 2:
Sodium carbonate amount changes 2g into, and changing dip time is 40 minutes, and all the other step conditions are identical with embodiment 1.Obtain catalyst 2, its NiO content is 14.4%, radially anti-crushing power 167N/cm.
Embodiment 3:
Sodium carbonate amount changes 1g into, and changing dip time is 60 minutes, and all the other step conditions are identical with embodiment 1.Obtain catalyst 3, its NiO content is 14.6%, radially anti-crushing power 195N/cm.
Embodiment 4:
Get that the potash of 2.2 g is soluble in water is made into certain density solution of potassium carbonate, solution of potassium carbonate is added in 100g commercial alumina to mixed grind 50 minutes, then granulation, compressing tablet, calcining, calcining heat is 400 ~ 800 ℃, the time is within 1 ~ 10 hour, to make carrier.
Get Ni (NO
3)
26H
2o, is placed in 90 ℃ of temperature heating water baths, dissolves completely to nickel nitrate;
Carrier is immersed in 90 ℃ of nickel nitrate solutions of constant temperature, flood 60 minutes, take out, drain and be placed in another beaker and be placed in 90 ℃ of temperature constant temperature water baths slaking 1 ~ 10 hour; Catalyst Precursors through dipping cooked at constant is dried 2 ~ 12 hours at 80 ~ 200 ℃; Dry rear catalyst parent is calcined 2 ~ 10 hours at 200 ~ 600 ℃, obtains catalyst 4, and its NiO content is 16%, radially anti-crushing power 177N/cm.
Embodiment 5:
Potash consumption changes 2.1g into, and changing dip time is 80 minutes, and all the other step conditions are identical with embodiment 4.Obtain catalyst 5, its NiO content is 19.6%, radially anti-crushing power 165N/cm.
Embodiment 6: activity rating
Above-mentioned catalyst is simulated technical benzene hydroconversion condition and is carried out activity rating on original catalyst particle size pressurization evaluating apparatus.Appreciation condition is as follows:
A: catalyst reduces with following condition: reducing gases: high-purity hydrogen; Reduction pressure: normal pressure; Reduction temperature: 400 ℃; Catalyst loading amount: former granularity 30 ml; Air speed: 400 ~ 500h
-1; Time: 24 h
B: catalyst carries out activity rating with following condition: pressure: 0.6Mpa; Reaction temperature: 140 ~ 280 ℃; Catalyst loading amount: former granularity 30ml; Hydrogen/benzene (mol): 6:1; Liquid benzene air speed: 1.0h
-1
Benzene conversion ratio % under above-mentioned appreciation condition and the selective % of cyclohexane are as table 1:
Table 1
Note: total mole number * 100% of the molal quantity/benzene of the benzene that benzene conversion ratio be=has transformed
Cyclohexane is selectively molal quantity * 100% of the benzene of the cyclohexane molal quantity in=product/ transformed
In table 1, comparative example adopts commercially available conventional Raney nickel, and the catalyst being provided by the visible present technique of test data has higher conversion ratio and selective, and can at wider temperature range 140-280 ℃, normally use.
Claims (7)
1. a wide temperature range type aromatic hydrocarbon hydrogenation catalyst, is characterized in that catalyst take NiO as active constituent, Al
2o
3for carrier, one or more in carbonate, rare earth oxide of take are auxiliary agent; The gross weight of catalyst of take is benchmark, and it consists of: NiO is 5 ~ 30wt%, Al
2o
3be 50 ~ 90wt%, all the other are auxiliary agent.
2. catalyst as claimed in claim 1, is characterized in that catalyst is cylindrical particle, specification φ 5 * 5 mm, and bulk density 0.9 ~ 1.1 g/mL, radially anti-crushing power is greater than 150 ~ 200N/cm.
3. catalyst as claimed in claim 1, is characterized in that described auxiliary agent is one or more compositions in the carbonate of Na, K, Mg, Ca or La, Ce oxide.
4. the catalyst as described in claim 1 or 3, is characterized in that described auxiliary agent weight and the weight ratio of aluminium oxide are 0.1:100 ~ 4:100.
5. the preparation method of catalyst as claimed in claim 1, is characterized in that its adopts impregnation technology preparation, comprises carrier preparation 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 and add ionized water by required weight, through mixed grind, granulation, compressing tablet, calcining, make carrier; Dipping process comprises the following steps: 1) get nickel nitrate crystal, be placed in 80 ~ 100 ℃ of temperature heating water baths, dissolve completely to nickel nitrate; 2) carrier preparing is immersed in 80 ~ 100 ℃ of nickel nitrate solutions of constant temperature, flood 10 ~ 100 minutes, take out, drain and be placed in 80 ~ 100 ℃ of temperature constant temperature water baths slaking 1 ~ 10 hour; 3) catalyst Precursors through dipping cooked at constant is dried 2 ~ 12 hours at 80 ~ 200 ℃; 4) dry rear catalyst parent is calcined 2 ~ 10 hours at 200 ~ 600 ℃, obtains catalyst.
6. the preparation method of catalyst as claimed in claim 5, is characterized in that dipping process comprises the following steps: 1) get nickel nitrate crystal, be placed in 80 ~ 100 ℃ of temperature heating water baths, dissolve completely to nickel nitrate; 2) carrier preparing is immersed in 80 ~ 100 ℃ of nickel nitrate solutions of constant temperature, flood 50 ~ 80 minutes, take out, drain and be placed in 80 ~ 100 ℃ of temperature constant temperature water baths slaking 5 ~ 8 hours; 3) catalyst Precursors through dipping cooked at constant is dried 10 ~ 12 hours at 80 ~ 200 ℃; 4) dry rear catalyst parent is calcined 4 ~ 8 hours at 200 ~ 600 ℃, obtains catalyst.
7. the preparation method of catalyst as claimed in claim 5, is characterized in that the calcining heat in carrier preparation process is 400 ~ 800 ℃, and the time is 2 ~ 8 hours.
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|---|---|---|---|
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101757917A (en) * | 2008-12-25 | 2010-06-30 | 南化集团研究院 | Low nickel-content benzene hydrogenation catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101757917A (en) * | 2008-12-25 | 2010-06-30 | 南化集团研究院 | Low nickel-content benzene hydrogenation catalyst and preparation method thereof |
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Application publication date: 20140312 |