CN1268423C - Preparation of dehydrogenation catalyst - Google Patents
Preparation of dehydrogenation catalyst Download PDFInfo
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- CN1268423C CN1268423C CN 200310106563 CN200310106563A CN1268423C CN 1268423 C CN1268423 C CN 1268423C CN 200310106563 CN200310106563 CN 200310106563 CN 200310106563 A CN200310106563 A CN 200310106563A CN 1268423 C CN1268423 C CN 1268423C
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- benzene
- nickel
- rare earth
- oxide
- benzene hydrogenation
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Abstract
The present invention belongs to the technical field of a chemical industry catalyst, which particularly relates to a method for preparing a benzene hydrogenation catalyst. The present invention prepares a mixture of nickel oxide and rare earth oxide by a coprecipitation method or a mixture of the nickel oxide, the rare earth oxide and aluminum oxide, and the mixture is reduced by hydrogen gas; thereby, a benzene hydrogenation catalyst is prepared. The benzene hydrogenation catalyst of the present invention has fine benzene hydrogenation performance, can be used as a 'secondary benzene hydrogenation catalyst '(namely that benzene hydrogenation is carried out once more after the possible maximal benzene hydrogenation degree is achieved), and simultaneously has the specially obvious effect. The benzene hydrogenation catalyst of the present invention enables the content of benzene in gas and oil to be reduced to 5 ppm or even lower, and keeps the benzene hydrogenation catalyzing efficiency for a long term.
Description
Technical field: the invention belongs to the chemical catalyst technical field, be specifically related to a kind of preparation method of benzene hydrogenating catalyst.
Background technology: past people thinks that nickel has good benzene hydrogenation performance as a kind of benzene hydrogenating catalyst, during use usually by a kind of carrier such as activated carbon, aluminium oxide, silica or the load of analog institute.For example: nickel-alumina, nickel-activated carbon, nickel-silica etc.Yet,, make remaining benzene in the hydrogenation products be stabilized in 5PPm or lower level is difficult because these common its catalytic activitys of Ni-based benzene hydrogenating catalyst are not high; Simultaneously, its selectivity is also unstable, and total impurities all is difficult to be lower than 1000PPm; Also have be higher than the i.e. 200 ℃ of operations down of normal temperature, total impurities directly causes the decline of hydrogenated products quality all up to about 5000PPm.
Summary of the invention: in view of there are the problems referred to above in conventional nickel-base catalyst, the present invention has carried out broad research, and finds that the benzene hydrogenating catalyst that the mixture of the mixture of a kind of nickel oxide that makes with coprecipitation method and rare earth oxide or a kind of nickel oxide and rare earth oxide and aluminium oxide obtains through hydrogen reducing can make the benzene content in the benzene hydrogenation product reduce to 5PPm or lower.Simultaneously, be higher than the i.e. 200 ℃ of operations down of normal temperature, total impurities can be controlled in about 1000PPm.
Method by a kind of benzene hydrogenating catalyst of manufacturing provided by the invention, mainly be to make the mixture of a kind of nickel oxide and rare earth oxide or the mixture of a kind of nickel oxide and rare earth oxide and aluminium oxide, make benzene hydrogenating catalyst through hydrogen reducing with coprecipitation method.
More being described in detail of two kinds of technical schemes of the present invention is as follows.
I. first kind of scheme of the present invention:
The mixture for preparing a kind of nickel oxide-rare earth oxide earlier with a kind of coprecipitation method.Nickel compound as a kind of nickel source comprises water-soluble nickel compound, as nitrate, and sulfate, acetate etc.Rare earth oxide compound as a kind of rare earth oxide source comprises the water-solubility rare-earth compound, as nitrate, and sulfate, acetate etc.The available universal method of making catalyst that is similar to is carried out co-precipitation.For example, the aqueous solution that is dissolved with a kind of nickel compound and a kind of rare earth oxide compound water solution and a kind of sodium carbonate dropwise being added to temperature simultaneously with constant speed is that neutralization is carried out in stirring all the time, generates a kind of slurry sediment in 80 ℃ the pure water.Wash the precipitation that is generated then,, can add a kind of auxiliary agent such as graphite etc. in case of necessity, carry out compressing tablet then in 110～120 ℃ of dryings, and in about 360 ℃ of roastings.These conditions can be selected arbitrarily and there is no particular limitation according to the kind of used nickel compound and rare earth oxide compound.As above resulting nickel oxide-rare earth oxide mixture contains and evenly mixes each other and two kinds of finely divided compositions.The blending ratio of nickel oxide and rare earth oxide can change in wide region.General nickel-rare earth ratio can be taken as 1: 0.02～4.1 (mol ratios), and 1: 0.05～1 (mol ratio) is better.If the amount of rare earth oxide very little, can not fully show the benzene hydrogenation performance of nickel-base catalyst.Use the resulting nickel oxide of hydrogen reducing-rare earth oxide mixture then.Although the fusing point of nickel is higher, tend to produce sintering under the heat effect, impel its grain growth to reduce specific surface simultaneously, thereby reduce its catalytic performance.Therefore, the hydrogen reducing of nickel oxide of the present invention is a kind of exothermic reaction, preferably under the situation of the mist of a kind of inert gas (as nitrogen) and hydrogen (content of hydrogen is not more than 20% (volume)), carry out, keep reaction temperature to be about 300～400 ℃ simultaneously.
The crystal grain of nickel has big specific surface usually in the benzene hydrogenating catalyst that makes with said method, and these crystal grain and rare earth oxide are among the even dispersion, have partly nickel crystallite and chemical action has taken place rare earth oxide and make it have more high activity, the result makes this benzene hydrogenating catalyst catalytic performance obtain more significantly improving.
II. second kind of scheme of the present invention:
The mixture for preparing a kind of nickel oxide-rare earth oxide-aluminium oxide with a kind of coprecipitation method.Nickel compound as a kind of nickel source comprises water-soluble nickel compound, as nitrate, and sulfate, acetate etc.Rare earth oxide compound as a kind of rare earth oxide source comprises the water soluble oxidized rare earth compound, as nitrate, and sulfate, acetate etc.The example in aluminium source comprise water soluble aluminum compound as, nitrate, sulfate, sodium aluminate etc.The available universal method of making catalyst that is similar to is carried out co-precipitation.For example, it is in 80 ℃ the pure water that the aqueous solution that is dissolved with the mixed aqueous solution of a kind of nickel compound, a kind of rare earth oxide compound and a kind of aluminium compound and sodium carbonate dropwise is added to temperature simultaneously with constant speed, in this mixture of neutralization, stir on the limit, generates a kind of slurry sediment.Wash the precipitation that is generated then,, can add a kind of auxiliary agent such as graphite etc. in case of necessity, carry out compressing tablet then in about 110-120 ℃ drying, and in about 400 ℃ of roastings.These conditions can be selected arbitrarily and there is no particular limitation according to the kind of used all cpds.The mixture of as above resulting nickel oxide-rare earth oxide-aluminium oxide contains all even each other three kinds of finely divided compositions.The blending ratio of used nickel oxide, rare earth oxide and aluminium oxide can change in wide region.General nickel-rare earth oxide-aluminum ratio can be taken as 1: 0.02～and 6: 0.02～8.1; With 1: 0.05-2: 0.2-2 better (mol ratio).If the amount of rare earth oxide very little, can not fully show the benzene hydrogenation performance of nickel-base catalyst.If the amount of aluminium very little, nickel and rare earth oxide structure less stable.Otherwise,, then reduce benzene hydrogenation activity if the amount of aluminium is too many.Use the resulting nickel oxide-rare earth oxide of hydrogen reducing-alumina mixture then.The hydrogen reducing of nickel oxide of the present invention is a kind of exothermic reaction, preferably carries out under the situation of the hydrogen (content of hydrogen is not more than 30% (volume)) that a kind of inert gas (as nitrogen) dilutes, and keeps reaction temperature to be about 300-400 ℃ simultaneously.
The crystal grain of nickel all has bigger specific surface in the benzene hydrogenating catalyst that makes with said method, and it is to be dispersed in rare earth oxide and the aluminium oxide, may chemical action take place and made it have higher benzene hydrogenation activity with rare earth oxide.And, because the effect of aluminium oxide not only makes the intensity raising of this mixture itself, can significantly reduce the decline of intensity under the high temperature, and further stablize nickel and rare earth oxide crystal grain, make it benzene hydrogenation activity stability be improved significantly.
Its usage of the benzene hydrogenating catalyst of the present invention all similar benzene hydrogenating catalyst with known is identical, for example, it is inserted in a kind of benzene hydrogenation device of given shape, feeds benzene to be processed then or contains the benzene oil product.Because the benzene hydrogenation superior performance of benzene hydrogenating catalyst of the present invention, also has special obvious effects when can be used as a kind of " secondary benzene hydrogenating catalyst " (promptly the benzene hydrogenation degree that reaches maximum possible with commonsense method is carried out benzene hydrogenation later on once more).
Benzene hydrogenating catalyst of the present invention can make the content of benzene in gas and the oils be reduced to 5ppm or lower.And can in long-term, keep its benzene hydrogenation catalysis efficiency.
Particularly the benzene hydrogenating catalyst that makes of second kind of scheme of the present invention even under 240 ℃ temperature, still has good stable.
The specific embodiment:
Further illustrate feature of the present invention below by following reference, embodiment.
Reference example 1
According to a conventional method, a kind of common nickel aluminium benzene hydrogenating catalyst is arranged, 180 ℃ of temperature, pressure is 0.5Mpa, advances benzene liquid space speed (SV) and is 0.6h
-1And the hydrogen benzene mole carries out benzene hydrogenation than being under 4 the condition, and the end conversion benzene content in its product is about 500ppm, and other side reaction total impurities is about 500ppm.
Embodiment 1
In the mixed aqueous solution that is dissolved with nickel nitrate and nitric acid rare earth, add sodium carbonate liquor and carry out neutralization precipitation, washing is also filtered the precipitation that is generated.This precipitation made be pressed into diameter and be 4mm, highly be about the cylinder of 4mm, in about 300 ℃ of roastings.Through the contained nickel of the product of roasting and the ratio of rare earth oxide is 2: 1 (mol ratio).
The nitrogen that will contain 10% hydrogen feeds 100ml embodiment 1 sample is housed, and reduces under 400 ℃ temperature.180 ℃ of temperature, pressure is 0.5Mpa, advances benzene liquid space speed (SV) and is 0.6h
-1And the hydrogen benzene mole carries out benzene hydrogenation than being under 4 the condition, and the end conversion benzene content in its product is about 400ppm, and other side reaction total impurities is about 400ppm.
Reference example 2
According to a conventional method, a kind of common nickel aluminium benzene hydrogenating catalyst is arranged, 180 ℃ of temperature, pressure is 0.7Mpa, advances benzene liquid space speed (SV) and is 0.6h
-1And the hydrogen benzene mole carries out benzene hydrogenation than being under 4 the condition, and the end conversion benzene content in its product is about 400ppm, and other side reaction total impurities is about 500ppm.
Embodiment 2
In the mixed aqueous solution that is dissolved with nickel nitrate and nitric acid rare earth, add sodium carbonate liquor and carry out neutralization precipitation, washing is also filtered the precipitation that is generated.This precipitation made be pressed into diameter and be 4mm, highly be about the cylinder of 4mm, in about 300 ℃ of roastings.Through the contained nickel of the product of roasting and the ratio of rare earth oxide is 2: 1 (mol ratio).
The nitrogen that will contain 10% hydrogen feeds 100ml embodiment 2 samples is housed, and reduces under 400 ℃ temperature.180 ℃ of temperature, pressure is 0.5Mpa, advances benzene liquid space speed (SV) and is 0.6h
-1And the hydrogen benzene mole carries out benzene hydrogenation than being under 4 the condition, and the end conversion benzene content in its product is about 350ppm, and other side reaction total impurities is about 400ppm.
Reference example 3
According to a conventional method, a kind of common nickel aluminium benzene hydrogenating catalyst is arranged, 180 ℃ of temperature, pressure is 0.7Mpa, advances benzene liquid space speed (SV) and is 0.6h
-1And the hydrogen benzene mole carries out benzene hydrogenation than being under 4 the condition, and the end conversion benzene content in its product is about 400ppm, and other side reaction total impurities is about 500ppm.
Embodiment 3
In the mixed aqueous solution that is dissolved with nickel nitrate and nitric acid rare earth and aluminum nitrate, add sodium carbonate liquor and carry out neutralization precipitation, washing is also filtered the precipitation that is generated.This precipitation is pressed into diameter to be 4mm, highly to be about the cylinder of 4mm, in about 300 ℃ of roastings.Through the contained nickel of the product of roasting and the ratio of rare earth oxide and aluminium oxide is 2: 0.5: 0.5 (mol ratio).
The nitrogen that will contain 10% hydrogen feeds 100ml embodiment 3 samples is housed, and reduces under 400 ℃ temperature.180 ℃ of temperature, pressure is 0.5Mpa, advances benzene liquid space speed (SV) and is 0.6h
-1And the hydrogen benzene mole carries out benzene hydrogenation than being under 4 the condition, and the end conversion benzene content in its product is about 220ppm, and other side reaction total impurities is about 300ppm.
Claims (6)
1, a kind of preparation method of benzene hydrogenating catalyst is characterized in that making the mixture of a kind of nickel oxide and rare earth oxide or the mixture of a kind of nickel oxide and rare earth oxide and aluminium oxide with coprecipitation method, makes benzene hydrogenating catalyst through hydrogen reducing.
2, a kind of Preparation of catalysts method as claimed in claim 1 is characterized in that being water soluble compound as nickel compound, the rare earth oxide compound in rare earth oxide source, the aluminum source compound in a kind of nickel source.
3, a kind of Preparation of catalysts method as claimed in claim 1 is characterized in that nickel-rare earth mol ratio is 1: 0.02～4.1.
4, a kind of Preparation of catalysts method as claimed in claim 1 is characterized in that nickel-rare earth mol ratio is 1: 0.05～1.
5, a kind of Preparation of catalysts method as claimed in claim 1 is characterized in that nickel-rare earth oxide-aluminum ratio mol ratio is 1: 0.02～6: 0.02～8.1.
6, a kind of Preparation of catalysts method as claimed in claim 1 is characterized in that nickel-rare earth oxide-aluminum ratio mol ratio 1: 0.05～2: 0.2～2.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200310106563 CN1268423C (en) | 2003-12-09 | 2003-12-09 | Preparation of dehydrogenation catalyst |
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| CN 200310106563 CN1268423C (en) | 2003-12-09 | 2003-12-09 | Preparation of dehydrogenation catalyst |
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| CN1546230A CN1546230A (en) | 2004-11-17 |
| CN1268423C true CN1268423C (en) | 2006-08-09 |
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| CN 200310106563 Expired - Fee Related CN1268423C (en) | 2003-12-09 | 2003-12-09 | Preparation of dehydrogenation catalyst |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9347857B2 (en) | 2011-03-24 | 2016-05-24 | Sakura Finetek U.S.A., Inc. | Microtome with surface orientation sensor to sense orientation of surface of sample |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9347857B2 (en) | 2011-03-24 | 2016-05-24 | Sakura Finetek U.S.A., Inc. | Microtome with surface orientation sensor to sense orientation of surface of sample |
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