CN102125878A - Modified Al2O3 carrier and preparation method thereof - Google Patents
Modified Al2O3 carrier and preparation method thereof Download PDFInfo
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- CN102125878A CN102125878A CN 201110004999 CN201110004999A CN102125878A CN 102125878 A CN102125878 A CN 102125878A CN 201110004999 CN201110004999 CN 201110004999 CN 201110004999 A CN201110004999 A CN 201110004999A CN 102125878 A CN102125878 A CN 102125878A
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Abstract
The invention relates to a modified Al2O3 carrier and a preparation method thereof. The invention first provides the modified Al2O3 carrier, Al2O3 is used as a matrix in the carrier, and the surface of the carrier is provided with a layer of spinel compound formed by modifying the Al2O3 with a modifying element M, wherein the modifying element M is one of La, Ce, Pr, Mg, Ca, Sr, Ba and Zn. The invention also provides the preparation method for the modified Al2O3 carrier. By selecting the proper modifying element for modifying the surface of the Al2O3 matrix, the modifying element and the Al2O3 form the spinel compound on the surface of the matrix, so the acidity of the carrier surface can be greatly reduced, the reaction between the active metal on the surface of the catalyst and the carrier is inhibited, the surface structure of the carrier is improved, and a catalyst obtained by using the surface modified carrier as a carrier can keep high activity and stability in long-time operation.
Description
Technical field
The present invention relates to a kind of Modification on Al
2O
3Carrier and preparation method thereof belongs to oil catalyst carrier for hydrgenating field.
Background technology
Carrier is the important component part of catalyst, and for a lot of industrial catalysts, after active component was determined, the kind of carrier and character tended to catalyst performance is produced a very large impact.US Patent No. 4839329 discloses with TiO
2Be the catalyst of carrier, German patent DE 2156544 discloses with SiO
2Be the catalyst of carrier, Chinese patent CN1176291A and CN1356377A disclose with CaCO respectively
3With magnesium aluminate spinel be the catalyst of carrier.
Activated alumina is one of most important catalyst carrier, is widely used in the PETROLEUM PROCESSING catalyst field.At present, selective hydrocatalyst has been carried out a large amount of research both at home and abroad, the catalyst used carrier of better performances, comparative maturity mostly is γ-Al
2O
3Prior art has also adopted the method for adding the support modification cocatalyst component in catalyst, improves the performance of catalyst.CN1218713A has introduced the ball-aluminium oxide that a kind of lithium content is 0.1-2wt%.This aluminium oxide is directly used lithium compound solution impregnation χ-Al
2O
3After dry in 600-970 ℃ of dry air roasting make.This aluminium otide containing lighium has characteristics such as macropore, low specific surface area, low acidity, is suitable as the carrier of selective hydrogenation catalyst.
CN1356377A discloses a kind of selective hydrocatalyst, and carrier is a magnesium aluminate spinel, and alkali metal or alkaline-earth metal add as the form of auxiliary agent with its mineral structure, and wherein the weight content of alkali metal or alkali earth metal is the 0.1-5% of catalytic amount.Active component loads on the carrier by the equivalent impregnation method is disposable.Active component is typically chosen in molybdenum or tungsten and cobalt or nickel, and molybdenum and cobalt are the most frequently used.
United States Patent (USP) 5525211 discloses a kind of catalyst, and its carrier is through K
2CO
3The magnesium aluminate spinel of modification, K
2CO
3Be to load on the carrier through infusion process, molybdenum, cobalt active component load on the carrier by the twice minute method of soaking respectively.The Preparation of catalysts method is comparatively complicated, and the loss easily in the catalyst use of the potash on the catalyst, thereby causes catalyst activity and stability decreases.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of novel Modification on Al
2O
3Carrier and preparation method thereof carries out modification by modifying element to carrier surface and obtains a kind of novel oil hydrogenation catalyst carrier, improves the surface texture of carrier, reduces its acidity.
For achieving the above object, the present invention at first provides a kind of Modification on Al
2O
3Carrier, it is with Al
2O
3Be matrix, and, the surface of this carrier have one deck by modifying element M to Al
2O
3(the Al of matrix surface
2O
3) carry out modification and the spinel compound that forms.
When carrying out modification and handle, the modifying element M that is adopted is preferably a kind of among La, Ce, Pr, Mg, Ca, Sr, Ba and the Zn etc.
Modifying element M is to the Al of matrix surface
2O
3Carry out modification, form one deck spinel compound at matrix surface, preferably, above-mentioned spinel compound has following structural formula: M
xAl
yO
z, and 0＜x＜2,0＜y＜3,2＜z＜5.
According to concrete technical scheme of the present invention, preferably, the content of modifying element M may be controlled to not pass through the Al of modification
2O
3The 0.1-10wt% of quality.When carrying out modification, a part of modifying element M and Al
2O
3Reaction participates in forming spinel compound, preferably, the ratio that the mass content of modifying element M in the spinel compound accounts for described modifying element gross mass content is u (namely entering the content ratio of the modifying element M of spinel compound by modification), and, 50%≤u＜100%.
Al of the present invention
2O
3Can be various types of Al
2O
3, be preferably α-Al
2O
3, β-Al
2O
3, γ-Al
2O
3, δ-Al
2O
3, η-Al
2O
3And θ-Al
2O
3Deng in a kind of; γ-Al more preferably
2O
3, δ-Al
2O
3, η-Al
2O
3And θ-Al
2O
3Deng in a kind of.And, in the above-mentioned carrier, as the Al of matrix
2O
3Can make certain shape by moulding, for example bar shaped, sphere, gear-like or granular are preferably sphere.
According to concrete technical scheme of the present invention, preferably, the specific area of above-mentioned carrier can be 100-350m
2/ g (150-250m more preferably
2/ g), pore volume is 0.5-0.6cm
3/ g, average pore size is greater than 10nm (10-30nm more preferably).
The present invention also provides above-mentioned Modification on Al
2O
3The preparation method of carrier, it may further comprise the steps:
According to Al
2O
3The water absorption rate data of carrier adopt equi-volume impregnating with the salt solution impregnation matrix certain hour that contains a kind of element among the modifying element M, then matrix are carried out drying and process, and at last high-temperature roasting in Muffle furnace obtains Modification on Al
2O
3Carrier.
Above-mentioned preparation method can also comprise Al
2O
3Carry out the step of moulding, namely before incipient impregnation with Al
2O
3Make needed matrix (carrier) shape.
Above-mentioned preparation method provided by the invention can comprise following concrete steps:
Preparation contains the salting liquid of modifying element M, to the matrix (Al of moulding
2O
3) carry out 2-5 hour incipient impregnation, wherein, the content of modifying element M is the 0.1-10wt% of substrate quality in the described salting liquid;
Impregnation product is carried out the processing that vacuumizes of 100-200 ℃, 2-4 hour, 800-1100 ℃ of calcination process of carrying out 3-8 hour, obtain Modification on Al then
2O
3Carrier.
At the initial stage of dipping, can stir matrix, so that modifying element M can load to matrix surface equably, preferably, the salting liquid that is adopted is to contain the acetate solution of modifying element M and/or nitrate solution etc.
The present invention also provides above-mentioned Modification on Al
2O
3The application of carrier in preparation oil hydrogenation catalyst.By in above-mentioned Modification on Al
2O
3The resulting oil hydrogenation catalyst of dipping active component has good activity, selective and stable on the carrier in the oil selective hydrogenation reaction.
Illustrate, adopt Modification on Al provided by the invention
2O
3When the carrier preparation contains the catalyst of nickel active component, can carry out according to the following step:
The maceration extract that is made into suitable concentration with the solution that contains active metal nickel carries out 2-5 hour dipping (incipient impregnation) by the carrier of equi-volume impregnating after to modification, nickel content is 5-20wt% (with the total restatement of carrier), soaked carrier carried out 2-5 hour common drying or vacuum drying in 100-200 ℃ of temperature range, in 250-350 ℃ of temperature range roasting 1-3 hour at last, make catalyst.Wherein, the reactive metal nickel salt of employing can be acetate, nitrate, chlorate etc.
By selecting suitable modifying element to Al
2O
3Surface modification is carried out on the surface of matrix, makes modifying element and Al
2O
3Form one deck spinel compound at matrix surface, can greatly reduce carrier surface acidity, react between the reactive metal of inhibition catalyst surface and the carrier, improve the surface texture of carrier, it is higher active and stable that the catalyst that the carrier with this process surface modification is obtained as carrier all can keep in long time running.Prepare hydrogenation catalyst with carrier provided by the present invention, can obviously improve the activity and selectivity of hydrogenation catalyst in the selective acetylene hydrocarbon hydrogenation reaction.
Description of drawings
Fig. 1 is the XRD comparison diagram of catalyst B-5 Yu the unmodified catalyst B-1 of zinc modification.
The specific embodiment
Understand for technical characterictic of the present invention, purpose and beneficial effect being had more clearly, technical scheme of the present invention is carried out following detailed description, but but can not be interpreted as qualification practical range of the present invention referring now to Figure of description.
Modification on Al among Comparative Examples and the embodiment
2O
3The used matrix of carrier is γ-Al
2O
3, diameter is Φ 1-2mm, specific area is 150-300m
2/ g bead.In the process of preparation carrier, baking temperature is controlled to be 100-150 ℃, be controlled to be 2-3 hour drying time, the carrier sintering temperature is controlled to be 900-1000 ℃, the carrier roasting time is controlled to be 5-7 hour, the concentration of needed various solution is prepared according to the water absorption rate data of carrier and according to equi-volume impregnating.
Comparative Examples 1
Diameter is spherical gamma-Al of Φ 1.6-2mm
2O
3, be designated as carrier A-1.
With carrier A-1 in Muffle furnace in 1000 ℃ of following roastings 3 hours, obtain carrier after the cooling, be designated as carrier A-2.The bulk specific weight of measuring carrier A-2 is 0.61g/mL, and pore volume is 0.53cm
3/ g, average pore size is 17.7nm, specific area is 132m
2/ g.
Comparative Examples 2
Take by weighing carrier A prepared in the 10g Comparative Examples 1-2, with 7.42g nitric acid nickel (NO
3)
26H
2The solution that O and 6-7g distilled water are made into carries out 3 hours incipient impregnations, 110 ℃ of lower freeze-day with constant temperature are after 2 hours in air dry oven, again dry 2 hours of 150 ℃ of lower constant-temperature vacuums, at last in Muffle furnace, under air atmosphere, carry out 300 ℃ of roastings of 2 hours, can prepare the catalyst B that the reactive metal nickel loading is 15wt%-1.
Embodiment 1
Take by weighing the carrier A-1 in the 10g Comparative Examples 1, with 1.25g lanthanum nitrate La (NO
3)
36H
2The solution that O and 6-7g distilled water are made into carries out 3 hours incipient impregnations, in air dry oven in 110 ℃ of lower freeze-day with constant temperature after 2 hours, again dry 2 hours of 150 ℃ of lower constant-temperature vacuums, at last carry out 1000 ℃ of roastings of 2 hours in Muffle furnace under air atmosphere, preparing lanthanum content is the carrier La of 4wt%
2O
3-Al
2O
3, its La that enters spinel compound accounts for 85wt%, is designated as carrier A-3.The structural formula of the spinel compound that carrier surface forms is LaAlO
3
Embodiment 2
Take by weighing the carrier A-3 of preparation among the 10g embodiment 1, with 7.42g nitric acid nickel (NO
3)
26H
2The solution that O and 3-4g distilled water are made into carries out 3 hours incipient impregnations, in air dry oven in 110 ℃ of lower freeze-day with constant temperature after 2 hours, again dry 2 hours of 150 ℃ of lower constant-temperature vacuums, at last in Muffle furnace, under air atmosphere, carry out 300 ℃ of roastings of 2 hours, can prepare the lanthanum modification, nickel loading is the catalyst B-2 of 15wt%.
Embodiment 3
Take by weighing the carrier A-1 in the 10g Comparative Examples 1, with 0.72g magnesium nitrate Mg (NO
3)
26H
2The solution that O and 6-7g distilled water are made into carries out 3 hours incipient impregnations, carries out drying according to the drying condition among the embodiment 1, carries out 900 ℃ of roastings of 4 hours at last in Muffle furnace under air atmosphere, and preparing content of magnesium is the carrier MgO-Al of 0.7wt%
2O
3, its Mg that enters spinel compound accounts for 92wt%, is designated as carrier A-4.The structural formula of the spinel compound that carrier surface forms is MgAl
2O
4
Embodiment 4
Take by weighing the carrier A-4 among the 10g embodiment 3, can prepare catalyst B-3 magnesium-modified, that nickel loading is 15wt% according to the method among the embodiment 2.
Embodiment 5
Take by weighing the carrier A-1 in the 10g Comparative Examples 1, with 0.6g calcium nitrate Ca (NO
3)
24H
2The solution that O and 6-7g distilled water are made into carries out 3 hours incipient impregnations, carries out drying according to the drying condition among the embodiment 1, carries out 1000 ℃ of roastings of 4 hours at last in Muffle furnace under air atmosphere, prepares the support C aO-Al that calcium content is 1wt%
2O
3, its Ca that enters spinel compound accounts for 87wt%, is designated as carrier A-5.The structural formula of the spinel compound that carrier surface forms is CaAl
2O
4
Embodiment 6
Take by weighing the carrier A-5 among the 10g embodiment 5, according to the method among the embodiment 2 can prepare the calcium modification, nickel loading is the catalyst B-4 of 15wt%.
Embodiment 7
Take by weighing the carrier A-1 in the 10g Comparative Examples 1, with 0.9g calcium nitrate Zn (NO
3)
26H
2The solution that O and 6-7g distilled water are made into carried out incipient impregnation 3 hours, carried out drying according to the drying condition among the embodiment 1, carried out 900 ℃ of roastings of 4 hours at last in Muffle furnace under air atmosphere, and preparing zinc content is the carrier ZnO-Al of 2wt%
2O
3, its Zn that enters spinel compound accounts for 87wt%, is designated as carrier A-6.The structural formula of the spinel compound that carrier surface forms is ZnAl
2O
4
Embodiment 8
Take by weighing the carrier A-6 among the 10g embodiment 7, according to the method among the embodiment 2 can prepare zinc modification, nickel loading is the catalyst B-5 of 15wt%.
Embodiment 9
Take by weighing the carrier A-1 in the 10g Comparative Examples 1, with 2.5g lanthanum nitrate La (NO
3)
36H
2The solution that O and 6-7g distilled water are made into carries out 3 hours incipient impregnations, in air dry oven in 110 ℃ of lower freeze-day with constant temperature after 2 hours, again dry 2 hours of 150 ℃ of lower constant-temperature vacuums, at last carry out 1000 ℃ of roastings of 2 hours in Muffle furnace under air atmosphere, preparing lanthanum content is the carrier La of 8wt%
2O
3-Al
2O
3, its La that enters spinel compound accounts for 80wt%, is designated as carrier A-7.The structural formula of the spinel compound that carrier surface forms is LaAlO
3
Embodiment 10
Take by weighing the carrier A-7 among the 10g embodiment 9, can prepare lanthanum content according to the method among the embodiment 2 is that 8wt%, nickel loading are the catalyst B-6 of 15wt%.
Embodiment 11
Catalyst B-1, B-5, B-6 are reduced with hydrogen at 400 ℃, carry out XPS analysis then.Analysis result sees Table 1.As can be seen from Table 1, the content of the active component nickel on the catalyst surface behind the support modification increases.In addition, the nickel content of the catalyst coating of lanthanum modification is higher than the catalyst of zinc modification.
Table 1 support modification is to the impact of each constituent content of catalyst coating
| Catalyst | The top layer component | Content, Atom.% |
| B-1 | Ni 2p3 | 2.91 |
| B-5 | Ni 2p3 | 4.05 |
| B-6 | Ni 2p3 | 4.33 |
Embodiment 12
Adopt the upper reaches feeding manner to estimate the diolefin hydrogenation activity and selectivity of above-mentioned non-precious metal catalyst in the small pressurized fixed-bed reactor, concrete evaluation method is as follows:
A certain amount of catalyst is placed the middle part of reactor flat-temperature zone, fill with quartz sand up and down, be warming up to 400 ℃ under the hydro condition, constant temperature reduction 4 hours, reduction pressure is normal pressure, the reducing gases air speed is 420h
-1, then will install cool to room temperature, with vulcanizing agent passivation preliminary treatment 1 hour;
It is temperature required to be warming up to reaction afterwards, feeds catalytic cracking full distillate gasoline, and the reaction time is 10 hours, faces the hydrogen hydrogenation conditions: 150 ℃ of reaction temperatures, and reactive hydrogen dividing potential drop 1.6MPa, the long-pending air speed of liquid is 24h under the STP
-1(the per hour ratio of liquid feed volume and catalyst volume), hydrogen to oil volume ratio 30 under the STP.The content of main component is in the catalytically cracked gasoline material liquid: total carbon five 21.46wt%, isoprene 0.065wt%, total sulfur 250ppm, total nitrogen 38.9ppm, mercaptan 19ppm.Take in test accurately to analyze being converted of isoprene component and analyze the conversion (this analytical method substitutes the analysis of full constituent, and its accuracy reaches more than 94% by checking) of full constituent alkadienes with gas-chromatography.Reaction evaluating result such as table 2.
The evaluation result of table 2 non-noble metal Ni catalyst
Identical mol ratio, different element have been listed in the table 2 to γ-Al
2O
3The Raney nickel evaluation result of support modification.Can find out that several elements that the present invention adopts are to γ-Al
2O
3The Raney nickel that carrier carries out making after the modification is with respect to adopting unmodified Al
2O
3Single Raney nickel of carrier, the activity of catalyst has raising in various degree.Wherein La and Zn modification are more obvious to the raising of catalyst activity, and the catalyst after the modification has all kept selectivity preferably.
Embodiment 13
Catalytic cracking full distillate gasoline with above-mentioned (embodiment 12) is raw material, in the small pressurized fixed-bed reactor catalyst B among the embodiment 10-6 is estimated, and evaluation method and reaction condition are with embodiment 12.Evaluation result: diene conversion rate is 83.9%, and the pentane increment rate is 5.0%.As seen, the activity of catalyst B-6 will be higher than 5 kinds of catalyst estimating among the embodiment 12.
Embodiment 14
Catalyst B-5 can characterize with X-ray diffraction (XRD) with unmodified catalyst B-1, the results are shown in Figure 1 (a, catalyst B-1; B, catalyst B-5).As can be seen from Figure 1, catalyst B-5 is a little less than the NiO crystalline phase diffraction peak intensity of 2 θ=43.27 ° is obviously than single Raney nickel B-1, that is to say the good dispersion of NiO on catalyst B-5 in catalyst B-1, illustrate that the gahnite structure of carrier surface formation helps the dispersion of active metal nickel.The reactive metal decentralization of catalyst surface is good more, and the activity that exposes of catalyst surface is counted just manyly so, helps the carrying out of hydrogenation reaction.
Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above only is specific embodiments of the invention; and be not intended to limit the scope of the invention; within the spirit and principles in the present invention all, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. Modification on Al
2O
3Carrier, it is with Al
2O
3Be matrix, and, the surface of this carrier have one deck by modifying element M to Al
2O
3The spinel compound that carries out modification and form, wherein, described modifying element M is a kind of among La, Ce, Pr, Mg, Ca, Sr, Ba and the Zn.
2. carrier according to claim 1, wherein, described spinel compound has following structural formula: M
xAl
yO
z, and 0＜x＜2,0＜y＜3,2＜z＜5.
3. carrier according to claim 1, wherein, the content of described modifying element M is not for passing through the Al of modification
2O
3The 0.1-10wt% of quality.
4. according to claim 1 or 3 described carriers, wherein, the ratio that the mass content of the modifying element M in the described spinel compound accounts for described modifying element gross mass content is u, and, 50%≤u＜100%.
5. carrier according to claim 1, wherein, described Al
2O
3Be α-Al
2O
3, β-Al
2O
3, γ-Al
2O
3, δ-Al
2O
3, η-Al
2O
3And θ-Al
2O
3In a kind of.
6. carrier according to claim 5, wherein, described Al
2O
3Be γ-Al
2O
3, δ-Al
2O
3, η-Al
2O
3And θ-Al
2O
3In a kind of.
7. carrier according to claim 1, wherein, the specific area of this carrier is 100-350m
2/ g, average pore size is greater than 10nm.
8. each described Modification on Al of claim 1-7
2O
3The preparation method of carrier, it may further comprise the steps:
Preparation contains the salting liquid of modifying element M, and matrix is carried out 2-5 hour incipient impregnation, and wherein, the content of modifying element M is the 0.1-10wt% of substrate quality in the described salting liquid;
Impregnation product is carried out the processing that vacuumizes of 100-200 ℃, 2-4 hour, 800-1100 ℃ of calcination process of carrying out 3-8 hour, obtain described Modification on Al then
2O
3Carrier.
9. preparation method according to claim 8, wherein, described salting liquid is acetate solution and/or the nitrate solution that contains modifying element M.
10. each described Modification on Al of claim 1-7
2O
3The application of carrier in preparation oil hydrogenation catalyst.
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|---|---|---|---|
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| CN102614935A (en) * | 2012-03-05 | 2012-08-01 | 阳光凯迪新能源集团有限公司 | Surface modification method of aluminum oxide carrier |
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| CN101850250A (en) * | 2009-03-31 | 2010-10-06 | 中国石油化工股份有限公司 | selective hydrogenation catalyst for removing alkadiene in mixed C4 and preparation method thereof |
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2011
- 2011-01-11 CN CN2011100049993A patent/CN102125878B/en not_active Expired - Fee Related
Patent Citations (1)
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| CN101850250A (en) * | 2009-03-31 | 2010-10-06 | 中国石油化工股份有限公司 | selective hydrogenation catalyst for removing alkadiene in mixed C4 and preparation method thereof |
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| CN102614935B (en) * | 2012-03-05 | 2013-11-06 | 阳光凯迪新能源集团有限公司 | Surface modification method of aluminum oxide carrier |
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| CN106881127A (en) * | 2017-03-17 | 2017-06-23 | 钦州学院 | A kind of catalyst and preparation method for gasoline desulfurization modification |
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| CN106927996A (en) * | 2017-03-17 | 2017-07-07 | 钦州学院 | A kind of method of producing cyclohexane by adding hydrogen in benzene |
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| CN108339541A (en) * | 2018-02-07 | 2018-07-31 | 武汉凯迪工程技术研究总院有限公司 | The preparation method for the alumina support that spinelle is modified |
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| CN102125878B (en) | 2012-11-14 |
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