CN104056650B - A kind of Supported Nickel Catalyst and its preparation method and application - Google Patents
A kind of Supported Nickel Catalyst and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to catalyst preparation technical field, specifically a kind of Supported Nickel Catalyst and its preparation method and application.With Al-SBA-15 for carrier and active specy presoma Nickelous nitrate hexahydrate, reduce and obtain Supported Nickel Catalyst.Specifically with Al-SBA-15 for carrier, Nickelous nitrate hexahydrate is active specy presoma, is through impregnation with, dries, reduces and obtain Supported Nickel Catalyst.It is used in ethylene selectivity polyreaction by catalyst of the present invention conversion of ethylene higher than 99%；In product liquid, C9+ constituent content is higher than 35%.
Description
Technical field
The invention belongs to catalyst preparation technical field, specifically a kind of Supported Nickel Catalyst and its preparation method and application.
Background technology
Low-carbon alkene polymerization is the important course of reaction producing and having longer carbon chain alkene, long-chain products after polymerization can be directly used as transport fuel or for transporting the additive of fuel, having important advantages in that of low-carbon alkene polyreaction can directly be docked thus realizing large-scale production with low-carbon alkene production process.Currently, with respect to the polyreaction research of low-carbon alkene mainly for C3 and C4 component alkene, using ethylene as the polyreaction research of raw material also in the laboratory research stage.
Ethylene is the most large basic chemical raw materials, and its annual production can be used to weigh a national Industry Development Level, 2012, and the ethylene annual production of China breaks through 15,000,000 tons, occupies the whole world second.For expanding the downstream product of ethylene, exploitation is the focus studied at present with the transport fuel production new technology that ethylene is raw material.It addition, use the transport fuel generated by low-carbon alkene polymerization can also effectively reduce the destruction to environment.Therefore, exploitation has important practical significance suitable in the novel catalyst system of ethylene oligomerization reaction.
At present, the catalyst system of ethylene oligomerization reaction mainly includes the non-molecular screen base with certain acidity and molecular screen base two class of transition metal load.For the former, Ni shows good catalytic performance in the ethylene oligomerization reaction at the catalyst system of gamma-alumina, silicon dioxide and amorphous silica-alumina, especially the pore passage structure of carrier makes it react the life-span to have reached more than 500 hours [J.Hevelingetal.Appl.Catal.A, 173,1998,1.;T.X.Cai, Catal.Today, 51,1999,153.].Molecular sieve based catalyst system can be divided into pore type and mesoporous type according to molecular sieve pore passage size, the catalyst that Ni obtains on X, Y, MCM-22 and MCM-36 type zeolite molecular sieve is adopted to show the catalysis activity [M.Lallemandetal.Appl.Catal.A of excellence in the ethylene oligomerization reaction, 301,2006,196.;M.Lallemandetal.Appl.Catal.A, 338,2008,37.], but, aperture that zeolite molecular sieve is less (< 2nm) cause rapid catalyst deactivation, and also the framing structure of its crystal is unfavorable for regulating the acid distribution of catalyst.Get the attention in consideration of it, an other class has the Ni of large hole road structure at the catalyst system of mesostructured material.[V.Huleaetal.J.Catal.225,2004,213.] MCM-41 molecular sieve is reported in 1992 by Mobil company at first, has orderly Jie's view hole road arrangement, space group: p6mm.This bigger pore passage structure and surface area make it be provided with more excellent product diffusion in the ethylene oligomerization reaction, thus the strong overall catalytic performance that improve catalyst.But, the pore wall thickness of MCM-41 molecular sieve only has about 1nm, is not enough to the reaction condition that reply is harsh, therefore, it is necessary to exploitation has the new catalyst of more high stability.
1998, the synthesis in strong acid system of Zhao et al. [Zhao, D.Y.etal.Science, 1998,279,548.] reported first had the SBA-15 mesoporous material of two-dimentional hexagonal hole road structure.SBA-15 has the specific surface area bigger than MCM-41 and thicker hole wall structure, and therefore it has more superior structural stability and active specy mixes motility.The focus of field of catalyst preparation it was always up in recent years around the applied research of SBA-15 type mesopore molecular sieve.But, adopt framework aluminum content in the Al-SBA-15 of known method synthesis relatively low and distribution be difficult to control, therefore yet there are no the research report being applied to ethylene oligomerization reaction so far.2011, Lin [Lin, S.etal.Micro.Meso.Mater.2011,142,526.] et al. in the system without outer acid adding, promote the polycondensation process of inorganic species merely with the aluminum source spontaneous acidity of hydrolysis, one-step synthesis goes out to be situated between the orderly Al-SBA-15 of view hole road structure height.But, the heat of above-mentioned material and hydrothermal stability are still relatively low, and the method for there is no meets some and requires harsh chemical reaction process.Then obtain can be suitably used for the catalyst that ethylene oligomerization reaction requires currently without relevant record.
Summary of the invention
It is an object of the invention to provide a kind of Supported Nickel Catalyst and its preparation method and application.
For achieving the above object, the technical solution used in the present invention is:
A kind of Supported Nickel Catalyst, with Al-SBA-15 for carrier, carrier reduces with active specy presoma Nickelous nitrate hexahydrate, obtains Supported Nickel Catalyst.
Described with Al-SBA-15 for carrier, Nickelous nitrate hexahydrate is active specy presoma, is through impregnation with, dries, reduces and obtain Supported Nickel Catalyst.
The preparation method of Supported Nickel Catalyst, with Al-SBA-15 for carrier, Nickelous nitrate hexahydrate is active specy presoma, is through impregnation with, dries, reduces and obtain Supported Nickel Catalyst.
Nickelous nitrate hexahydrate is mixed with carrier Al-SBA-15, dries in 60-100 ° of C；It is warming up to 100-120 ° of C with the heating rate of 2-5 ° of C/min by drying products therefrom and keeps 1-3 hour, being then warming up to 400-500 ° of C with the heating rate of 2-5 ° of C/min and keep again 1-3 hour；Then process 1-4 hour 400-500 ° of C in-situ reducing with hydrogen, be then cooled to 20-30 ° of C, obtain Supported Nickel Catalyst.
Described Nickelous nitrate hexahydrate concentration of aqueous solution is 0.5-3mol/L.
Described carrier is Al-SBA-15, prepares and is:
1) under room temperature condition, by triblock copolymer EO20PO70EO20It is dissolved in deionized water；Add aluminium salt stirring and dissolving；Wherein, deionized water and triblock copolymer EO20PO70EO20Mol ratio be 10000-17000:1；
2) in step 1), add tetraethyl orthosilicate again, stir 10-15 hour under room temperature；Wherein, triblock copolymer EO20PO70EO20It is 0.0075-0.015:1 with the mol ratio of tetraethyl orthosilicate；
3) by step 2) mixing after mixture be placed in 35-40 ° of C constant temperature stir 18-24 hour；
4) by step 3) mixture static treatment under 80-110 ° of C hydrothermal condition, then filter and with deionized water wash, then dry, stand-by；
5) above-mentioned products therefrom it is warming up to 100-120 ° of C with the heating rate of 3-5 ° of C/min and keeps 1-2 hour, then proceeding to be warming up to 500-550 ° of C with the heating rate of 3-5 ° of C/min again and keep 4-8 hour, obtain Al-SBA-15 white powder.
Described aluminium salt is ANN aluminium nitrate nonahydrate (Al (NO3)3·9H2O), Patent alum (Al2(SO4)3·18H2Or Aluminium chloride hexahydrate (AlCl O)3·6H2O)。
The application of Supported Nickel Catalyst, described catalyst can as the application of catalyst in ethylene oligomerization reaction.
Described catalyst can be used for ethylene selectivity to be polymerized in more than C9 low-carbon alkene processed reaction.
Advantage for present invention: the present invention utilizes the structural stability substantially increasing catalyst itself in mesoporous material duct enclosed inside plug-like structure, enables the reaction under high pressure condition of significantly more efficient adaptation ethylene oligomerization；Second, the introducing of plug-like structure makes catalyst duct internal acid active sites more be enriched with, and is conducive to product carbochain to increase, it is thus achieved that higher C9+ constituent content；3rd, all right limited reactions intermediate product of the existence of plug-like structure, in the diffusion within duct, improves the probability of secondary response, is beneficial to acquisition C9+ component products.Supported Nickel Catalyst of the present invention has mesoscopic size pore passage structure.It is used in ethylene selectivity polyreaction by catalyst of the present invention conversion of ethylene higher than 99%；In product liquid, C9+ constituent content is higher than 35%, and its catalytic performance is higher than reported Ni/MCM-41 catalyst.
Accompanying drawing explanation
The little angle XRD spectra of Fig. 1 Ni/Al-SBA-15 synthesized by the embodiment of the present invention 1 offer and N2(wherein Figure 1A is little angle XRD result to adsorption isotherm line chart；Figure 1B is N2Adsorption-desorption result).
The little angle XRD spectra of Fig. 2 Ni/Al-SBA-15 synthesized by the embodiment of the present invention 2 offer and N2(wherein Fig. 2 A is little angle XRD result to adsorption isotherm；Fig. 2 B is N2Adsorption-desorption result).
The little angle XRD spectra of Fig. 3 Ni/Al-SBA-15 synthesized by the embodiment of the present invention 3 offer and N2Adsorption isotherm.(wherein Fig. 3 A is little angle XRD result；Fig. 3 B is N2Adsorption-desorption result).
The pore size distribution curve of the gained Ni/Al-SBA-15 sample that Fig. 4 provides for the embodiment of the present invention.Wherein curve a is derived from embodiment 1 gained sample；Wherein curve b is derived from embodiment 2 gained sample；Wherein curve c is derived from embodiment 3 gained sample.
The TEM photo of the gained Ni/Al-SBA-15 sample that Fig. 5 provides for the embodiment of the present invention.Wherein photo a is derived from embodiment 1 gained sample；Photo b is derived from embodiment 2 gained sample；Photo c is derived from embodiment 3 gained sample.
Fig. 6 is with the Al-SBA-15 of known method synthesis for carrier, the chromatogram of catalyst gained liquid product in the ethylene oligomerization reaction of preparation after nickel-loaded.
The typical color spectrogram of the Ni/Al-SBA-15 catalyst gained liquid product in the ethylene oligomerization reaction of the present invention synthesis that Fig. 7 provides for the embodiment of the present invention.
Detailed description of the invention
For further illustrating the solution of the present invention, elaborate below in conjunction with drawings and Examples.
The present invention is with Al-SBA-15 for carrier, and Nickelous nitrate hexahydrate is active specy presoma, be through impregnation with, dry, reduce after prepare be applicable to ethylene oligomerization reaction catalyst.
The preparation of catalyst of the present invention, comprises the following steps:
1) at ambient temperature, in deionized water, triblock copolymer EO is added20PO70EO20(P123) P123 is made to be completely dissolved under strong agitation；Wherein, deionized water and triblock copolymer EO20PO70EO20Molar ratio range be 10000-17000:1；
2) in above-mentioned stirring and dissolving gained settled solution, add aluminium salt, be again stirring for dissolving；
3) in the settled solution of above-mentioned addition aluminium salt, add tetraethyl orthosilicate, stir 10-15 hour under room temperature, triblock copolymer EO20PO70EO20It is 0.0075-0.015:1 with the molar ratio range of tetraethyl orthosilicate；
4) gained mixture is placed in 30-40 ° of C water bath with thermostatic control, stirs 18-24 hour；
5) gained mixture is proceeded in the rustless steel synthesis reactor of inner liner polytetrafluoroethylene set again, under 80-110 ° of C hydrothermal condition static treatment 2-3 days, through filtering, dry 10 hours in 80-100 ° of C after deionized water wash；
6) being warming up to 100-120 ° of C with the heating rate of 3-5 ° of C/min in Muffle furnace, keep 1-2 hour, rear continuation is warming up to 500-550 ° of C with the heating rate of 3-5 ° of C/min, keeps 5-7 hour, obtains Al-SBA-15 white powder.
7) certain density Nickelous nitrate hexahydrate is mixed with step 6 gained white powder, dry in 60-100 ° of C；
8) dry afterproduct be warming up to 100-120 ° of C with the heating rate of 2-5 ° of C/min and keep 1-3 hour, be then warming up to 400-500 ° of C with the heating rate of 2-5 ° of C/min and keep 1-3 hour.
9) step 8) products therefrom hydrogen is processed 1-4 hour under 400-500 ° of C, be then cooled to 20-30 ° of C, obtain catalyst.
Gained Ni/Al-SBA-15 catalyst X-ray diffractometer (XRD), N is prepared by above-mentioned2The technology such as adsorption-desorption, transmission electron microscope (TEM) characterize.It is shown that adopt the inventive method to prepare the pore canal system that sample has the two-dimentional Hexagonal array of high-sequential, space group: P6mm.Difference according to be suitable for aluminum source species, Al-SBA-15 structural property is essentially identical, and after supported active species nickel, Jie's view hole road structural property is approximate in order for it.All there is desorption platform in 0.5-0.6 is than pressure scope in all catalyst, and display Ni species enter inside duct.
Embodiment 1
Prepared by Al-SBA-15 carrier: at room temperature, adds triblock copolymer EO in 80 ml deionized water20PO70EO20(P123 poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer) 1.5 grams, strong agitation is to triblock copolymer EO20PO70EO20It is completely dissolved；Add 0.35 gram of ANN aluminium nitrate nonahydrate stirring to dissolving；In above-mentioned solution, add 7.4 milliliters of tetraethyl orthosilicates and stir；Said mixture is kept 15 hours when 40 ° of C；After proceed in the rustless steel hydrothermal reaction kettle of inner liner polytetrafluoroethylene set, react 2 days under 90 ° of C hydrothermal conditions, through filtering, drying 10 hours at 80 ° of C after deionized water wash；Then in Muffle furnace, it is warming up to 120 ° of C with the heating rate of 3 ° of C/min, keeps 1 hour, then continue to be warming up to 550 ° of C with the heating rate of 3 ° of C/min, keep 5 hours, obtain Al-SBA-15 white powder.
2 grams of above-mentioned gained Al-SBA-15 be impregnated in the Nickelous nitrate hexahydrate aqueous solution that 2.5 ml concns are 0.5 mol/L by the preparation of catalyst at ambient temperature, then dry in 60 ° of C；After drying sample is ground, in air atmosphere, it is warming up to 120 ° of C with the heating rate of 2 ° of C/min and keeps 1 hour, be then warming up to 400 ° of C with the heating rate of 2 ° of C/min and keep 2 hours；Then replacing air atmosphere with hydrogen again, (400 ° of C) continues roasting sample 2 hours with the hydrogen flowing quantity of 30mL/min at the same temperature, is naturally cooling to 20-30 ° of C, namely obtains catalyst (referring to Fig. 1) after roasting.
The little angle XRD spectra result of Ni/Al-SBA-15 shown in Figure 1A, Figure 1B is N2Adsorption-desorption result.According to XRD result it can be seen that catalyst has two-dimentional six side's phase structures and one-dimensional straight hole road, illustrate that nickel is effectively carried on the surface of Al-SBA-15 and preparation process and the structure of carrier does not produce impact.It addition, according to N2In adsorption experiment there is platform it can be seen that there is a certain amount of plug-like structure inside the one-dimensional straight hole road of catalyst in desorption curve.
Embodiment 2:
Difference from Example 1 is in that, substitutes ANN aluminium nitrate nonahydrate, other permanence condition with 0.62 gram of Patent alum in the preparation of Al-SBA-15 carrier；Hydrogen reducing temperature is set as 450 ° of C, other condition constant (referring to Fig. 2) by the preparation of catalyst.
Embodiment 3:
Difference from Example 1 is in that, substitutes ANN aluminium nitrate nonahydrate with 0.23 gram of Aluminium chloride hexahydrate in the preparation of Al-SBA-15 carrier, other permanence condition；In the preparation of catalyst, after nickel species dipping, the drying temperature of sample is set as 100 ° of C, other condition constant (referring to Fig. 3).
As shown in Figure 4, wherein curve a is derived from embodiment 1 gained sample to the pore size distribution curve of the Ni/Al-SBA-15 sample prepared by above-described embodiment 1,2 and 3, and curve b is derived from embodiment 2 gained sample, and curve c is derived from embodiment 3 gained sample.As shown in Figure 4, in all embodiments, gained catalyst is respectively provided with the duct being sized to 7.4 nanometers, and pore-size distribution is narrow.
The TEM photo of the Ni/Al-SBA-15 sample prepared by above-described embodiment 1,2 and 3, as it is shown in figure 5, wherein photo a is derived from embodiment 1 gained sample, photo b is derived from embodiment 2 gained sample, and photo c is derived from embodiment 3 gained sample.In Figure 5, relatively dark part is the wall portion that density is bigger, and relatively bright part is channel section.The standby catalyst of the ownership is respectively provided with the mesopore orbit of one dimensional arrangement, and hole wall exists uneven part, corresponding plug-like structure.
The specific surface area of above-described embodiment 1,2 and 3 gained Al-SBA-15 molecular sieve, average pore size and pore volume (referring to table 1) simultaneously.
The structural parameters of table 1:Al-SBA-15 molecular sieve
Application examples
By the Ni/Al-SBA-15 catalyst prepared by above-described embodiment 1,2 and 3, and with known method [A.Vinuetal, J.Phys.Chem.B2004,108,11496;Lin, S.etal.Micro.Meso.Mater.2011,142,526] Al-SBA-15 synthesized is carrier, and the catalyst prepared by prior art after nickel-loaded, as catalyst in ethylene oligomerization reaction；Experimentation is as follows:
1) catalyst of molding is loaded in reactor, in helium atmosphere, carry out activation processing 1-2 hour when 150 ° of C；
2) with helium, reaction system being carried out supercharging, make pressure reach reaction requirement, pressure is: 3.0-3.5MPa, and Stress control uses counterbalance valve；
3) under reaction pressure, with mass-flow gas meter, reactant ethylene is squeezed into reactor to react；
4), after the reaction separated device of liquid product, analyze with chromatography of gases；
5) reaction gas-phase product gas chromatogram carries out on-line analysis；
6) conversion ratio and the C9+ component content (referring to Fig. 6 and Fig. 7) in liquid product of ethylene is calculated according to chromatography result.
Table 2, Ni/Al-SBA-15 reactivity worth in the ethylene oligomerization reaction.
Conversion of ethylene=(in 1-gas-phase product total sample size of ethylene volume/ethylene) * 100%
C9+ component content=(each component peaks area sum of the liquid product after C9+ component peaks area/normalization after normalization) * 100% in product liquid
It is C9+ component that the known wherein retention time of Fig. 6 is longer than the spectral peak of 12 minutes.Calculate after normalized and obtain C9+ product content in liquid product lower than 29%.In Fig. 7, C9+ product content in liquid product is higher than 35%.
Claims (6)
1. a Supported Nickel Catalyst, it is characterised in that: with Al-SBA-15 for carrier, carrier reduces with active specy presoma Nickelous nitrate hexahydrate, obtains Supported Nickel Catalyst；
With Al-SBA-15 for carrier, Nickelous nitrate hexahydrate is active specy presoma, is through impregnation with, dries, reduces and obtain Supported Nickel Catalyst；
Nickelous nitrate hexahydrate is mixed with carrier Al-SBA-15, in 60-100 DEG C of drying；It is warming up to 100-120 DEG C with the heating rate of 2-5 DEG C/min by drying products therefrom and keeps 1-3 hour, being then warming up to 400-500 DEG C with the heating rate of 2-5 DEG C/min and keep again 1-3 hour；Then process 1-4 hour 400-500 DEG C of in-situ reducing with hydrogen, be then cooled to 20-30 DEG C, obtain Supported Nickel Catalyst；
Described carrier is Al-SBA-15, prepares and is:
1) under room temperature condition, by triblock copolymer EO20PO70EO20It is dissolved in deionized water；Add aluminium salt stirring and dissolving；Wherein, deionized water and triblock copolymer EO20PO70EO20Mol ratio be 10000-17000:1；
2) again to step 1) middle addition tetraethyl orthosilicate, stirs 10-15 hour under room temperature；Wherein, triblock copolymer EO20PO70EO20It is 0.0075-0.015:1 with the mol ratio of tetraethyl orthosilicate；
3) by step 2) mixing after mixture be placed in 35-40 DEG C of constant temperature stir 18-24 hour；
4) by step 3) mixture static treatment under 80-110 DEG C of hydrothermal condition, then filter and with deionized water wash, then dry, stand-by；
5) above-mentioned products therefrom it is warming up to 100-120 DEG C with the heating rate of 3-5 DEG C/min and keeps 1-2 hour, then proceeding to be warming up to 500-550 DEG C with the heating rate of 3-5 DEG C/min again and keep 4-8 hour, obtain Al-SBA-15 white powder.
2. the preparation method of the Supported Nickel Catalyst described in a claim 1, it is characterised in that: with Al-SBA-15 for carrier, Nickelous nitrate hexahydrate is active specy presoma, is through impregnation with, dries, reduces and obtain Supported Nickel Catalyst；
Nickelous nitrate hexahydrate is mixed with carrier Al-SBA-15, in 60-100 DEG C of drying；It is warming up to 100-120 DEG C with the heating rate of 2-5 DEG C/min by drying products therefrom and keeps 1-3 hour, being then warming up to 400-500 DEG C with the heating rate of 2-5 DEG C/min and keep again 1-3 hour；Then process 1-4 hour 400-500 DEG C of in-situ reducing with hydrogen, be then cooled to 20-30 DEG C, obtain Supported Nickel Catalyst；
Described carrier is Al-SBA-15, prepares and is:
1) under room temperature condition, by triblock copolymer EO20PO70EO20It is dissolved in deionized water；Add aluminium salt stirring and dissolving；Wherein, deionized water and triblock copolymer EO20PO70EO20Mol ratio be 10000-17000:1；
2) again to step 1) middle addition tetraethyl orthosilicate, stirs 10-15 hour under room temperature；Wherein, triblock copolymer EO20PO70EO20It is 0.0075-0.015:1 with the mol ratio of tetraethyl orthosilicate；
3) by step 2) mixing after mixture be placed in 35-40 DEG C of constant temperature stir 18-24 hour；
4) by step 3) mixture static treatment under 80-110 DEG C of hydrothermal condition, then filter and with deionized water wash, then dry, stand-by；
5) above-mentioned products therefrom it is warming up to 100-120 DEG C with the heating rate of 3-5 DEG C/min and keeps 1-2 hour, then proceeding to be warming up to 500-550 DEG C with the heating rate of 3-5 DEG C/min again and keep 4-8 hour, obtain Al-SBA-15 white powder.
3. by the preparation method of the Supported Nickel Catalyst described in claim 2, it is characterised in that: described Nickelous nitrate hexahydrate concentration of aqueous solution is 0.5-3mol/L.
4. by the preparation method of the Supported Nickel Catalyst described in claim 2, it is characterised in that: described aluminium salt is ANN aluminium nitrate nonahydrate (Al (NO3)3·9H2O), Patent alum (Al2(SO4)3·18H2Or Aluminium chloride hexahydrate (AlCl O)3·6H2O)。
5. the application of the Supported Nickel Catalyst described in a claim 1, it is characterised in that: described catalyst can as the application of catalyst in ethylene oligomerization reaction.
6. by the application of the Supported Nickel Catalyst described in claim 5, it is characterised in that: described catalyst can be used for ethylene selectivity to be polymerized in more than C9 low-carbon alkene processed reaction.
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| CN101618343A (en) * | 2008-06-30 | 2010-01-06 | 中国石油化工股份有限公司 | Load-type olefin oligomerization catalyst and preparation method thereof |
| CN102963905A (en) * | 2012-11-13 | 2013-03-13 | 中国科学院青岛生物能源与过程研究所 | Method for synthetizing Al-SBA-15 containing plug type silicon/aluminum structure in pore channel |
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| CN101618343A (en) * | 2008-06-30 | 2010-01-06 | 中国石油化工股份有限公司 | Load-type olefin oligomerization catalyst and preparation method thereof |
| CN102963905A (en) * | 2012-11-13 | 2013-03-13 | 中国科学院青岛生物能源与过程研究所 | Method for synthetizing Al-SBA-15 containing plug type silicon/aluminum structure in pore channel |
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| Title |
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| "Ethanol steam reforming on Ni/Al-SBA-15 catalysts: Effect of the aluminium content";M. Lindo et al;《International Journal of Hydrogen Energy》;20100127;第35卷;第2.1节 * |
| "Ethylene oligomerization over Ni-containing mesostructured catalysts with MCM-41, MCM-48 and SBA-15 topologies";M. Lallemand et al;《Studies in Surface and Catalysis》;20071231;第170卷;第1864页第3-6段，第1867页Table 2 * |
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