CN104056650A - Nickel group-supported catalyst and preparation method and application thereof - Google Patents

Nickel group-supported catalyst and preparation method and application thereof Download PDF

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CN104056650A
CN104056650A CN201310091315.7A CN201310091315A CN104056650A CN 104056650 A CN104056650 A CN 104056650A CN 201310091315 A CN201310091315 A CN 201310091315A CN 104056650 A CN104056650 A CN 104056650A
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catalyst
supported nickel
sba
nickel catalyst
hour
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CN104056650B (en
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张洪鹏
林森
郭鹏
李学兵
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention belongs to the technical field of catalyst preparation, and concretely relates to a nickel group-supported catalyst and a preparation method and an application thereof. According to the invention, Al-SBA-15 taken as a carrier is reduced with an active matter precursor nickel nitrate hexahydrate to obtain the nickel group-supported catalyst. Al-SBA-15 taken as the carrier is reduced with the active matter precursor nickel nitrate hexahydrate through dipping and drying to obtain the nickel group-supported catalyst. When the catalyst is used for an ethylene selectivity polymerization, the ethylene conversion rate is higher than 99%; and the C9+ component content in the liquid product is higher than 35%.

Description

A kind of Supported Nickel Catalyst and its preparation method and application
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 to produce the important course of reaction with longer carbochain alkene, long-chain product after polymerization can be directly as transport fuel or for the additive of transport fuel, thereby the main advantage of low-carbon alkene polymerisation is directly to dock and to realize large-scale production with low-carbon alkene production process.At present, about the polymerisation research of low-carbon alkene mainly for C3 and C4 component alkene, using ethene as the polymerisation research of raw material also in the laboratory research stage.
Ethene is the most large basic chemical raw materials, and its annual production can be used for weighing a national Industry Development Level, and 2012, the ethene annual production of China broke through 1,500 ten thousand tons, occupied the whole world second.For expanding the downstream product of ethene, it is the focus of research at present that transport fuel production new technique that ethene is raw material is take in exploitation.In addition, use the transport fuel generating by low-carbon alkene polymerization can also effectively reduce the destruction to environment.Therefore the novel catalyst system that, exploitation is applicable to ethylene oligomerization reaction has important practical significance.
At present, the catalyst system of ethylene oligomerization reaction mainly comprises the non-molecular screen base with certain acidity and molecular screen base two classes of transition metal load.Take the former as example; Ni has shown good catalytic performance in the caltalyst of gamma-alumina, silica and amorphous aluminum silicide ties up to ethylene oligomerization reaction; especially the pore passage structure of carrier makes its reaction life-span reach 500 hours above [J.Hevelinget al.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 adopts Ni to obtain on X, Y, MCM-22 and MCM-36 type zeolite molecular sieve has shown excellent catalytic activity [M.Lallemand et al.Appl.Catal.A in ethylene oligomerization reaction; 301; 2006,196.; M.Lallemand et al.Appl.Catal.A, 338,2008,37.], still, the aperture that zeolite molecular sieve is less (<2nm) causes catalyst rapid deactivation, and the skeleton structure of its crystal is unfavorable for regulating the acid of catalyst to distribute.Given this, an other class has the catalyst system at mesopore molecular sieve MCM-41 compared with the Ni of macropore structure and gets the attention.[V.Hulea et al.J.Catal.225,2004,213.] MCM-41 molecular sieve was reported to have orderly Jie's view hole road and arrange, space group: p6mm at first in 1992 by Mobil company.This larger pore passage structure and surface area make it in ethylene oligomerization reaction, have more excellent product diffusion, thus strong raising the whole catalytic performance of catalyst.But the pore wall thickness of MCM-41 molecular sieve only has 1nm left and right, is not enough to tackle harsh reaction condition, therefore, be necessary that exploitation has the more new catalyst of high stability.
1998, the people such as Zhao [Zhao, D.Y.et al.Science, 1998,279,548.] reported first in strong acid system the synthetic SBA-15 mesoporous material with two-dimentional hexagonal hole road structure.SBA-15 has than the larger specific area of MCM-41 and thicker hole wall structure, so it has more superior structural stability and active specy mixes flexibility.Application study around SBA-15 type mesopore molecular sieve was the focus of catalyst preparation field always in recent years.But, adopt in the synthetic Al-SBA-15 of known method framework aluminum content lower and distribute and be difficult to control, therefore yet there are no so far the research report that is applied to ethylene oligomerization reaction.2011, Lin[Lin, S.et al.Micro.Meso.Mater.2011,142,526.] etc. people, in the system without outer acid adding, only utilizes aluminium source to be hydrolyzed the polycondensation process that spontaneous acidity promotes inorganic species, the one-step synthesis orderly Al-SBA-15 of view hole road structure height that goes out to be situated between.Yet the heat of above-mentioned material and hydrothermal stability are still lower, the method for there is no meets the chemical reaction process of ask for something harshness.Then not relevant record obtains being applicable to the catalyst that ethylene oligomerization reaction requires at present.
Summary of the invention
The object of the present invention is 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 Supported Nickel Catalyst, take Al-SBA-15 as carrier, and carrier and the reduction of active specy presoma Nickelous nitrate hexahydrate, obtain Supported Nickel Catalyst.
Describedly take Al-SBA-15 as carrier, Nickelous nitrate hexahydrate is active specy presoma, through dipping, dry, reduce and obtain Supported Nickel Catalyst.
The preparation method of Supported Nickel Catalyst, take Al-SBA-15 as carrier, and Nickelous nitrate hexahydrate is active specy presoma, through flooding, dry, reduce and obtain Supported Nickel Catalyst.
Nickelous nitrate hexahydrate is mixed with carrier A l-SBA-15, in 60-100 ° of C, dry; By drying the heating rate of products therefrom with 2-5 ° of C/min, be warming up to 100-120 ° of C and keep 1-3 hour, then with the heating rate of 2-5 ° of C/min, being warming up to 400-500 ° of C and keeping again 1-3 hour; Then with hydrogen, 400-500 ° of C in-situ reducing, process 1-4 hour, 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, is prepared as:
1) under room temperature condition, by triblock copolymer EO 20pO 70eO 20be dissolved in deionized water; Add aluminium salt stirring and dissolving; Wherein, deionized water and triblock copolymer EO 20pO 70eO 20mol ratio be 10000-17000:1;
2) in step 1), add tetraethyl orthosilicate again, under room temperature, stir 10-15 hour; Wherein, triblock copolymer EO 20pO 70eO 20with the mol ratio of ethyl orthosilicate be 0.0075-0.015:1;
3) by step 2) mixture after mixing is placed in 35-40 ° of C constant temperature and stirs 18-24 hour;
4) by step 3) mixture static treatment under 80-110 ° of C hydrothermal condition, then filter and wash by deionized water, then drying, stand-by;
5) by above-mentioned products therefrom, the heating rate with 3-5 ° of C/min is warming up to 100-120 ° of C and keeps 1-2 hour, and then continuation is warming up to 500-550 ° of C and keeps 4-8 hour with the heating rate of 3-5 ° of C/min again, obtains Al-SBA-15 white powder.
Described aluminium salt is ANN aluminium nitrate nonahydrate (Al (NO 3) 39H 2o), Patent alum (Al 2(SO 4) 318H 2o) or Aluminium chloride hexahydrate (AlCl 36H 2o).
The application of Supported Nickel Catalyst, described catalyst can be used as the application of catalyst in ethylene oligomerization reaction.
Described catalyst can be used in the above low-carbon alkene reaction of ethylene selectivity polymerization C9 processed.
The present invention has advantages of: utilization of the present invention has improved the structural stability of catalyst itself greatly in inside, mesoporous material duct encapsulation plug shape structure, enables more effectively to adapt to the reaction under high pressure condition of ethylene oligomerization; The second, the introducing of plug shape structure makes the enrichment more of catalyst duct internal acid active sites, is conducive to product carbon chain growth, obtains higher C9+ constituent content; The 3rd, all right limited reactions intermediate product of existence of plug shape structure, in the diffusion of inside, duct, improves the possibility of secondary response, is beneficial to and obtains C9+ component product.Supported Nickel Catalyst of the present invention has mesoscopic size pore passage structure.Catalyst of the present invention is used for to ethylene selectivity polymerisation 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
Little angle XRD spectra and the N of the Ni/Al-SBA-15 of the synthesized that Fig. 1 provides for the embodiment of the present invention 1 2(wherein Figure 1A is little angle XRD result to adsorption isotherm line chart; Figure 1B is N 2adsorption-desorption result).
Little angle XRD spectra and the N of the Ni/Al-SBA-15 of the synthesized that Fig. 2 provides for the embodiment of the present invention 2 2(wherein Fig. 2 A is little angle XRD result to adsorption isotherm; Fig. 2 B is N 2adsorption-desorption result).
Little angle XRD spectra and the N of the Ni/Al-SBA-15 of the synthesized that Fig. 3 provides for the embodiment of the present invention 3 2adsorption isotherm.(wherein Fig. 3 A is little angle XRD result; Fig. 3 B is N 2adsorption-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 samples; Wherein curve c is derived from embodiment 3 gained samples.
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 samples; Photo c is derived from embodiment 3 gained samples.
Fig. 6 is carrier for take the synthetic Al-SBA-15 of known method, the chromatogram of the catalyst of preparing after nickel-loaded gained liquid product in ethylene oligomerization reaction.
The typical color spectrogram of Ni/Al-SBA-15 catalyst gained liquid product in ethylene oligomerization reaction that the present invention that Fig. 7 provides for the embodiment of the present invention is synthetic.
The specific embodiment
For further illustrating the solution of the present invention, below in conjunction with drawings and Examples, elaborate.
The present invention be take Al-SBA-15 as carrier, and Nickelous nitrate hexahydrate is active specy presoma, after dipping, oven dry, reduction, makes the catalyst that is applicable to ethylene oligomerization reaction.
The preparation of catalyst of the present invention, comprises the following steps:
1) at ambient temperature, in deionized water, add triblock copolymer EO 20pO 70eO 20(P123) under strong agitation, P123 is dissolved completely; Wherein, deionized water and triblock copolymer EO 20pO 70eO 20molar ratio range be 10000-17000:1;
2) in above-mentioned stirring and dissolving gained settled solution, add aluminium salt, again stirring and dissolving;
3) in the above-mentioned settled solution that adds aluminium salt, add again tetraethyl orthosilicate, under room temperature, stir 10-15 hour, triblock copolymer EO 20pO 70eO 20with the molar ratio range of ethyl orthosilicate be 0.0075-0.015:1;
4) gained mixture is placed in to 30-40 ° of C water bath with thermostatic control, stirs 18-24 hour;
5) gained mixture is proceeded to again in the stainless steel synthesis reactor of inner liner polytetrafluoroethylene cover, static treatment 2-3 days under 80-110 ° of C hydrothermal condition, after filtration, dries 10 hours in 80-100 ° of C after deionized water washing;
6) in Muffle furnace, the heating rate with 3-5 ° of C/min is warming up to 100-120 ° of C, keeps 1-2 hour, and 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, in 60-100 ° of C, dry;
8) oven dry afterproduct is warming up to 100-120 ° of C and keeps 1-3 hour with the heating rate of 2-5 ° of C/min, and then the heating rate with 2-5 ° of C/min is warming up to 400-500 ° of C and keeps 1-3 hour.
9) step 8) products therefrom is processed to 1-4 hour with hydrogen under 400-500 ° of C, be then cooled to 20-30 ° of C, obtain catalyst.
By above-mentioned gained Ni/Al-SBA-15 X-ray diffractometer (XRD), the N for catalyst of preparing 2the technology such as adsorption-desorption, transmission electron microscope (TEM) characterize.Result shows, adopts the inventive method to make the pore canal system that sample has the two-dimentional Hexagonal array of high-sequential, space group: P6mm.According to the difference of be suitable for aluminium source species, Al-SBA-15 structural property is basic identical, and after supported active species nickel, its view hole road structural property that is situated between is in order approximate.All there is desorption platform in all catalyst, show that Ni species enter inside, duct within the scope of 0.5-0.6 specific pressure.
Embodiment 1
Al-SBA-15 carrier preparation: at room temperature, add triblock copolymer EO in 80 ml deionized water 20pO 70eO 20(P123 PEO-PPOX-PEO triblock copolymer) 1.5 grams, strong agitation is to triblock copolymer EO 20pO 70eO 20dissolve completely; Add 0.35 gram of ANN aluminium nitrate nonahydrate to be stirred to dissolving; In above-mentioned solution, add again 7.4 milliliters of ethyl orthosilicates and stir; Said mixture is kept 15 hours under 40 ° of C conditions; After proceed in the stainless steel hydrothermal reaction kettle of inner liner polytetrafluoroethylene cover, under 90 ° of C hydrothermal conditions, react 2 days, after filtration, after deionized water washing dry 10 hours of 80 ° of C; Then in Muffle furnace, the heating rate with 3 ° of C/min is warming up to 120 ° of C, keeps 1 hour, then continues to be warming up to 550 ° of C with the heating rate of 3 ° of C/min, keeps 5 hours, obtains Al-SBA-15 white powder.
The preparation of catalyst, impregnated in by 2 grams of above-mentioned gained Al-SBA-15 the Nickelous nitrate hexahydrate aqueous solution that 2.5 ml concns are 0.5 mol/L at ambient temperature, then in 60 ° of C, dries; After drying sample is ground, the heating rate with 2 ° of C/min in air atmosphere is warming up to 120 ° of C and keeps 1 hour, and then the heating rate with 2 ° of C/min is warming up to 400 ° of C and keeps 2 hours; Then with hydrogen, replace air atmosphere again, (400 ° of C) continues roasting sample 2 hours with the hydrogen flowing quantity of 30mL/min at the same temperature, is naturally cooled to 20-30 ° of C after roasting, obtains catalyst (referring to Fig. 1).
By the little angle XRD spectra result of Ni/Al-SBA-15 shown in Figure 1A, Figure 1B is N 2adsorption-desorption result.Known according to XRD result, catalyst has two-dimentional six side's phase structures and one dimension straight hole road, illustrates that surface and preparation process that nickel is effectively carried on Al-SBA-15 do not exert an influence to the structure of carrier.In addition, according to N 2in adsorption experiment, desorption curve exists platform known, and the inside, one dimension straight hole road of catalyst exists a certain amount of plug shape structure.
Embodiment 2:
Difference from Example 1 is, in the preparation of Al-SBA-15 carrier, with 0.62 gram of Patent alum, substitutes ANN aluminium nitrate nonahydrate, other permanence condition; In the preparation of catalyst, by hydrogen reducing Temperature Setting, be 450 ° of C, other condition constant (referring to Fig. 2).
Embodiment 3:
Difference from Example 1 is, in the preparation of Al-SBA-15 carrier, with 0.23 gram of Aluminium chloride hexahydrate, substitutes ANN aluminium nitrate nonahydrate,, other permanence condition; In the preparation of catalyst, after nickel species dipping, the bake out temperature of sample is set as 100 ° of C, other condition constant (referring to Fig. 3).
By the pore size distribution curve of the prepared Ni/Al-SBA-15 sample of above-described embodiment 1,2 and 3 as shown in Figure 4, wherein curve a is derived from embodiment 1 gained sample, and curve b is derived from embodiment 2 gained samples, and curve c is derived from embodiment 3 gained samples.As shown in Figure 4, in all embodiment, gained catalyst all has the duct that size is 7.4 nanometers, and pore-size distribution is narrow.
By the TEM photo of the prepared Ni/Al-SBA-15 sample of above-described embodiment 1,2 and 3, as shown in Figure 5, wherein photo a is derived from embodiment 1 gained sample, and photo b is derived from embodiment 2 gained samples, and photo c is derived from embodiment 3 gained samples.In Fig. 5, relatively dark part is the hole wall part that density is larger, and relatively bright part is duct part.The standby catalyst of the ownership all has the mesopore orbit that one dimension is arranged, and hole wall exists inhomogeneous part, corresponding plug shape structure.
Specific area, average pore size and the pore volume (referring to table 1) of while above-described embodiment 1,2 and 3 gained Al-SBA-15 molecular sieves.
The structural parameters of table 1:Al-SBA-15 molecular sieve
Application examples
By the prepared Ni/Al-SBA-15 catalyst of above-described embodiment 1,2 and 3, and with known method [A.Vinu et al, J.Phys.Chem.B2004,108,11496; Lin, S.etal.Micro.Meso.Mater.2011,142,526] synthetic Al-SBA-15 is carrier, the catalyst of preparing by prior art after nickel-loaded, as catalyst in ethylene oligomerization reaction; Experimentation is as follows:
1) catalyst of moulding is packed in reactor, in helium atmosphere, under 150 ° of C conditions, carry out activation processing 1-2 hour;
2) with helium, reaction system is carried out to supercharging, make pressure reach reaction requirement, pressure is: 3.0-3.5MPa, and pressure is controlled and is used counterbalance valve;
3) under reaction pressure, with mass-flow gas meter, reactant ethylene being squeezed into reactor reacts;
4) reaction liquid product, after separator, is analyzed with chromatography of gases;
5) reaction gas-phase product carries out on-line analysis by gas-chromatography;
6) according to chromatography result, calculate conversion ratio and the content (referring to Fig. 6 and Fig. 7) of C9+ component in liquid product of ethene.
Table 2, the reactivity worth of Ni/Al-SBA-15 in ethylene oligomerization reaction.
Conversion of ethylene=(total sample size of ethene amount/ethene in 1-gas-phase product) * 100%
C9+ component content=(each component peaks area sum of the liquid product after the C9+ component peaks area/normalization after normalization) * 100% in product liquid
The spectrum peak that the known wherein retention time of Fig. 6 is longer than 12 minutes is C9+ component.After normalized, calculate the content of C9+ product in liquid product lower than 29%.In Fig. 7, the content of C9+ product in liquid product is higher than 35%.

Claims (9)

1. a Supported Nickel Catalyst, is characterized in that: take Al-SBA-15 as carrier, carrier and the reduction of active specy presoma Nickelous nitrate hexahydrate, obtain Supported Nickel Catalyst.
2. by Supported Nickel Catalyst claimed in claim 1, it is characterized in that: the described Al-SBA-15 of take is carrier, Nickelous nitrate hexahydrate is active specy presoma, through flooding, dry, reduce and obtain Supported Nickel Catalyst.
3. a preparation method for Supported Nickel Catalyst claimed in claim 1, is characterized in that: take Al-SBA-15 as carrier, Nickelous nitrate hexahydrate is active specy presoma, through flooding, dry, reduce and obtain Supported Nickel Catalyst.
4. by the preparation method of Supported Nickel Catalyst claimed in claim 3, it is characterized in that: Nickelous nitrate hexahydrate is mixed with carrier A l-SBA-15, in 60-100 ° of C, dry; By drying the heating rate of products therefrom with 2-5 ° of C/min, be warming up to 100-120 ° of C and keep 1-3 hour, then with the heating rate of 2-5 ° of C/min, being warming up to 400-500 ° of C and keeping again 1-3 hour; Then with hydrogen, 400-500 ° of C in-situ reducing, process 1-4 hour, be then cooled to 20-30 ° of C, obtain Supported Nickel Catalyst.
5. by the preparation method of the Supported Nickel Catalyst described in claim 3 or 4, it is characterized in that: described Nickelous nitrate hexahydrate concentration of aqueous solution is 0.5-3mol/L.
6. by the preparation method of the Supported Nickel Catalyst described in claim 3 or 4, it is characterized in that: described carrier is Al-SBA-15, is prepared as:
1) under room temperature condition, by triblock copolymer EO 20pO 70eO 20be dissolved in deionized water; Add aluminium salt stirring and dissolving; Wherein, deionized water and triblock copolymer EO 20pO 70eO 20mol ratio be 10000-17000:1;
2) in step 1), add tetraethyl orthosilicate again, under room temperature, stir 10-15 hour; Wherein, triblock copolymer EO 20pO 70eO 20with the mol ratio of ethyl orthosilicate be 0.0075-0.015:1;
3) by step 2) mixture after mixing is placed in 35-40 ° of C constant temperature and stirs 18-24 hour;
4) by step 3) mixture static treatment under 80-110 ° of C hydrothermal condition, then filter and wash by deionized water, then drying, stand-by;
5) by above-mentioned products therefrom, the heating rate with 3-5 ° of C/min is warming up to 100-120 ° of C and keeps 1-2 hour, and then continuation is warming up to 500-550 ° of C and keeps 4-8 hour with the heating rate of 3-5 ° of C/min again, obtains Al-SBA-15 white powder.
7. by the preparation method of Supported Nickel Catalyst claimed in claim 6, it is characterized in that: described aluminium salt is ANN aluminium nitrate nonahydrate (Al (NO 3) 39H 2o), Patent alum (Al 2(SO 4) 318H 2o) or Aluminium chloride hexahydrate (AlCl 36H 2o).
8. an application for Supported Nickel Catalyst claimed in claim 1, is characterized in that: described catalyst can be used as the application of catalyst in ethylene oligomerization reaction.
9. by the application of Supported Nickel Catalyst claimed in claim 8, it is characterized in that: described catalyst can be used in the above low-carbon alkene reaction of ethylene selectivity polymerization C9 processed.
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