CN103736524B - The preparation method of hydrocarbon conversion catalyst carrier - Google Patents
The preparation method of hydrocarbon conversion catalyst carrier Download PDFInfo
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- CN103736524B CN103736524B CN201310460452.3A CN201310460452A CN103736524B CN 103736524 B CN103736524 B CN 103736524B CN 201310460452 A CN201310460452 A CN 201310460452A CN 103736524 B CN103736524 B CN 103736524B
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Abstract
The present invention discloses the preparation method of a kind of hydrocarbon conversion catalyst carrier, the preparation method of a hydrocarbon conversion catalyst carrier, with pseudo-boehmite AlOOH nH2O is as initial material, and add the first auxiliary agent and appropriate salpeter solution, through ball mill mixing, mixed water is shaping, steam treatment, calcination operation obtained, in ball mill mixing process, also adds the 2nd auxiliary agent and antisticking agent, and the 2nd auxiliary agent is MgCO3��CaCO3��SrCO3Or BaCO3. Binding agent is Xylo-Mucine (CMC), carboxymethyl cellulose, methylcellulose gum (MC) or PVOH sodium (PVA). Perforate technology in the hole of this support of the catalyst preparation method, the support of the catalyst hole obtained holds high, is 0.25 ~ 0.45mL/g, and specific surface area is big, is 5 ~ 20m2/ g. The bulk density of carrier is low compared with the bulk density that ordinary process obtains simultaneously.
Description
Technical field
The present invention relates to the preparation method of a kind of hydrocarbon conversion catalyst carrier.
Background technology
Especially higher hydrocarbons composition is more complicated for hydrocarbon class, comprises various alkane, naphthenic hydrocarbon and aromatic hydrocarbons. In conversion process, these hydrocarbon class generation catalytic cracking reaction and heat scission reactions on the one hand; On the other hand, hydrocarbon class and intermediate product thereof and water vapour generation catalytic conversion reaction. Split product generates hydrogen and oxycarbide through steam reforming, through adding hydrogen evolution methane, forms charcoal through polymerization, dehydrogenation and further cracking. So hydrocarbon steam conversion process is a complex system comprising the reactions such as cracking, steam reforming, methanation, hydrogenation, dehydrogenation, oxycarbide conversion, finally reach methanation reaction and the balance of CO transformationreation. The principal reaction of hydrocarbon steam conversion shows as:
CnHm+nH2O=nCO+(n+m/2)H2(thermo-negative reaction)
CO+H2O=CO2+H2(thermopositive reaction)
CO+3H2=CH4+H2O(thermopositive reaction)
CO2+4H2=CH4+2H2O(thermopositive reaction)
Due to the composition of higher hydrocarbon complexity, in reaction process, the thermo-cracking of higher hydrocarbon easily causes the deposition of charcoal. The reaction forming charcoal also may have:
2CO=C+CO2
CO+H2=C+H2O
CH4=C+2H2
Hydrocarbon steam reforming reaction mechanism on nickel catalysts has been carried out a large amount of research work by many investigators, thinks that hydrocarbon vapours pre-inversion reaction is undertaken by following mechanism:
(1) hydrocarbon adsorbs on a catalyst, carries out cracking and generate CHx under active ingredient and carrier function.
CH4=C+2H2
Hydrocarbon vapours pre-conversion process requires to carry out in 350��550 DEG C of temperature ranges, and under this condition, hydrocarbon class completes cracking, conversion, hydrogenation, methanation and transformationreation. Cracking, conversion reaction etc. are thermo-negative reaction, and methanation, transformationreation etc. are thermopositive reaction, and thermo-negative reaction and thermopositive reaction form coupling, and mutual heat supplied, decreases and heat exchange with outside.
Hydrocarbon conversion reactions catalyzer used is that load nickel oxide is made in high temperature resistant support of the catalyst mostly, it is also possible to add other elements to improve catalyst activity simultaneously. The catalytic activity of hydrocarbon vapor reforming catalyst is by the control of gas inner diffusing rate, and the size of the apparent activity of catalyzer and its outside surface is proportional, i.e. the big then corresponding raising of apparent activity of outside surface. At high temperature the conversion reaction speed on catalyst surface is very fast, and now in catalyst pores, the mass transfer of gas has become the rate-determining steps of speed of reaction. In order to improve the reactive behavior of catalyzer, it is desirable to develop a kind of large pore volume, the low density catalyzer that specific surface area is high. In order to improve the outer surface area of catalyzer, generally all adopt the way changing catalyst appearance. The domestic activity in order to improve the catalyzer that outer hydrocarbon vapor reforming uses at present, its carrier generally all adopts the axial aperture at cylindrical catalyst, has wheel shape, porous card shape, porous spherical, gear-like etc. When increasing the outer surface area of this type of catalyzer further, muscle, the wall of these special-shaped catalysts are all thinner, cause the physical strength of catalyzer to reduce, and are easy to broken, and catalyzer is once fragmentation, and broken grain is less, it is easy to cause resistance sharply to increase.
Usual hydrocarbon conversion catalyst carrier is using aluminium and calcium cpd as initial material, and, calcination operation shaping through ball mill mixing, mixed water obtains, and usually obtains the Kong Rong of carrier at 0.15��0.25mL/g, specific surface area 2��8m2/ g. Traditional Hydrocarban coversion catalysts preparation method is difficult to obtain the carrier of large pore volume and specific surface area.
Summary of the invention
The present invention is directed to this problem, it provides the preparation method of a kind of hydrocarbon conversion catalyst carrier.
The preparation method of one hydrocarbon conversion catalyst carrier, by pseudo-boehmite AlOOH nH2O is as initial material, and add the first auxiliary agent and appropriate salpeter solution, through ball mill mixing, mixed water is shaping, steam treatment, calcination operation obtained, in ball mill mixing process, also adds the 2nd auxiliary agent, and the 2nd auxiliary agent is MgCO3��CaCO3��SrCO3Or BaCO3��
In ball mill mixing process, also adding binding agent, binding agent is Xylo-Mucine (CMC), carboxymethyl cellulose, methylcellulose gum (MC) or PVOH sodium (PVA).
Described first auxiliary agent is TiO2��WO3Or MoO3��
After ball mill mixing steam treatment is dried, first at 300��650 DEG C, it is preferable that 450��550 DEG C, calcining 1��3h, it is preferable that 1.5��2h. Now pseudo-boehmite AlOOH nH2Water evaporation in O, outputs macropore, aperture 100��1000nm.
Pseudo-boehmite AlOOH nH2O is a kind of crystalline phase generated at first in synthesis aluminium hydroxide process, the transition state of aluminium hydroxide.
Al2O3(s)+H2O(l)=2AlOOH(s)
AlOOH(s)+H2O(l)=Al(OH)3(s)
Al2O3(s)+3H2O(l)=2Al(OH)3(s)
The most frequently used preparation method of pseudo-boehmite is with sodium metaaluminate or sodium aluminate solution and carbonic acid gas synthesis.
At 300��650 DEG C calcined in this preparation method, the water evaporation in pseudo-boehmite, outputs macropore.
And then it is fired to 750��1200 DEG C, it is preferable that 850��1000 DEG C, calcination time is 1��3h, it is preferable that 1.5��2h. Now carbonate auxiliary agent decomposes, and opens aperture in macropore, and aperture is 50��500nm, makes the carrier of large pore volume and specific surface area.
The carbonate of the method can be miscible with pseudo-boehmite, has suitable decomposition humidity, can decomposite CO within the scope of 750��1200 DEG C or other proper temperatures2Gas forms metal carbonate or other carbonate in hole, it is also possible to be other salt that can decomposite innocuous gas under suitable calcining temperature. The application is through a large amount of test, it is preferable that the carbonate of II A race metallic element, it is more preferable to MgCO3��CaCO3��SrCO3Or BaCO3. Because beryllium and compound thereof have severe toxicity, the unsafe factor in production can be caused; Radium is radioelement, can not afford.
Last calcining temperature rises to 1100-1350 DEG C, calcining 2��5h, it is preferable that 3��4h. Complete pseudo-boehmite to Al2O3Turn brilliant, obtain final carrier.
In calcination process, TiO2��WO3And MoO3Chemical Composition does not change, and it can improve activity and the stability of final catalyzer in the catalyzer made afterwards.
This support of the catalyst, under the prerequisite not affecting catalyst strength, further increases catalyzer outer surface area than traditional catalyst, it is to increase the activity of catalyzer. Perforate in hole, add catalyzer by pore porosity, it is to increase the service efficiency of catalyzer. Increase fluid through-hole simultaneously, reduce fluid resistance, make fluid Rational flow, reach the effect improving hydrocarbon vapor reforming reaction in reaction tubes, energy-saving and cost-reducing, reduce the running cost of factory.
The support of the catalyst height hole that in hole, perforate technology obtains holds 0.25��0.45mL/g and bigger serface 5��20m2/ g. The bulk density of carrier is low compared with the bulk density that ordinary process obtains simultaneously.
Accompanying drawing explanation
Fig. 1 is the reaction process schematic diagram of hydrocarbon steam conversion.
Embodiment
Below in conjunction with a preferred embodiment, the invention will be further described, to help understand the content of the present invention. But this should not being interpreted as, the scope of the above-mentioned theme of the present invention is only limitted to following examples. Without departing from the idea case in the present invention described above, the various replacement made according to ordinary skill knowledge and customary means or change, all should be included in protection scope of the present invention.
Embodiment 1
A preparation method for novel hydrocarbon conversion catalyst carrier, using pseudo-boehmite as initial material, adds auxiliary agent TiO2, binding agent Xylo-Mucine (CMC) and calcium carbonate, through ball mill mixing, mixed water is shaping, steam treatment, calcination operation obtained. After ball mill mixing steam treatment is dried, being first fired to 350 DEG C, now the evaporation of the water in pseudo-boehmite, outputs macropore, aperture 150nm. And then it being fired to 750 DEG C, calcium carbonate builder decomposes, and opens aperture in macropore, and aperture is 50nm, makes the carrier of large pore volume and specific surface area. Last calcining temperature rises to 1200 DEG C, completes Al2O3Turn brilliant, obtain final carrier. The support of the catalyst that in this support of the catalyst employing hole, the technology of perforate obtains, hole content is 0.25mL/g, and specific surface area is 5m2/ g, bulk density is 0.66kg/L.
Embodiment 2
A preparation method for novel hydrocarbon conversion catalyst carrier, using pseudo-boehmite as initial material, adds auxiliary agent WO3, PVOH sodium (PVA) and magnesiumcarbonate, through ball mill mixing, mixed water is shaping, steam treatment, calcination operation obtained. After ball mill mixing steam treatment is dried, being first fired to 460 DEG C, now pseudo-boehmite outputs macropore, aperture 560nm. And then it being fired to 800 DEG C, carbonate builders decomposes, and opens aperture in macropore, and aperture is 78nm, makes the carrier of large pore volume and specific surface area. Last calcining temperature rises to 1150 DEG C, completes Al2O3Turn brilliant, obtain final carrier. Recording Kong Rongwei 0.30mL/g, specific surface area is 13m2/ g, the bulk density of carrier is 0.65kg/L.
Embodiment 3
A preparation method for novel hydrocarbon conversion catalyst carrier, using pseudo-boehmite as initial material, adds auxiliary agent MoO3, methylcellulose gum (MC) and Strontium carbonate powder, through ball mill mixing, mixed water is shaping, steam treatment, calcination operation obtained. After ball mill mixing steam treatment is dried, being first fired to 650 DEG C, now pseudo-boehmite outputs macropore, aperture 100nm. And then it being fired to 900 DEG C, carbonate builders decomposes, and opens aperture in macropore, and aperture is 500nm, makes the carrier of large pore volume and specific surface area. Last calcining temperature rises to 1350 DEG C, completes Al2O3Turn brilliant, obtain final carrier. Recording Kong Rongwei 0.45mL/g, specific surface area is 20m2/ g, the bulk density of carrier is 0.635kg/L.
The support of the catalyst that in this support of the catalyst employing hole, the technology of perforate obtains, hole content is 0.25��0.45mL/g, and specific surface area is 5��20m2/ g. The bulk density of carrier is low compared with the bulk density that ordinary process obtains simultaneously. Add catalyzer by pore porosity, it is to increase the service efficiency of catalyzer. Increase fluid through-hole simultaneously, reduce fluid resistance, make fluid Rational flow, reach the effect improved and improve hydrocarbon vapor reforming reaction in reaction tubes, energy-saving and cost-reducing, reduce factory's running cost.
Claims (4)
1. the preparation method of a hydrocarbon conversion catalyst carrier, by pseudo-boehmite AlOOH nH2O is as initial material, and add the first auxiliary agent and appropriate salpeter solution, through ball mill mixing, mixed water is shaping, steam treatment, calcination operation obtained, it is characterized in that: in ball mill mixing process, and also adding the 2nd auxiliary agent, the 2nd auxiliary agent is MgCO3��CaCO3��SrCO3Or BaCO3; After ball mill mixing steam treatment is dried, at 300��650 DEG C, first calcine 1��3h; And then it is warming up to 750��1200 DEG C, calcining 1��3h; Finally it is warming up to 1100-1350 DEG C, calcining 2��5h.
2. the preparation method of hydrocarbon conversion catalyst carrier as claimed in claim 1, is characterized in that: the 2nd auxiliary agent is CaCO3��SrCO3Or BaCO3; After ball mill mixing steam treatment is dried, first at 450��550 DEG C, calcining 1.5��2h; Then 850��1000 DEG C it are warming up to, calcining 1.5��2h; Finally it is warming up to 1150��1200 DEG C, calcining 3��4h.
3. the preparation method of hydrocarbon conversion catalyst carrier as claimed in claim 1 or 2, it is characterized in that: in ball mill mixing process, also adding binding agent, binding agent is Xylo-Mucine CMC, carboxymethyl cellulose, methylcellulose gum MC or PVOH sodium PVA.
4. the preparation method of hydrocarbon conversion catalyst carrier as claimed in claim 3, it is characterised in that: the first auxiliary agent is TiO2��WO3Or MoO3��
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| CN114632503B (en) * | 2020-12-16 | 2023-07-28 | 中国石油化工股份有限公司 | Small-particle capsule cell alumina material and preparation method thereof |
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| CN1332762C (en) * | 2004-07-29 | 2007-08-22 | 中国石油化工股份有限公司 | Method for preparing alumina supporter in structure of double peak holes |
| CN100558638C (en) * | 2006-09-07 | 2009-11-11 | 中国科学院理化技术研究所 | Layer stephanoporate gamma-aluminum oxide and its production and use |
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Inventor after: Xu Yunbo Inventor after: Li Huabo Inventor after: Li Wenjing Inventor after: Yan Huicheng Inventor after: Wang Lingyi Inventor after: Wu Xiaoqiang Inventor before: Xu Yunbo Inventor before: Yang Dianming Inventor before: Li Wenjing Inventor before: Yan Huicheng Inventor before: Wang Lingyi |
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Free format text: CORRECT: INVENTOR; FROM: XU YUNBO YANG DIANMING LI WENJING YAN HUICHENG WANG LINGYI TO: XU YUNBO LIHUABO LI WENJING YAN HUICHENG WANG LINGYI WU XIAOQIANG |
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