CN102949999A - Clean type hydrocarbon steam pre-conversion catalyst and preparation method thereof - Google Patents
Clean type hydrocarbon steam pre-conversion catalyst and preparation method thereof Download PDFInfo
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- CN102949999A CN102949999A CN2011102519476A CN201110251947A CN102949999A CN 102949999 A CN102949999 A CN 102949999A CN 2011102519476 A CN2011102519476 A CN 2011102519476A CN 201110251947 A CN201110251947 A CN 201110251947A CN 102949999 A CN102949999 A CN 102949999A
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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
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- 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
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Abstract
The invention relates to a preparation method of a catalyst, and in particular relates to a clean type hydrocarbon steam pre-conversion catalyst and a preparation method thereof. The catalyst takes mixed oxide of aluminum oxide and titanium dioxide as carriers, one or more of lanthanum oxide, cerium protoxide and magnesium oxide in any proportion as an accelerant, and nickel oxide as an active component, wherein a precursor of lanthanum oxide, cerium protoxide, magnesium oxide or nickel oxide is a nonnitrogenous salt or compound, preferably corresponding acetate and oxalate. The prepared clean type hydrocarbon steam pre-conversion catalyst has the characteristics of being high in mechanical strength, good in activity, good in strength stability, structure stability, activity stability and the like, all materialization properties can achieve industrial use requirements, no pollutant gas such as nitrogen oxide is emitted in a preparation process, the pollution problem in the production process of the catalyst can be solved, and the cleanness of the gaseous hydrocarbon steam pre-conversion catalyst in the preparation process can be realized.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst, be specifically related to a kind of clean type steam preconversion catalyst for hydrocarbon and preparation method thereof.
Background technology
The hydrocarbon raw material pre-inversion more and more is applied in the technical process of hydrocarbon material catalytic steam-reforming hydrogen making or synthesis gas by domestic and international Petrochemical Enterprises at present, carries out the process of pre-inversion before transforming such as the catalytic steam of producing hydrogen-rich gas and/or carbon monoxide, hydrogen gas mixture in the gaseous hydrocarbons such as natural gas, liquefied petroleum gas (LPG), refinery gas.
The catalyst activity component that steam preconversion catalyst for hydrocarbon adopts mostly is greatly nickel, no matter this catalyst adopts dry pigmentation, coprecipitation still to adopt the infusion process preparation, the active component precursor that it adopts mostly is nitrate, in the catalyst roasting process, can discharge a large amount of oxynitrides, not only cause atmosphere pollution, also damaged the healthy of producers.Have at present Some Enterprises to adopt the alkali cleaning absorption process to reduce the discharging of oxynitrides, but effect is unsatisfactory, and the problem of easily bringing absorption liquid to process.To the environmental protection requirement increasingly stringent, demand developing the free of contamination clean type hydrocarbon vapours of a kind of production process pre-inversion catalyst for preparing hydrogen urgently, to adapt to the demand in market along with in recent years.
The non-pollution technology that CN85102809 discloses a kind of dip type nickel series catalysts replaces the method for conventional Kaolinite Preparation of Catalyst.It is characterized in that, after the nickel nitrate maceration extract adds catalyst carrier, introduce again an amount of urea.Make its reaction generate nickel hydroxide.Whole process does not produce the nitrogen oxide (N O x) that pollutes, and the molten mistake of nickel is few, and activity intensity and surface strength all improve than conventional method.Owing to having used urea in this catalyst preparation process, thereby having had the ammonia generation, will affect preparation personnel's health.
CN200610052788 discloses a kind of composite catalyst for the carbon dioxide adsorption forced methane steam reforming hydrogen manufacturing, mainly by take micron order and/or nano level calcium carbonate and/or calcium hydroxide powder as the calcium oxide of presoma and active nickel composition and alumina support take nickelous carbonate, nickel oxide or nickel nitrate aqueous solution as presoma be composited, the each component mol ratio is: CaO: NiO: Al
2O
3=1: (0.1～2.0): (0.1～3.0).This invention raw material is micron order or nanoscale, and production cost is higher.
University Of Nanchang's journal (natural sciences version) 03 phase Li Xiancai in 2003 etc. take butyl titanate, glacial acetic acid, absolute ethyl alcohol, barium acetate and nickel acetate as raw material, adopt sol-gel process to prepare Ni/BaTiO in " sol-gel process preparation and the catalytic activity of ultra-fine (nanometer) barium titanate nickel-base catalyst "
3System CH
4-CO
2Catalyst for preparing synthetic gas by reforming.Old lucky the grade " different nickel salt predecessors are to CH of chemistry of fuel journal 06 phase of calendar year 2001
4-CO
2Reformation Ni/ γ-Al
2O
3The impact of catalyst performance " in adopt dipping method with γ-Al
2O
3Be carrier, prepared respectively three kinds of catalyst take nickel nitrate, nickel chloride, nickel acetate as precursor salt, and be applied to catalysis CH
4-CO
2Reforming reaction.Journal of Molecular Catalysis 03 phase of calendar year 2001 is waited " Ni/MgO/Al in rope palm bosom
2O
3The Ni precursor is on the impact of methane-CO 2 reforming reaction activity in the catalyst " in investigated Ni/MgO/Al with nickel nitrate, nickel chloride, nickelous sulfate, nickel acetate and 5 kinds of Ni salt preparations of nitric acid hexamine nickel
2O
3Catalyst is at CO-CH
4Catalytic activity in the preparing synthetic gas by reforming reaction.It is that the catalyst of predecessor preparation is on the impact of catalytic methane partial oxidation reaction that catalysis journal 05 phase Ji Yaying in 2000 etc. have investigated by nickel nitrate, nickel acetate and nickel chloride in " different predecessors on the Ni catalyst on the impact of methane portion oxidation synthesis gas reaction ".
Summary of the invention
The purpose of this invention is to provide a kind of clean type steam preconversion catalyst for hydrocarbon and preparation method thereof, can have preparation method's simple possible, production cost is low, the characteristics of the pollution gas such as nitrogenfree oxide discharging in the preparation process.
Clean type steam preconversion catalyst for hydrocarbon of the present invention, this catalyst is take aluminium oxide and titanium dioxide mixed oxide as carrier, the mixture that one or more arbitrary proportions in lanthana, the inferior cerium of oxidation or magnesia mix is as promoter, take nickel oxide as active component, each component is according to the mass percent meter, aluminium oxide 40～87%, titanium dioxide 2～8%, promoter 0.1～18% and nickel oxide 4～35%.
Aluminium oxide is to obtain take boehmite, alumina powder, aluminium glue powder or activated aluminum powder etc. as raw material, and the best is selected the modified oxidized aluminium powder of carbonizatin method preparation.
Wherein, all preferably take the salt of nonnitrogenous element or its compound as raw material, the precursor of lanthana, the inferior cerium of oxidation, magnesia and nickel oxide can adopt corresponding acetate or oxalates for the inferior cerium of lanthana, oxidation, magnesia and nickel oxide.
Each component is preferably aluminium oxide 60～85%, titanium dioxide 3～6%, promoter 1～11.5% and nickel oxide 10～30% according to the mass percent meter.
The preparation method of clean type steam preconversion catalyst for hydrocarbon of the present invention may further comprise the steps:
(1) with aluminium oxide, titanium dioxide, water, expanding agent and binding agent, be dry mixed, kneading, moulding, drying, roasting, make carrier;
(2) promoter is mixed with the solution of 0.01～1mol/L with deionized water, carrier impregnation is in solution, dipping 90～150min, taking-up drains, put into baking oven in 80～150 ℃ of lower oven dry, dried 2～4 hours, put into afterwards Muffle furnace at 350～1050 ℃ of lower Roasting Decompositions, roasting 2～4 hours obtains modified support;
(3) active component is dissolved in deionized water, obtain the living solution of 1～4mol/L, modified support be impregnated in the living solution, dipping 90～150min, taking-up drains, and puts into baking oven in 80～150 ℃ of lower oven dry, dried 2～4 hours, put into afterwards Muffle furnace at 350～1050 ℃ of lower Roasting Decompositions, roasting 2～4 hours obtains product.
Wherein, the preparation technology of carrier is routine techniques in the step (1), expanding agent and binding agent are also all selected conventional products, expanding agent is selected polyvinyl alcohol, poly amic acid, field mountain valley with clumps of trees and bamboo powder, citric acid or starch usually, preferred sesbania powder, binding agent is selected a kind of or any several combination, optimization citric acid and the oxalic acid in water, acetic acid, citric acid, oxalic acid or the nitric acid usually.Bake out temperature in step (2) and the step (3) is preferably 110～130 ℃, and sintering temperature is preferably 450～650 ℃.Can be according to load capacity repeated impregnations, oven dry, the roasting of active component 1～2 time in the step (3).
The preparation method of clean type steam preconversion catalyst for hydrocarbon of the present invention can also may further comprise the steps:
(1) with aluminium oxide, titanium dioxide, water, expanding agent and binding agent, be dry mixed, kneading, moulding, drying, roasting, make carrier;
(2) promoter and active component are mixed with hybrid infusion solution with deionized water, wherein promoter concentration is 0.01～1mol/L, active component concentration is 1～4mol/L, and carrier impregnation is flooded 90～150min in hybrid infusion solution, taking-up drains, put into baking oven in 80～150 ℃ of lower oven dry, dried 2～4 hours, put into afterwards Muffle furnace at 350～1050 ℃ of lower Roasting Decompositions, roasting 2～4 hours obtains product.
Wherein, the preparation technology of carrier is routine techniques in the step (1), expanding agent and binding agent are also all selected conventional products, expanding agent is selected polyvinyl alcohol, poly amic acid, field mountain valley with clumps of trees and bamboo powder, citric acid or starch usually, preferred sesbania powder, binding agent is selected a kind of or any several combination, optimization citric acid and the oxalic acid in water, acetic acid, citric acid, oxalic acid or the nitric acid usually.The bake out temperature of step (2) is preferably 110～130 ℃, and sintering temperature is preferably 450～650 ℃, can be according to needs repeated impregnations, oven dry, the roasting of activity component load quantity 1～2 time.
The main phase of the catalyst carrier of the present invention's preparation is γ-Al
2O
3Phase can also contain a small amount of α-Al
2O
3Phase and θ-Al
2O
3Phase, the water absorption rate of carrier are 30.0～75.0%, preferably are controlled at 40.0～60.0%, and carrier can be prepared into the particle of Φ 1.0～16.0mm particle diameter, are shaped as strip, sheet, spherical or Raschig ring shape.
The specific area of catalyst of the present invention is 120～250m
2/ g preferably is controlled at 150～200m
2/ g; The specific pore volume of catalyst is long-pending to be 0.20～0.75mL/g, preferably is controlled at 0.30～0.50mL/g.
The invention has the advantages that the clean type steam preconversion catalyst for hydrocarbon of preparing has mechanical strength high, active good, the characteristics such as strength stability, structural stability and activity stability are good, every physical and chemical performance has reached the industrial application requirement, the pollution gas dischargings such as its preparation process nitrogenfree oxide of while, solve the pollution problem of Catalyst Production process, realized cleaning of gaseous hydrocarbons steam preconversion catalyst preparation process.
The specific embodiment
The present invention will be further described below in conjunction with embodiment.
Embodiment 1:
Take by weighing 500.0g aluminium glue powder, add 50.0g titanium dioxide, the sesbania powder of 2.6g and the polyvinyl alcohol of 3.4g, and the water of 280mL, 20mL oxalic acid, fully mediate, be shaped to the sheet of external diameter Φ 5.0mm, length 5.0mm, calcination process under 950 ℃ of temperature conditions makes alumina support; Preparation lanthanum acetate dipping solution, concentration 0.01mol/L, carrier flood 140min in solution, and taking-up drains, under 120 ℃ temperature, oven dry 180min, then under 900 ℃ temperature, Roasting Decomposition 180min obtains modified support; Preparation nickel acetate living solution, concentration 1.50mol/L, modified support floods 140min in living solution, taking-up drains, under 120 ℃ temperature, and oven dry 180min, then under 400 ℃ temperature, Roasting Decomposition 180min with nickel acetate solution repeated impregnations, oven dry, roasting once, makes catalyst A-1.The content of each component, pore structure data, intensity data and evaluating data see Table 1 in the catalyst A-1.
Change the addition of each component in the above-mentioned preparation process, make respectively catalyst A-2, A-3, A-4, A-5, A-6, the content of its each component, pore structure data, intensity data and evaluating data are also listed in the table 1.
Table 1
Embodiment 2
Take by weighing the 500.0g boehmite, add 50.0g titanium dioxide, the acetic acid of 4.5g and the sesbania powder of 3.2g, and the water of 300mL, 20mL citric acid, fully mediate, be shaped to the Raschig ring shape of external diameter Φ 4.5mm, length 4.0mm, calcination process under 860 ℃ of temperature conditions makes alumina support; The oxalates hybrid infusion solution of preparation nickel, magnesium, nickel oxalate concentration 1.00mol/L, magnesium oxalate concentration 0.01mol/L, carrier floods 140min in hybrid infusion solution, and taking-up drains, under 130 ℃ temperature, oven dry 180min, under 400 ℃ temperature, Roasting Decomposition 180min, repeated impregnations, oven dry, roasting once make catalyst B-1.The content of each component, pore structure data, intensity data and evaluating data see Table 2 in the catalyst B-1.
Change the addition of each component in the above-mentioned preparation process, make respectively catalyst B-2, B-3, B-4, B-5, B-6, the content of its each component, pore structure data, intensity data and evaluating data are also listed in the table 2.
Table 2
Embodiment 3:
Take by weighing the 500.0g alumina powder, add 5.2g citric acid and 8.6g sesbania powder, and add 320mL water, 20mL oxalic acid, fully mediate, be shaped to the bunge bedstraw herb of internal diameter Φ 2.0mm, length 4.5mm, 800 ℃ of calcination process make alumina support; The acetate hybrid infusion solution of preparation nickel, lanthanum, magnesium, nickel acetate concentration 1.50mol/L, lanthanum acetate concentration 0.01mol/L, magnesium acetate concentration 0.05mol/L, carrier floods 140min in hybrid infusion solution, and taking-up drains, at 120 ℃ of lower oven dry 120min, 400 ℃ of Roasting Decomposition 180min, repeated impregnations, oven dry, roasting once make catalyst C-1.The content of each component, pore structure data, intensity data and evaluating data see Table 3 among the catalyst C-1.
Change the addition of each component in the above-mentioned preparation process, make respectively catalyst C-2, C-3, C-4, C-5, C-6, the content of its each component, pore structure data, intensity data and evaluating data are also listed in the table 3.
Table 3
Claims (14)
1. clean type steam preconversion catalyst for hydrocarbon, it is characterized in that: this catalyst is take aluminium oxide and titanium dioxide mixed oxide as carrier, the mixture that one or more arbitrary proportions in lanthana, the inferior cerium of oxidation or magnesia mix is as promoter, take nickel oxide as active component, each component is according to the mass percent meter, aluminium oxide 40～87%, titanium dioxide 2～8%, promoter 0.1～18% and nickel oxide 4～35%.
2. clean type steam preconversion catalyst for hydrocarbon according to claim 1 is characterized in that lanthana is take the salt of nonnitrogenous element or its compound as raw material.
3. clean type steam preconversion catalyst for hydrocarbon according to claim 2, the precursor that it is characterized in that lanthana is lanthanum acetate or lanthanum oxalate.
4. clean type steam preconversion catalyst for hydrocarbon according to claim 1 is characterized in that the inferior cerium of oxidation is take the salt of nonnitrogenous element or its compound as raw material.
5. clean type steam preconversion catalyst for hydrocarbon according to claim 4 is characterized in that the precursor of the inferior cerium of oxidation is cerous acetate or cerium oxalate.
6. clean type steam preconversion catalyst for hydrocarbon according to claim 1 is characterized in that magnesia is take the salt of nonnitrogenous element or its compound as raw material.
7. clean type steam preconversion catalyst for hydrocarbon according to claim 6 is characterized in that magnesian precursor is magnesium acetate or magnesium oxalate.
8. clean type steam preconversion catalyst for hydrocarbon according to claim 1 is characterized in that nickel oxide is take the salt of nonnitrogenous element or its compound as raw material.
9. clean type steam preconversion catalyst for hydrocarbon according to claim 8, the precursor that it is characterized in that nickel oxide is nickel acetate or nickel oxalate.
10. clean type steam preconversion catalyst for hydrocarbon according to claim 1 is characterized in that each component according to the mass percent meter, aluminium oxide 60～85%, titanium dioxide 3～6%, promoter 1～11.5% and nickel oxide 10～30%.
11. the preparation method of a clean type steam preconversion catalyst for hydrocarbon claimed in claim 1 is characterized in that may further comprise the steps:
(1) with aluminium oxide, titanium dioxide, water, expanding agent and binding agent, be dry mixed, kneading, moulding, drying, roasting, make carrier;
(2) promoter is mixed with the solution of 0.01～1mol/L with deionized water, carrier impregnation is in solution, dipping 90～150min, taking-up drains, put into baking oven in 80～150 ℃ of lower oven dry, dried 2～4 hours, put into afterwards Muffle furnace at 350～1050 ℃ of lower Roasting Decompositions, roasting 2～4 hours obtains modified support;
(3) active component is dissolved in deionized water, obtain the living solution of 1～4mol/L, modified support be impregnated in the living solution, dipping 90～150min, taking-up drains, and puts into baking oven in 80～150 ℃ of lower oven dry, dried 2～4 hours, put into afterwards Muffle furnace at 350～1050 ℃ of lower Roasting Decompositions, roasting 2～4 hours obtains product.
12. the preparation method of clean type steam preconversion catalyst for hydrocarbon according to claim 11 is characterized in that the bake out temperature of step (2) and step (3) is 110～130 ℃, sintering temperature is 450～650 ℃.
13. the preparation method of a clean type steam preconversion catalyst for hydrocarbon claimed in claim 1 is characterized in that may further comprise the steps:
(1) with aluminium oxide, titanium dioxide, water, expanding agent and binding agent, be dry mixed, kneading, moulding, drying, roasting, make carrier;
(2) promoter and active component are mixed with hybrid infusion solution with deionized water, wherein promoter concentration is 0.01～1mol/L, active component concentration is 1～4mol/L, and carrier impregnation is flooded 90～150min in hybrid infusion solution, taking-up drains, put into baking oven in 80～150 ℃ of lower oven dry, dried 2～4 hours, put into afterwards Muffle furnace at 350～1050 ℃ of lower Roasting Decompositions, roasting 2～4 hours obtains product.
14. the preparation method of clean type steam preconversion catalyst for hydrocarbon according to claim 13, the bake out temperature that it is characterized in that step (2) is 110～130 ℃, and sintering temperature is 450～650 ℃.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK201400705A1 (en) * | 2014-12-03 | 2016-04-18 | Haldor Topsoe As | A catalyst for prereforming and/or steam reforming |
| CN110385133A (en) * | 2019-07-22 | 2019-10-29 | 四川蜀泰化工科技有限公司 | A kind of pre-converting catalyst and preparation method thereof |
| CN111068772A (en) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | Lower catalyst for hydrocarbon steam conversion and preparation method thereof |
| CN112844398A (en) * | 2021-02-10 | 2021-05-28 | 中国海洋石油集团有限公司 | Catalyst for hydrogenation of carbon tetra-polymerization product and preparation method thereof |
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| US20040166056A1 (en) * | 2003-02-20 | 2004-08-26 | Eyman Darrell P. | Sulfur-tolerant catalysts and related precursors and processes |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK201400705A1 (en) * | 2014-12-03 | 2016-04-18 | Haldor Topsoe As | A catalyst for prereforming and/or steam reforming |
| CN111068772A (en) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | Lower catalyst for hydrocarbon steam conversion and preparation method thereof |
| CN111068772B (en) * | 2018-10-22 | 2023-12-26 | 中国石油化工股份有限公司 | Lower catalyst for hydrocarbon steam conversion and preparation method thereof |
| CN110385133A (en) * | 2019-07-22 | 2019-10-29 | 四川蜀泰化工科技有限公司 | A kind of pre-converting catalyst and preparation method thereof |
| CN112844398A (en) * | 2021-02-10 | 2021-05-28 | 中国海洋石油集团有限公司 | Catalyst for hydrogenation of carbon tetra-polymerization product and preparation method thereof |
| CN112844398B (en) * | 2021-02-10 | 2023-05-30 | 中国海洋石油集团有限公司 | Catalyst for hydrogenation of carbon four-superimposed product and preparation method thereof |
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Application publication date: 20130306 |