CN1043965C - Catalyst containing rare-earth for preparing city gas from heavy oil - Google Patents
Catalyst containing rare-earth for preparing city gas from heavy oil Download PDFInfo
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- CN1043965C CN1043965C CN93102722A CN93102722A CN1043965C CN 1043965 C CN1043965 C CN 1043965C CN 93102722 A CN93102722 A CN 93102722A CN 93102722 A CN93102722 A CN 93102722A CN 1043965 C CN1043965 C CN 1043965C
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- catalyst
- nitrate
- carrier
- rare earth
- heavy oil
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Abstract
The present invention relates to a novel catalyst with high activity and high gas production rate, which is used for city gas and is prepared through catalytic cracking of heavy oil containing rare earth. The catalyst of the present invention is prepared by that nickel, rare earth compounds and magnesium oxide (or magnesium oxide is not added) are loaded on a ceramic material carrier with the advantages of high temperature resistance, high strength, high geometric outer surface, little bed layer resistance and a magnesia alumina spinel (MgAl2O4) structure; the catalyst of the present invention has the chemical constitution 3 to 15 wt% of NiO3, 0 to 10 wt% of La2O3, 0 to 8 wt% of CeO, 0 to 5 wt% of MgO and carrier as the rest. The catalyst of the present invention can enhance the gas production rate about 19.2% and has better intensity.
Description
The invention belongs to Preparation of catalysts and the application in preparing city gas from heavy oil thereof.
With heavy oil is raw material, contains CH through the catalytic pyrolysis manufacturing in regenerative furnace
4, H
2And combustible component such as CO starts from the fifties in this century as the way of domestic gas.Can distinguish according to the difference of aspects such as catalyst type and process units and Gas Production technology and to be Weng Niya-Gage method, Britain southeast coal gas office method, Tokyo gas method etc.The methods that ground adopted such as China Beijing, Shanghai, Tianjin, Dalian, Guangzhou, Dandong mostly are Weng Niya-Gage method.The catalyst that Weng Niya-Gage method is used contains NiO and is about 2～7%, and used carrier can be divided into two classes, and a class is based on MgO, and is another kind of with Al
2O
3-SiO
2Be main; The catalyst carrier of Britain southeast coal gas office method is also added active CaO except that containing MgO, be called the MgO-CaO series catalysts; The catalyst that China produces also is the main component of carrier with MgO, and for example the catalyst of Shanghai production contains NiO 2.5～3.0%, and MgO 83.0%, Al
2O
310.58%; The catalyst that Yixing, Jiangsu produces is a carrier with magnesium slag (MgO is a main component), contains NiO and is about 7%.
Recent two decades comes, and does not see the relevant report that is used for regenerative furnace heavy oil catalytic pyrolysis system coal gas catalyst.Relevant document and patent report mostly is the catalyst of the heavy oil catalytic pyrolysis system coal gas that fluidized bed plant uses.The Japan Patent report was with containing SiO in 1975
2, MgO, Fe, Co etc. so-called nickel ores as catalyst, produce hydrogen-rich gas from heavy oil; Eiichi in 1979, people such as KiKuChi delivered the Raney nickel with the dolomite load, were used for the reformation system hydrogen containing synthesis gas of high-sulfur residual oil water vapour at fluid bed; Nineteen eighty-three Japan, Steel works, the patent of Ltd is α-Al
2O
3The CaO-Fe of load
2O
3Catalyst is used for the fluid bed heavy oil gasification; People such as Kojima in 1985 proposed to be used to make the energy-conservation catalyst NiO/SiO of town gas
2-Al
2O
3
The purpose of this invention is to provide that a kind of heavy oil catalytic pyrolysis system town gas uses, and have active high, catalyst that factor of created gase is high.This catalyst with add rare earth, nickeliferous nitrate or add again magnesium nitrate be carried on together have high temperature resistant, high strength, high geometric outer surface, bed resistance are little with magnesium aluminate spinel (MgAl
2O
4) structure is to make on the main ceramic carrier.
Preparation of catalysts process provided by the invention can be expressed as with through metering and pretreated carrier at the nitrate interpolation rare earth, nickeliferous that has prepared or add in the magnesium nitrate solution dip operation again through being no less than twice, drying again, heating reduces nitrate, and can make catalyst provided by the invention through calcining more at last.
The concrete preparation process of the catalyst of interpolation rare earth compound provided by the invention is as follows:
1. to adopt a kind of high temperature ceramic material of industrial production be carrier in the present invention, and this material contains that MgO is 20～30%, Al
2O
3Be 65～75%, CaO is 0.2～6% and impurity such as micro Fe, Si, measures with X light diffracting analysis, wherein main thing is magnesium aluminate spinel (MgAl mutually
2O
4) structure, this carrier material has been processed into shapes such as Raschig ring, spoke-like ring or ball with holes when producing; Specific area is 2～5 meters
2/ gram; Side pressure strength is greater than 2.5MPa/, and malleation intensity is greater than 8MPa/; About 18 * 18 * 5 millimeters of the size of annular, about 16 millimeters of spherical diameter, the through hole that has 5～7 diameters to be about 2 millimeters on the spheroid.
Under 100～150 ℃, is after rare nitric acid about 2M soaks one hour at least, to wash to neutrality drying preliminary treatment again through at least two hours dry preliminary treatment or with carrier through concentration with above-mentioned carrier.
2. will be single lanthanum nitrate or nitrous acid cerium through nickel nitrate, the rare earth nitrades of metering, or two kinds of salt together, or add magnesium nitrate again and be dissolved in through in the distilled water of metering and it is dissolved fully.
3. will place through pretreated above-mentioned carrier and dissolve good nitrate solution and be no less than twice dip operation, make carrier loaded amount reach the scheduled volume of preparation catalyst, but once take out leaching earlier in the back at every dipping, through 100～130 ℃ heating, drying, and then flood next time.
4. after dipping is finished, material was carried out heating, drying at least two hours under 100～130 ℃, be warming up to 400～600 ℃ again and nitrate all decomposed at least one hour, at last 750～1000 ℃ of calcinings 4～8 hours down.
Through above-mentioned technical process, can obtain the said catalyst that contains rare earth of the present invention.
The chemical composition that contains the catalyst of rare earth provided by the invention is:
NiO 3～15％(wt％)
La
2O
3?2～8％(wt％)
CeO
2 0～8％(wt％)
MgO 0～5％(wt％)
All the other are formed for carrier.
Realize that optimum process condition of the present invention has the porous spherical carrier that magnesia-alumina spinel structure is the master for adopting, after aforementioned preliminary treatment, repeatedly flood in the nitrate mixed solution that has prepared then, will thoroughly give drying between the dipping each time, the optimum temperature that adds thermal decomposition is 500～550 ℃, resolving time is decomposed into suitable with nitrate fully, at least one hour, calcining at last, optimum temperature is not less than 850 ℃, calcined 4～6 hours, and finally obtained catalyst.
Utilize the industrial catalyst of catalyst of the present invention and China Yixing to compare experiment under the same conditions, the unit gas production of catalyst of the present invention (milliliter/milliliter catalyst gram oil) is 242, and industrial catalyst is 203, improves factor of created gase 19.2%; The compressive resistance of catalyst of the present invention (MPa/): malleation for greater than 10.7, side pressure is 8.68 (balls with holes), and the compressive resistance of industrial catalyst is 4.35～10.4 (industrial catalyst is solid sphere, no malleation, the branch of side pressure).
Embodiments of the invention are as follows:
Example one takes by weighing the 13.6 Ni (NO that restrain
3)
26H
2O, 4 gram La (NO
3)
36H
2Mg (the NO of O and 19 grams
3)
26H
2O places beaker, adds about 60 ml distilled waters (or deionized water) nitrate is dissolved fully.Again 92 carriers that restrain after the preliminary treatment are soaked in the above-mentioned solution, with repeatedly flooding solution are loaded on the carrier, until reaching scheduled volume.Leaching should be pulled out between flooding at every turn and flooding next time earlier, heat drying, dipping again.Dipping is finished the back in 100～130 ℃ of oven dry, at least 2 hours, be warming up to 450～500 ℃ of decomposition then, about 1.5 hours, after 750～800 ℃ calcined 8 hours, promptly make the catalyst finished product.
Example two takes by weighing 38.9 gram Ni (NO
3)
26H
2O and 10.6 gram La (NO
3)
36H
2O places beaker altogether, makes it to dissolve fully with about 70 ml distilled waters, again 86 carriers that restrain after the preliminary treatment is immersed above-mentioned solution, and dipping method is with example one.After having soaked, in 100～130 ℃ of dryings at least 2 hours, 550 ℃～600 ℃ added thermal decomposition about 2 hours, in 950～1000 ℃ of calcinings 4 hours, promptly made catalyst at last.
Example three takes by weighing 23.4 gram Ni (NO
3)
26H
2O, 21.3 gram La (NO
3)
36H
2O and 2.52 gram Ce (NO
3)
36H
2O places beaker altogether, adding about 70 ml distilled waters makes it to dissolve fully, then 85 gram carriers (after the preliminary treatment) are inserted above-mentioned solution, dipping method is with example one, drying condition is also with example one, and decomposition temperature is 500～550 ℃, at least 2 hours, in 800～850 ℃ of calcinings 6 hours, promptly make catalyst at last.
Example four claims 46.7 gram Ni (NO
3)
26H
2O and 17.6 gram Ce (NO
3)
36H
2O places beaker altogether, adds about 80 ml distilled waters and makes it to dissolve fully, then 81 carriers that restrain after the preliminary treatment is immersed in the above-mentioned solution, and dipping method and drying condition are with example one.Decomposition temperature is 550～600 ℃, at least 2 hours, in 900～950 ℃ of calcinings 6 hours, promptly makes catalyst at last.
Claims (4)
1. preparing city gas from heavy oil catalyst that contains rare earth, it is characterized in that with through pretreated with magnesium aluminate spinel (MgAl
2O
4) structure is main ceramic carrier, adding nitrate rare earth, nickeliferous or adding again in the solution of magnesium nitrate through dip operation, drying again, heating reduces nitrate, and makes catalyst through calcining more at last, and its chemical composition is:
NiO 3～15％(wt％)，
La
2O
3?2～8％(wt％)，
CeO
2 0～8％(wt％)，
MgO 0～5％(wt％)
All the other are formed for carrier.
2. according to the said catalyst of claim 1, wherein said ceramic carrier, it is characterized in that above-mentioned carrier under 100～150 ℃, after in concentration is rare nitric acid about 2M, soaking one hour through at least two hours dry preliminary treatment or with above-mentioned carrier at least, wash to neutrality drying preliminary treatment again.
3. according to the said catalyst of claim 1, wherein said interpolation rare earth, nickeliferous nitrate or add again in the solution of magnesium nitrate through dip operation, it is characterized in that to place through pretreated carrier and dissolve good nitrate solution and be no less than twice dip operation, once take out leaching earlier in the back at every dipping, through 100～130 ℃ of oven dry, flood again next time, reach until its chemical composition till the scheduled volume of preparation catalyst.
4. according to the said catalyst of claim 1, wherein said drying again, heating reduces nitrate, it is characterized in that the material of finishing dipping was dried two hours down at 100～130 ℃ earlier at least through calcining again, be warming up to 400～600 ℃ at least one hour, nitrate is all decomposed, calcined 4～8 hours down at 750～1000 ℃ at last.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93102722A CN1043965C (en) | 1993-03-17 | 1993-03-17 | Catalyst containing rare-earth for preparing city gas from heavy oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93102722A CN1043965C (en) | 1993-03-17 | 1993-03-17 | Catalyst containing rare-earth for preparing city gas from heavy oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1076171A CN1076171A (en) | 1993-09-15 |
| CN1043965C true CN1043965C (en) | 1999-07-07 |
Family
ID=4984241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93102722A Expired - Fee Related CN1043965C (en) | 1993-03-17 | 1993-03-17 | Catalyst containing rare-earth for preparing city gas from heavy oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1043965C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2666977A1 (en) * | 2006-10-23 | 2008-05-02 | Bp P.L.C. | Process and catalyst for hydrocarbon conversion |
| CN101693204B (en) * | 2009-10-15 | 2011-10-26 | 江汉大学 | Biomass gasification tar cracking catalyst and preparation method thereof |
| CN103055874A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Methanation catalyst used for preparing substitute natural gas from synthesis gas, and preparation method and application thereof |
| CN103723680B (en) * | 2012-10-12 | 2015-05-20 | 中国石油化工股份有限公司 | Method, device and reaction system for producing hydrogen by heavy oil fluidization |
| CN104587997B (en) * | 2013-10-30 | 2017-07-25 | 中国石油化工股份有限公司 | It is a kind of for gasifying catalyst of processing of heavy oil and its preparation method and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100025A (en) * | 1985-04-01 | 1985-11-10 | 天津大学 | Rare earth-nickel catalyst for producing hydrogen from steam conversion of hydrocarbons |
| CN85102194A (en) * | 1985-04-01 | 1986-08-13 | 中国科学院成都有机化学研究所 | Hydrocarbon vapor reforming catalyst |
| CN85103556A (en) * | 1985-04-29 | 1986-10-29 | 化学工业部西南化工研究院 | Low steam carbon ratio hydrocarbon gas conversion catalyst and manufacturing thereof and purposes |
| CN1033578A (en) * | 1987-09-18 | 1989-07-05 | 英国石油公司 | Alumina base catalyst, preparation and purposes |
| CN1042696A (en) * | 1989-10-28 | 1990-06-06 | 齐鲁石油化工公司研究院 | Hydrocarbon steam conversion catalyst and application |
-
1993
- 1993-03-17 CN CN93102722A patent/CN1043965C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100025A (en) * | 1985-04-01 | 1985-11-10 | 天津大学 | Rare earth-nickel catalyst for producing hydrogen from steam conversion of hydrocarbons |
| CN85102194A (en) * | 1985-04-01 | 1986-08-13 | 中国科学院成都有机化学研究所 | Hydrocarbon vapor reforming catalyst |
| CN85103556A (en) * | 1985-04-29 | 1986-10-29 | 化学工业部西南化工研究院 | Low steam carbon ratio hydrocarbon gas conversion catalyst and manufacturing thereof and purposes |
| CN1033578A (en) * | 1987-09-18 | 1989-07-05 | 英国石油公司 | Alumina base catalyst, preparation and purposes |
| CN1042696A (en) * | 1989-10-28 | 1990-06-06 | 齐鲁石油化工公司研究院 | Hydrocarbon steam conversion catalyst and application |
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| Publication number | Publication date |
|---|---|
| CN1076171A (en) | 1993-09-15 |
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