CN1076171A - The preparing city gas from heavy oil catalyzer that contains rare earth - Google Patents
The preparing city gas from heavy oil catalyzer that contains rare earth Download PDFInfo
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- CN1076171A CN1076171A CN 93102722 CN93102722A CN1076171A CN 1076171 A CN1076171 A CN 1076171A CN 93102722 CN93102722 CN 93102722 CN 93102722 A CN93102722 A CN 93102722A CN 1076171 A CN1076171 A CN 1076171A
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- catalyzer
- carrier
- nitrate
- rare earth
- drying
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Abstract
The invention provides a kind of heavy oil catalytic pyrolysis system town gas that contains rare earth with and have active high, a new catalyst that factor of created gase is high.
Catalyzer of the present invention be nickel, rare earth compound, magnesium oxide (or not adding magnesium oxide) are carried on together have high temperature resistant, high strength, high geometric outer surface, bed resistance are little with magnesium-aluminium spinel (MgAl
2O
4) structure is to make on the main ceramic carrier.Its chemical constitution is (Wt%) NiO
3～15%, La
2O
30～10%, CeO
20～8%, MgO0～5%, all the other are formed for carrier.
It is about 19.2% that catalyzer of the present invention can improve factor of created gase, and intensity is preferably arranged.
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 combustiblecomponents such as CO starts from the fifties in this century as the method for domestic gas.Difference according to aspects such as catalyst type and production equipment and gas production technologies can be divided into Weng Niya-Gage method, Britain southeast coal gas office method, Tokyo gas method etc.China Beijing, Shanghai, Tianjin, Dalian, Guangzhou, the methods that ground adopted such as Dandong mostly are Weng Niya-Gage method.The catalyzer 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 support of the catalyst of Britain southeast coal gas office method is also added active CaO except that containing MgO, be called the MgO-CaO series catalysts; The catalyzer that China produces also is the main component of carrier with MgO, and for example the catalyzer of Shanghai production contains NiO2.5～3.0%, MgO83.0%, Al
2O
310.58%; The catalyzer 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 catalyzer.Relevant document and patent report mostly is the catalyzer of the heavy oil catalytic pyrolysis system coal gas that fluidizer uses.The Japanese Patent report was with containing SiO in 1975
2, MgO, Fe, Co etc. so-called nickel ores as catalyzer, produce hydrogen-rich gas from heavy oil; Eiichi in 1979, people such as KiKuChi delivered the nickel catalyzator with the rhombspar load, were used for the reformation system hydrogen containing synthesis gas of high-sulfur residual oil water vapor at fluidized-bed; Nineteen eighty-three Japan, Steel works, the patent of Ltd is α-Al
2O
3The CaO-Fe of load
2O
3Catalyzer is used for the fluidized-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, catalyzer that factor of created gase is high.This catalyzer with add rare earth, nickeliferous nitrate (or adding magnesium nitrate again) be carried on together have high temperature resistant, high strength, high geometric outer surface, bed resistance are little with magnesium-aluminium spinel (MgAl
2O
4) structure is to make on the main ceramic carrier.
The preparation process of new catalyst provided by the invention can be expressed as with through metering and pretreated carrier the interpolation rare earth that has prepared, in nickeliferous nitrate (or adding magnesium nitrate again) solution through being no less than twice dip operation, drying (drying) again, thermal degradation nitrate can make new catalyst provided by the invention through calcining at last again.
The concrete preparation process of the new 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-aluminium spinel (MgAl mutually
2O
4) structure, this solid support material has been processed into shapes such as Raschig ring, spoke-like ring or ball with holes when producing; Specific surface area is 2～5 meters
2/ gram; Side pressure strength is greater than 2.5MP
a/, malleation intensity is greater than 8MP
a/; About 18 * 18 * 5 millimeters of annular size, about 16 millimeters of spherical diameter, it is about 2 millimeters through hole that 5～7 diameters are arranged on the spheroid.
Under 100～150 ℃, is after rare nitric acid about 2M soaks one hour at least, to wash to neutrality drying pre-treatment again through at least two hours dry pre-treatment or with carrier through concentration with above-mentioned carrier.
Will through the metering nickelous nitrate, rare earth nitrate (refer to single lanthanum nitrate or nitrous acid cerium, or two kinds of salt together), or add again magnesium nitrate be dissolved in through the metering distilled water in 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 predetermined amount of preparation catalyzer, 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 (or roasting) 4～8 hours down.
Through above-mentioned technological process, can obtain the said new catalyst that contains rare earth of the present invention.
The chemical constitution (comprising carrier) that contains the new catalyst of rare earth provided by the invention is:
NiO 3～15%(Wt%), are preferably 4～10%(Wt%)
La
2O
30～10%(Wt%), be preferably 2～8%(Wt%)
CeO
20～8%（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 pre-treatment, in the nitrate mixed solution that has prepared, repeatedly flood then, will thoroughly give drying between the dipping each time, the optimum temps of thermal degradation is 500～550 ℃, and the resolving time is decomposed into suitable with nitrate fully, at least one hour, calcining (or roasting) optimum temps is not less than 850 ℃ at last, calcines 4～6 hours, finally obtains catalyzer.
Utilize the industrial catalyzer of catalyzer of the present invention and China Yixing to compare experiment under the same conditions, the unit gas production rate of catalyzer of the present invention (milliliter/milliliter catalyzer gram oil) is 242, and industrial catalyzer is 203, improves factor of created gase 19.2%; The compressive strength of catalyzer of the present invention (MPa/): malleation for greater than 10.7, side pressure is 8.68(ball with holes), and the compressive strength of industrial catalyzer be the industrial catalyzer of 4.35～10.4(is solid sphere, the branch of no malleation, side pressure)
Embodiments of the invention are as follows:
Example one takes by weighing 13.6 Ni(NO that restrain
3)
26H
2O, 4 gram La(NO
3)
36H
2The Mg(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 pre-treatment are soaked in the above-mentioned solution, with repeatedly flooding solution are loaded on the carrier, until reaching predetermined amount.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 catalyzer 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 pre-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, about 2 hours of 550 ℃～600 ℃ thermal degradation in 950-1000 ℃ of calcining 4 hours, promptly made catalyzer 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 pre-treatment) are inserted above-mentioned solution, dipping method is with example one, drying conditions is also with example one, and decomposition temperature is 500～550 ℃, at least 2 hours, in 800～850 ℃ of calcinings 6 hours, promptly make catalyzer 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 pre-treatment is immersed in the above-mentioned solution, and dipping method and drying conditions are with example one.Decomposition temperature is 550～600 ℃, at least 2 hours, in 900～950 ℃ of calcinings 6 hours, promptly makes catalyzer at last.
Claims (6)
1, a kind of preparing city gas from heavy oil new catalyst that contains rare earth, it is characterized in that pretreated ceramic carrier, add rare earth, in nickeliferous nitrate (or adding magnesium nitrate again) solution through dip operation, drying (drying) again, thermal degradation nitrate makes catalyzer through calcining at last again;
2, it is characterized in that with magnesium-aluminium spinel (MgAl according to the said ceramic carrier of claim one
2O
4) structure is main ceramic carrier;
3, according to the said pretreated ceramic carrier of claim one, 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 pre-treatment or with above-mentioned carrier at least, wash to neutrality drying pre-treatment again;
4, according to the said interpolation rare earth of claim one, in nickeliferous nitrate (or adding magnesium nitrate again) solution through dip operation, it is characterized in that pretreated carrier is no less than twice dip operation in above-mentioned nitrate solution, need to take out earlier leaching at every dipping after once, under 100～130 ℃ of conditions, dry, and then flood next time, reach until its chemical constitution till the predetermined amount of preparation catalyzer
5, according to the said drying again of claim one (drying), thermal degradation nitrate, again through calcining, the material that it is characterized in that finishing dipping earlier minimum two hours of 100～130 ℃ of following heating, dryings, is warming up to 400～600 ℃ at least one hour (optimum temps is 500～550 ℃), it is suitable that nitrate is decomposed into fully, calcining (or roasting) temperature is 750～1000 ℃, and optimum temps is for being not less than 850 ℃, and calcination time is 4～8 hours, Best Times is 4～6 hours
6,, it is characterized in that the chemical constitution (comprising carrier) of catalyzer is according to the said catalyzer that makes of claim one:
NiO 3～15%(Wt%), are preferably 4～10%(wt%),
La
2O
30～10%(Wt%), be preferably 2～8%(wt%),
CeO
20～8%（wt%），
MgO 0～5%（wt%），
All the other are formed for carrier.
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 true CN1076171A (en) | 1993-09-15 |
| CN1043965C 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) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008049266A1 (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 |
| CN103723680A (en) * | 2012-10-12 | 2014-04-16 | 中国石油化工股份有限公司 | Method, device and reaction system for producing hydrogen by heavy oil fluidization |
| CN104587997A (en) * | 2013-10-30 | 2015-05-06 | 中国石油化工股份有限公司 | Gasification catalyst for heavy oil processing, and preparation method and application thereof |
Family Cites Families (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 |
| CN85102194B (en) * | 1985-04-01 | 1988-08-24 | 四川化工厂催化剂分厂 | 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 |
| GB8722008D0 (en) * | 1987-09-18 | 1987-10-28 | British Petroleum Co Plc | Catalysts |
| CN1025158C (en) * | 1989-10-28 | 1994-06-29 | 齐鲁石油化工公司研究院 | Hydrocarbon steam conversion catalyst and its application |
-
1993
- 1993-03-17 CN CN93102722A patent/CN1043965C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008049266A1 (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 |
| CN103723680A (en) * | 2012-10-12 | 2014-04-16 | 中国石油化工股份有限公司 | Method, device and reaction system for producing hydrogen by heavy oil fluidization |
| 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 |
| CN104587997A (en) * | 2013-10-30 | 2015-05-06 | 中国石油化工股份有限公司 | Gasification catalyst for heavy oil processing, and preparation method and application thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1043965C (en) | 1999-07-07 |
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