CN102059122A - Catalyst for splitting oil tar and preparation method thereof - Google Patents
Catalyst for splitting oil tar and preparation method thereof Download PDFInfo
- Publication number
- CN102059122A CN102059122A CN201010542525XA CN201010542525A CN102059122A CN 102059122 A CN102059122 A CN 102059122A CN 201010542525X A CN201010542525X A CN 201010542525XA CN 201010542525 A CN201010542525 A CN 201010542525A CN 102059122 A CN102059122 A CN 102059122A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- mixed rear
- rear earth
- tar
- accounts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a catalyst for splitting oil tar and a preparation method thereof, wherein the catalyst is prepared by mixing rare earth, CaO2, Fe2O3 and MgO2; the catalyst is used as a novel catalyst; the catalyst is capable of catalyzing and splitting heavy hydrocarbon such as oil tar, heavy oil, diesel oil and the like; the yield of light oil is increased; and the catalyst is high in catalyzing efficiency, large in strength, simple in practical application process and the like.
Description
Technical field
The invention provides a kind of catalyst that is used for coke tar cracking, be a kind of new compound, also disclose this Preparation of catalysts technology simultaneously, belong to biomass coke tar catalytic pyrolysis technical field.
Background technology
In biomass coke tar catalytic pyrolysis technical field, biomass coke tar catalytic pyrolysis principle is similar to the catalytic pyrolysis of oil, so can from petroleum industry, gain enlightenment but because the added value of catalytic cracking of tar is little, its cost will very lowly just be of practical significance about selecting for use of catalyst.So, people except that the catalyst that utilizes petroleum industry, also big quantity research material cheaply, as natural products such as lime stone, quartz sand and dolomites.
A large amount of experiments show that a lot of materials all have catalytic action to coke tar cracking, and wherein effect better has the typical material of application prospect to mainly contain three kinds again, i.e. charcoal, dolomite, nickel-base catalyst.Wherein, the effect of nickel-base catalyst is best, but because nickel-base catalyst is expensive, and cost is higher, general biomass gasification technology is difficult to use, thus can only gas need make with extra care or the technology of synthetic gasoline in use.In fact the catalytic action of charcoal uses apparent in view in the downdraft gasification furnace, but because charcoal participates in reaction in pyrolysis fuel oil, so consumption is very big, it is unrealistic to make catalyst concerning the gasification of extensive living beings, but its catalytic action has certain directive significance to the design and the small evaporator stove of gasification furnace.Dolomite is to study at most so far and the most successful catalyst.Though the composition of each place of production dolomite slightly changes, catalytic effect is arranged all.Dolomite is that catalytic efficiency height, cost are low as the major advantage of tar cracking catalyst, so have good practical values.But its hardness is low, easily characteristics crisp and easy to wear make it be difficult to be applied in fluid bed, and can be because of the carbon deposit inactivation.
No matter the systematicness that has no lack of again of a great variety of tar cracking catalyst is the natural crystal catalyst, and still artificial synthetic catalyst all has distinct advantage, but all imperfect.
Summary of the invention
The invention provides a kind of catalyst that is used for coke tar cracking, be a kind of new catalyst, can catalytic pyrolysis tar, heavy hydrocarbons such as heavy oil, diesel oil, also can increase the productive rate of light oil, have advantages such as catalytic efficiency height, intensity is big, practical application technology is simple.
The present invention also provides above-mentioned Preparation of catalysts technology, and technology simply is suitable for suitability for industrialized production.
Tar cracking catalyst of the present invention,It is characterized in that being making by the following material that accounts for catalyst weight percentage:
Mixed rear earth is (0.1～15) %, CaO
2Be (0.1～45) %, Fe
2O
3Be (0.1～30) %, all the other are MgO
2
Described catalyst is characterized in that being being made by the following material that accounts for catalyst weight percentage:
Mixed rear earth is (5～10) %, CaO
2Be (25～45) %, Fe
2O
3Be (10～20) %, all the other are MgO
2
Wherein, described mixed rear earth is made by the following material that accounts for the mixed rear earth percentage by weight:
La
2O
3Be (20～30) %, CeO
2Be (10～30) %, Nd
2O
3Be (10～20) %, Y
2O
3Be (10～20) %, PrO
11Be (5～15) %, Gd
2O
3Be (5～15) %, Sm
2O
3Be (1～10) %.
Wherein, described mixed rear earth is preferably made by the following material that accounts for the mixed rear earth percentage by weight:
La
2O
3Be 25%, CeO
2Be 20%, Nd
2O
3Be 15%, Y
2O
3Be 15%, PrO
11Be 10%, Gd
2O
3Be 10%, Sm
2O
3Be 5%.
Preparation of catalysts technology of the present invention may further comprise the steps:
With CaO
2, Fe
2O
3, MgO
2And mishmetal (RE
2O
3) pulverize the back complexing according to aforementioned proportion, dry under 100～150 ℃ of conditions, under 800～900 ℃ condition, calcine again, form the composite type metallic oxide of Ca, Fe, Mg, mixed rare earth ions composition, obtain final catalyst.
The physical characteristic of this catalyst is specific area: 151m
2/ g, pore volume 0.13mL/g, granularity 50～200nm, bulk density 1.373g/mL, the light oil oil yield can reach more than 70%.
Catalyst for cracking among the present invention is mainly used in the low temperature distillation process of living beings, organic matter, coal etc., in 550～600 ℃ of retort processes, fugitive constituent in the living beings can be full of whole dry distillation reactor device, under this condition, add tar cracking catalyst and can increase substantially fugitive constituent molecule and the interactional chance of catalyst, improve the productive rate of light oil greatly, can also increase the productive rate of combustible gas to a certain extent.
Catalyst of the present invention is mainly to be to use at the relatively poor brown coal of ature of coal, but can not therefore be defined for brown coal, also can be applicable to the catalytic pyrolysis in above-mentioned each field.
Good effect of the present invention is:Catalyst can promote product and the H after the cracking
2O and CO
2React, increase the output of coal gas; Can reach more than 70% to goudron lysis rate; Can be widely used in the energy, organic matter, biomass energy source domain, comprise: fossil fuels such as coal, gangue, oil shale, chemical materials such as waste or used plastics, rubber, living beings comprise crop material, timber wood chip, grass, etc. agriculture and forestry organic waste material, animal bone skin etc.
Description of drawings
Fig. 1 is that the light oil sample composition gas chromatograph-mass spectrometer behind the catalytic pyrolysis detects collection of illustrative plates.
The specific embodiment
Below by specific embodiment the present invention is further specified, but can not therefore be limited the present invention.
Embodiment 1
Take by weighing 35.0g CaO
2, 15.0g Fe
2O
3, 43.0g MgO
2, 7.0g mixed rear earth RE
2O
3Pulverize hybrid bonding, dry under 100～150 ℃ of conditions, under 800～900 ℃ condition, calcine again, form the composite type metallic oxide of Ca, Fe, Mg, mishmetal plasma composition, make catalyst.
Mixed rear earth (RE in the catalyst
2O
3) comprising: La
2O
3Be 25%, CeO
2Be 20%, Nd
2O
3Be 15%, Y
2O
3Be 15%, PrO
11Be 10%, Gd
2O
3Be 10%, Sm
2O
3Be 5%.
Use above-mentioned catalyst, with tar is raw material, occupy the majority with cycloalkane, toluene and condensed nucleus aromatic material in the tar, to having carried out distillation test through the light oil sample behind the catalyst action, the product that obtains under different vapo(u)rizing temperatures has carried out constituent analysis, the result show this catalyst can so that the light oil conversion ratio of tar bring up to more than 70%, under the effect of catalyst, the cycloalkane molecule is cleaved fully basically, and part aromatics molecule is also cleaved.
Detailed process: 500 ℃ of fugitive constituents with the destructive distillation coal react in the core reaction device, catalyst is fully contacted with the fugitive constituent molecule, and the fugitive constituent molecule presents comparatively active state, and molecule activation can be bigger, fully contact with catalyst molecule this moment, reacts comparatively thorough.
The catalytic pyrolysis product yield sees Table 1
Light oil sample composition gas chromatograph-mass spectrometer behind the catalytic pyrolysis detects collection of illustrative plates and sees Fig. 1.
Embodiment 2
Take by weighing 22.0g CaO
2, 20.0g Fe
2O
3, 53.0gMgO
2, 5.0g mixed rear earth RE
2O
3: pulverize the back complexing, fully bonding, dry under 100～150 ℃ of conditions, under 800～900 ℃ condition, calcine again, form the composite type metallic oxide of Ca, Fe, Mg, mishmetal plasma composition, make catalyst.
Mixed rear earth (RE in the catalyst
2O
3) comprising: La
2O
3Be 25%, CeO
2Be 20%, Nd
2O
3Be 15%, Y
2O
3Be 15%, PrO
11Be 10%, Gd
2O
3Be 10%, Sm
2O
3Be 5%.
Use above-mentioned catalyst, with tar is raw material, occupy the majority with cycloalkane, toluene and condensed nucleus aromatic material in the tar, to having carried out distillation test through the light oil sample behind the catalyst action, the product that obtains under different vapo(u)rizing temperatures has carried out constituent analysis, the result show this catalyst can so that the light oil conversion ratio of tar bring up to more than 70%, under the effect of catalyst, the cycloalkane molecule is cleaved fully basically, and part aromatics molecule is also cleaved.
Detailed process: 550 ℃ of fugitive constituents with the destructive distillation coal react in the core reaction device, catalyst of the present invention is fully contacted with the fugitive constituent molecule, and the fugitive constituent molecule presents comparatively active state, and molecule activation can be bigger, fully contact with catalyst molecule this moment, reacts comparatively thorough.
The catalytic pyrolysis product yield sees Table 1.
Embodiment 3
Take by weighing CaO
2: 40.0g, Fe
2O
3: 10.0g, MgO
2: 40.0g, mixed rear earth RE
2O
3: 10.0g pulverizes hybrid bonding, and is dry under 100～150 ℃ of conditions, calcines under 800～900 ℃ condition again, forms the composite type metallic oxide of Ca, Fe, Mg, mixed rare earth ions composition, makes catalyst.
Mixed rear earth RE in the catalyst
2O
3Comprise: La
2O
3Be 25%, CeO
2Be 20%, Nd
2O
3Be 15%, Y
2O
3Be 15%, PrO
11Be 10%, Gd
2O
3Be 10%, Sm
2O
3Be 5%.
Use above-mentioned catalyst, with tar is raw material, occupy the majority with cycloalkane, toluene and condensed nucleus aromatic material in the tar, to having carried out distillation test through the light oil sample behind the catalyst action, the product that obtains under different vapo(u)rizing temperatures has carried out constituent analysis, the result show this catalyst can so that the light oil conversion ratio of tar bring up to more than 70%, under the effect of catalyst, the cycloalkane molecule is cleaved fully basically, and part aromatics molecule is also cleaved.
Detailed process: 600 ℃ of fugitive constituents with the destructive distillation coal react in the core reaction device, catalyst is fully contacted with the fugitive constituent molecule, and the fugitive constituent molecule presents comparatively active state, and molecule activation can be bigger, fully contact with catalyst molecule this moment, reacts comparatively thorough.
The catalytic pyrolysis product yield sees Table 1.
Embodiment 4
% takes by weighing CaO by catalyst weight
2: Fe 30.0%,
2O
3: MgO 18.0%,
2: RE 44.0%,
2O
3: 8.0% pulverizes hybrid bonding, dry under 100～150 ℃ of conditions, calcines under 800～900 ℃ condition again, forms the composite type metallic oxide of Ca, Fe, Mg, mishmetal plasma composition, makes catalyst.
Mixed rear earth RE in the catalyst
2O
3Comprise: La
2O
3Be 25%, CeO
2Be 20%, Nd
2O
3Be 15%, Y
2O
3Be 15%, PrO
11Be 10%, Gd
2O
3Be 10%, Sm
2O
3Be 5%.
Use above-mentioned catalyst, with tar is raw material, occupy the majority with cycloalkane, toluene and condensed nucleus aromatic material in the tar, to having carried out distillation test through the light oil sample behind the catalyst action, the product that obtains under different vapo(u)rizing temperatures has carried out constituent analysis, the result show this catalyst can so that the light oil conversion ratio of tar bring up to more than 70%, under the effect of catalyst, the cycloalkane molecule is cleaved fully basically, and part aromatics molecule is also cleaved.
Detailed process: 650 ℃ of fugitive constituents with the destructive distillation coal react in the core reaction device, catalyst is fully contacted with the fugitive constituent molecule, and the fugitive constituent molecule presents comparatively active state, and molecule activation can be bigger, fully contact with catalyst molecule this moment, reacts comparatively thorough.
The catalytic pyrolysis product yield sees Table 1.
Claims (5)
1. catalyst that is used for coke tar cracking is characterized in that being being made by the following material that accounts for catalyst weight percentage:
Mixed rear earth is (0.1～15) %, CaO
2Be (0.1～45) %, Fe
2O
3Be (0.1～30) %, all the other are MgO
2
2. the described catalyst of claim 1 is characterized in that being being made by the following material that accounts for catalyst weight percentage:
Mixed rear earth is (5～10) %, CaO
2Be (25～45) %, Fe
2O
3Be (10～20) %, all the other are MgO
2
3. claim 1 or 2 described catalyst, it is characterized in that: mixed rear earth is made by the following material that accounts for the mixed rear earth percentage by weight:
La
2O
3Be (20～30) %, CeO
2Be (10～30) %, Nd
2O
3Be (10～20) %, Y
2O
3Be (10～20) %, PrO
11Be (5～15) %, Gd
2O
3Be (5～15) %, Sm
2O
3Be (1～10) %.
4. claim 1,2 or 3 described catalyst, it is characterized in that: mixed rear earth is made by the following material that accounts for the mixed rear earth percentage by weight:
La
2O
3Be 25%, CeO
2Be 20%, Nd
2O
3Be 15%, Y
2O
3Be 15%, PrO
11Be 10%, Gd
2O
3Be 10%, Sm
2O
3Be 5%.
5. claim 1 or 2 described Preparation of catalysts technologies may further comprise the steps:
With CaO
2, Fe
2O
3, MgO
2And mishmetal is dry under 100～150 ℃ of conditions according to aforementioned proportion pulverizing back complexing, calcines under 800～900 ℃ condition again, and the composite type metallic oxide that formation Ca, Fe, Mg, mixed rare earth ions are formed obtains catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010542525XA CN102059122A (en) | 2010-11-15 | 2010-11-15 | Catalyst for splitting oil tar and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010542525XA CN102059122A (en) | 2010-11-15 | 2010-11-15 | Catalyst for splitting oil tar and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102059122A true CN102059122A (en) | 2011-05-18 |
Family
ID=43994734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010542525XA Pending CN102059122A (en) | 2010-11-15 | 2010-11-15 | Catalyst for splitting oil tar and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102059122A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103394356A (en) * | 2013-08-20 | 2013-11-20 | 山东省科学院能源研究所 | Biomass pyrolysis gasification multifunctional iron-based catalyst and preparation method thereof |
| CN104525179A (en) * | 2014-12-29 | 2015-04-22 | 江苏健神生物农化有限公司 | Process for preparing catalyst used for catalytic cracking of waste plastics |
| CN107457246A (en) * | 2017-09-04 | 2017-12-12 | 华中科技大学 | The method of the broken apart recovery copper remnants non-metal powders catalysis pyrolysis of useless circuit board |
| CN108059969A (en) * | 2017-12-21 | 2018-05-22 | 安徽工业大学 | A kind of method with waste iron filing and bloodstone catalytic pyrolysis high temperature coal-tar |
| CN108085051A (en) * | 2017-12-21 | 2018-05-29 | 安徽工业大学 | A kind of method with iron scale catalytic pyrolysis high temperature coal-tar |
| CN108085050A (en) * | 2017-12-21 | 2018-05-29 | 安徽工业大学 | A kind of method with iron scale and magnetic iron ore catalytic pyrolysis high temperature coal-tar |
| CN111744487A (en) * | 2020-07-20 | 2020-10-09 | 威尔能环保科技(苏州)有限公司 | Supported catalyst, preparation method thereof and treatment method of tar-containing gas |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5275649A (en) * | 1992-02-18 | 1994-01-04 | Colorsil B.V. | Doped zirconium mixed silicate pigment, method for the preparation thereof and products containing such pigment or a thus prepared pigment |
| CN101024179A (en) * | 2002-10-21 | 2007-08-29 | 格雷斯公司 | NOx reduction compositions for use in FCC processes |
| CN101396660A (en) * | 2008-10-22 | 2009-04-01 | 中国林业科学研究院林产化学工业研究所 | Biomass gasification tar cracking composite catalyst and preparation method thereof |
| CN101485989A (en) * | 2009-02-24 | 2009-07-22 | 上海大学 | Catalyst for cracking coke tar component in coke oven gas and preparation method thereof |
-
2010
- 2010-11-15 CN CN201010542525XA patent/CN102059122A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5275649A (en) * | 1992-02-18 | 1994-01-04 | Colorsil B.V. | Doped zirconium mixed silicate pigment, method for the preparation thereof and products containing such pigment or a thus prepared pigment |
| CN101024179A (en) * | 2002-10-21 | 2007-08-29 | 格雷斯公司 | NOx reduction compositions for use in FCC processes |
| CN101396660A (en) * | 2008-10-22 | 2009-04-01 | 中国林业科学研究院林产化学工业研究所 | Biomass gasification tar cracking composite catalyst and preparation method thereof |
| CN101485989A (en) * | 2009-02-24 | 2009-07-22 | 上海大学 | Catalyst for cracking coke tar component in coke oven gas and preparation method thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103394356A (en) * | 2013-08-20 | 2013-11-20 | 山东省科学院能源研究所 | Biomass pyrolysis gasification multifunctional iron-based catalyst and preparation method thereof |
| CN104148081A (en) * | 2013-08-20 | 2014-11-19 | 山东省科学院能源研究所 | Biomass pyrolysis gasification multifunctional iron-based catalyst |
| CN103394356B (en) * | 2013-08-20 | 2014-11-26 | 山东省科学院能源研究所 | Biomass pyrolysis gasification multifunctional iron-based catalyst and preparation method thereof |
| CN104148081B (en) * | 2013-08-20 | 2016-05-11 | 山东省科学院能源研究所 | The multi-functional ferrum-based catalyst of biomass pyrogenation gasification |
| CN104525179A (en) * | 2014-12-29 | 2015-04-22 | 江苏健神生物农化有限公司 | Process for preparing catalyst used for catalytic cracking of waste plastics |
| CN107457246A (en) * | 2017-09-04 | 2017-12-12 | 华中科技大学 | The method of the broken apart recovery copper remnants non-metal powders catalysis pyrolysis of useless circuit board |
| CN108059969A (en) * | 2017-12-21 | 2018-05-22 | 安徽工业大学 | A kind of method with waste iron filing and bloodstone catalytic pyrolysis high temperature coal-tar |
| CN108085051A (en) * | 2017-12-21 | 2018-05-29 | 安徽工业大学 | A kind of method with iron scale catalytic pyrolysis high temperature coal-tar |
| CN108085050A (en) * | 2017-12-21 | 2018-05-29 | 安徽工业大学 | A kind of method with iron scale and magnetic iron ore catalytic pyrolysis high temperature coal-tar |
| CN111744487A (en) * | 2020-07-20 | 2020-10-09 | 威尔能环保科技(苏州)有限公司 | Supported catalyst, preparation method thereof and treatment method of tar-containing gas |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102059122A (en) | Catalyst for splitting oil tar and preparation method thereof | |
| Speight | Handbook of petrochemical Processes | |
| Lu et al. | Investigation on the characteristics of pyrolysates during co-pyrolysis of Zhundong coal and Changji oil shale and its kinetics | |
| Moradi-Choghamarani et al. | Determining organo-chemical composition of sugarcane bagasse-derived biochar as a function of pyrolysis temperature using proximate and Fourier transform infrared analyses | |
| Hu et al. | The catalytic pyrolysis of microalgae to produce syngas | |
| CN101955181B (en) | Method for preparing active carbon by using carbon byproduct of fast pyrolysis of larchwood | |
| Chen et al. | Spent lithium-ion battery materials recycling for catalytic pyrolysis or gasification of biomass | |
| Narzari et al. | Biochar: an overview on its production, properties and potential benefits | |
| Feng et al. | In-situ steam reforming of biomass tar over sawdust biochar in mild catalytic temperature | |
| Lu et al. | Investigation on the catalytic effect of AAEMs on the pyrolysis characteristics of Changji oil shale and its kinetics | |
| CN102154044A (en) | Method for preparing engine fuel gas by using biomass and/or organic waste | |
| CN102844408A (en) | Multi-purpose renewable fuel for isolating contaminants and storing energy | |
| Gao et al. | Co-pyrolysis of municipal solid waste (MSW) and biomass with Co/sludge fly ash catalyst | |
| Hu et al. | Experimental study and economic feasibility analysis on the production of bio-oil by catalytic cracking of three kinds of microalgae | |
| He et al. | Feedstock and pyrolysis temperature influence biochar properties and its interactions with soil substances: Insights from a DFT calculation | |
| Liu et al. | Decomposition of benzyl phenyl ether over char-supported Ni: The effect of char structures | |
| Hong et al. | Catalytic upgrading of penicillin fermentation residue bio-oil by metal-supported HZSM-5 | |
| CN101723364B (en) | Method for preparing activated carbon by using plasmas to crack solid coal product | |
| CN103878031B (en) | A kind of oil shale pyrolysis Catalysts and its preparation method and using method | |
| CN107365597A (en) | A kind of method for deriving fuel oil using organic matter waste gasification synthetic fluid | |
| Pan et al. | Influence of transition metal salts and pyrolysis conditions on the product yield via Jimsar oil shale pyrolysis | |
| CN101735841B (en) | Oil shale powder slag cold-pressing balls and preparation method thereof | |
| CN102247857A (en) | Mixed rare earth catalyst and preparation method thereof | |
| Xu et al. | Production of C5-C12 olefins by catalytic pyrolysis of low-density polyethylene with MCM-41 in CO2/N2 | |
| Kapkaev et al. | Production of motor biofuels in the context of environmental management of the oil industry |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20110518 |