CN109589981B - Loofah sponge-like biomass pyrolysis decoking catalyst and preparation method and application thereof - Google Patents
Loofah sponge-like biomass pyrolysis decoking catalyst and preparation method and application thereof Download PDFInfo
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- CN109589981B CN109589981B CN201811479349.2A CN201811479349A CN109589981B CN 109589981 B CN109589981 B CN 109589981B CN 201811479349 A CN201811479349 A CN 201811479349A CN 109589981 B CN109589981 B CN 109589981B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
- C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/18—Modifying the properties of the distillation gases in the oven
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Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a loofah sponge-shaped biomass pyrolysis decoking catalyst, and a preparation method and application thereof. The preparation method comprises the following steps: 1) preparing a premixed solution; 2) preparing slurry, wherein the slurry comprises 4-6 parts of Ni/palygorskite catalyst, 1-2 parts of mullite fiber, 1-2 parts of fused quartz, 1-2 parts of dispersant and 3-5 parts of premixed liquid obtained in the step 1); 3) pouring the slurry into a mold filled with loofah sponge for molding, fixing and forming, demolding and drying to obtain a sample; 4) and firing the sample to obtain the loofah sponge-shaped biomass pyrolysis decoking catalyst. The invention uses the loofah sponge as a framework to prepare the nickel-based catalyst for biomass pyrolysis decoking, thereby realizing resource recycling. The prepared loofah sponge-shaped biomass pyrolysis decoking catalyst has a developed network structure, so that the retention time of tar-containing gas in the pyrolysis process is prolonged, and the aim of decoking is fulfilled.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a loofah sponge-shaped biomass pyrolysis decoking catalyst, and a preparation method and application thereof.
Background
The loofah sponge is a fiber pipe system for drying mature fruits, has a highly developed porous network structure with criss-cross internal fibers, is tough, is widely planted in Asia, China and south America, and is a good biomass material with high quality and low price. At present, loofah sponge is taken as a raw material, developed loofah sponge bath, washing and other articles are commercially applied, besides, the research on loofah sponge in China mainly focuses on the extraction of polysaccharide, cellulose and glycosides, a small amount of research is carried out in the environmental field, and considerable loofah sponge is not effectively and comprehensively utilized. The highly developed porous network structure can be used as a framework to prepare a catalyst, and the excellent structural characteristics of the loofah sponge are utilized to prepare a product with high added value, so that the loofah sponge has excellent ecological and economic benefits.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a loofah sponge-like biomass pyrolysis decoking catalyst and a preparation method and application thereof.
The technical scheme provided by the invention is as follows:
a preparation method of a loofah sponge-like biomass pyrolysis decoking catalyst comprises the following steps:
1) preparing a premixed solution;
2) preparing a slurry, wherein the slurry comprises 4-6 parts of Ni/palygorskite catalyst, 1-2 parts of mullite fiber, 1-2 parts of fused quartz, 1-2 parts of a dispersing agent and 3-5 parts of the premixed liquid obtained in the step 1);
3) pouring the slurry obtained in the step 2) into a mold filled with loofah sponge for molding, fixing and forming, demolding and drying to obtain a sample;
4) firing the sample obtained in the step 3) to obtain the cucurbituril-shaped biomass pyrolysis decoking catalyst.
According to the technical scheme, the loofah sponge is used as a framework to prepare various catalysts for biomass pyrolysis decoking, so that resource recycling is realized. Due to the developed network structure, the residence time of tar gas in the pyrolysis process is prolonged, namely the tar gas can be in contact with the catalyst more fully, so that the aim of removing coke is fulfilled. In addition, the loofah sponge is cheap and easy to obtain, and the preparation cost is reduced.
Specifically, in step 1): the premix comprises 14-16 parts of methyl cellulose, 2-4 parts of sodium silicate and 100 parts of water.
In the technical scheme, the sodium carboxymethyl cellulose has the function of increasing the viscosity of the premixed solution, so that all components are uniformly dispersed and generate air holes after high-temperature gasification; the sodium silicate is used for increasing the viscosity of the premixed liquid and enhancing the strength of the catalyst; the catalyst comprises a premixed solution of 14-16 parts of methyl cellulose, 2-4 parts of sodium silicate and 100 parts of water, and has the functions of dispersing all components of the catalyst and enhancing the strength of the catalyst.
Specifically, in the step 2): the Ni/palygorskite catalyst has Ni loading amount of 5-15 wt%.
In the technical scheme, the catalytic effect is not obvious enough due to the excessively low load; too high loading can result in sintering of the active component, affecting the catalytic effect of the catalyst and making catalyst regeneration difficult and increasing cost.
Specifically, in the step 2): the slurry is obtained by mixing the components and then performing ball milling.
In the technical scheme, the raw materials can be ball-milled to 5-10 microns by ball milling, so that high dispersion is realized, the components are fully and uniformly mixed, and the pores of the loofah sponge can be filled with the slurry.
Specifically, in the step 2): the ball milling speed is 650 to 750 rad/min; the ball milling time is 2-3 h.
In the technical scheme, the ball milling speed is too low, so that the slurry is not uniformly mixed, and the ball milling time is prolonged; the over-high ball milling speed can cause the structural damage of the catalyst; too low a ball milling time can result in non-uniform slurry mixing; too high a time for ball milling may result in structural destruction of the catalyst.
Specifically, in step 3): the weight ratio of the slurry to the loofah sponge is 14-16: 1 to 3.
In the technical scheme, the pores of the loofah sponge cannot be completely filled due to the excessively low weight ratio of the slurry to the loofah sponge; too high a weight ratio of the slurry to the loofah sponge leads to material waste and a reduction in the porosity of the finished catalyst product.
Specifically, in step 3): and heating the die under a sealed condition for fixing and forming, wherein the heating temperature is 85-95 ℃, and the heating time is 100-150 min.
In the technical scheme, the cracking of the catalyst can be avoided by heating under a sealed condition; too low a heating temperature results in a longer heating time; too high a heating temperature may cause too rapid evaporation of water and cracking of the catalyst; too short a heating time may result in insufficient evaporation of water; excessive heating times can lead to catalyst cracking.
Specifically, in step 3): and (4) placing the fixed and molded die at room temperature for 5-8 h, and then demolding.
In the technical scheme, the water which is not removed can be uniformly removed after being placed at room temperature; too short a standing time may result in incomplete removal of water; too long a residence time can lead to catalyst cracking.
Specifically, in step 3): and after demolding, drying the sample for 6-8 days under natural conditions, and then drying the sample in a constant-temperature drying oven at 100-110 ℃ for 3-5 hours to obtain the sample.
In the technical scheme, the drying is carried out under natural conditions, so that the water removal speed can be controlled, and the cracking of the catalyst after demolding is avoided; too short a drying time may result in incomplete water removal; too long a drying time can lead to cracking of the catalyst. Excessively low constant-temperature drying temperature may cause moisture residue and increase drying time; excessive constant temperature drying temperature can cause cracking of the catalyst; too short constant-temperature drying time can cause incomplete water extraction; too long drying times at constant temperature can lead to cracking of the catalyst.
Specifically, the method is characterized in that in the step 3): firing at 900-1100 ℃ for 2-4h at a heating rate of 5-10 ℃/min in an air atmosphere to obtain the catalyst for pyrolysis and decoking of the cucurbituril biomass.
In the technical scheme, the loofah sponge is fired in the air atmosphere, so that the loofah sponge can be directly gasified at high temperature; too low temperature rise rate can result in too low gasification speed and influence the molding of the mesh structure; an excessively high temperature rise rate leads to an increase in energy consumption; the catalyst is easy to break due to the excessively low firing temperature, and the hardness cannot meet the requirement; too high firing temperature leads to increased energy consumption and cracking of the catalyst; too short firing time can cause the catalyst to be easy to break, and the hardness can not meet the requirement; too long firing times can lead to increased energy consumption and cracking of the catalyst.
The invention also provides a preparation method of the loofah sponge-shaped biomass pyrolysis decoking catalyst, and the prepared loofah sponge-shaped biomass pyrolysis decoking catalyst.
The loofah sponge-shaped biomass pyrolysis decoking catalyst provided by the invention has a developed network structure, and the retention time of tar-containing gas in the pyrolysis process is prolonged, namely the tar-containing gas can be more fully contacted with the catalyst, so that the aim of decoking is fulfilled.
The invention also provides application of the cucurbituril-shaped biomass pyrolysis decoking catalyst provided by the invention as a biomass pyrolysis decoking catalyst.
The catalyst for pyrolysis and decoking of cucurbituril biomass, provided by the invention, is used for catalytic pyrolysis of biomass, and has good performances of reducing tar content in biomass gas and increasing gas yield; compared with other existing catalysts of the same type, the catalyst can obviously improve H in fuel gas2And the content of CO is reduced, and the content of tar in the fuel gas is reduced.
Drawings
Fig. 1 is a microscopic structural diagram of a cross section of the loofah sponge-like biomass pyrolysis decoking catalyst provided by the invention.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
In one embodiment, the preparation method of the loofah sponge-like biomass pyrolysis decoking catalyst comprises the following steps:
1. preparation of the Mixed solution
The ratio of sodium carboxymethylcellulose to sodium silicate is 5: 1 preparing mixed solution, accurately weighing 15g of carboxymethyl cellulose and 3g of sodium silicate by using a balance, adding the weighed materials into a beaker filled with 100ml of sodium silicate, and stirring the materials on a magnetic stirrer until the materials are completely dissolved. Adding the prepared premixed solution into a preservative film and standing for later use.
2. Preparation of the slurry
The invention takes Ni/palygorskite catalyst as main material, mullite fiber and fused quartz with different proportions are added, the mixture and premixed liquid with proper proportion are poured into a ball milling tank to prepare slurry, and a proper amount of dispersant is added to stabilize and disperse the slurry. Ball milling was carried out at 700rad/min for 2.5 h. Pouring the ground slurry into a grinding tool filled with loofah sponge, and uniformly coating a layer of vaseline on the inner side of the mould so as to facilitate demoulding.
3. Sample forming and fixing
Sealing the preservative film for the mold, putting the preservative film into a constant-temperature drying oven for fixing and molding at 90 ℃, taking out the preservative film after 120min, standing the preservative film at room temperature for 200min, and demolding. The demolded sample was dried for one week under natural conditions and then further dried in a 105 ℃ oven.
4. Sample firing
Firing at the temperature rising rate of 5-10 ℃/min at the temperature of 900-1100 ℃ for 2-4 h.
As shown in fig. 1, the loofah sponge used in the invention has a porous network structure, after the loofah sponge is poured, dried and calcined by a feed liquid, the loofah sponge is directly gasified at high temperature, and the porous network structure is left in the catalyst.
Examples of effects
20g of loofah sponge-shaped biomass pyrolysis decoking catalyst (namely loofah sponge nickel-based catalyst with the active component content of 5%) and 5g of rice straw are placed into a horizontal tubular furnace, a nitrogen valve is opened, and N is adjusted2The flow is 1L/min, the air in the pipe is discharged to ensure that the pipe is in an anaerobic environment, and the valve is closed after 20 min. Pyrolyzing at 700 deg.C for 20min, opening outlet valve, collecting gas generated by pyrolysis, analyzing gas content and tar content, and detecting gas components and content, the results are shown in Table 1 and Table 2 below.
TABLE 1 analysis of gas and tar contents of rice straw under the pyrolysis action of loofah sponge-like biomass pyrolysis decoking catalyst
| NiO content/(wt%) in nickel-based catalyst | Gas yield(N/m3) | Tar yield(g/Kg) |
| 5 | 1.21 | 6.4 |
TABLE 2 analysis of gas components and contents of rice straw under the pyrolysis action of loofah sponge-like biomass pyrolysis decoking catalyst
Comparative example
Under the condition of no nickel-based catalyst, 20g of palygorskite and 5g of rice straw are put into a horizontal tubular furnace, a nitrogen valve is opened, and N is adjusted2The flow is 1L/min, the air in the pipe is discharged to ensure that the pipe is in an anaerobic environment, and the valve is closed after 20 min. Pyrolyzing at 700 ℃ for 20min, then opening an outlet valve, collecting gas generated by pyrolysis, analyzing the gas content and tar content, detecting the gas components and content, and comparing the detection result with the catalytic pyrolysis result of the rice straws, wherein the comparison results are shown in tables 3 and 4.
TABLE 3 comparison of gas and Tar content of Rice straw with and without catalyst pyrolysis
| NiO content/(wt%) of nickel-based catalyst | Gas yield(N/m3) | Tar yield(g/Kg) |
| 0 | 0.66 | 66.7 |
| 5 | 1.21 | 6.4 |
TABLE 4 comparison of gas composition and content of rice straw in the presence or absence of catalyst pyrolysis
The data show that the loofah sponge-shaped biomass pyrolysis decoking catalyst provided by the invention has the capability of remarkably improving gas yield and decoking, the gas yield is improved by 90% after the catalyst is added, and the tar yield is reduced by 90.4%; h in gas2The content is improved by 137 percent, and the content of CO is improved by 64 percent. The prepared loofah sponge-shaped biomass pyrolysis decoking catalyst can obviously improve the yield of straw pyrolysis and the content of combustible gas in fuel gas, reduce the content of tar and improve the quality of the fuel gas, so that the loofah sponge-shaped biomass pyrolysis decoking catalyst prepared by the invention can be used for pyrolyzing or gasifying and decoking biomass such as rice straw, corn straw, wheat straw and the like, and the quality of the biomass pyrolysis or gasified fuel gas is improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is defined by the following claims.
Claims (9)
1. A preparation method of a loofah sponge-like biomass pyrolysis decoking catalyst is characterized by comprising the following steps:
1) preparing a premixed solution, wherein the premixed solution comprises 14-16 parts of methyl cellulose, 2-4 parts of sodium silicate and 100 parts of water;
2) preparing a slurry, wherein the slurry comprises 4-6 parts of Ni/palygorskite catalyst, 1-2 parts of mullite fiber, 1-2 parts of fused quartz, 1-2 parts of a dispersing agent and 3-5 parts of the premixed liquid obtained in the step 1);
3) pouring the slurry obtained in the step 2) into a mold filled with loofah sponge for molding, fixing and forming, demolding and drying to obtain a sample;
4) firing the sample obtained in the step 3) to obtain the loofah sponge-shaped biomass pyrolysis decoking catalyst.
2. The method for preparing the loofah sponge-like biomass pyrolysis decoking catalyst according to claim 1, wherein in step 2): the Ni/palygorskite catalyst has Ni loading amount of 5-15 wt%.
3. The method for preparing the loofah sponge-like biomass pyrolysis decoking catalyst according to claim 1, wherein in step 2): the slurry is obtained by mixing the components and then performing ball milling.
4. The preparation method of the loofah sponge-like biomass pyrolysis decoking catalyst according to claim 3, characterized in that in step 2): the ball milling speed is 650 to 750 rad/min; the ball milling time is 2-3 h.
5. The method for preparing the loofah sponge-like biomass pyrolysis decoking catalyst according to claim 1, wherein in step 3): the weight ratio of the slurry to the loofah sponge is 14-16: 1 to 3.
6. The method for preparing the loofah sponge-like biomass pyrolysis decoking catalyst according to claim 1, wherein in step 3):
heating the die under a sealed condition for fixing and forming, wherein the heating temperature is 85-95 ℃, and the heating time is 100-150 min;
placing the fixed and molded die at room temperature for 5-8 h, and then demolding;
and after demolding, drying the sample for 6-8 days under natural conditions, and then drying in a constant-temperature drying oven at 100-110 ℃ for 200-250 min to obtain the sample.
7. The method for preparing the loofah sponge-like biomass pyrolysis decoking catalyst according to any one of claims 1 to 6, wherein in step 3): firing at 900-1100 ℃ for 2-4h at a heating rate of 5-10 ℃/min in an air atmosphere to obtain the catalyst for pyrolysis and decoking of the cucurbituril biomass.
8. The loofah sponge-like biomass pyrolysis decoking catalyst prepared by the preparation method of the loofah sponge-like biomass pyrolysis decoking catalyst according to any one of claims 1 to 7.
9. The application of the catalyst for pyrolysis and decoking of cucurbituril biomass as claimed in claim 8, wherein the catalyst comprises the following components in percentage by weight: as a biomass pyrolysis decoking catalyst.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007229548A (en) * | 2006-02-27 | 2007-09-13 | Nippon Steel Engineering Co Ltd | Reforming catalyst acted in biomass pyrolysis gasification process, its manufacturing method and modification process using the reforming catalyst, biomass pyrolytic gasifying device, and method for regenerating catalyst |
| CN101172232A (en) * | 2007-10-10 | 2008-05-07 | 大连理工大学 | Palygorskite load nickel base biomass tar oil recapitalization hydrogen manufacturing catalyzer and preparation method thereof |
| CN104446417A (en) * | 2014-12-04 | 2015-03-25 | 浙江大学 | Porous block-shaped ferrite prepared based on loofah sponge and preparation method of porous block-shaped ferrite |
| CN108927131A (en) * | 2018-07-09 | 2018-12-04 | 江苏俊镕环保设备有限公司 | A kind of preparation method of tar gas cracking composite catalyzing material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007229548A (en) * | 2006-02-27 | 2007-09-13 | Nippon Steel Engineering Co Ltd | Reforming catalyst acted in biomass pyrolysis gasification process, its manufacturing method and modification process using the reforming catalyst, biomass pyrolytic gasifying device, and method for regenerating catalyst |
| CN101172232A (en) * | 2007-10-10 | 2008-05-07 | 大连理工大学 | Palygorskite load nickel base biomass tar oil recapitalization hydrogen manufacturing catalyzer and preparation method thereof |
| CN104446417A (en) * | 2014-12-04 | 2015-03-25 | 浙江大学 | Porous block-shaped ferrite prepared based on loofah sponge and preparation method of porous block-shaped ferrite |
| CN108927131A (en) * | 2018-07-09 | 2018-12-04 | 江苏俊镕环保设备有限公司 | A kind of preparation method of tar gas cracking composite catalyzing material |
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