CN106378186B - A kind of preparation method of base metal type biogas dehydrogenation catalyst - Google Patents
A kind of preparation method of base metal type biogas dehydrogenation catalyst Download PDFInfo
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- CN106378186B CN106378186B CN201610947808.XA CN201610947808A CN106378186B CN 106378186 B CN106378186 B CN 106378186B CN 201610947808 A CN201610947808 A CN 201610947808A CN 106378186 B CN106378186 B CN 106378186B
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Abstract
A kind of preparation method of base metal type biogas dehydrogenation catalyst, it is characterized in that it is the following steps are included: first, preparation has the characteristics that the strong Titanium Sieve Molecular Sieve carrier of hydrophobicity, avoids vapor to the influence of deoxidation catalysis reaction, controls the aperture of Titanium Sieve Molecular Sieve carrier between 2.3-3.7 nm；Secondly, being modified processing to Titanium Sieve Molecular Sieve carrier, exchanged by Fe, Mg, Li cation, effectively increase molecular sieve bore diameter, reinforces mass transferring in gas phase process；Third carries out active component load to the Titanium Sieve Molecular Sieve after modification, and by loading Mn, Cu, Zr metal oxide active component, the acid-base property of Effective Regulation catalyst improves catalytic activity and inhibits the aging of catalysis.Present invention process is simple, at low cost, prepares that resulting catalyst activity is strong, and the service life is long.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst, especially a kind of technology of preparing of dehydrogenation catalyst, specifically
Say be a kind of base metal type biogas dehydrogenation catalyst preparation method.
Background technique
Biogas mostlys come from sewage treatment plant, Municipal Solid-state Garbage-disposal Facilities, refuse landfill etc., is that organic waste exists
Gaseous products in anaerobic digestion process.Biogas is rich in methane, is maximum discharge of methane source caused by mankind's activity, therefore at
For the greenhouse gases for needing strict control to discharge.
In order to control firedamp drainage, biogas is carried out combustion power generation or is purified to become what methane recovery utilized for vehicle fuel
Major way.During methane purification refines vehicle fuel, a small amount of oxygen that will contain in biogas is needed to remove.Tradition
Biogas deoxidation mode be to be supported on activated alumina or perovskite metal oxides material using noble metal (such as Pt, Pd)
It is prepared into dehydrogenation catalyst, makes biogas that catalytic oxidation occur on catalyst surface, utilizes the methane and oxygen in biogas
Reaction generates carbon dioxide and water, to realize deoxidation treatment.But there are catalyst cost is inclined in practical application for such catalyst
The problems such as high, catalyst is easy to inactivate, high-temperature temperature is higher, causes the increased costs of biogas deoxidation treatment.
Summary of the invention
The purpose of the present invention is for existing biogas dehydrogenation catalyst need to use noble-metal-supported and there are high expensive,
The problems such as catalyst is easy to inactivate, high-temperature temperature is higher, causes the increased costs of biogas deoxidation treatment, invents a kind of base metal
The preparation method of type biogas dehydrogenation catalyst.
The technical scheme is that
A kind of preparation method of base metal type biogas dehydrogenation catalyst, it is characterized in that it the following steps are included:
Firstly, preparation has the characteristics that the strong Titanium Sieve Molecular Sieve carrier of hydrophobicity, avoid vapor to deoxidation catalysis reaction
It influences, controls the aperture of Titanium Sieve Molecular Sieve carrier between 2.3-3.7 nm；
Secondly, being modified processing to Titanium Sieve Molecular Sieve carrier, exchanged by Fe, Mg, Li cation, effectively increase molecule
Mesh size reinforces mass transferring in gas phase process；
Third carries out active component load to the Titanium Sieve Molecular Sieve after modification, by loading Mn, Cu, Zr metal oxygen
Compound active component, the acid-base property of Effective Regulation catalyst improve catalytic activity and inhibit the aging of catalysis.
The Titanium Sieve Molecular Sieve support preparation method refers to: being in proportion 5~20 parts of sodium metasilicate, 2~8 parts parts by weight
White carbon black, 3~8 parts of NaOH, 1~3 part of KCl and 1~3 part of part waterglass are added in 50 parts of deionized water, at room temperature strongly
Stirring is uniformly mixed it, persistently stirs 30~120min, gained suspension is transferred in autoclave, in 200~280
DEG C 36~72h of hydro-thermal reaction, is cooled to room temperature, and is filtered, washed and in 70 ± 5 DEG C of dry 6~12h, and Titanium Sieve Molecular Sieve is obtained
Material；The specific surface area of preparation-obtained Titanium Sieve Molecular Sieve carrier is in 620~650m2In/g range.
It is described processing is modified to Titanium Sieve Molecular Sieve carrier to refer to: 3~8 parts of FeCl by weight3, 1~4 part
MgCl2It is added in 50 parts of deionized water with 4~8 parts of LiCl, 10~20 parts of Titanium Sieve Molecular Sieve carrier is added after dissolution,
It stirs evenly, adjusts pH between 6~8,24~48h is stirred at 60 ± 5 DEG C, carry out cationic exchange, be cooled to room temperature,
It is filtered, washed and in 70 ± 5 DEG C of dry 6~12h, obtains modified Titanium Sieve Molecular Sieve carrier.
The active component load refers to 3~6 parts of Mn (NO by weight3)2, 2~5 parts of Zr (NO3)4, 3~8 parts
Ce(NO3)3With 1~3 part of Cu (NO3)2It is added in 50 parts of deionized water, 10~20 parts of modified titanium silicon is added after dissolution
Molecular sieve carrier impregnates 5~10h, dries 4~6h after filtering at 105 ± 5 DEG C, is then placed in Muffle furnace 450~600
5~10h is roasted under DEG C air atmosphere, obtains dehydrogenation catalyst after cooling.
Beneficial effects of the present invention:
Catalyst of the invention has the characteristics that hydrophobicity is strong using Titanium Sieve Molecular Sieve, can avoid vapor and is catalyzed to deoxidation
The influence of reaction；By carrying out Fe, Mg, the exchange of Li et al. cation, it can effectively increase molecular sieve bore diameter, reinforce mass transferring in gas phase mistake
Journey；By metal oxide actives components such as load Mn, Cu, Zr, the acid-base property of energy Effective Regulation catalyst improves catalytic activity
And inhibit the aging of catalysis.
In practical applications using dehydrogenation catalyst of the invention, the activated alumina bead for being 3~5mm coated in diameter
On surface, the coating thickness of catalyst is 0.06~0.1mm, is filled in catalytic deoxidation tank.Operating condition be temperature 250~
300 DEG C, air speed 4000h-1, in unstripped gas oxygen content in the case where 0.5~1.5%, it can reach the deoxidation effectiveness greater than 95%,
Concentration of hydrogen sulfide is 300mg/m in the tolerable unstripped gas of catalyst3, sustainable work 8000h.
Present invention process is simple, at low cost, prepares that resulting catalyst activity is strong, and the service life is long.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated.
Embodiment one.
A kind of preparation method of base metal type biogas dehydrogenation catalyst, it the following steps are included:
Step 1 Titanium Sieve Molecular Sieve carrier preparation: in following ratio 20g sodium metasilicate, 2 white carbon blacks, 8gNaOH, 3g KCl,
3g waterglass is added in 50g deionized water, and strong stirring is uniformly mixed it at room temperature, 120min is persistently stirred, by gained
Suspension is transferred in 300mL autoclave, in 280 DEG C of hydro-thermal reaction 72h, is cooled to room temperature, through being filtered, washed and in 75
DEG C dry 6h, obtains titanium-silicon molecular screen material.Between 2.3~3.7nm, specific surface area exists preparation-obtained molecular sieve bore diameter
620~650m2/ g range.
Step 2 Titanium Sieve Molecular Sieve support modification: by following proportion 8g FeCl3、4g MgCl2, 4g LiCl is added to
In 50g deionized water, the Titanium Sieve Molecular Sieve of 20g preparation is added after dissolution, stirs evenly, adjusting pH is 6, is stirred at 65 DEG C
48h carries out cationic exchange, is cooled to room temperature, and is filtered, washed and in 65 DEG C of dry 12h, and modified Titanium Sieve Molecular Sieve is obtained
Carrier.
Step 3 active component load: by following proportion 6g Mn (NO3)2、2g Zr(NO3)4、8g Ce(NO3)3、1g Cu
(NO3)2It is added in 50g deionized water, the modified Titanium Sieve Molecular Sieve of 10g is added after dissolution, 10h is impregnated, at 110 DEG C after filtering
Lower drying 4h, is then placed in Muffle furnace under 450 DEG C of air atmospheres and roasts 10h, obtains dehydrogenation catalyst after cooling.
Embodiment two.
A kind of preparation method of base metal type biogas dehydrogenation catalyst, it the following steps are included:
Step 1 Titanium Sieve Molecular Sieve carrier preparation: in following ratio 5g sodium metasilicate, 8g white carbon black, 3gNaOH, 1g KCl,
1g waterglass is added in 50g deionized water, and strong stirring is uniformly mixed it at room temperature, persistently stirs 30min, gained is hanged
Supernatant liquid is transferred in 300mL autoclave, in 200 DEG C of hydro-thermal reaction 36h, is cooled to room temperature, and is filtered, washed and in 65 DEG C
Dry 12h, obtains titanium-silicon molecular screen material.Between 2.3~3.7nm, specific surface area exists preparation-obtained molecular sieve bore diameter
620~650m2/ g range.
Step 2 Titanium Sieve Molecular Sieve support modification: by following proportion 3g FeCl3、1g MgCl2, 8g LiCl is added to
In 50g deionized water, the Titanium Sieve Molecular Sieve of 10g preparation is added after dissolution, stirs evenly, adjusts pH to 8, stirred at 55 DEG C
48h carries out cationic exchange, is cooled to room temperature, and is filtered, washed and in 75 DEG C of dry 6h, and modified Titanium Sieve Molecular Sieve is obtained
Carrier.
Step 3 active component load: by following proportion 3g Mn (NO3)2、5g Zr(NO3)4、3g Ce(NO3)3、3g Cu
(NO3)2It is added in 50g deionized water, the modified Titanium Sieve Molecular Sieve of 20g is added after dissolution, 5h is impregnated, at 100 DEG C after filtering
Lower drying 6h, is then placed in Muffle furnace under 600 DEG C of air atmospheres and roasts 5h, obtains dehydrogenation catalyst after cooling.
Embodiment three.
A kind of preparation method of base metal type biogas dehydrogenation catalyst, it the following steps are included:
Step 1 Titanium Sieve Molecular Sieve carrier preparation: in following ratio 15g sodium metasilicate, 5g white carbon black, 6gNaOH, 2g
KCl, 1~3g waterglass are added in 50g deionized water, and strong stirring is uniformly mixed it at room temperature, persistently stir 60min,
Gained suspension is transferred in 300mL autoclave, in 240 DEG C of hydro-thermal reaction 50h, is cooled to room temperature, through being filtered, washed
And in 70 DEG C of dry 9h, titanium-silicon molecular screen material is obtained.Preparation-obtained molecular sieve bore diameter compares table between 2.3~3.7nm
Area is in 620~650m2/ g range.
Step 2 Titanium Sieve Molecular Sieve support modification: by following proportion 6g FeCl3、3g MgCl2, 3g LiCl be added 50g
In deionized water, the Titanium Sieve Molecular Sieve of 15g preparation is added after dissolution, stirs evenly, adjusts pH to 7, stir 32h at 60 DEG C,
Cationic exchange is carried out, is cooled to room temperature, is filtered, washed and in 70 DEG C of dry 9h, modified Titanium Sieve Molecular Sieve carrier is obtained.
Step 3 active component load: by following proportion 5g Mn (NO3)2、3g Zr(NO3)4、5g Ce(NO3)3、2g Cu
(NO3)2It is added in 50g deionized water, the modified Titanium Sieve Molecular Sieve of 15g is added after dissolution, 8h is impregnated, after filtering at 105 DEG C
5h is dried, is then placed in Muffle furnace under 500 DEG C of air atmospheres and roasts 8h, obtains dehydrogenation catalyst after cooling.
The embodiment of the present invention one to three is prepared into resulting dehydrogenation catalyst, the active oxidation for being 3~5mm coated in diameter
On aluminium bead surface, the coating thickness of catalyst is 0.06~0.1mm, is filled in catalytic deoxidation tank.Operating condition is temperature
250~300 DEG C, air speed 4000h-1, in unstripped gas oxygen content in the case where 0.5~1.5%, can reach the deoxidation greater than 95%
Efficiency, concentration of hydrogen sulfide is 300mg/m in the tolerable unstripped gas of catalyst3, sustainable work 8000h.
Part that the present invention does not relate to is the same as those in the prior art or can be realized by using the prior art.
Claims (3)
1. a kind of preparation method of base metal type biogas dehydrogenation catalyst, it is characterized in that it the following steps are included:
Firstly, preparation has the characteristics that the strong Titanium Sieve Molecular Sieve carrier of hydrophobicity, influence of the vapor to deoxidation catalysis reaction is avoided,
The aperture of Titanium Sieve Molecular Sieve carrier is controlled between 2.3-3.7 nm；
Secondly, being modified processing to Titanium Sieve Molecular Sieve carrier, exchanged by Fe, Mg, Li cation, effectively increase molecular sieve pores
Diameter reinforces mass transferring in gas phase process；
Third carries out active component load to the Titanium Sieve Molecular Sieve after modification, by loading Mn, Cu, Zr metal oxide
Active component, the acid-base property of Effective Regulation catalyst improve catalytic activity and inhibit the aging of catalysis；
The preparation process of the Titanium Sieve Molecular Sieve carrier refers to: in proportion parts by weight be 5~20 parts of sodium metasilicate, 2~8 parts it is white
Carbon black, 3~8 parts of NaOH, 1~3 part of KCl and 1~3 part of waterglass are added in 50 parts of deionized water, at room temperature strong stirring
It is uniformly mixed it, 30~120min is persistently stirred, gained suspension is transferred in autoclave, in 200~280 DEG C of water
36~72h of thermal response, is cooled to room temperature, and is filtered, washed and in 70 ± 5 DEG C of dry 6~12h, and titanium-silicon molecular screen material is obtained；
The specific surface area of preparation-obtained Titanium Sieve Molecular Sieve carrier is in 620~650m2In/g range.
2. according to the method described in claim 1, it is characterized in that described be modified processing to Titanium Sieve Molecular Sieve carrier and refer to:
3~8 parts of FeCl by weight3, 1~4 part of MgCl2It is added in 50 parts of deionized water with 4~8 parts of LiCl, adds after dissolution
The Titanium Sieve Molecular Sieve carrier for entering 10~20 parts, stirs evenly, and adjusts pH between 6~8,24~48h is stirred at 60 ± 5 DEG C,
Cationic exchange is carried out, is cooled to room temperature, is filtered, washed and in 70 ± 5 DEG C of dry 6~12h, modified titanium silicon molecule is obtained
Sieve carrier.
3. according to the method described in claim 1, it is characterized in that the active component load refers to 3~6 parts by weight
Mn(NO3)2, 2~5 parts of Zr (NO3)4, 3~8 parts of Ce (NO3)3With 1~3 part of Cu (NO3)2It is added in 50 parts of deionized water,
After dissolution be added 10~20 parts of modified Titanium Sieve Molecular Sieve carriers, impregnate 5~10h, after filtering at 105 ± 5 DEG C drying 4~
6h is then placed in Muffle furnace 5~10h of roasting under 450~600 DEG C of air atmospheres, obtains dehydrogenation catalyst after cooling.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101322942A (en) * | 2008-07-29 | 2008-12-17 | 西南化工研究设计院 | Oxygen-containing coal bed gas deoxidation catalyst and preparation thereof as well as applications |
| CN102872883A (en) * | 2012-09-26 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Supported non-noble metal oxygen-containing coalbed methane deoxidation catalyst and preparation method and application thereof |
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| US9555401B2 (en) * | 2011-01-25 | 2017-01-31 | Zeochem Llc | Molecular sieve adsorbent blends and uses thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101322942A (en) * | 2008-07-29 | 2008-12-17 | 西南化工研究设计院 | Oxygen-containing coal bed gas deoxidation catalyst and preparation thereof as well as applications |
| CN102872883A (en) * | 2012-09-26 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Supported non-noble metal oxygen-containing coalbed methane deoxidation catalyst and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 袁善良，等."催化燃烧法用于煤层气脱氧的研究进展".《天然气化工•C1 化学与化工》.2016,第41卷(第5期),第73-77页. |
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