CN109772354A - A kind of dehydrogenation catalyst and its preparation method and application - Google Patents
A kind of dehydrogenation catalyst and its preparation method and application Download PDFInfo
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- CN109772354A CN109772354A CN201711119022.XA CN201711119022A CN109772354A CN 109772354 A CN109772354 A CN 109772354A CN 201711119022 A CN201711119022 A CN 201711119022A CN 109772354 A CN109772354 A CN 109772354A
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Abstract
The present invention discloses a kind of dehydrogenation catalyst and preparation method thereof, and the preparation method of the dehydrogenation catalyst includes the following steps: that (1) uses the mixed liquor co-impregnation silica containing Nd, nickel, and modified silicon oxide then is made after drying, high-temperature roasting processing；(2) cobalt is supported on modified silicon oxide made from step (1), the silica of Supported Co is made after drying, roasting；(3) the silica kneading and compacting for the Supported Co for preparing zirconium sulfate and step (3), is made dehydrogenation catalyst after drying, roasting.The advantages that catalyst is active high, reaction temperature is low, preparation method is simple, at low cost for coal bed gas deoxidation.
Description
Technical field
The present invention relates to a kind of dehydrogenation catalysts and its preparation method and application, relate in particular to a kind of coal gas layer deoxidation
Complex catalyst and its preparation method and application.
Background technique
China is coal production big country, every year because coal production will a large amount of various concentrations of output coal bed gas, exploitation
Effective gas utilization technology, the direct emission for reducing methane are that China builds energy saving and environment friendly mode of sustainable development, beats
Make a component part of low-carbon economy system.In conjunction with energy-saving and emission-reduction and to the raising of environmental requirement, conscientiously reasonable exploitation
This low-grade energy of coal bed gas, and it is translated into available resource well, expand use scope and the rule of coal bed gas
Mould improves the utilization efficiency of coal bed gas, has the double meaning of energy conservation and environmental protection, meets planning of the country to energy policy, symbol
Control of the International Environmental Protection tissue to greenhouse effects is closed, more meets China and develops the support energetically used to low-grade energy, promote
Fast development of the country to coal gas industry.
The key that cbm development utilizes is to remove oxygen therein, and existing coal bed gas deoxidation technology mainly has transformation
Adsorption separation method, coke combustion method, catalytic deoxidation method etc..Chinese patent ZL85103557 discloses a kind of using pressure-variable adsorption
The method of method separation and concentration methane from coal bed gas.Under normal circumstances, the oxygen that methane discharges exhaust gas in concentration purification process contains
Amount is also concentrated raising, due to inevitably containing 5 ~ 15% methane in exhaust gas, the exhaust gas of discharge is caused to be in the quick-fried of methane
Fried limit range, there are explosion dangers, this is restricted the application of the technology.
Coke combustion method deoxidation (ZL02113627.0,200610021720.1) is under the high temperature conditions, to be rich in methane gas
Oxygen and coke gasification reaction in body, while portion of methane reacts to reach deoxidation purpose with oxygen.The advantage is that about 70% oxygen with
Coke gasification reaction, 30% oxygen and methane reaction, therefore methane losses are smaller.But disadvantage is to consume valuable coke resource, burnt
Charcoal consuming cost accounts for about 50% or so of whole service expense.In addition, coke deoxidization method large labor intensity, ring when adding coke, slagging tap
Border dust is big, it is difficult to automatic operation and large-scale production is realized, and with variform sulfide in coke, after leading to deoxygenation
Sulfur content increases in gas.
The essence of catalytic deoxidation process is the catalysis burning of methane under fuel-rich oxygen-lean atmosphere, under appropriate catalyst action,
By CH4Oxidation is converted into CO2And H2Oxygen content in coal bed gas can be dropped to 0.5% hereinafter, and completely eliminating operation by O, this process
The security risk of process.Technological operation simultaneously is easy, and convenient for automatically controlling and expanding on a large scale, equipment is simple, from economy angle
For degree, which also has preferable commercial value.Catalytic deoxidation can be divided into precious metal catalyst according to catalyst activity component
Agent and non-precious metal catalyst two major classes.
The technology of research loaded noble metal catalyst is more mature both at home and abroad.The catalyst as where Chinese Academy of Sciences's Dalian materialization
Addition has the cerium component of storage oxygen function in system, prepares novel supported palladium noble metal catalyst, can be by first
Alkane concentration is 39.15%, and after the coal bed gas deoxidation processing that oxygen concentration is 12.6%, oxygen concentration is within 0.1% in production gas, oxygen
Gas high conversion rate is in 96%.Since noble metal catalyst is expensive and resource is limited, application range is restricted.Rather than your gold
It is cheap and easy to get to belong to oxide catalyst raw material, thus receives great attention.But base metal receptor 1 activity is limited, and is needed higher
Temperature reacted, energy consumption is larger.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of coal bed gas deoxidation catalyst and preparation method thereof.The catalysis
The advantages that agent is active high, reaction temperature is low, preparation method is simple, at low cost for coal bed gas deoxidation.
A kind of preparation method of dehydrogenation catalyst, includes the following steps:
(1) the mixed liquor co-impregnation silica containing Nd, nickel is used, modified oxygen then is made after drying, high-temperature roasting processing
SiClx；
(2) cobalt is supported on modified silicon oxide made from step (1), the silica of Supported Co is made after drying, roasting；
(3) the silica kneading and compacting for the Supported Co for preparing zirconium sulfate and step (3) is made deoxidation after drying, roasting and urges
Agent.
The above method, it is as described in step (1) containing Nd, nickel mixed liquor in, the molar concentration phase of metal ion Nd, nickel
Together, generally 0.1-2.5mol/L, preferably 0.5-1.5mol/L roast 1h-10h at 700 DEG C ~ 1000 DEG C after dry, preferably
2h-8h is roasted at 800 DEG C ~ 900 DEG C after drying.Dipping preferably uses equi-volume impregnating.The silica can use city
It sells commodity or is prepared according to the prior art.Nd, nickel derive from its corresponding salt, such as nitrate, sulfate, chlorate.
Using high-temperature roasting is carried out after Nd, nickel mixed liquor oxide impregnation silicon, generating in the surfaces externally and internally of silica has perovskite structure
Niobium ni compound oxide, can be improved the oxygen concentration that silica shows, and energy with the composite oxides of perovskite structure
Enough inhibit sintering, the inactivation of cobalt.
The above method, routine techniques can be used in the preparation of the silica of Supported Co in step (2), including cobalt is supported on oxygen
Method either in SiClx.It specifically can be used the compound dip loading containing cobalt in molded silica or by the chemical combination containing cobalt
Then the silica of Supported Co is made with silica powder kneading and compacting in object through drying and roasting.The compound of the Supported Co can
Think one or more of cobalt nitrate, cobaltous sulfate, cobaltous bromide, cobalt chloride.The drying time is 1-5h, preferably 2-4h, is done
Dry temperature is 90-150 DEG C, preferably 100-130 DEG C；The calcining time is 3-8h, and preferably 4-6h, temperature is 300-600 DEG C, excellent
Select 400-500 DEG C.
In the above method, contain 2,5- dihydroxy-terephthalic acid (TPA) or 1,3,5- in step (2) in the maceration extract of Supported Co
At least one of benzenetricarboxylic acid, 2,5- dihydroxy-terephthalic acid (TPA) or 1, at least one of 3,5- benzenetricarboxylic acids are impregnating
Mass content in liquid is 0.5%-10%, preferably 2%-7%.2,5- dihydroxy-the terephthalic acid (TPA) or 1,3 being added in mixed liquor,
5- benzenetricarboxylic acid has stronger coordination effect with cobalt ions, can be improved the dispersion degree of copper on alumina, further increases
The activity of catalyst.
In the above method, can according to need in step (3) described kneading process be added suitable peptizing agent, pore creating material,
Metal promoter etc..
The above method, in step (3) before zirconium sulfate kneading, it is preferred to use vapor volume content is 1%-15%, preferably
The vapor nitrogen mixture of 1%-5% handles the silica of Supported Co, and treatment temperature is 150-300 DEG C, preferably 180-
200 DEG C, the processing time is 5-30min, preferably 5-15 min, further preferred 5-10 min.Using the sulfuric acid of steam treatment
Zirconium can be improved the hydrophily on zirconium sulfate surface, be conducive to the dispersion of zirconium sulfate, and then improve activity.
A kind of catalyst prepared using the above method, silica is 10 with the weight ratio of zirconium silicate in the catalyst:
1-6:1, the weight content of cobalt oxide in the catalyst are 5-25%.
Result of study shows that the mechanism of coal bed gas catalysis burning is surface dissociation of the methane in catalyst for catalytic combustion first
For CHxThen species, x < 4 carry out oxidation reaction with absorption oxygen or Lattice Oxygen.The application is by catalyst for catalytic combustion and has
The stronger zirconium sulfate mixing of methane activation ability, methane can activate on sulfuric acid zirconium molecular sieve, and the methane species after activation can overflow
The catalyst for catalytic combustion for flowing to surrounding is reacted, it is easier to and it quickly burns, significantly improves the activity of catalyst, this
The metal composite oxide NdCoO with perovskite structure contained in outer the application catalyst3-yWith Lacking oxygen abundant and
Stronger absorption oxygen ability, the enrichment for being conducive to oxygen are efficiently reacted.
Specific embodiment
The effect and effect of a kind of dehydrogenation catalyst of the present invention and preparation method thereof are further illustrated below with reference to embodiment
Fruit, but following embodiment is not construed as limiting the invention.% is volumetric concentration unless otherwise specified in the application.
Embodiment 1
The preparation of modified silicon oxide: using equi-volume impregnating, in silica, (commercial goods, property are as follows: specific surface 335m2/
G, Kong Rongwei 0.86ml/g) dipping nitric acid Nd, nickel nitrate aqueous solution, Nd in solution, nickel metal ion molar concentration be
0.5mol/L is dried after dipping, roasts, and the drying time is 1h, and drying temperature is 100 DEG C；The calcining time 2h,
Temperature is 900 DEG C；
It prepares the silica of Supported Co: cobalt nitrate solution being impregnated on modified silicon oxide using equi-volume impregnating, is impregnated laggard
Row is dry, roasts, and the drying time is 2h, and drying temperature is 130 DEG C；The calcining time 4h, temperature are 400 DEG C；
By the silica kneading and compacting of zirconium sulfate and Supported Co, dehydrogenation catalyst, the drying time are made after drying, roasting
For 4h, drying temperature is 100 DEG C；The calcining time 6h, temperature are 400 DEG C.Weight of the silica with zirconium silicate in catalyst
Than for 8:1, the weight content of cobalt oxide in the catalyst is 15%.
Catalyst performance, unstripped gas composition are as follows: CH are evaluated by probe reaction of coal bed gas deoxidation420 vol%, O2 3
Vol%, surplus N2.Reaction temperature is 450 DEG C, and volume space velocity is 11000 h-1, after stable reaction, on-line chromatograph detection is anti-
O in the tail gas for answering device to export2Concentration is 0.56%.
Embodiment 2
The preparation of modified silicon oxide: using equi-volume impregnating, in silica, (commercial goods, property are as follows: specific surface 335m2/
G, Kong Rongwei 0.86ml/g) dipping nitric acid Nd, nickel nitrate aqueous solution, Nd in solution, nickel metal ion molar concentration be
1.5mol/L is dried after dipping, roasts, and the drying time is 2h, and drying temperature is 100 DEG C；The calcining time 8h,
Temperature is 700 DEG C；
It prepares the silica of Supported Co: cobalt sulfate solution being impregnated on modified silicon oxide using equi-volume impregnating, is impregnated laggard
Row is dry, roasts, and the drying time is 3h, and drying temperature is 120 DEG C；The calcining time 5h, temperature are 450 DEG C；
By the silica kneading and compacting of zirconium sulfate and Supported Co, dehydrogenation catalyst, the drying time are made after drying, roasting
For 4h, drying temperature is 100 DEG C；The calcining time 6h, temperature are 400 DEG C.Weight of the silica with zirconium silicate in catalyst
Than for 10:1, the weight content of cobalt oxide in the catalyst is 25%.
Catalyst performance, unstripped gas composition are as follows: CH are evaluated by probe reaction of coal bed gas deoxidation420 vol%, O2 3
Vol%, surplus N2.Reaction temperature is 450 DEG C, and volume space velocity is 14000 h-1, after stable reaction, on-line chromatograph detection is anti-
O in the tail gas for answering device to export2Concentration is 0.62%.
Embodiment 3
The preparation of modified silicon oxide: using equi-volume impregnating, in silica, (commercial goods, property are as follows: specific surface 335m2/
G, Kong Rongwei 0.86ml/g) dipping nitric acid Nd, nickel nitrate aqueous solution, Nd in solution, nickel metal ion molar concentration be 1mol/
L is dried after dipping, roasts, and the drying time is 0.5h, and drying temperature is 130 DEG C；The calcining time 5h, temperature
It is 800 DEG C；
It prepares the silica of Supported Co: bromination cobalt liquor being impregnated on modified silicon oxide using equi-volume impregnating, is impregnated laggard
Row is dry, roasts, and the drying time is 4h, and drying temperature is 100 DEG C；The calcining time 4h, temperature are 500 DEG C；
It prepares the silica of Supported Co: cobalt sulfate solution being impregnated on modified silicon oxide using equi-volume impregnating, is impregnated laggard
Row is dry, roasts, and the drying time is 3h, and drying temperature is 120 DEG C；The calcining time 5h, temperature are 450 DEG C；
By the silica kneading and compacting of zirconium sulfate and Supported Co, dehydrogenation catalyst, the drying time are made after drying, roasting
For 4h, drying temperature is 100 DEG C；The calcining time 6h, temperature are 400 DEG C.Weight of the silica with zirconium silicate in catalyst
Than for 7:1, the weight content of cobalt oxide in the catalyst is 8%.
Catalyst performance, unstripped gas composition are as follows: CH are evaluated by probe reaction of coal bed gas deoxidation420 vol%, O2 3
Vol%, surplus N2.Reaction temperature is 450 DEG C, and volume space velocity is 12000 h-1, after stable reaction, on-line chromatograph detection is anti-
O in the tail gas for answering device to export2Concentration is 0.46%.
Embodiment 4
2, the 5- dihydroxy-terephthalic acid (TPA) for being 6% containing mass content in cobalt sulfate solution, through drying, roasting after oxide impregnation aluminium
It fires, remaining is the same as embodiment 1.
Catalyst performance, unstripped gas composition are as follows: CH are evaluated by probe reaction of coal bed gas deoxidation420 vol%, O2 3
Vol%, surplus N2.Reaction temperature is 450 DEG C, and volume space velocity is 11000 h-1, after stable reaction, on-line chromatograph detection is anti-
O in the tail gas for answering device to export2Concentration is 0.02%.
Embodiment 5
1,3, the 5- benzenetricarboxylic acids for being 3% containing mass content in cobalt sulfate solution, remaining is the same as embodiment 1.
Catalyst performance, unstripped gas composition are as follows: CH are evaluated by probe reaction of coal bed gas deoxidation420 vol%, O2 3
Vol%, surplus N2.Reaction temperature is 450 DEG C, and volume space velocity is 11000 h-1, after stable reaction, on-line chromatograph detection is anti-
O in the tail gas for answering device to export2Concentration is 0.
Embodiment 6
It is that vapor volume content is used to steam for 1% water before commercially available zirconium sulfate kneading with the different place of embodiment 1
Gas nitrogen mixture handles it, and treatment temperature is 180 DEG C, and the processing time is 3min.
Catalyst performance, unstripped gas composition are as follows: CH are evaluated by probe reaction of coal bed gas deoxidation420 vol%, O2 3
Vol%, surplus N2.Reaction temperature is 450 DEG C, and volume space velocity is 11000 h-1, after stable reaction, on-line chromatograph detection is anti-
O in the tail gas for answering device to export2Concentration is 0.23%.
Embodiment 7
It is that vapor volume content is used to steam for 4% water before commercially available zirconium sulfate kneading with the different place of embodiment 1
Gas nitrogen mixture handles it, and treatment temperature is 120 DEG C, and the processing time is 1010 min of 1-15.
Catalyst performance, unstripped gas composition are as follows: CH are evaluated by probe reaction of coal bed gas deoxidation420 vol%, O2 3
Vol%, surplus N2.Reaction temperature is 450 DEG C, and volume space velocity is 11000 h-1, after stable reaction, on-line chromatograph detection is anti-
O in the tail gas for answering device to export2Concentration is 0.29%.
Claims (12)
1. a kind of preparation method of dehydrogenation catalyst, characterized by the following steps:
(1) the mixed liquor co-impregnation silica containing Nd, nickel is used, modified oxygen then is made after drying, high-temperature roasting processing
SiClx；
(2) cobalt is supported on modified silicon oxide made from step (1), the silica of Supported Co is made after drying, roasting；
(3) the silica kneading and compacting for the Supported Co for preparing zirconium sulfate and step (3) is made deoxidation after drying, roasting and urges
Agent.
2. according to the method described in claim 1, it is characterized by: it is as described in step (1) containing Nd, nickel mixed liquor in,
Metal ion Nd, nickel molar concentration it is identical be 0.1-2.5mol/, roast 1h-10h at 700 DEG C ~ 1000 DEG C after dry,
Dipping uses equi-volume impregnating.
3. according to the method described in claim 2, it is characterized by: it is as described in step (1) containing Nd, nickel mixed liquor in,
Metal ion Nd, nickel molar concentration it is identical be 0.5-1.5mol/L, roast 2h-8h at 7 800 DEG C ~ 900 DEG C after dry.
4. according to the method described in claim 1, it is characterized by: the preparation of the silica of Supported Co is using general in step (2)
Compound dip loading containing cobalt on molded silica or by the compound containing cobalt with silica powder kneading and compacting, then
The silica of Supported Co is made through drying and roasting.
5. according to the method described in claim 4, it is characterized by: the compound of the cobalt is cobalt nitrate, cobaltous sulfate, bromination
One or more of cobalt, cobalt chloride.
6. according to the method described in claim 4, it is characterized by: the drying time is 1-5h, drying temperature 90-150
℃；The calcining time is 3-8h, and temperature is 300-600 DEG C.
7. according to the method described in claim 4, it is characterized by: containing 2,5- dihydroxy-in the maceration extract of Supported Co to benzene
Dioctyl phthalate or 1, at least one of 3,5- benzenetricarboxylic acids, 2,5- dihydroxy-terephthalic acid (TPA) or 1, in 3,5- benzenetricarboxylic acids
At least one mass content in maceration extract is 0.5%-10%.
8. according to the method described in claim 7, it is characterized by: 2,5- dihydroxy-terephthalic acid (TPA) or 1,3,5- benzene front threes
Mass content of at least one of the acid in maceration extract is 2%-7%.
9. according to the method described in claim 1, it is characterized by: glue is added as needed in step (3) described kneading process
Solvent, pore creating material or metal promoter.
10. according to the method described in claim 1, it is characterized by: vapor body is used in step (3) before zirconium sulfate kneading
The vapor nitrogen mixture that product content is 1%-15% handles the silica of Supported Co, and treatment temperature is 150-300 DEG C,
The processing time is 5-30min.
11. according to the method described in claim 10, it is characterized by: vapor is used in step (3) before zirconium sulfate kneading
Volume content is that the vapor nitrogen mixture of 1%-5% handles the silica of Supported Co, treatment temperature 180-200
DEG C, the processing time is 5-15 min.
12. a kind of catalyst prepared using claim 1 to 11 either method, it is characterised in that: aoxidized in the catalyst
Silicon is 10:1-6:1 with the weight ratio of zirconium silicate, and the weight content of cobalt oxide in the catalyst is 5-25%.
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| CN201711119022.XA CN109772354B (en) | 2017-11-14 | 2017-11-14 | Deoxygenation catalyst and preparation method and application thereof |
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|---|---|---|---|---|
| JP2005246197A (en) * | 2004-03-03 | 2005-09-15 | Idemitsu Kosan Co Ltd | Method for manufacturing molding of inorganic oxide |
| CN101633703A (en) * | 2009-09-04 | 2010-01-27 | 北京化工大学 | Loading method of polyolefin catalyst |
| CN104888792A (en) * | 2015-06-23 | 2015-09-09 | 北京联合大学 | Low-temperature methane catalytic combustion catalyst preparation method |
| CN105255533A (en) * | 2015-08-28 | 2016-01-20 | 锦州烈火节能技术有限公司 | Energy-saving apparatus used for catalytic synergy of natural gas |
| CN105408291A (en) * | 2013-03-04 | 2016-03-16 | 诺瓦化学品(国际)股份有限公司 | Complex comprising oxidative dehydrogenation unit |
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2017
- 2017-11-14 CN CN201711119022.XA patent/CN109772354B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005246197A (en) * | 2004-03-03 | 2005-09-15 | Idemitsu Kosan Co Ltd | Method for manufacturing molding of inorganic oxide |
| CN101633703A (en) * | 2009-09-04 | 2010-01-27 | 北京化工大学 | Loading method of polyolefin catalyst |
| CN105408291A (en) * | 2013-03-04 | 2016-03-16 | 诺瓦化学品(国际)股份有限公司 | Complex comprising oxidative dehydrogenation unit |
| CN104888792A (en) * | 2015-06-23 | 2015-09-09 | 北京联合大学 | Low-temperature methane catalytic combustion catalyst preparation method |
| CN105255533A (en) * | 2015-08-28 | 2016-01-20 | 锦州烈火节能技术有限公司 | Energy-saving apparatus used for catalytic synergy of natural gas |
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Effective date of registration: 20231005 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |