CN109590003A - A kind of base metal catalysts and its application - Google Patents
A kind of base metal catalysts and its application Download PDFInfo
- Publication number
- CN109590003A CN109590003A CN201811624775.0A CN201811624775A CN109590003A CN 109590003 A CN109590003 A CN 109590003A CN 201811624775 A CN201811624775 A CN 201811624775A CN 109590003 A CN109590003 A CN 109590003A
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- CN
- China
- Prior art keywords
- base metal
- metal catalysts
- olivine
- present
- hybrid heating
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- 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
-
- 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
Abstract
The invention discloses a kind of base metal catalysts and its applications.The base metal catalysts are prepared by the preparation method included the following steps: alkali carbonate, olivine and water being sealed after mixing, is aged, dries and obtain the base metal catalysts after calcining.The present invention is using alkali metal as active component, using olivine as carrier, by infusion process, based on different raw material proportionings, calcination temperature, prepares the catalyst for having the characteristics that large specific surface area, preparation method are simple, process is easy to operate；Catalyst of the invention has high catalytic activity, and life time is long, cheap and easy to get, and separation and recovery is simple, is especially used in straw biomass catalytic pyrolysis decoking.
Description
Technical field
The invention belongs to catalyst fields, more particularly, to a kind of base metal catalysts and its application.
Background technique
Being constantly progressive and develop with human society, the mankind are faced with huge energy and environment problem.On the one hand,
Traditional fossil fuel resource total amount is increasingly depleted；On the other hand, fossil fuel is excessively used due to the mankind,
The problems such as having caused the environmental pollution got worse, such as the acidification (SO of soil and lake2) and greenhouse gas emission cause
(the CO such as global warming2).The energy is the basis of socio-economic development, and influence socio-economic development it is main because
Element, therefore under the triple burden of New Economy growth, energy crisis and environmental pollution, find and develop new low pollution, green
The renewable energy of environmental protection is extremely urgent.Biomass energy is inhaled again as a kind of renewable energy using long history
People's attention is drawn.Biomass energy has the huge amount of containing, it is often more important that there is biomass energy fossil fuel not have
Reproducibility and CO2The features such as discharge balance, it is made to occupy critical positions in current energy strategy system.Biomass conversion
Be exactly thermal transition as most effective means in the entire chain of fuel, biomass thermal transformation technology be using biomass as raw material,
The process of imflammable gas is converted biomass by thermal chemical reaction under the high temperature conditions.Biomass thermal conversion can will be biological
Matter raw material is converted into CO and H2Based on gaseous fuel, can directly convert realize combustion gas, the supply of thermal energy and electric energy.China's agriculture
On the one hand industry straw biomass rich reserves can convert fuel or the raw material of industry for reproducible agricultural biomass, for workers and peasants
Industry uses；On the other hand it can avoid a large amount of biomass resource discard or arbitrarily to be burned and cause environmental pollution, turn waste into wealth.
Therefore more and more cause the concern of people to the research of biomass energy and application in recent years.It taps a new source of energy and renewable energy spy
It is not they to be converted into high-grade energy, adaptation to local conditions, various energy resources are complementary, to gradually reduce and substitute making for fossil energy
With being to preserve the ecological environment, walk the vital measure on the road of the sustainable development of socio-economy.
During biomass thermal conversion, generated combustion gas contains a large amount of tar, and tar is that structure is complicated for one kind
Mixture.Tar aerosol is formed with synthesis gas at high temperature, is condensed into when temperature is lower than 200 DEG C auburn sticky
Shape liquid, be easy to cause filter and line clogging.In addition, tar ingredients are complicated, component is mostly to contain 1-5 benzene ring structure
Aromatic hydrocarbon, the even increasingly complex polycyclic aromatic hydrocarbon of structure is carcinogen, if not being pocessed direct emission, it will
Human health is caused to seriously affect.In order to solve problem above, the side of catalyst In-stiu catalysis is added in pyrolysis oven
Method can not only reduce gasification of biomass temperature using deep catalytic cracking technology, but also improve gas componant to a certain extent, increase
Add combustible component content.
And catalytic pyrolysis research emphasis is then that efficiently, therefore the preparation of cheap catalyst is prepared with specific surface area
Greatly, the catalyst for the advantages that preparation method is simple, process is easy to operate is a target being pursued.
Summary of the invention
The purpose of the present invention is to solve the above problem, using alkali metal as active component, using olivine as carrier, passes through leaching
Stain method is prepared with large specific surface area, preparation method is simple, process is easy based on different raw material proportionings, calcination temperature
The catalyst of the features such as operation.
To achieve the goals above, the first aspect of the present invention provides a kind of base metal catalysts, the base metal catalysts
It is prepared by the preparation method included the following steps:
Alkali carbonate, olivine and water Hybrid Heating are sealed after mixing evenly, be aged, dry and obtained after calcining
The base metal catalysts.
It as a preferred embodiment of the present invention, further include pulverizing the base metal catalysts semi-finished product after drying.
As a preferred embodiment of the present invention, the revolving speed of Hybrid Heating stirring is 15~35r/s, Hybrid Heating stirring
Temperature is 110-120 DEG C, and the time of Hybrid Heating stirring is 2-2.5h.
As a preferred embodiment of the present invention, the carbonate bases metal is Na2CO3、K2CO3Or Li2CO3。
As a preferred embodiment of the present invention, the weight of the alkali carbonate is the 30 of the weight of the olivine
~35%.
As a preferred embodiment of the present invention, the time of ageing is 20~28h.
As a preferred embodiment of the present invention, the temperature of drying is 105~120 DEG C.
As a preferred embodiment of the present invention, the temperature of calcining is 500~900 DEG C.
In the present invention, those skilled in the art can be as needed adjusted the length of time of calcining, as the present invention
Preferred embodiment, the time of calcining are 1.5-2.5h.
As a preferred embodiment of the present invention, the aperture of the base metal catalysts is 15~80nm.
As a preferred embodiment of the present invention, the specific surface area of the base metal catalysts is 10.67~97.56m2/
g。
According to the present invention, preservative film can be used after mixing and be sealed for alkali carbonate, olivine and water.
According to the present invention, drying can carry out in thermostatic drying chamber, and calcining can carry out in the reaction vessels such as Muffle furnace.
According to the present invention, those skilled in the art can adjust the additive amount of water as needed, guarantee that its dosage can dissolve alkali
Metal carbonate simultaneously submerges olivine.
According to the present invention, it is not necessary to guaranty that environment is anaerobic state when sealing.
According to the present invention, base metal catalysts semi-finished product are usually dried to surface anhydrous state.
The second aspect of the present invention provides application of the above-mentioned base metal catalysts in catalytic decomposition tar.
Beneficial effects of the present invention:
1, the present invention, using olivine as carrier, by infusion process, is matched using alkali metal as active component with different raw materials
Than preparing the catalyst for having the characteristics that large specific surface area, preparation method are simple, process is easy to operate based on, calcination temperature.
2, catalyst of the invention has high catalytic activity, and life time is long, cheap and easy to get, and separation and recovery is simple,
Especially it is used in straw biomass catalytic pyrolysis decoking.
3, compared with other catalyst, the present invention is using olivine cheap and easy to get as carrier, using alkali metal as active component
The base metal catalysts of preparation not only have biggish specific surface area, and used carrier is olivine, and olivine itself contains
There is a large amount of Fe2O3、Al2O3And a small amount of yttrium (praseodymium, neodymium etc.), it is obtained by infusion process carrying alkali metal
Catalyst so that can more be played well between metal oxide and alkali metal that natural olivine itself is held cooperate with it is excellent
Gesture generates better catalytic effect.Using catalyst prepared by the method for the present invention, not only there is high catalytic activity, warp
The conversion ratio of experimental verification, catalytic pyrolysis toluene (main component is toluene in tar) can reach 93% or more, significant purification life
Substance combustible gas promotes combustion gas quality, and has strong anti-carbon capacity, and resistance to deactivation is good, long service life.
Other features and advantages of the present invention will then part of the detailed description can be specified.
Specific embodiment
The preferred embodiment of the present invention is described in more detail below.Although the following describe preferred implementations of the invention
Mode, however, it is to be appreciated that may be realized in various forms the present invention without that should be limited by the embodiments set forth herein.Phase
Instead, these embodiments are provided so that the present invention is more thorough and complete, and can be by the scope of the present invention completely
It is communicated to those skilled in the art.
Embodiment 1:
9.91g sodium carbonate, 30g olivine and 40mL deionized water Hybrid Heating are stirred evenly (Hybrid Heating stirring
Revolving speed is 15~35r/s, and the temperature of Hybrid Heating stirring is 115 DEG C, and stirring 2h is placed in reaction vessel to be sealed with preservative film,
Ageing for 24 hours, is subsequently placed in 120 DEG C of thermostatic drying chambers and is dried, until base metal catalysts surface of semi-finished is anhydrous, pulverized,
Finally solid product is put in Muffle furnace, obtains base metal catalysts after being calcined at 500 DEG C, the base metal catalysts
Specific surface area be 45.89~50.56m2/ g, aperture 17.88-25.45nm.
Embodiment 2:
9.91g lithium carbonate, 30g olivine and 40mL deionized water Hybrid Heating are stirred evenly (Hybrid Heating stirring
Revolving speed is 15~35r/s, and the temperature of Hybrid Heating stirring is 115 DEG C, and stirring 2h is placed in reaction vessel to be sealed with preservative film,
Ageing for 24 hours, is subsequently placed in 120 DEG C of thermostatic drying chambers and is dried, until base metal catalysts surface of semi-finished is anhydrous, pulverized,
Finally solid product is put in Muffle furnace, obtains base metal catalysts after being calcined at 700 DEG C, the base metal catalysts
Specific surface area be 34.78~41.56m2/ g, aperture 26.34-35.89nm.
Embodiment 3:
9.91g potassium carbonate, 30g olivine and 40mL deionized water Hybrid Heating are stirred evenly (Hybrid Heating stirring
Revolving speed is 15~35r/s, and the temperature of Hybrid Heating stirring is 115 DEG C, and stirring 2h is placed in reaction vessel to be sealed with preservative film,
Ageing for 24 hours, is subsequently placed in 120 DEG C of thermostatic drying chambers and is dried, until base metal catalysts surface of semi-finished is anhydrous, pulverized,
Finally solid product is put in Muffle furnace, obtains base metal catalysts after being calcined at 700 DEG C, the base metal catalysts
Specific surface area be 37.89~43.23m2/ g, aperture 23.15-29.44nm.
Embodiment 4:
Difference from example 1 is that addition 8.5g sodium carbonate.
Embodiment 5:
Difference from example 1 is that addition 11.5g sodium carbonate.
Embodiment 6:
The difference is that, 8.5g lithium carbonate is added with embodiment 2.
Embodiment 7:
The difference is that, 8.5g potassium carbonate is added with embodiment 3.
Changing effect of the base metal catalysts made from embodiment 1-3 to tar is detected, the results are shown in Table 1:
Table 1
| Project | Gas yield (L/g) | Tar conversion (%) |
| Embodiment 1 | 1.46 | 94.46 |
| Embodiment 2 | 1.38 | 94.11 |
| Embodiment 3 | 1.17 | 93.66 |
| Embodiment 4 | 0.89 | 87.67 |
| Embodiment 5 | 1.11 | 80.12 |
| Embodiment 6 | 1.12 | 83.56 |
| Embodiment 7 | 0.97 | 84.33 |
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.
Claims (10)
1. a kind of base metal catalysts, which is characterized in that the base metal catalysts are prepared by the preparation method included the following steps
It obtains:
Alkali carbonate, olivine and water Hybrid Heating are sealed after mixing evenly, be aged, dry and obtained after calcining is described
Base metal catalysts.
2. preparation method according to claim 1, wherein the revolving speed of Hybrid Heating stirring is 15~35r/s, Hybrid Heating
The temperature of stirring is 110-120 DEG C, and the time of Hybrid Heating stirring is 2-2.5h.
3. base metal catalysts according to claim 1, wherein the carbonate bases metal is Na2CO3、K2CO3Or
Li2CO3。
4. base metal catalysts according to claim 1, wherein the weight of the alkali carbonate is the olivine
Weight 30~35%.
5. base metal catalysts according to claim 1, wherein the time of ageing is 20~28h.
6. base metal catalysts according to claim 1, wherein the temperature of drying is 105~120 DEG C.
7. base metal catalysts according to claim 1, wherein the temperature of calcining is 500~900 DEG C.
8. base metal catalysts according to claim 1, wherein the aperture of the base metal catalysts is 15~80nm.
9. base metal catalysts according to claim 1, wherein the specific surface area of the base metal catalysts is 10.67
~97.56m2/g。
10. application of the base metal catalysts described in any one of claim 1-9 in catalytic decomposition tar.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811624775.0A CN109590003A (en) | 2018-12-28 | 2018-12-28 | A kind of base metal catalysts and its application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811624775.0A CN109590003A (en) | 2018-12-28 | 2018-12-28 | A kind of base metal catalysts and its application |
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| CN109590003A true CN109590003A (en) | 2019-04-09 |
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ID=65964612
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112159672A (en) * | 2020-09-28 | 2021-01-01 | 天津壹新环保工程有限公司 | Novel biomass pyrolysis carbonization system and method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5624022A (en) * | 1979-08-03 | 1981-03-07 | Mitsubishi Rayon Co Ltd | Treatment of tar containing exhaust gas |
| CN101195759A (en) * | 2007-12-19 | 2008-06-11 | 贵州大学 | Technique for producing Chinese tallow tree stillingia oil biological diesel oil with solid base catalyst katalysis |
| CN106010667A (en) * | 2016-06-23 | 2016-10-12 | 中国科学院广州能源研究所 | Catalytic cracking and purifying method for biomass gas tar |
-
2018
- 2018-12-28 CN CN201811624775.0A patent/CN109590003A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5624022A (en) * | 1979-08-03 | 1981-03-07 | Mitsubishi Rayon Co Ltd | Treatment of tar containing exhaust gas |
| CN101195759A (en) * | 2007-12-19 | 2008-06-11 | 贵州大学 | Technique for producing Chinese tallow tree stillingia oil biological diesel oil with solid base catalyst katalysis |
| CN106010667A (en) * | 2016-06-23 | 2016-10-12 | 中国科学院广州能源研究所 | Catalytic cracking and purifying method for biomass gas tar |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112159672A (en) * | 2020-09-28 | 2021-01-01 | 天津壹新环保工程有限公司 | Novel biomass pyrolysis carbonization system and method |
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Application publication date: 20190409 |