CN109097077A - A kind of method of CO yield in reduction catalytic pyrolysis of biomass - Google Patents
A kind of method of CO yield in reduction catalytic pyrolysis of biomass Download PDFInfo
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- CN109097077A CN109097077A CN201811220237.5A CN201811220237A CN109097077A CN 109097077 A CN109097077 A CN 109097077A CN 201811220237 A CN201811220237 A CN 201811220237A CN 109097077 A CN109097077 A CN 109097077A
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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
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
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Abstract
本发明提供了一种减少生物质催化热解中CO产量的方法，用于减少生物质在作为燃料被催化热解时CO的产量，其特征在于，包括如下步骤：步骤S1，将生物质原料进行粉碎处理成生物质粉末；步骤S2，将生物质粉末进行干燥处理；步骤S3，将金属粉末添加剂按照质量百分比为10％～15％的掺混比加入生物质粉末中，从而得到混合物；步骤S4，将混合物放入反应容器中；步骤S5，向反应容器通入保护气体从而置换反应容器内的空气；步骤S6，待保护气体达到稳定后，将反应容器的温度在保护气体的气氛条件下升高至700℃～900℃并且持续恒温加热30min～45min，从而对混合物进行催化热解。The present invention provides a method for reducing CO production in biomass catalytic pyrolysis, which is used to reduce CO production when biomass is catalytically pyrolyzed as fuel, and is characterized in that it includes the following steps: Step S1, biomass raw material Carry out pulverization processing into biomass powder; step S2, dry the biomass powder; step S3, add the metal powder additive to the biomass powder according to the blending ratio of 10% to 15% by mass, so as to obtain the mixture; step S4, put the mixture into the reaction vessel; step S5, pass the protective gas into the reaction vessel to replace the air in the reaction vessel; step S6, after the protective gas reaches a stable temperature, the temperature of the reaction vessel is kept under the atmosphere condition of the protective gas Raise the temperature to 700°C-900°C and continue heating at a constant temperature for 30min-45min, so as to perform catalytic pyrolysis on the mixture.
Description
Technical field
Present invention relates particularly to a kind of methods of CO yield in reduction catalytic pyrolysis of biomass.
Background technique
It is faced with the dual-pressure of economic growth and environmental protection, exploitation is clean, renewable energy is to establishing sustainable development
The energy resource system of exhibition has great significance.Not only nitrogen sulfur content is low for biomass fuel, but also renewable energy realizes carbon dioxide
Zero-emission, therefore become the hot spot of Recent study to the utilization of biomass fuel.
Countries in the world are concentrated mainly on the research of biomass thermal chemical transformation to the utilization of biomass energy at present, and are pyrolyzed then
It is biomass process most basic and important in heat chemistry transformation.Since ash is high in biomass, metal element content is abundant,
The influence that it decomposes biomass macromolecular is very big, it is therefore necessary to which the influence to metallic element in biomass pyrolysis process carries out
Research.
There is influence of the scholar to metallic element in biomass pyrolysis process to be studied, but very due to reaction condition difference
Greatly, the conclusion obtained is not consistent to the greatest extent.There is scholar research shows that the dolomite containing more calcium and magnesium elements can be substantially reduced life
CO and CH during material pyrolysis4Yield, and separately there is scholar's research then to point out that NiO and CaO can promote CO and CH respectively4's
It generates, the influence that CO is precipitated in Ca and K is little.
Summary of the invention
In order to probe into influence of the metallic element to CO yield in biomass pyrolysis process to find reduction biomass catalyzing
The method of CO yield in pyrolysis, the present invention are studied by several different catalysts.
To solve the above problems, present invention employs following technical solutions:
The present invention provides a kind of methods of CO yield in reduction catalytic pyrolysis of biomass, for reducing biomass in conduct
Fuel is by the yield of CO when catalytic pyrolysis, which comprises the steps of:
Biomass material is carried out pulverization process into powdered biomass by step S1；
Powdered biomass is dried step S2 under the conditions of 75 DEG C~105 DEG C of temperature；
Biomass powder is added according to the Blend proportion that mass percent is 10%~15% in metal powder additive by step S3
It is uniformly mixed in end and by metal powder additive and powdered biomass, to obtain metal powder additive and biomass powder
The mixture at end；
Mixture is put into the reaction vessel for being used for catalytic pyrolysis mixture by step S4；
Step S5 is continually fed into protective gas with the flow of 3L/min~4L/min to reaction vessel to replace reaction and hold
Air in device；
The mass signal of step S6, the discharge gas of the reaction vessel measured by mass spectrograph determine the protection gas in container
Whether body reaches stable, and after gas to be protected reaches stable, the temperature of reaction vessel is risen under the atmospheric condition of protective gas
Up to 700 DEG C~900 DEG C and continue heated at constant temperature 30min~45min, to carry out catalytic pyrolysis to mixture.
The present invention provides a kind of methods of CO yield in reduction catalytic pyrolysis of biomass, can also have such spy
Sign, wherein the metal in metal powder additive is Fe2O3, any one in ZnO, NaCl, CaO, KCl.
The present invention provides a kind of methods of CO yield in reduction catalytic pyrolysis of biomass, can also have such spy
Sign, wherein the temperature of reaction vessel is 900 DEG C.
The present invention provides a kind of methods of CO yield in reduction catalytic pyrolysis of biomass, can also have such spy
Sign, wherein the heating rate of the temperature of reaction vessel is 20 DEG C/min~30 DEG C/min in step S6.
The present invention provides a kind of methods of CO yield in reduction catalytic pyrolysis of biomass, can also have such spy
Sign, wherein protective gas is the argon gas or nitrogen that purity is 99.999% in step S5.
The present invention provides a kind of methods of CO yield in reduction catalytic pyrolysis of biomass, can also have such spy
Sign, wherein the number replaced in step S5 is 3 times.
The present invention provides a kind of methods of CO yield in reduction catalytic pyrolysis of biomass, can also have such spy
Sign, wherein the time being dried in step S2 is 1h~2h.
The present invention provides a kind of methods of CO yield in reduction catalytic pyrolysis of biomass, can also have such spy
Sign, wherein the granular size of powdered biomass is 60~100 mesh in step S1.
The present invention provides a kind of methods of CO yield in reduction catalytic pyrolysis of biomass, can also have such spy
Sign, wherein the raw material of biomass is sawdust, straw, corn stover, any one in bark.
Invention action and effect
The method of CO yield in reduction catalytic pyrolysis of biomass according to the present invention, due to by metal powder additive according to
The Blend proportion that mass percent is 10%~15%, which is added in powdered biomass, uniformly to be mixed and at 700 DEG C~900 DEG C
Catalytic pyrolysis is carried out under the conditions of temperature, therefore CO can be effectively reduced in catalytic pyrolysis of biomass to terminate from starting to precipitate into precipitation
Time, to reduce CO yield in catalytic pyrolysis of biomass.Since the raw material to biomass carries out pulverization process to obtain
Powdered biomass, therefore the response area of biomass fuel can be increased, be conducive to the abundant reaction of biomass fuel.Due to right
Powdered biomass is dried, therefore can remove the moisture in powdered biomass, to reduce the wet of biomass fuel
Degree, and then reduce influence of the subsequent pyrolytic process China and foreign countries water to experimental result.
Specific embodiment
The present invention provides a kind of method of CO yield in reduction catalytic pyrolysis of biomass, detailed description below is of the invention
Specific embodiment.
The method for reducing CO yield in catalytic pyrolysis of biomass specifically comprises the following steps:
Biomass material is carried out pulverization process into powdered biomass by step S1, and the granular size of the powdered biomass is
60~100 mesh；
Powdered biomass is dried step S2 under the conditions of 75 DEG C -105 DEG C of temperature, drying process when
Between be 1h~2h；
Biomass powder is added according to the Blend proportion that mass percent is 10%~15% in metal powder additive by step S3
It is uniformly mixed in end and by metal powder additive and powdered biomass, to obtain metal powder additive and biomass powder
The mixture at end；
Mixture is put into the reaction vessel for being used for catalytic pyrolysis mixture by step S4；
Step S5 is continually fed into protective gas with the flow of 3L/min~4L/min to reaction vessel to replace reaction and hold
Air in device；
The mass signal of step S6, the discharge gas of the reaction vessel measured by mass spectrograph determine the protection gas in container
Whether body reaches stable, gas to be protected reach stablize after, by the temperature of reaction vessel under the atmospheric condition of protective gas with
The heating rate of 20 DEG C/min~30 DEG C/min is increased to 700 DEG C~900 DEG C and continues heated at constant temperature 30min~45min, from
And catalytic pyrolysis is carried out to mixture.
In following each embodiments, in order to measure CO yield in catalytic pyrolysis of biomass, survey is also added after step S6
Measure step, it may be assumed that
Step S7, by the mass signal that measures to biomass fuel during catalytic pyrolysis generated CO with when
Between change the intensity that CO is precipitated in fuel and carry out real-time measurement, and by being integrated to the mass signal curve measured, obtain
The yield of CO.
<embodiment 1>
Wood raw material is carried out pulverization process into sawdust powder by step S1, and the granular size of the sawdust powder is 60~100
Mesh；
Step S2 sawdust powder is dried under the conditions of 75 DEG C~105 DEG C of temperature, the time of drying process
For 1h~2h；
Step S3, by Fe2O3Powder is added in sawdust powder according to the Blend proportion that mass percent is 15% and will
Fe2O3Powder and sawdust powder uniformly mix, to obtain Fe2O3The mixture of powder and sawdust powder；
Mixture is put into the reaction vessel for being used for catalytic pyrolysis mixture by step S4；
Step S5 is continually fed into the high-purity argon that purity is 99.999% to reaction vessel with the flow of 3L/min~4L/min
Gas replaces the air in reaction vessel as protective gas, and air emptying is replaced as 1 time using in reactor, repeats to replace
3 times；
The mass signal of step S6, the discharge gas of the reaction vessel measured by mass spectrograph determine the protection gas in container
Whether body reaches stable, after gas to be protected reaches stable, by the temperature of reaction vessel under the atmospheric condition of protective gas, with
The heating rate of 30 DEG C/min is increased to 900 DEG C and continues heated at constant temperature 30min, to carry out catalytic pyrolysis to mixture.
Step S7, by the mass signal that measures to biomass fuel during catalytic pyrolysis generated CO yield into
Row real-time measurement.
Measurement result shows that in the identical situation of remaining condition, the mixture in the present embodiment 1 adds Fe with no2O3
The biomass fuel sample of powder is compared, and CO reduces from the time for starting to precipitate into precipitation end during catalytic pyrolysis
785s, to reduce the yield of CO during catalytic pyrolysis.
<embodiment 2>
In the present embodiment 2, identical symbol is given for method and condition same as Example 1, and omit identical
Explanation.
In embodiment 2, the method for reducing CO yield in catalytic pyrolysis of biomass is same as Example 1, but the gold being added
It is different to belong to powder additive, specifically:
The metal powder additive being added in sawdust powder in step S3 is ZnO powder, to obtain ZnO powder and wood
The mixture of crumbs powder.
Measurement result shows that in the identical situation of remaining condition, the mixture in the present embodiment 2 adds ZnO with no
The biomass fuel sample of powder is compared, and CO reduces from the time for starting to precipitate into precipitation end during catalytic pyrolysis
298s, to reduce the yield of CO during catalytic pyrolysis.
<embodiment 3>
In the present embodiment 3, identical symbol is given for method and condition same as Example 1, and omit identical
Explanation.
In embodiment 3, the method for reducing CO yield in catalytic pyrolysis of biomass is same as Example 1, but the gold being added
It is different to belong to powder additive, specifically:
It is NaCl powder that metal powder additive in sawdust powder is added in step S3, thus obtain NaCl powder and
The mixture of sawdust powder.
Measurement result shows that in the identical situation of remaining condition, the mixture in the present embodiment 3 adds NaCl with no
The biomass fuel sample of powder is compared, and CO reduces from the time for starting to precipitate into precipitation end during catalytic pyrolysis
625s, to reduce the yield of CO during catalytic pyrolysis.
<embodiment 4>
In the present embodiment 4, identical symbol is given for method and condition same as Example 1, and omit identical
Explanation.
In embodiment 4, the method for reducing CO yield in catalytic pyrolysis of biomass is same as Example 1, but the gold being added
It is different to belong to powder additive, specifically:
The metal powder additive being added in sawdust powder in step S3 is CaO powder, to obtain CaO powder and wood
The mixture of crumbs powder.
Measurement result shows that in the identical situation of remaining condition, the mixture in the present embodiment 4 adds CaO with no
The biomass fuel sample of powder is compared, and CO reduces from the time for starting to precipitate into precipitation end during catalytic pyrolysis
303s, to reduce the yield of CO during catalytic pyrolysis.
<embodiment 5>
In the present embodiment 5, identical symbol is given for method and condition same as Example 1, and omit identical
Explanation.
In embodiment 5, the method for reducing CO yield in catalytic pyrolysis of biomass is same as Example 1, but the gold being added
It is different to belong to powder additive, specifically:
The metal powder additive being added in sawdust powder in step S3 is KCl powder, to obtain KCl powder and wood
The mixture of crumbs powder.
Measurement result shows that in the identical situation of remaining condition, the mixture in the present embodiment 5 adds KCl with no
The biomass fuel sample of powder is compared, and CO reduces from the time for starting to precipitate into precipitation end during catalytic pyrolysis
185s, to reduce the yield of CO during catalytic pyrolysis.
Embodiment action and effect
According to the method for reducing CO yield in catalytic pyrolysis of biomass of above-described embodiment, due to by metal powder additive
The Blend proportion for being 10%~15% according to mass percent, which is added in powdered biomass, uniformly to be mixed and 700 DEG C~900
DEG C temperature under the conditions of carry out catalytic pyrolysis, therefore CO can be effectively reduced in catalytic pyrolysis of biomass from starting to precipitate into precipitation
The time of end, to reduce CO yield in catalytic pyrolysis of biomass.Due to biomass raw material carry out pulverization process to
Powdered biomass is obtained, therefore the response area of biomass fuel can be increased, is conducive to the abundant reaction of biomass fuel.By
It is dried in powdered biomass, therefore the moisture in powdered biomass can be removed, to reduce biomass fuel
Humidity, and then reduce influence of the subsequent pyrolytic process China and foreign countries water to experimental result.
Inventor did multiple comparative experiments, by the biomass fuel of the addition metal powder additive in each embodiment
It compares with the biomass fuel sample of no addition metal powder additive, to obtain various metal powder additives to CO
The influence of yield, specific as follows:
In Examples 1 to 5, metal powder additive is different, remaining catalytic pyrolysis condition is all the same, wherein implementing
Additive in example 1 is Fe2O3Powder, since CO gas reduced most being precipitated to the time terminated is precipitated in catalytic pyrolysis
More, the yield of CO is reduced also most, and the additive in embodiment 5 is KCl powder, and CO gas is opened from precipitation in catalytic pyrolysis
Begin to the minimum of the time reduction terminated is precipitated, the yield of CO is reduced also minimum.The result shows that different metal powders adds
Agent is different to the effect for reducing CO yield in catalytic pyrolysis of biomass, Fe2O3Powder is to CO gas in reduction catalytic pyrolysis of biomass
It is best to the effect that the time terminated is precipitated since being precipitated, thus to the effect of CO yield in catalytic pyrolysis of biomass is reduced most
It is good.
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that the ordinary skill of this field is without wound
The property made labour, which according to the present invention can conceive, makes many modifications and variations.Therefore, all technician in the art
Pass through the available technology of logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Scheme, all should be within the scope of protection determined by the claims.
For example, the protective gas for being passed through reaction vessel in step S5 in the above-described embodiments is argon gas, provided in the present invention
Reduce catalytic pyrolysis of biomass in CO yield method, be passed through reaction vessel protective gas be nitrogen.
Claims (9)
1. a kind of method for reducing CO yield in catalytic pyrolysis of biomass, for reducing the biomass burned as fuel
When CO yield, which comprises the steps of:
Biomass material is carried out pulverization process into powdered biomass by step S1；
The powdered biomass is dried step S2 under the conditions of 75 DEG C~105 DEG C of temperature；
The biomass powder is added according to the Blend proportion that mass percent is 10%~15% in metal powder additive by step S3
It is uniformly mixed in end and by the metal powder additive and the powdered biomass, to obtain the metal powder addition
The mixture of agent and the powdered biomass；
The mixture is put into the reaction vessel for being used for mixture described in catalytic pyrolysis by step S4；
Step S5 is continually fed into protective gas to replace described anti-with the flow of 3L/min~4L/min to the reaction vessel
Answer the air in container；
The mass signal of step S6, the discharge gas of the reaction vessel measured by mass spectrograph determine the institute in the container
State whether protective gas reaches stable, after the protective gas reaches and stablizes, by the temperature of the reaction vessel in the guarantor
It protects and is increased to 700 DEG C~900 DEG C under the atmospheric condition of gas and continues heated at constant temperature 30min~45min, thus to described mixed
It closes object and carries out catalytic pyrolysis.
2. the method according to claim 1 for reducing CO discharge amount in catalytic pyrolysis of biomass, it is characterised in that:
Wherein, the metal in the metal powder additive is Fe2O3, any one in ZnO, NaCl, CaO, KCl.
3. the method according to claim 1 for reducing CO discharge amount in catalytic pyrolysis of biomass, it is characterised in that:
Wherein, the temperature of the reaction vessel is 900 DEG C.
4. the method according to claim 1 for reducing CO discharge amount in catalytic pyrolysis of biomass, it is characterised in that:
Wherein, the heating rate of the temperature of reaction vessel described in step S6 is 20 DEG C/min~30 DEG C/min.
5. the method according to claim 1 for reducing CO discharge amount in catalytic pyrolysis of biomass, it is characterised in that:
Wherein, protective gas described in step S5 is the argon gas or nitrogen that purity is 99.999%.
6. the method according to claim 1 for reducing CO discharge amount in catalytic pyrolysis of biomass, it is characterised in that:
Wherein, the number of displacement described in step S5 is 3 times.
7. the method according to claim 1 for reducing CO discharge amount in catalytic pyrolysis of biomass, it is characterised in that:
Wherein, the time of drying process described in step S2 is 1h~2h.
8. the method according to claim 1 for reducing CO discharge amount in catalytic pyrolysis of biomass, it is characterised in that:
Wherein, the granular size of powdered biomass described in step S1 is 60~100 mesh.
9. the method according to claim 1 for reducing CO discharge amount in catalytic pyrolysis of biomass, it is characterised in that:
Wherein, the raw material of the biomass is sawdust, straw, corn stover, any one in bark.
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Citations (4)
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|---|---|---|---|---|
| CN104194808A (en) * | 2014-08-08 | 2014-12-10 | 南京理工大学 | Method for catalytic pyrolysis of rice hulls |
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| CN105419829A (en) * | 2015-10-09 | 2016-03-23 | 青海威德生物技术有限公司 | Method for preparing biomass gas by pyrolyzing chicory residues |
| CN108085032A (en) * | 2017-12-01 | 2018-05-29 | 辽宁科技大学 | A kind of method of alkali metal complex salt catalysis sawdust pyrolytic gas making |
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2018
- 2018-10-19 CN CN201811220237.5A patent/CN109097077A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015035077A1 (en) * | 2013-09-04 | 2015-03-12 | Foster Agblevor | Catalytic pyrolysis of olive mill waste |
| CN104194808A (en) * | 2014-08-08 | 2014-12-10 | 南京理工大学 | Method for catalytic pyrolysis of rice hulls |
| CN105419829A (en) * | 2015-10-09 | 2016-03-23 | 青海威德生物技术有限公司 | Method for preparing biomass gas by pyrolyzing chicory residues |
| CN108085032A (en) * | 2017-12-01 | 2018-05-29 | 辽宁科技大学 | A kind of method of alkali metal complex salt catalysis sawdust pyrolytic gas making |
Non-Patent Citations (1)
| Title |
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| 任献涛: "生物质催化热解实验研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 * |
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Application publication date: 20181228 |