CN110252319A - A kind of biomass tar oil recapitalization hydrogen manufacturing catalyzer and preparation method thereof - Google Patents
A kind of biomass tar oil recapitalization hydrogen manufacturing catalyzer and preparation method thereof Download PDFInfo
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B01J37/088—Decomposition of a metal salt
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
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Abstract
The invention discloses a kind of biomass tar oil recapitalization hydrogen manufacturing catalyzers, the biomass tar oil recapitalization hydrogen manufacturing catalyzer is made of following raw material: dolomite, olivine, calcite, lime stone, aluminum oxide, zirconium dioxide and ceria, the biomass tar oil recapitalization hydrogen manufacturing catalyzer is made of following ratio range: dolomite 40-45%, olivine 20-35%, calcite 13-18%, lime stone 2-7%, aluminum oxide 3-7%, zirconium dioxide 4-6% and ceria 2-7%, structure of the invention is scientific and reasonable, it is safe and convenient to use, dolomite and olivine are natural crystal, abundance, it is cheap, the activity done well after calcining, and the low activity component FeO of olivine becomes the Fe of high activity after calcining3O4, it can be handled in order to increase the initial stage of tar, and aluminum oxide, zirconium dioxide and ceria activity with higher, not oxidizable, high temperature resistant and anti-sintering, to improve the volatility of the active component in hydrogen production process.
Description
Technical field
The present invention relates to catalyst technical field, specially a kind of biomass tar oil recapitalization hydrogen manufacturing catalyzer and its preparation side
Method.
Background technique
In various renewable energy, since nuclear energy, large-scale water power have potential Ecological Environment Risk, wind energy and underground heat
Deng regional resource restriction, greatly develops and limited and queried, and biomass energy is all in property, rich, reproducibility
The features such as obtain people approval, the uniqueness of biomass, solar energy or a kind of reproducible carbon source can be stored by being not only in that,
It can be converted to conventional solid-state, liquid and fuel gas, the energy such as coal, petroleum, natural gas are substantially also to be turned by biomass energy
Become, and biomass coke tar is a kind of sticky, the complicated component, oxygen content that biomass generates during pyrolytic gasification
The high, black by-product with penetrating odor, the presence of tar not only influence equipment normal operation, but also can be to environment and people
Body health causes to seriously endanger, and then influences the development of biomass pyrogenation gasification technological industrialization, and catalysis method is efficient removal life
The important means of substance tar, although traditional catalysis method can effectively decompose tar component, because tar existing for it turns
The problems such as rate is low, catalyst anti-carbon performance is poor, inactivation is fast and hydrogen low yield, limits it in the extensive of pyrolytic gasification field
Using the problems such as inactivation for the removal efficiency and the easy carbon distribution of solution catalyst for how improving tar, it is desirable to provide a kind of biology
Matter tar oil recapitalization hydrogen manufacturing catalyzer solves the above problems.
Summary of the invention
The present invention provides a kind of biomass tar oil recapitalization hydrogen manufacturing catalyzer and preparation method thereof, can effectively solve above-mentioned back
It is proposed that catalysis method is the important means of efficient removal biomass coke tar in scape technology, although traditional catalysis method can be decomposed effectively
Tar component, but because tar conversion is low, catalyst anti-carbon performance is poor existing for it, inactivation is fast and hydrogen low yield etc. is asked
Topic, limits it in the extensive use in pyrolytic gasification field, and for the removal efficiency for how improving tar and to solve catalyst easy
The problems such as carbon distribution inactivates.
To achieve the above object, the invention provides the following technical scheme: a kind of biomass tar oil recapitalization hydrogen manufacturing catalyzer, institute
It states biomass tar oil recapitalization hydrogen manufacturing catalyzer to be made of following raw material: dolomite, olivine, calcite, lime stone, three
Al 2 O, zirconium dioxide and ceria.
According to the above technical scheme, the biomass tar oil recapitalization hydrogen manufacturing catalyzer is made of following ratio range: white clouds
Stone 40-45%, olivine 20-35%, calcite 13-18%, lime stone 2-7%, aluminum oxide 3-7%, zirconium dioxide 4-
6% and ceria 2-7%.
According to the above technical scheme, the biomass tar oil recapitalization hydrogen manufacturing catalyzer is made of following proportion: dolomite
42%, olivine 28%, calcite 13%, lime stone 5%, aluminum oxide 3%, zirconium dioxide 4% and ceria 5%.
A kind of biomass tar oil recapitalization hydrogen manufacturing catalyzer preparation method, includes the following steps:
S1, dolomite, olivine, calcite and lime stone are calcined；
Dolomite, olivine, calcite and lime stone are rolled into particle after S2, calcining, and pass through Multi-stage screening machine
It is screened, screening is underproof to roll again；
S3, garbled particle are added aluminum oxide, zirconium dioxide and ceria and are stirred, and detect after stirring；
Packing is handled after S4, detection are qualified, and is inspected by random samples.According to the above technical scheme；
According to the above technical scheme, calcination temperature is in 650-800 degree in the step S1, and calcination time was at 7-11 hours.
According to the above technical scheme, Multi-stage screening machine revolving speed is 1500-2000r/min, multistage screening in the step S2
Machine is three level screen, and Multi-stage screening machine sieve diameter 20-25 mesh.
According to the above technical scheme, aluminum oxide, zirconium dioxide and ceria are primary addition in the step S3,
And it stirs and is stirred by blender, speed of agitator 2000-2500r/min, mixing time is 3-5 minutes.
According to the above technical scheme, it is detected as 2-7 times in the step S3, removes a peak and a minimum,
Then it carries out for remaining detection parameters being averaged.
According to the above technical scheme, it is packaged in the step S4 by barreled machine, and sampling observation rate is 2-3%.
Compared with prior art, beneficial effects of the present invention: structure of the invention is scientific and reasonable, safe and convenient to use, white clouds
Stone and olivine are natural crystal, and abundance is cheap, and the activity done well after calcining, dolomite ingredient is CaMg
(Co3) 2,90-95% or more is extremely difficult to for the conversion ratio of tar in use, but after dolomite contains Fe3O4, it can
To increase the conversion ratio of its tar, it is maintained at 95%, the main component of olivine is (Mg3Fe) 2SiO4, in the low work of olivine
Property component FeO become the Fe3O4 of high activity after calcining, mixed with dolomite, so as to convenient for increasing tar
Initial stage processing；
And aluminum oxide, zirconium dioxide and ceria activity with higher, not oxidizable, high temperature resistant and anti-burning
Knot solves the problems, such as dolomite to be easy sintering in basic raw material, and to improve the active component in hydrogen production process
Volatility is mutually used with natural crystal, and while reducing cost, its hydrogen production efficiency can be improved, and allows the low work of natural crystal
Property component be combined with each other with aluminum oxide, zirconium dioxide and ceria, and the treatment effect for compensating for ore early period is insufficient
Defect is suitble to promote the use of.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.
In the accompanying drawings:
Fig. 1 is step flow diagram of the invention；
Fig. 2 is preparation facilities structural schematic diagram of the invention；
Appended drawing reference: 1, nitrogen cylinder；2, gas flowmeter；3, two-channel intelligent micro-injection pump；4, fixed bed；5, add
Heat pipe；6, temperature sensor；7, A.C. contactor；8, intelligent temperature controller；9, spherical condensation tube；10, liquid collects flask；11
Ice water bath.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings, it should be understood that preferred reality described herein
Apply example only for the purpose of illustrating and explaining the present invention and is not intended to limit the present invention.
Embodiment 1: as shown in Figure 1, the present invention provides technical solution, a kind of biomass tar oil recapitalization hydrogen manufacturing catalyzer is raw
Substance tar oil recapitalization hydrogen manufacturing catalyzer is made of following raw material: dolomite, olivine, calcite, lime stone, three oxidations
Two aluminium, zirconium dioxide and ceria.
According to the above technical scheme, biomass tar oil recapitalization hydrogen manufacturing catalyzer is made of following proportion: dolomite 42%, olive
Olive stone 28%, calcite 13%, lime stone 5%, aluminum oxide 3%, zirconium dioxide 4% and ceria 5%.
A kind of biomass tar oil recapitalization hydrogen manufacturing catalyzer preparation method, includes the following steps:
S1, dolomite, olivine, calcite and lime stone are calcined；
Dolomite, olivine, calcite and lime stone are rolled into particle after S2, calcining, and pass through Multi-stage screening machine
It is screened, screening is underproof to roll again；
S3, garbled particle are added aluminum oxide, zirconium dioxide and ceria and are stirred, and detect after stirring；
Packing is handled after S4, detection are qualified, and is inspected by random samples.According to the above technical scheme；
According to the above technical scheme, calcination temperature is at 800 degree in step S1, and calcination time was at 10 hours.
According to the above technical scheme, Multi-stage screening machine revolving speed is 1700r/min in step S2, and Multi-stage screening machine is three-level sieve
Choosing, and 20 mesh of Multi-stage screening machine sieve diameter.
According to the above technical scheme, aluminum oxide, zirconium dioxide and ceria are primary addition in step S3, and
Stirring is stirred by blender, speed of agitator 2000r/min, and mixing time is 5 minutes.
According to the above technical scheme, be detected as in step S3 5 times, remove a peak and a minimum, then into
It is about to remaining detection parameters to be averaged.
According to the above technical scheme, it is packaged in step S4 by barreled machine, and sampling observation rate is 2%.
Embodiment 2: as shown in Figure 1, the present invention provides technical solution, a kind of biomass tar oil recapitalization hydrogen manufacturing catalyzer is raw
Substance tar oil recapitalization hydrogen manufacturing catalyzer is made of following raw material: dolomite, olivine, calcite, lime stone, three oxidations
Two aluminium, zirconium dioxide and ceria.
According to the above technical scheme, biomass tar oil recapitalization hydrogen manufacturing catalyzer is made of following proportion: dolomite 40%, olive
Olive stone 30%, calcite 15%, lime stone 2%, aluminum oxide 3%, zirconium dioxide 4% and ceria 6%.
A kind of biomass tar oil recapitalization hydrogen manufacturing catalyzer preparation method, includes the following steps:
S1, dolomite, olivine, calcite and lime stone are calcined；
Dolomite, olivine, calcite and lime stone are rolled into particle after S2, calcining, and pass through Multi-stage screening machine
It is screened, screening is underproof to roll again；
S3, garbled particle are added aluminum oxide, zirconium dioxide and ceria and are stirred, and detect after stirring；
Packing is handled after S4, detection are qualified, and is inspected by random samples.According to the above technical scheme；
According to the above technical scheme, calcination temperature is at 650 degree in step S1, and calcination time was at 1 hour.
According to the above technical scheme, Multi-stage screening machine revolving speed is 1500r/min in step S2, and Multi-stage screening machine is three-level sieve
Choosing, and 25 mesh of Multi-stage screening machine sieve diameter.
According to the above technical scheme, aluminum oxide, zirconium dioxide and ceria are primary addition in step S3, and
Stirring is stirred by blender, speed of agitator 2000r/min, and mixing time is 5 minutes.
According to the above technical scheme, be detected as in step S3 7 times, remove a peak and a minimum, then into
It is about to remaining detection parameters to be averaged.
According to the above technical scheme, it is packaged in step S4 by barreled machine, and sampling observation rate is 3%.
Embodiment 3: as shown in Figure 1, the present invention provides technical solution, a kind of biomass tar oil recapitalization hydrogen manufacturing catalyzer is raw
Substance tar oil recapitalization hydrogen manufacturing catalyzer is made of following raw material: dolomite, olivine, calcite, lime stone, three oxidations
Two aluminium, zirconium dioxide and ceria.
According to the above technical scheme, biomass tar oil recapitalization hydrogen manufacturing catalyzer is made of following proportion: dolomite 41%, olive
Olive stone 31%, calcite 14%, lime stone 3%, aluminum oxide 3%, zirconium dioxide 6% and ceria 2%.
A kind of biomass tar oil recapitalization hydrogen manufacturing catalyzer preparation method, includes the following steps:
S1, dolomite, olivine, calcite and lime stone are calcined；
Dolomite, olivine, calcite and lime stone are rolled into particle after S2, calcining, and pass through Multi-stage screening machine
It is screened, screening is underproof to roll again；
S3, garbled particle are added aluminum oxide, zirconium dioxide and ceria and are stirred, and detect after stirring；
Packing is handled after S4, detection are qualified, and is inspected by random samples.According to the above technical scheme；
According to the above technical scheme, calcination temperature is at 700 degree in step S1, and calcination time was at 9 hours.
According to the above technical scheme, Multi-stage screening machine revolving speed is 1800r/min in step S2, and Multi-stage screening machine is three-level sieve
Choosing, and 25 mesh of Multi-stage screening machine sieve diameter.
According to the above technical scheme, aluminum oxide, zirconium dioxide and ceria are primary addition in step S3, and
Stirring is stirred by blender, speed of agitator 2500r/min, and mixing time is 3 minutes.
According to the above technical scheme, be detected as in step S3 6 times, remove a peak and a minimum, then into
It is about to remaining detection parameters to be averaged.
According to the above technical scheme, it is packaged in step S4 by barreled machine, and sampling observation rate is 2%.
Embodiment 4: as shown in Fig. 2, the present invention provides evaluating catalyst scheme and as a result, evaluating apparatus includes nitrogen cylinder
1, nitrogen cylinder is connected by pipeline with gas flowmeter 2, and gas flowmeter 2 is connected by pipeline with fixed bed 4, fixed bed 4
Outside is socketed with heating tube 5, and fixed bed 4 is connected by A.C. contactor 7 with intelligent temperature controller 8, intelligent temperature controller 8 and temperature
It spends sensor 6 to be connected, 4 bottom end of fixed bed is connected by pipeline with spherical condensation tube 9, and 9 bottom end of spherical condensation tube is placed with liquid
Flask 10 is collected, liquid is collected flask 10 and is placed in ice water bath 11, and 4 top of fixed bed is micro- by pipeline and two-channel intelligent
Syringe pump 3 is measured to be connected.
Experiment flow: before reaction starts, first by the distribution of net of catalyst addition 4 bottom of fixed bed again by fixed bed 4
The components such as flange be completely embedded heating tube 5 heating before, with the flow of 2L/min be continually fed into high pure nitrogen 30min. then by
Be close to 4 outer wall of fixed bed heating tube 5 be heated to set temperature, after temperature stablize after, by two-channel intelligent micro-injection pump 3 with
The flow respectively set will start to react after reaction starts and stops being passed through nitrogen in tar and deionized water injection fixed bed 4,
Start to collect gaseous product after reaction 30min, stops experiment after collecting gaseous product 90min, protected with the high pure nitrogen of 1L/min
Inert atmosphere is down to room temperature in shield fixed bed 4, and the gaseous product being collected into reaction process passes through gas chromatograph (Agilent
7890B) analyze its gas composition.
Carbon distribution on catalyst is analyzed using temperature programmed oxidation, and the catalyst after reaction is placed in quartzy tube reaction
In device, it is passed through 15% (mole percent) O2/N2 of 60mL/h, temperature is raised to 900 DEG C from room temperature with the rate of 10K/min,
Tail gas composition carries out on-line continuous analysis by on-line mass spectroscopy instrument (the mono- LG type of Max300 of Extrel company, U.S. production), according to
The average carbon distribution rate calculations formula that CO, CO2 production quantity calculate the carbon deposition quantity catalyst of catalyst is as follows:
The tar after 700-900 DEG C of high-temperature gasification, can not be coagulated under obtained room temperature with biomass material
Product liquid, also referred to as biomass coke tar.Biomass material is the biomass material of this field routine, can be agriculture waste
One of object, forestry waste, forestry processing waste, water plant and energy crop are a variety of.
Biomass material selected by the present embodiment is sawdust, and gasification temperature is 750 DEG C, resulting biomass char oil ingredient
It is as shown in the table.
The chemical composition of biomass coke tar
| Number | Chemical composition | Percentage composition/wt.% | Number | Chemical composition | Percentage composition/wt.% |
| 1 | Toluene | 44.29 | 2 | Styrene | 27.83 |
| 3 | Ethylbenzene | 12.35 | 4 | Paraxylene | 9.60 |
| 5 | Naphthalene | 1.78 | 6 | Indenes | 1.69 |
| 7 | Acenaphthene | 0.78 | 8 | Phenol | 0.65 |
| 9 | Paracresol | 0.34 | 10 | 1- methyl naphthalene | 0.27 |
| 11 | Luxuriant and rich with fragrance anthracene | 0.15 | 12 | 2- methyl naphthalene | 0.13 |
| 13 | O-cresol | 0.08 | 14 | Fluorenes | 0.06 |
| 15 | Anthracene | It is micro | 16 | Anthracene | It is micro |
Following table is made by embodiment 1-3:
It is compared by embodiment 1-3, it is known that embodiment 1 preferably can produce hydrogen rate, H2Content and H2Selectivity with
Embodiment 2 and embodiment 3 are promoted the use of so as to be more suitable.
Compared with prior art, beneficial effects of the present invention: structure of the invention is scientific and reasonable, safe and convenient to use, white clouds
Stone and olivine are natural crystal, and abundance is cheap, and the activity done well after calcining, dolomite ingredient is CaMg
(Co3) 2,90-95% or more is extremely difficult to for the conversion ratio of tar in use, but after dolomite contains Fe3O4, it can
To increase the conversion ratio of its tar, it is maintained at 95%, the main component of olivine is (Mg3Fe) 2SiO4, in the low work of olivine
Property component FeO become the Fe3O4 of high activity after calcining, mixed with dolomite, so as to convenient for increasing tar
Initial stage processing；
And aluminum oxide, zirconium dioxide and ceria activity with higher, not oxidizable, high temperature resistant and anti-burning
Knot solves the problems, such as dolomite to be easy sintering in basic raw material, and to improve the active component in hydrogen production process
Volatility is mutually used with natural crystal, and while reducing cost, its hydrogen production efficiency can be improved, and allows the low work of natural crystal
Property component be combined with each other with aluminum oxide, zirconium dioxide and ceria, and the treatment effect for compensating for ore early period is insufficient
Defect is suitble to promote the use of.
Finally, it should be noted that being not intended to restrict the invention the foregoing is merely preferred embodiment of the invention, to the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, for those skilled in the art, still can be with
It modifies the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.It is all
Within the spirit and principles in the present invention, any modification, equivalent replacement, improvement and so on should be included in guarantor of the invention
Within the scope of shield.
Claims (9)
1. a kind of biomass tar oil recapitalization hydrogen manufacturing catalyzer, it is characterised in that: the biomass tar oil recapitalization hydrogen manufacturing catalyzer by
Following raw material is made: dolomite, olivine, calcite, lime stone, aluminum oxide, zirconium dioxide and ceria.
2. a kind of biomass tar oil recapitalization hydrogen manufacturing catalyzer according to claim 1, which is characterized in that the biomass char
Oil reforming hydrogen production catalyst is made of following ratio range: dolomite 40-45%, olivine 20-35%, calcite 13-18%,
Lime stone 2-7%, aluminum oxide 3-7%, zirconium dioxide 4-6% and ceria 2-7%.
3. a kind of biomass tar oil recapitalization hydrogen manufacturing catalyzer according to claim 1, which is characterized in that the biomass char
Oil reforming hydrogen production catalyst is made of following proportion: dolomite 42%, olivine 28%, calcite 13%, lime stone 5%, three
Al 2 O 3%, zirconium dioxide 4% and ceria 5%.
4. a kind of biomass tar oil recapitalization hydrogen manufacturing catalyzer preparation method according to claim 1-3, feature
It is: includes the following steps:
S1, dolomite, olivine, calcite and lime stone are calcined；
Dolomite, olivine, calcite and lime stone are rolled into particle after S2, calcining, and carried out by Multi-stage screening machine
Screening, screening is underproof to roll again；
S3, garbled particle are added aluminum oxide, zirconium dioxide and ceria and are stirred, and detect after stirring；
Packing is handled after S4, detection are qualified, and is inspected by random samples.
5. a kind of biomass tar oil recapitalization hydrogen manufacturing catalyzer preparation method according to claim 4, which is characterized in that described
Calcination temperature is in 650-800 degree in step S1, and calcination time was at 7-11 hours.
6. a kind of biomass tar oil recapitalization hydrogen manufacturing catalyzer preparation method according to claim 4, which is characterized in that described
Multi-stage screening machine revolving speed is 1500-2000r/min in step S2, and Multi-stage screening machine is three level screen, and Multi-stage screening machine sieve
Diameter 20-25 mesh.
7. a kind of biomass tar oil recapitalization hydrogen manufacturing catalyzer preparation method according to claim 4, which is characterized in that described
Aluminum oxide, zirconium dioxide and ceria are primary addition in step S3, and stir and be stirred by blender, are stirred
Mixing revolving speed is 2000-2500r/min, and mixing time is 3-5 minutes.
8. a kind of biomass tar oil recapitalization hydrogen manufacturing catalyzer preparation method according to claim 4, which is characterized in that described
It is detected as 2-7 times in step S3, removes a peak and a minimum, then carry out asking it to be averaged remaining detection parameters
Value.
9. a kind of biomass tar oil recapitalization hydrogen manufacturing catalyzer preparation method according to claim 4, which is characterized in that described
It is packaged in step S4 by barreled machine, and sampling observation rate is 2-3%.
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| CN110562916A (en) * | 2019-09-25 | 2019-12-13 | 华南理工大学 | Method for producing hydrogen by adsorption and enhancement of lignin black liquor through reforming |
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