CN108970616A - A kind of preparation method of biomass tar cracking catalyst - Google Patents
A kind of preparation method of biomass tar cracking catalyst Download PDFInfo
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- CN108970616A CN108970616A CN201710394897.4A CN201710394897A CN108970616A CN 108970616 A CN108970616 A CN 108970616A CN 201710394897 A CN201710394897 A CN 201710394897A CN 108970616 A CN108970616 A CN 108970616A
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- Prior art keywords
- naphthalene
- biomass
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- temperature
- cracking catalyst
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation methods of biomass tar cracking catalyst, using naphthalene as biomass tar model compound, catalytic pyrolysis experimental study has been carried out on the Ni base catalyst prepared using dolomite as carrier, experimental analysis has been carried out to the technology of preparing of catalyst, activity, coking deactivation performance and regeneration.The result shows that: in 700 DEG C of cracking temperatures, air speed 0.8Lh‑1Reaction condition under, the conversion per pass of naphthalene burns carbon, the catalyst regeneration time is short, and catalytic pyrolysis is more advantageous to the deep pyrolytic of naphthalene compared with synthermal thermal cracking up to 95% under conditions of temperature programming.
Description
Technical field
The present invention relates to a kind of preparation methods of biomass tar cracking catalyst.
Background technique
Biomass is as a kind of renewable energy, in terms of the sustainable supply of the energy and low content greenhouse gas emission
The advantages of, become the most ideal new energy for replacing fossil fuel.Gasification of biomass and indirect liquefaction are biomass energy Gao Pin
Position utilizes most rapid most practical one of the technology of development.Biomass gasified gas further includes having one in addition to containing a large amount of fuel gas
Determine the dust particle, volatile alkali and tar of content.Biomass coke tar is fragrant hydrocarbons and their derivates and polycyclic aromatic hydrocarbon
Mixture, five kinds of representative compounds are respectively benzene, toluene, naphthalene, anthracene, pyrene, and ingredient one of of the naphthalene as more difficult cracking is shared to contain
It measures higher.
Therefore, a kind of preparation method of biomass tar cracking catalyst is worth inquiring into.
Summary of the invention
Goal of the invention: naphthalene is as the higher ingredient of content in biomass coke tar, but more difficult cracking, and the invention proposes one kind
The preparation method of biomass tar cracking catalyst, by experimental analysis, conditional filtering prepares high conversion rate, reproduction time
Catalyst short, stability is good.
Technical solution: in order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is as follows: a kind of biomass coke tar
The preparation method of catalyst for cracking includes the following steps: nickel nitrate crystal dissolving in wiring solution-forming in distilled water, by dolomite dust
It is broken into certain particle size and nickel nitrate solution wet mixing, binder and forming agent is added, dry, compression molding, certain temperature calcining one
It the section time, pulverizes and sieves.Biomass coke tar is fitted into evaporator again, the temperature of evaporator is controlled at 88-92 DEG C, by micro- reaction
Device setting heating parameter, make temperature of reactor from room temperature cracking temperature is raised to the heating rate of 40 DEG C/min after one section of constant temperature
Time, by carrier gas N2The steam for carrying naphthalene is cracked by catalyst bed, is controlled carrier gas flux, is made naphthalene in reactor feed gas
Content is substantially suitable with the content of naphthalene in biomass gasified gas, and the product after cracking collects and surveys gas after dehydrated alcohol washs
Ingredient.
Further, the calcination temperature is set as 700-1000 DEG C, and calcination time is set as 1-5h.
Further, the biomass coke tar is the crystal of naphthalene.
Further, the crack temperature range is set as 500-750 DEG C.
Further, the carrier gas flux control is in 0.8Lh-1。
Further, the analysis gas uses gas chromatography analysis method.
The utility model has the advantages that a kind of preparation method of biomass tar cracking catalyst provided by the invention, using naphthalene as biomass
Tar model compound has carried out catalytic pyrolysis experimental study on the Ni base catalyst prepared using dolomite as carrier, to urging
Technology of preparing, activity, coking deactivation performance and the regeneration of agent have carried out experimental analysis.The result shows that: in 700 DEG C split
Solve temperature, air speed 0.8Lh-1 reaction condition under, the conversion per pass of naphthalene is burnt under conditions of temperature programming up to 95%
Carbon, the catalyst regeneration time is short, and catalytic pyrolysis is more advantageous to the deep pyrolytic of naphthalene compared with synthermal thermal cracking.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail:
Embodiment 1:
Nickel nitrate crystal is dissolved in wiring solution-forming in distilled water by a kind of preparation method of biomass tar cracking catalyst,
Dolomite dust is broken into certain particle size and nickel nitrate solution wet mixing, binder and forming agent is added, dry, compression molding, 700 DEG C
2h is calcined, is pulverized and sieved.The crystal of naphthalene is fitted into evaporator again, the temperature of evaporator is controlled at 90 DEG C, by micro-reaction device
Setting heating parameter, make temperature of reactor from room temperature be raised to 500 DEG C with the heating rate of 40 DEG C/min after constant temperature, by carrier gas N2It takes
Steam with naphthalene is cracked by catalyst bed, and control carrier gas flux is 0.8Lh-1, make the content of naphthalene in reactor feed gas
It is substantially suitable with the content of naphthalene in biomass gasified gas, the product after cracking collected and surveyed after dehydrated alcohol washs gas at
Point.
Embodiment 2:
Nickel nitrate crystal is dissolved in wiring solution-forming in distilled water by a kind of preparation method of biomass tar cracking catalyst,
Dolomite dust is broken into certain particle size and nickel nitrate solution wet mixing, binder and forming agent is added, dry, compression molding, 800 DEG C
3h is calcined, is pulverized and sieved.The crystal of naphthalene is fitted into evaporator again, the temperature of evaporator is controlled at 92 DEG C, by micro-reaction device
Setting heating parameter, make temperature of reactor from room temperature be raised to 600 DEG C with the heating rate of 40 DEG C/min after constant temperature, by carrier gas N2It takes
Steam with naphthalene is cracked by catalyst bed, and control carrier gas flux is 0.8Lh-1, make the content of naphthalene in reactor feed gas
It is substantially suitable with the content of naphthalene in biomass gasified gas, the product after cracking collected and surveyed after dehydrated alcohol washs gas at
Point.
Embodiment 3:
Nickel nitrate crystal is dissolved in wiring solution-forming in distilled water by a kind of preparation method of biomass tar cracking catalyst,
Dolomite dust is broken into certain particle size and nickel nitrate solution wet mixing, binder and forming agent is added, dry, compression molding, 900 DEG C
4h is calcined, is pulverized and sieved.The crystal of naphthalene is fitted into evaporator again, the temperature of evaporator is controlled at 90 DEG C, by micro-reaction device
Setting heating parameter, make temperature of reactor from room temperature be raised to 700 DEG C with the heating rate of 40 DEG C/min after constant temperature, by carrier gas N2It takes
Steam with naphthalene is cracked by catalyst bed, and control carrier gas flux is 0.8Lh-1, make the content of naphthalene in reactor feed gas
It is substantially suitable with the content of naphthalene in biomass gasified gas, the product after cracking collected and surveyed after dehydrated alcohol washs gas at
Point.
Finally, it should be noted that above embodiments are only to illustrate the present invention and not limit technology described in the invention
Scheme, therefore, although this specification is referring to above-mentioned various embodiments, the present invention has been described in detail, this
Field it is to be appreciated by one skilled in the art that still can modify to the present invention or equivalent replacement, and all do not depart from this
The technical solution and improvement of the spirit and scope of invention, should all cover within the scope of the claims of the present invention.
Claims (6)
1. a kind of preparation method of biomass tar cracking catalyst, which comprises the steps of: by nickel nitrate crystal
Wiring solution-forming in distilled water is dissolved in, dolomite dust is broken into certain particle size and nickel nitrate solution wet mixing, binder and molding is added
Agent, dry, compression molding, pulverize and sieve certain temperature calcining a period of time.Biomass coke tar is fitted into evaporator again, is steamed
The temperature for sending out device is controlled at 88-92 DEG C, and micro-reaction device is set heating parameter, makes temperature of reactor from room temperature with 40 DEG C/min
Heating rate be raised to cracking temperature after constant temperature for a period of time, by carrier gas N2The steam for carrying naphthalene is cracked by catalyst bed,
Carrier gas flux is controlled, keeps the content of naphthalene in the content of naphthalene and biomass gasified gas in reactor feed gas substantially suitable, after cracking
Product collect and survey gas componant after dehydrated alcohol washs.
2. a kind of preparation method of biomass tar cracking catalyst according to claim 1, it is characterised in that: described to forge
It burns temperature and is set as 700-1000 DEG C, calcination time is set as 1-5h.
3. a kind of preparation method of biomass tar cracking catalyst according to claim 1, it is characterised in that: the life
Substance tar is the crystal of naphthalene.
4. a kind of preparation method of biomass tar cracking catalyst according to claim 1, it is characterised in that: described to split
Solution temperature range is set as 500-750 DEG C.
5. a kind of preparation method of biomass tar cracking catalyst according to claim 1, it is characterised in that: the load
Throughput is controlled in 0.8Lh-1。
6. a kind of preparation method of biomass tar cracking catalyst according to claim 1, it is characterised in that: described point
Gassing body uses gas chromatography analysis method.
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| CN201710394897.4A CN108970616A (en) | 2017-05-30 | 2017-05-30 | A kind of preparation method of biomass tar cracking catalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569612A (en) * | 2018-12-25 | 2019-04-05 | 哈尔滨工业大学 | It is a kind of using active carbocoal as nanometer binary metal-base catalytic cracking of tar catalyst of carrier and preparation method thereof |
| CN110935453A (en) * | 2019-12-16 | 2020-03-31 | 山东科技大学 | Dolomite catalyst without noble metal and its prepn and use |
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| CN1935380A (en) * | 2006-09-30 | 2007-03-28 | 中国科学院广州能源研究所 | Method for preparing integral biomass gasified tarcracking catalyst |
| CN101396660A (en) * | 2008-10-22 | 2009-04-01 | 中国林业科学研究院林产化学工业研究所 | Biomass gasification tar cracking composite catalyst and preparation method thereof |
| CN104611060A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Method for producing clean fuel oil by using waste plastic and high aromatic component |
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2017
- 2017-05-30 CN CN201710394897.4A patent/CN108970616A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935380A (en) * | 2006-09-30 | 2007-03-28 | 中国科学院广州能源研究所 | Method for preparing integral biomass gasified tarcracking catalyst |
| CN101396660A (en) * | 2008-10-22 | 2009-04-01 | 中国林业科学研究院林产化学工业研究所 | Biomass gasification tar cracking composite catalyst and preparation method thereof |
| CN104611060A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Method for producing clean fuel oil by using waste plastic and high aromatic component |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569612A (en) * | 2018-12-25 | 2019-04-05 | 哈尔滨工业大学 | It is a kind of using active carbocoal as nanometer binary metal-base catalytic cracking of tar catalyst of carrier and preparation method thereof |
| CN109569612B (en) * | 2018-12-25 | 2020-12-11 | 哈尔滨工业大学 | Nano binary metal base tar catalytic cracking catalyst using active semicoke as carrier and preparation method thereof |
| CN110935453A (en) * | 2019-12-16 | 2020-03-31 | 山东科技大学 | Dolomite catalyst without noble metal and its prepn and use |
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