CN106861749A - A kind of catalyst for producing high added value bio oil and preparation method thereof - Google Patents
A kind of catalyst for producing high added value bio oil and preparation method thereof Download PDFInfo
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- CN106861749A CN106861749A CN201710041715.5A CN201710041715A CN106861749A CN 106861749 A CN106861749 A CN 106861749A CN 201710041715 A CN201710041715 A CN 201710041715A CN 106861749 A CN106861749 A CN 106861749A
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
-
- 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
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- 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
- C10G2300/1014—Biomass of vegetal origin
-
- 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
- C10G2300/70—Catalyst aspects
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- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention discloses a kind of catalyst for producing high added value bio oil and preparation method thereof, including:The transition metal oxide that will be weighed is dissolved in 100mL deionized waters.The molecular sieve catalysts of ZSM 5 that silica alumina ratio is 46 are added in stirring;Solution is continuously stirred into 6h using magnetic stirring apparatus;Suction filtration, shaping, 12h is dried in 105 DEG C of baking ovens;Then in 550 DEG C of high temperature process furnances crystallizations, shapings in the atmosphere of air;Then activated at the same temperatures under the gaseous mixture atmosphere of nitrogen and hydrogen, reduction, be made and modified contain transition metal respectively(Co、Zn、Ni)The molecular sieve catalysts of ZSM 5.The modified catalyst of the present invention can improve biology oily yield and its selectivity obtained by rice straw catalysis pyrolysis.
Description
Technical field
The invention belongs to catalytic pyrolysis of biomass technical field, and in particular to a kind of for producing high added value bio oil
Catalyst and its method for preparation.
Background technology
With the exhaustion of fossil energy, renewable resource is increasingly paid close attention to by people in recent decades, biomass energy
Also one of object of people's research is turned into.China is extensive as large agricultural country's Biomass Energy Resources, including corn, wheat, paddy rice
It is annual up to several hundreds of millions tons Deng agricultural crop straw and rice hulls, sugarcane processing of farm products residue.And these are urged as biomass
The raw material for changing cracking reaction can alleviate the current energy problem for facing and problem of environmental pollution.But during the course of the reaction still
So there are problems that it is many such as:Gained liquid oil low yield, liquid oil quality is still relatively low, selectivity it is poor, catalyst activity compared with
Low, easy in inactivation etc., it is therefore necessary to improve the yield and quality of biomass pyrolytic liquid product.
The reacted vapor catalyzed reformation of biomass pyrolytic effectively can be modified to carry to complex component in bio oil
The yield and its selectivity of bio oil high, improve the utilization space of bio oil.That commonly used in research at present is ZMS-5 and H-ZSM5
Molecular sieve catalyst, although ZMS-5 has preferable catalytic effect in the reaction because the easy coking in surface can cause to urge
Agent is inactivated.H-ZSM5 acidity can influence more by force its deoxygenation ability and catalyst can be caused to inactivate.Therefore can pass through
To the regulation such as oxide modifying of molecular sieve catalyst acid intensity, to ensure to improve feed stock conversion, the formation of carbon deposit is reduced,
Improve the active of catalyst, selectivity and service life.
The content of the invention
It is an object of the invention to provide a kind of catalyst for producing high added value bio oil and preparation method thereof, with
Modified catalyst is obtained, so as to improve liquid in catalytic pyrolysis of biomass reaction(Bio oil)Yield and quality, specific body
Improve the chemical constituent selectivity of feed stock conversion and bio oil now, reduce the formation of carbon deposit, improve catalyst activity and
Selectivity.
In order to solve upper technical problem, the present invention discloses different oxo transition metals with ZSM-5 molecular sieve as catalyst carrier
The modified influence to prepared catalyst of compound, transition metal modified point prepared by means analysis is analyzed by XRD, SEM etc.
Sub- sieve catalyst microscopic pattern change, the combination and distribution of active component and carrier, concrete technical scheme are as follows:
A kind of preparation method for producing the catalyst of high added value bio oil, it is characterised in that comprise the following steps:
Step one, the various transition metal oxides that will be weighed are dissolved in deionized water respectively, obtain solution A, are constantly being stirred
To ZSM-5 molecular sieve catalyst is added in solution A in the case of mixing, solution B is obtained;Metallic element in the transition metal oxide
Quality than content is selected ZSM-5 molecular sieve catalyst 5%;
Step 2, using magnetic stirring apparatus continuous stirring solution B, obtains solution C;
Step 3, suction filtration, shaping are carried out to solution C, are then dried in an oven, obtain product one;
Step 4, is calcined using high temperature process furnances in the atmosphere of air to product one, and product is obtained after making its crystallization, shaping
Two;
Step 5, is activated to product two with the temperature same with step 4 under the gaseous mixture atmosphere of nitrogen and hydrogen, is gone back
Original, so as to prepare final product, i.e., the modified ZSM-5 molecular sieve catalyst for being loaded with transition metal respectively;
The transition metal is any one in Co, Zn, Ni.
The various transition metal oxides are with the proportionate relationship of deionized water:Co (the NO of 11.04g3)2.6H2O、
Ni (the NO of 10.71g3)2.6H2Zn (the NO of O, 10.13g3)2.6H2O, the respectively deionized water with 100mL;ZSM-5 molecular sieve is urged
Agent is 40g.
The silica alumina ratio of ZSM-5 molecular sieve catalyst is 46 in the step one.
The step 2 is specially:Solution B is placed on magnetic stirring apparatus, magnetic stir bar is added in the solution, 60
6h is continuously stirred at a temperature of DEG C.
The step 3 is specially:
Suction filtration, shaping are a metafiltration paper to be put in Buchner funnel and then Buchner funnel is connected into vavuum pump, and solution C is being ready to
Buchner funnel in carry out suction filtration, the solid matter on filter paper is retained after suction filtration is complete, be then made into diameter 5 using plastic tube
Millimeter, small cylinder long 7 millimeters, use when conveniently testing;
The material of shaping is put into quartz boat 12h is dried in baking oven at 105 DEG C.
The atmosphere of the air refer to tube furnace bakee during be not passed through gas;The step 4 is specially in air atmosphere
It is middle to make catalyst crystal, shaping to be calcined under the conditions of 550 DEG C through high-temperature tubular furnace temperature;Crystallization, the time of shaping are 3h.
Gaseous mixture atmosphere in the step 5 refers to that the gaseous mixture atmosphere of nitrogen and hydrogen refers to be bakeed in tube furnace
During to be passed through nitrogen and hydrogen mixing ratio be 99:1 gas;The step 5 is specially and is passed through in described gaseous mixture atmosphere
High-temperature tubular furnace temperature makes activation of catalyst, reduction to be calcined under the conditions of 550 DEG C, and roasting time is 2h.
A kind of catalyst for producing high added value bio oil, it is characterised in that:Prepared using above-mentioned preparation method
And obtain.
The present invention has beneficial effect.In the present invention prepare it is transition metal modified after ZSM-5 molecular sieve catalyst, often
Individual sample maintains the feature mode of ZSM-5 topological structures, and molecular sieve catalyst after modified still keeps regular molecule
Sieve structure form.Illustrate that the dispersiveness of modified molecular sieve catalyst is still preferable.It is with the ZSM-5 molecular sieve that silica alumina ratio is 46
Carrier, it is transition metal modified after the molecular sieve peak intensity of ZSM-5 molecular sieve catalyst increase, generate by skeletal substance it
It is highly crystalline that outer material is formed, and transition metal is easier to mix framework of molecular sieve with this understanding.Can be led from sem analysis
Want crystal grain and its agglomerate to be slightly changed with transition metal change in the sample, compared with undressed sample, pass through
The monocrystalline size of the sample after treatment is slightly reduced, and the surface of same order elements sample is more smooth, and catalytic performance is better.
Brief description of the drawings
Fig. 1 is the XRD diffraction patterns of influence of the difference transition metal oxide of the invention to modified molecular sieve catalyst;
Fig. 2 is for the present invention compared for adding modified catalysts and not add catalyst rice straw microwave-heating product yield
Influence;
Fig. 3 is flow chart of the method for the present invention.
Specific embodiment
Below in conjunction with the accompanying drawings and specific embodiment, technical scheme is described in further details.
Load weighted transition metal oxide is dissolved in the deionized water of 100mL respectively.In stirring, addition silica alumina ratio is
46 ZSM-5 molecular sieve catalyst, 6h is being continuously stirred using magnetic stirring apparatus;Suction filtration, shaping, dry in baking oven at 105 DEG C
Dry 12h;Then crystallized at 550 DEG C using high temperature process furnances in the atmosphere of air, be molded, then in nitrogen and the atmosphere of hydrogen
Under activate at the same temperatures, reduction, be made and modified contain transition metal respectively(Co、Zn、Ni)Silica alumina ratio be 46
ZSM-5 molecular sieve catalyst.Flow chart of the method for the present invention is as shown in Figure 3.
Embodiment one
Co (the NO of the 11.04g that will be weighed3)2.6H2Ni (the NO of O, 10.71g3)2.6H2Zn (the NO of O, 10.13g3)2.6H2O
100mL deionized waters are dissolved in respectively.The ZSM-5 molecular sieve catalyst that silica alumina ratio is 46 is separately added into stirring, using magnetic force
Agitator continuously stirs 6h at 60 DEG C;Suction filtration, shaping are carried out in Buchner funnel, 12h is dried in an oven at 105 DEG C;
Then 3h are calcined at 550 DEG C using high temperature process furnances in the atmosphere of air makes its crystallization, shaping, then in nitrogen and hydrogen
Than being 99:2h activation, reduction are calcined under 1 atmosphere at the same temperatures, are made and modified are loaded with transition metal respectively
(Co、Zn、Ni)Silica alumina ratio be 46 ZSM-5 molecular sieve catalyst.Urged in order to the catalyst for contrasting modified is undressed
The crystal characteristic of agent, contrast modified catalyst carries out XRD signs with undressed catalyst, as shown in figure 1, modified
Molecular sieve catalyst afterwards maintains the feature mode and regular molecular sieve structure form of the topological structure of raw catalyst, explanation
The dispersiveness of modified molecular sieve catalyst is still preferable.
Embodiment two
In order to verify the influence that modified catalyst is converted to biomass pyrolytic, using catalytic fixed bed reactor and microwave
Pyrolysis installation combination has carried out catalysis Pyrolysis Experiment.Experiment raw material used is straw:The straw raw material for weighing 30g first is put in
During capacity is for the quartzy bottle of 500ml, the activated carbon for being subsequently adding 1.5g mixes as microwave absorbing material with straw, then by quartz
Bottle is placed in micro-wave oven, and the required catalyst of 1.5g is placed in catalytic fixed bed reactor.The reaction temperature of microwave-heating is set
It is 500 DEG C to spend, and the time is 8min, and microwave power is 750W;Pyrolysis gas enter after microwave-heating reacts by catalytic fixed bed
Row catalytic reforming reaction, then the collecting biological oil after rapid condensation, collect reacted bio oil organic component and catalyst warp
The characterization methods such as GC/MS, SEM, XRD are analyzed, and compared for being not added with catalyst in experiment with addition modified catalysts
Microwave-heating is tested, as a result as shown in Figure 2:It is substantially more than not adding the bio oil that catalyst is obtained using modified catalyst,
Influence of the transition metal to biological oily yield is Co>Zn>Ni, the bio oil obtained using Co/ZSM-5 molecular sieve catalysts is produced
Rate highest(It is 26.67%).By GC/MS analysis microwave-heating straw obtained by bio oil primary chemical compound be aldehyde/
Ketone, phenols, guaiacol, organic acid, alcohol, sugar and hydrocarbon.Wherein main compound compared with the result for being not added with catalyst,
Aldehyde/ketone, guaiacol, alcohol, the content of phenols increased, and illustrate that the use of catalyst improves the selectivity of bio oil, make it
Constituent becomes simpler.
Claims (8)
1. a kind of preparation method for producing the catalyst of high added value bio oil, it is characterised in that comprise the following steps:
Step one, the various transition metal oxides that will be weighed are dissolved in deionized water respectively, obtain solution A, are constantly being stirred
To ZSM-5 molecular sieve catalyst is added in solution A in the case of mixing, solution B is obtained;Metallic element in the transition metal oxide
Quality than content is selected ZSM-5 molecular sieve catalyst 5%;
Step 2, using magnetic stirring apparatus continuous stirring solution B, obtains solution C;
Step 3, suction filtration, shaping are carried out to solution C, are then dried in an oven, obtain product one;
Step 4, is calcined using high temperature process furnances in the atmosphere of air to product one, and product is obtained after making its crystallization, shaping
Two;
Step 5, is activated to product two with the temperature same with step 4 under the gaseous mixture atmosphere of nitrogen and hydrogen, is gone back
Original, so as to prepare final product, i.e., the modified ZSM-5 molecular sieve catalyst for being loaded with transition metal respectively;
The transition metal is any one in Co, Zn, Ni.
2. a kind of preparation method for producing the catalyst of high added value bio oil according to claim 1, its feature
It is:The various transition metal oxides are with the proportionate relationship of deionized water:Co (the NO of 11.04g3)2.6H2O、10.71g
Ni (NO3)2.6H2Zn (the NO of O, 10.13g3)2.6H2O, the respectively deionized water with 100mL;ZSM-5 molecular sieve catalyst is
40g。
3. a kind of preparation method for producing the catalyst of high added value bio oil according to claim 1, its feature
It is:The silica alumina ratio of ZSM-5 molecular sieve catalyst is 46 in the step one.
4. a kind of preparation method for producing the catalyst of high added value bio oil according to claim 1, its feature
It is:The step 2 is specially:Solution B is placed on magnetic stirring apparatus, magnetic stir bar is added in the solution, in 60 DEG C of temperature
6h is continuously stirred under degree.
5. a kind of preparation method for producing the catalyst of high added value bio oil according to claim 1, its feature
It is that the step 3 is specially:
Suction filtration, shaping are a metafiltration paper to be put in Buchner funnel and then Buchner funnel is connected into vavuum pump, and solution C is being ready to
Buchner funnel in carry out suction filtration, the solid matter on filter paper is retained after suction filtration is complete, be then made into diameter 5 using plastic tube
Millimeter, small cylinder long 7 millimeters, use when conveniently testing;
The material of shaping is put into quartz boat 12h is dried in baking oven at 105 DEG C.
6. a kind of preparation method for producing the catalyst of high added value bio oil according to claim 1, its feature
It is:The atmosphere of the air refer to tube furnace bakee during be not passed through gas;The step 4 is specially in air atmosphere
Enclose makes catalyst crystal, shaping through high-temperature tubular furnace temperature to be calcined under the conditions of 550 DEG C;Crystallization, the time of shaping are 3h.
7. a kind of preparation method for producing the catalyst of high added value bio oil according to claim 1, its feature
It is:Gaseous mixture atmosphere in the step 5 refers to the process of that the gaseous mixture atmosphere of nitrogen and hydrogen refers to be bakeed in tube furnace
In to be passed through nitrogen and hydrogen mixing ratio be 99:1 gas;The step 5 is specially in described gaseous mixture atmosphere through high temperature
Tubular type furnace temperature makes activation of catalyst, reduction to be calcined under the conditions of 550 DEG C, and roasting time is 2h.
8. a kind of catalyst for producing high added value bio oil, it is characterised in that:Using any right in claim 1-7
It is required that method be prepared.
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Cited By (2)
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CN107262139A (en) * | 2017-07-13 | 2017-10-20 | 江苏大学 | A kind of preparation method of catalyst of modified molecular screen ZSM 5 and its application in biomass pyrolytic |
CN109078652A (en) * | 2018-08-31 | 2018-12-25 | 中国矿业大学 | A kind of preparation method and application of the multi-stage porous ZSM-5 molecular sieve of W metal doping |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107262139A (en) * | 2017-07-13 | 2017-10-20 | 江苏大学 | A kind of preparation method of catalyst of modified molecular screen ZSM 5 and its application in biomass pyrolytic |
CN109078652A (en) * | 2018-08-31 | 2018-12-25 | 中国矿业大学 | A kind of preparation method and application of the multi-stage porous ZSM-5 molecular sieve of W metal doping |
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