CN110129084A - A kind of biomass hydrogen supply-catalytic liquefaction coupling process and a kind of support type biomass liquefying catalyst - Google Patents
A kind of biomass hydrogen supply-catalytic liquefaction coupling process and a kind of support type biomass liquefying catalyst Download PDFInfo
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- CN110129084A CN110129084A CN201910457900.1A CN201910457900A CN110129084A CN 110129084 A CN110129084 A CN 110129084A CN 201910457900 A CN201910457900 A CN 201910457900A CN 110129084 A CN110129084 A CN 110129084A
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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
- B01J23/75—Cobalt
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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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- 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
- B01J23/76—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
- B01J23/78—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 with alkali- or alkaline earth metals
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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
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
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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
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/086—Characterised by the catalyst used
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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
- 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
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Abstract
The present invention relates to biomass liquefying technical fields, provide a kind of biomass hydrogen supply-catalytic liquefaction coupling process, comprising the following steps: mix powdered biomass, hydrogen supply dissolvent and support type biomass liquefying catalyst and carry out liquefaction reaction, obtain liquid product.The present invention is by catalytic liquefaction and hydrogen supply liquefactions coupling, fully using the synergistic effect between hydrogen supply agent and catalyst, the Efficient Conversion of biomass is realized, the calorific value of liquid product is improved, the disadvantages of improving liquid phase yield, overcoming high single technique hydrogen consumption, bio oil low yield.The present invention also provides a kind of support type biomass liquefying catalyst, support type biomass liquefying catalyst provided by the invention has catalytic pyrolysis and promotes the active effect of free radical transmitting, and it is compared with the homogeneous catalyst of liquid, it is more environmentally-friendly, and it is easily isolated and recycles, it is applied in biomass hydrogen supply-catalytic liquefaction coupling technique, can be realized the efficient liquefaction conversion of biomass.
Description
Technical field
The present invention relates to biomass liquefying technical field, in particular to a kind of biomass hydrogen supply-catalytic liquefaction coupling process
With a kind of support type biomass liquefying catalyst.
Background technique
In world today's energy resource structure, fossil fuel is still occupied an leading position, but coal, oil and natural gas etc. rapidly deplete institute
Caused by energy shortage and environmental pollution be on the rise, the development and application of new cleaning fuel is extremely urgent.Biomass energy is
A kind of renewable and clean energy resource is derived from the photosynthesis of plant, the content of nitrogenous, sulphur and heavy metal will be lower than fossil energy
Source.Therefore, it the Efficient Conversion of biomass and has obtained widely paying close attention to using technology.
The thermochemical study mode of biomass is more suitable for advising in industry since its capacity usage ratio is high, the period of conversion is short
The production of modelling and be extensively studied.Wherein, the liquefaction technology of biomass can turn low-grade solid biomass
It is melted into the liquid biological oil of high added value, is efficiently using biomass energy, alleviates Pressure on Energy and protect the effective way of environment.
The liquefaction reaction technique of biomass includes hydrogenation liquefaction, for liquefaction of hydrogen and catalytic liquefaction.Hydrogenation liquefaction reaction be
It is carried out under the atmosphere of hydrogen, it is intended to reduce the oxygen content in bio oil.103509578 A of patent CN discloses a kind of corn
Stalk hydrogenation liquefaction prepares the technique of biomass fuel, and smashed corn stover is liquefied under high temperature and pressure, atmosphere of hydrogen
At bio oil, technological reaction condition is relatively harsh, hydrogen high consumption.In contrast, hydrogen supply liquefaction reaction is rich in reactive hydrogen
It is reacted in solvent, hydrogen supply agent can provide active hydroperoxyl radical for reaction, stablize the intermediate that liquefaction reaction generates, and promote
The liquefaction of raw material converts；It is able to suppress the condensation and polymerization of intermediate simultaneously, reduces the production quantity of coke.Such as patent CN
Biomass hydrogen supply pyrolytic process in the presence of a kind of naphthene crude oils hydrogen supply distillate involved in 103254923 A.
The catalytic liquefaction of biomass is to utilize the liquefaction reaction of catalyst biomass under inert atmosphere.Homogeneously
Or heterogeneous acid base catalysator is widely used in the catalytic liquefaction reaction of biomass, it is intended to improve feed stock conversion or production
The selectivity of object.As patent CN 101407727 uses solid acid (atlapulgite class, acidic metal oxide and solid super strong
Acid) catalytically liquefying biomass, catalyst is using significantly improving the yield of bio oil.
Catalyst in biomass liquefying can be divided into two classes, homogeneous catalyst and heterogeneous catalysis.Homogeneous catalyst
It mainly include some acidand basecatalysts (such as H2SO4、HCl、H3PO4With KOH, NaOH, Na2CO3Deng), but acid base catalysator pair
There is serious corrosion for reactor, subsequent to need neutralisation treatment, and there are problems that being difficult to separate and recover；In contrast, non-
Homogeneous catalyst is more environmentally friendly, such as loaded catalyst.Porous carrier, such as carbon material, metal oxide, molecular sieve are negative
Supported catalyst is widely used in the reaction of the catalytic liquefaction of biomass, such as patent CN 105251524 A, CN
108499598 A etc., these catalyst improve the quality or selectivity of product significantly.
But the liquefaction yield of current liquifying method biomass is still lower, and there is no about by catalytic liquid at present
The research changed and coupled for liquefaction of hydrogen.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of biomass, to be total to hydrogen supply-catalytic liquefaction coupling process and one kind negative
Load type biomass liquefying catalyst.The present invention utilizes support type biomass liquefying catalyst treatment biomass in hydrogen supply dissolvent,
Biomass is combined together for liquefaction of hydrogen and biomass catalyzing and liquefying, fully utilizes the collaboration between hydrogen supply agent and catalyst
Effect is effectively facilitated biomass liquefying conversion, provides new approaches for biomass liquefying.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
A kind of biomass hydrogen supply-catalytic liquefaction coupling process, comprising the following steps:
Powdered biomass, hydrogen supply dissolvent and support type biomass liquefying catalyst are mixed and carry out liquefaction reaction, obtains liquid
Phase product.
Preferably, the raw material of the powdered biomass be one of sawdust, algae, agricultural crop straw and nut shell or
It is several；
The granularity of the powdered biomass is 40~100 mesh.
Preferably, the powdered biomass and the solid-to-liquid ratio of hydrogen supply dissolvent are 1:2~10g/mL；Slurries obtained by the mixing
The mass content of middle support type biomass liquefying catalyst is 2~10%.
Preferably, the temperature of the liquefaction reaction is 280~360 DEG C, and the time is 20~60min；The liquefaction reaction exists
It is carried out under inert atmosphere.
Preferably, the hydrogen supply dissolvent includes the alcohol, the alkane containing active hydrogen, aromatic hydrocarbons or fraction containing the active hydrogen of-H containing α
One or more of oil.
Preferably, the support type biomass liquefying catalyst includes carrier and the activated centre that is supported on carrier；Institute
Stating carrier is porous material；The activated centre is Ni and/or Fe；In the catalyst load capacity in activated centre be 2~
10wt.%.
It preferably, further include the auxiliary agent being supported on carrier in the catalyst；The auxiliary agent includes Cu, Co, Mo and Ag
One or more of；The load capacity of auxiliary agent is 0.5~2.5wt.% in the catalyst.
Preferably, the porous material includes active carbon, γ-Al2O3, in HZSM-5, MCM-41 and porous magnesia one
Kind is several.
Preferably, the porous magnesia preparation method the following steps are included:
Magnesium salt solution and precipitant solution are mixed and are aged, ageing product is successively dried and is roasted, is obtained
Porous magnesia.
The present invention also provides a kind of support type biomass liquefying catalyst, including carrier and the activity being supported on carrier
Center；The carrier is porous material；The activated centre is Ni and/or Fe；The load capacity in activated centre in the catalyst
For 2~10wt.%.
The present invention provides a kind of biomass hydrogen supply-catalytic liquefaction coupling process, comprising the following steps: by biomass powder
End, hydrogen supply dissolvent and the mixing of support type biomass liquefying catalyst carry out liquefaction reaction, obtain liquid product.The present invention is in hydrogen supply
Support type biomass liquefying catalyst treatment biomass is utilized in solvent, realizes the efficient liquefaction conversion of biomass；The present invention will
The catalytic liquefaction of catalyst is coupled with hydrogen supply dissolvent for liquefaction of hydrogen, in support type biomass liquefying catalyst efficient catalytic
While crack biomass, the contracting of the unstable intermediate of biomass cracking is effectively blocked using reactive hydrogen provided by hydrogen supply agent
It closes, polymerization reaction, and then improves the conversion ratio of biomass material and the yield of liquid-phase product, while reducing the production of solid coke
Rate；In addition the presence of reactive hydrogen also effectively reduces the oxygen content of biological oil product in reaction system, to improve liquid phase mesh
Mark the calorific value of product；The present invention fully utilizes the synergistic effect between hydrogen supply agent and catalyst, overcomes previous single technique
The disadvantages of hydrogen consumption height, bio oil low yield, and the support type biomass liquefying catalyst that the present invention uses is readily isolated
Recycling, it is more environmentally-friendly.Embodiment the result shows that, liquefied using method of the invention to biomass, the conversion ratio energy of raw material
Enough reach 80%, the liquid phase yield of product can reach 64.7%, and the calorific value of liquid product can reach 33.04MJkg-1。
The present invention also provides a kind of support type biomass liquefying catalyst, support type biomass liquefying provided by the invention
Catalyst have catalytic pyrolysis and promote free radical transmitting active effect, and catalyst provided by the invention belong to it is heterogeneous
Catalyst is compared with the homogeneous catalyst of liquid, more environmentally-friendly, and is easily isolated and is recycled, and biomass hydrogen supply-is applied to
In catalytic liquefaction coupling technique, the efficient liquefaction conversion of biomass can be realized.
Detailed description of the invention
Fig. 1 is that the present invention carries out biomass hydrogen supply-catalytic liquefaction coupling schematic device；
In Fig. 1: 1- sink, 2- drier, 3- pulverizer, 4- standard screen, 5- tempering tank, 6- slurry feed pump, 7- high pressure
Reaction kettle, 8- gas flowmeter, 9- gas-chromatography, 10- equipment for separating liquid from solid, 11 products pots.
Specific embodiment
The present invention provides a kind of biomass hydrogen supply-catalytic liquefaction coupling process, comprising the following steps:
Powdered biomass, hydrogen supply dissolvent and support type biomass liquefying catalyst are mixed and carry out liquefaction reaction, obtains liquid
Phase product.
In the present invention, the raw material of the powdered biomass is preferably in sawdust, algae, agricultural crop straw and nut shell
One or more；The algae is preferably Enteromorpha；The granularity of the powdered biomass is preferably 40~100 mesh, more preferably
50~80 mesh；In the present invention, the powdered biomass is preferably prepared by following steps: by biomass material successively into
Row washing, is crushed and is sieved at drying, obtains powdered biomass；The present invention is specific to the washing, drying, crushing and screening
Condition does not have particular/special requirement, can obtain the powdered biomass of required granularity.
In the present invention, the hydrogen supply dissolvent preferably includes the alcohol, the alkane containing active hydrogen, the virtue containing the active hydrogen of-H containing α
One or more of hydrocarbon or distillate；The alcohol of-the H containing α preferably includes one of ethyl alcohol, isopropanol and cyclohexanol or several
Kind；The alkane containing active hydrogen preferably includes hexamethylene；The aromatic hydrocarbons containing active hydrogen preferably includes naphthane.In the present invention
In, the hydrogen supply dissolvent is rich in reactive hydrogen, can provide active hydroperoxyl radical for the liquefaction reaction of biomass, promote biomass
Liquefaction conversion.
In the present invention, the activity that the support type biomass liquefying catalyst preferably includes carrier and is supported on carrier
Center；The carrier is preferably porous material；The activated centre is preferably Ni and/or Fe；Activated centre in the catalyst
Load capacity be preferably 2~10wt%, more preferably 3~8wt%, further preferably 4~6wt.%.
In the present invention, the porous material preferably includes active carbon, γ-Al2O3, HZSM-5, MCM-41 and porous oxygen
Change one or more of magnesium, more preferably active carbon or porous magnesia, most preferably porous magnesia；The present invention is to described
Active carbon, γ-Al2O3, HZSM-5 and MCM-41 source there is no particular/special requirement, use commercially available above-mentioned material.
In the present invention, the porous magnesia, which preferably passes through, is voluntarily prepared, the preparation side of the porous magnesia
Method preferably includes following steps:
Magnesium salt solution and precipitant solution are mixed and are aged, ageing product is successively dried, roasted and formed,
Obtain porous magnesia.
In the present invention, the magnesium salts preferably includes Mg (CH3COO)3·4H2O and/or MgCl2·6H2O；The magnesium salts is molten
The solvent of liquid is preferably deionized water；The concentration of the magnesium salt solution is preferably 0.02~0.06mol/L, more preferably
0.04mol/L；The precipitating reagent is preferably H2C2O4·4H2O, (NH4)2C2O4·H2One of O and natrium carbonicum calcinatum or several
Kind；The solvent of the precipitant solution is preferably water；The concentration of the precipitant solution is preferably 0.04~0.08mol/L, more
Preferably 0.06mol/L；Magnesium salt solution is preferably added drop-wise in precipitant solution by the present invention, is aged after being added dropwise.
In the present invention, the temperature of the ageing is preferably 30~60 DEG C, and more preferably 40~50 DEG C；The ageing when
Between preferably 6~12h, more preferably 8~10h.In the present invention, in ageing process, magnesium ion and precipitating reagent are reacted, raw
It is precipitated at magnesia presoma.
After the completion of ageing, Washing of Filter Cake to neutrality preferably is obtained being aged product, then by the present invention by ageing liquid filtering
Ageing product is successively dried and is roasted, porous magnesia is obtained.In the present invention, the temperature of the drying is preferably
110 DEG C, the time is preferably 4h；The temperature of the roasting is preferably 400~800 DEG C, and more preferably 500~700 DEG C；The roasting
The time of burning is preferably 2~5h, more preferably 3~5h；The roasting preferably carries out under nitrogen atmosphere.N in roasting process2
The steam of roasting generation, carbon dioxide are taken away in time, prevent magnesia grained sintered.
After the completion of roasting, the present invention further preferably includes that will roast gained porous magnesia powder pressing forming.The present invention couple
The specific method of the compression moulding does not have particular/special requirement, using method well known to those skilled in the art, in the present invention
Specific embodiment in, the porous magnesia can suppress into strips, bulk etc., during compression moulding the size of size with
And the conditions such as dosage, adhesive type of required adhesive are determined according to the specific condition of production, the present invention does not do specific limit
It is fixed；Porous magnesia can be made to be more suitable industrialization by compression moulding.
The porous magnesia pore specific surface area prepared using method of the invention is in 86.54~203.51m2/ g, average hole
Diameter is in 5.68~26.58nm.
In the present invention, it is also preferable to include the auxiliary agents being supported on carrier in the support type biomass liquefying catalyst；
The auxiliary agent is preferably one or more of Cu, Co, Mo and Ag；In the catalyst load capacity of auxiliary agent be preferably 0.5~
2.5wt.%, more preferably 1~2wt.%, further preferably 1.5wt.%.
In the present invention, the preparation method of the support type biomass liquefying catalyst is preferably equi-volume impregnating, tool
Body the following steps are included:
Carrier is impregnated in the precursor solution of activated centre, the carrier after dipping is successively dried and is restored
Roasting, obtains support type biomass liquefying catalyst.
In the present invention, the activated centre presoma preferably includes Ni (NO3)2·6H2O and/or Fe (NO3)3·
9H2O；The temperature of the dipping is preferably room temperature, and the time is preferably for 24 hours；The temperature of the drying is preferably 120 DEG C, and the time is excellent
It is selected as 8h；The temperature of the reduction roasting is preferably 400~800 DEG C, more preferably 500~700 DEG C, the reduction roasting when
Between preferably 3~6h, more preferably 4~5h；The reduction roasting is preferably in 95%Ar-5%H2It is carried out in mixed atmosphere；It is restoring
In roasting process, the activated centre presoma being supported on carrier is reduced to Ni or Fe simple substance.
In the present invention, when further including auxiliary agent in the support type biomass liquefying catalyst, the present invention is preferably soaking
Auxiliary agent presoma is added in stain liquid, subsequent operating procedure is consistent with operating condition with above scheme, and details are not described herein；It is described
Auxiliary agent presoma preferably includes Cu (NO3)2·3H2O、 Co(NO3)2·6H2O、(NH4)6Mo7O24·4H2O、AgNO3And Ce
(NO3)3·6H2One or more of O；In a specific embodiment of the present invention, according to the water absorption of equi-volume impregnating carrier
Determine the concentration of activated centre presoma and auxiliary agent presoma in maceration extract.
The present invention by powdered biomass, hydrogen supply dissolvent and catalyst mix carry out liquefaction reaction, the powdered biomass and
The solid-to-liquid ratio of hydrogen supply dissolvent is preferably 1:2~10g/mL, more preferably 1:4~8g/mL；Catalyst in slurries obtained by the mixing
Mass content be preferably 2~10%, more preferably 3~8%, most preferably 4~5%.
In the present invention, the temperature of the liquefaction reaction is preferably 280~360 DEG C, and more preferably 300~340 DEG C, into
One step is preferably 320~330 DEG C；The time of the liquefaction reaction is preferably 20~60min, more preferably 30~50min；Institute
Liquefaction reaction is stated preferably to carry out in an inert atmosphere；In a specific embodiment of the present invention, preferably mixing gained slurries are pumped into
In autoclave, purging discharge air then is carried out to reaction kettle using high pure nitrogen, is stirred under conditions of not pressurising
It mixes and is warming up to liquefaction reaction temperature；Biomass simultaneously urging for liquefaction of hydrogen and catalytic liquefaction in closed reaction kettle
While agent efficient catalytic crack biomass, the reactive hydrogen that hydrogen supply dissolvent provides can effectively block biomass cracking unstable
The condensation of intermediate, polymerization reaction, to improve the conversion ratio and liquid phase yield of biomass material, the oxygen for reducing liquid product contains
Amount improves the calorific value of bio oil (i.e. liquid product)；In addition, under the conditions of high-temperature closed, biomass in addition to generating liquid product,
Gas and solid coke can be also generated, in a specific embodiment of the present invention, preferred using gas stream after the completion of liquefaction reaction
Then meter meter gaseous volume uses gas-chromatography on-line analysis gas composition, calculate gas phase yields, while will be in reaction kettle
Solid-liquid phase product be separated by solid-liquid separation, gained liquid product is bio oil, and solid product be (solid coke and catalyst
Mixture) dry after acetone washing to constant weight, according to the Mass Calculation biomass conversion ratio of gas phase yields and solid product and
Liquid phase yield；In the present invention, the catalyst is loaded catalyst, will not be mixed in one with liquid product after separation of solid and liquid
It rises, can be difficult to the problem of separating to avoid homogeneous catalyst, and containing having magnetic Ni in the catalyst that uses of the present invention
Or Fe is recycled catalyst using ferromagnetic magnet after solid product is dry.
In a specific embodiment of the present invention, it is preferable to use Fig. 1 shown device realizes biomass hydrogen supply-catalytic liquefaction coupling
Close, described device include sink 1, drier 2, pulverizer 3, standard screen 4, tempering tank 5, slurry feed pump 6, autoclave 7,
Gas flowmeter 8, gas-chromatography 9, equipment for separating liquid from solid 10 and products pot 11；In a specific embodiment of the present invention, biomass
It is dried, is then crushed in pulverizer 3, crushed material is in standard screen 4 in drier 2 after being cleaned in sink 1
Powdered biomass is obtained after screening, powdered biomass, hydrogen supply dissolvent and support type biomass liquefying catalyst mix in tempering tank 5
Progress hydrogen supply-catalytic liquefaction in autoclave 7 is pumped by slurry feed pump 6 after conjunction, after the reaction was completed using gas flowmeter 8
Meter gaseous volume, and with gas chromatographic analysis gas composition；Solid-liquid phase product in simultaneous reactions kettle is by being separated by solid-liquid separation dress
It sets 10 to be separated, liquid product (bio oil), which enters in products pot 11, to be stored.
The present invention also provides a kind of support type biomass liquefying catalyst, including carrier and the activity being supported on carrier
Center；The carrier is porous material；The activated centre is Ni and/or Fe；The load capacity in activated centre in the catalyst
For 2~10wt.%, preferably 3~8wt.%, further preferably 4~6wt.%；The support type biomass liquefying catalysis
It is also preferable to include the auxiliary agents being supported on carrier in agent；The auxiliary agent is preferably one or more of Cu, Co, Mo and Ag；Institute
The load capacity for stating auxiliary agent in catalyst is preferably 0.5~2.5wt.%, more preferably 1~2wt.%, further preferably
1.5wt.%.
In the present invention, the type of the carrier, support type biomass liquefying catalyst the equal and above-mentioned side of preparation method
Case is consistent, and details are not described herein；Support type biomass liquefying catalyst provided by the invention has catalytic pyrolysis and promotes freely
The active effect of base transmitting, is easily isolated and recycles, be applied in biomass hydrogen supply-catalytic liquefaction coupling technique, energy
Enough realize the efficient liquefaction conversion of biomass.
Scheme provided by the invention is described in detail below with reference to embodiment, but they cannot be interpreted as pair
The restriction of the scope of the present invention.
Embodiment 1
Support type biomass liquefying catalyst is prepared using equi-volume impregnating:
(1) preparation of 10%Fe/MgO catalyst
By the MgCl of 50mL 0.04mol/L2·6H2O solution is added drop-wise to the H of 200mL 0.06mol/L2C2O4·4H2O is molten
In liquid, 6h is aged after being added dropwise at 30 DEG C, then will ageing product filtration washing to neutrality, after 110 DEG C of dry 4h
N2The lower 400 DEG C of roastings 3h of atmosphere, obtains porous magnesia.
By porous magnesia in Fe (NO3)3·9H2It is impregnated in O solution for 24 hours, the porous magnesia after dipping is taken out
120 DEG C of dry 8h, then in 95%Ar-5%H2400 DEG C of reduction roasting 3h in mixed atmosphere, obtain support type biomass liquefying
Catalyst, wherein carrier is porous magnesia, and the load capacity of activated centre Fe, Fe are 10wt.%, is denoted as 10%Fe/MgO.
(2) preparation of 10%Ni/AC catalyst
By active carbon in Ni (NO3)3·6H2It is impregnated in O solution for 24 hours, the active carbon after dipping is taken out in 120 DEG C of dryings
8h, then in 95%Ar-5%H2500 DEG C of reduction roasting 4h in mixed atmosphere obtain support type biomass liquefying catalyst,
Middle carrier is active carbon, and the load capacity of activated centre Ni, Ni are 10wt.%, is denoted as 10%Ni/AC.
(3) preparation of 10%Ni-2.5%Co/AC catalyst
By active carbon in Ni (NO3)3·6H2O and Co (NO3)3·6H2It is impregnated for 24 hours in the mixed solution of O；After dipping
Active carbon takes out in 120 DEG C of dry 8h, then in 95%Ar-5%H2600 DEG C of reduction roasting 3h, are loaded in mixed atmosphere
Type biomass liquefying catalyst, wherein carrier be active carbon, activated centre Ni, load capacity 10wt.%, auxiliary agent Co, bear
Carrying capacity is 2.5wt.%, is denoted as 10%Ni-2.5%Co/AC.
Catalyst prepared by embodiment 1 is applied in embodiment 2~6.
Embodiment 2
By the mixed serum of sawdust, ethyl alcohol and 10%Fe/MgO, (wherein the solid-to-liquid ratio of sawdust and ethyl alcohol is 1:8g/mL, slurry
The content of 10%Fe/MgO is 8wt.% in liquid) it is pumped into autoclave, the air in logical nitrogen discharge kettle, not pressurising, then
340 DEG C, after reaction stops 30min are warming up to, at once with cold water cooling reactor to room temperature, takes out material processing.Obtain the liquid of product
The yield of phase is 64.7%, and the conversion ratio of raw material is 80.0%, and the calorific value of bio oil is 33.04MJkg-1。
Embodiment 3
By the mixed serum of Enteromorpha, ethyl alcohol and 10%Fe/MgO, (wherein the solid-to-liquid ratio of Enteromorpha and ethyl alcohol is 1:8g/mL, slurry
The content of 10%Fe/MgO is 8wt.% in liquid) it is pumped into autoclave, the air in logical nitrogen discharge kettle, not pressurising, then
340 DEG C, after reaction stops 30min are warming up to, at once with cold water cooling reactor to room temperature, takes out material processing.Obtain the liquid of product
The yield of phase is 54.3%, and the conversion ratio of raw material is 66.8%, and the calorific value of bio oil is 27.38MJkg-1。
Embodiment 4
By the mixed serum of sawdust, isopropanol and 10%Ni/AC (wherein the solid-to-liquid ratio of sawdust and isopropanol is 1:8g/mL,
The content of 10%Ni/AC is 8wt.% in slurries) it is pumped into autoclave, the air in logical nitrogen discharge kettle, not pressurising, then
340 DEG C, after reaction stops 30min are warming up to, at once with cold water cooling reactor to room temperature, takes out material processing.Obtain the liquid of product
The yield of phase is 57.4%, and the conversion ratio of raw material is 74.8%, and the calorific value of bio oil is 30.44MJkg-1。
Embodiment 5
By the mixed serum of sawdust, ethyl alcohol and 10%Ni/AC, (wherein the solid-to-liquid ratio of sawdust and ethyl alcohol is 1:8 g/mL, slurry
The content of 10%Ni/AC is 8wt.% in liquid) it is pumped into autoclave, lead to the air in nitrogen discharge kettle, then not pressurising rises
Temperature is to 340 DEG C, after reaction stops 30min, at once with cold water cooling reactor to room temperature, takes out material processing.Obtain the liquid phase of product
Yield be 60.7%, the conversion ratio of raw material is 74.3%, and the calorific value of bio oil is 32.67MJkg-1。
Embodiment 6
By sawdust, ethyl alcohol and 10%Ni-2.5%Co/AC mixing slurry liquid pump (wherein the solid-to-liquid ratio of sawdust and ethyl alcohol is 1:
8g/mL, the content of 10%Ni-2.5%Co/AC is 8wt.% in slurries) enter into autoclave, lead to the sky in nitrogen discharge kettle
Gas, not pressurising then heat to 340 DEG C, after reaction stops 30min, at once with cold water cooling reactor to room temperature, take out at material
Reason.The yield for obtaining the liquid phase of product is 62.6%, and the conversion ratio of raw material is 77.2%, and the calorific value of bio oil is 32.83MJ
kg-1。
Comparative example 1
Other conditions and embodiment 2 are identical, are only added without 10%Fe/MgO.The yield for obtaining the liquid phase of product is
57.0%, the conversion ratio of raw material is 70.2%, and the calorific value of bio oil is 29.67MJkg-1。
Comparative example 2
Other conditions and embodiment 3 are identical, are only added without 10%Fe/MgO.The yield for obtaining the liquid phase of product is
48.4%, the conversion ratio of raw material is 59.7%, and the calorific value of bio oil is 25.38MJkg-1。
The data such as process conditions and yield by embodiment 2~6 and comparative example 1~2 are listed in Table 1 below.
1 embodiment 2~6 of table and the liquefaction of comparative example 1~2 result compare
According to table 1, (i.e. single for liquefaction of hydrogen), conversion ratio, the product of raw material in the case where omitting catalyst
Liquid phase yield and the calorific value of bio oil have reduction, illustrate that support type biomass liquefying catalyst of the invention can be catalyzed life
The efficient liquefaction of substance converts, and hydrogen supply provided by the invention-catalytic liquefaction coupling process can make full use of synergistic effect, effectively
Promote the liquefaction conversion of biomass.
According to above embodiments it is found that biomass provided by the invention hydrogen supply-catalytic liquefaction coupling process is raw by support type
Substance deliquescence accelerant is applied to for fully using the synergistic effect between hydrogen supply agent and catalyst, improving life in liquefaction of hydrogen
The conversion ratio and liquid phase yield of raw material of substance, reduce the oxygen content of liquid product, improve the calorific value of bio oil, overcome previous list
The disadvantages of one technique hydrogen consumption height, bio oil low yield；And catalyst provided by the invention is to the catalytic liquefaction effect of biomass
It is good, it is applied in biomass hydrogen supply-catalytic liquefaction coupling technique, can be realized the efficient liquefaction conversion of biomass.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of biomass hydrogen supply-catalytic liquefaction coupling process, which comprises the following steps:
Powdered biomass, hydrogen supply dissolvent and support type biomass liquefying catalyst are mixed and carry out liquefaction reaction, obtains liquid phase production
Object.
2. the method according to claim 1, wherein the raw material of the powdered biomass is sawdust, algae, farming
One or more of object stalk and nut shell；
The granularity of the powdered biomass is 40~100 mesh.
3. the method according to claim 1, wherein the powdered biomass and the solid-to-liquid ratio of hydrogen supply dissolvent are 1:
2~10g/mL；The mass content of support type biomass liquefying catalyst is 2~10% in slurries obtained by the mixing.
4. the method according to claim 1, wherein the temperature of the liquefaction reaction be 280~360 DEG C, the time
For 20~60min；The liquefaction reaction carries out in an inert atmosphere.
5. the method according to claim 1, wherein the hydrogen supply dissolvent includes the alcohol of-H containing α, containing active hydrogen
One or more of alkane, the aromatic hydrocarbons containing active hydrogen or distillate.
6. the method according to claim 1, wherein the support type biomass liquefying catalyst include carrier and
It is supported on the activated centre on carrier；The carrier is porous material；The activated centre is Ni and/or Fe；The catalyst
The load capacity in middle activated centre is 2~10wt.%.
7. method according to claim 1 or 6, which is characterized in that further include being supported on carrier in the catalyst
Auxiliary agent；The auxiliary agent includes one or more of Cu, Co, Mo and Ag；In the catalyst load capacity of auxiliary agent be 0.5~
2.5wt.%.
8. method according to claim 1 or 6, which is characterized in that the porous material includes active carbon, γ-Al2O3、
One or more of HZSM-5, MCM-41 and porous magnesia.
9. according to the method described in claim 8, it is characterized in that, the preparation method of the porous magnesia includes following step
It is rapid:
Magnesium salt solution and precipitant solution are mixed and are aged, ageing product is successively dried and is roasted, is obtained porous
Magnesia.
10. a kind of support type biomass liquefying catalyst, which is characterized in that including carrier and be supported in the activity on carrier
The heart；The carrier is porous material；The activated centre is Ni and/or Fe；The load capacity in activated centre is 2 in the catalyst
~10wt.%.
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