CN104844264B - A kind of biomass catalyzing and liquefying porous ceramics supported catalyst and preparation method - Google Patents
A kind of biomass catalyzing and liquefying porous ceramics supported catalyst and preparation method Download PDFInfo
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Abstract
A kind of biomass catalyzing and liquefying porous ceramics supported catalyst, belong to porous functional ceramic technical field, it is characterized in that, the catalyst activity component is natural inorganic catalyst, natural inorganic catalyst is through crushing, grinding, after screening, with ceramic aggregate, pore creating material, binder mixes, it is processed into porous ceramics blank, then porous ceramics blank drying, sintering, activation procedure is process, wherein, the active component is dolomite, lime stone, diatomite, kaolin, olivine, cordierite, montmorillonite, hydrotalcite, carnallite, beryl, celestine, gypsum any one or more of combines, preferably dolomite or montmorillonite；Wherein, natural inorganic catalyst, ceramic aggregate, pore creating material, binder 30~40：40~50：5~10：10~15 quality proportioning is mixed.Porous ceramics produced by the present invention can be used as the heat carrier of the catalyst and inside reactor of biomass pyrolysis for liquid production process simultaneously, activity can be shown to biomass through pyrolysis process, the yield that can improve bio oil, reduces biomass through pyrolysis reaction condition at the quality for improving bio oil.
Description
Technical field
The invention belongs to porous functional ceramic technical field, be related to it is a kind of for biomass through pyrolysis, with porous ceramics
For the method for preparing catalyst of carrier.
Background technology
Biomass typically refers to water plant and terrestrial plant, mainly include agricultural crop straw, timber, branch, fallen leaves,
Water plant, seaweed and kitchen organic matter and animal wastes etc..The biomass generated by photosynthesis on the annual earth, total amount
Up to 1400~180,000,000,000 tons (dry weight), main component is hydrocarbon, can be converted thereof by different switch technologies
Solid, liquid or gaseous fuel are efficiently utilized.
According to State Statistics Bureau《National economy and social development statistical communique in 2014》Data, national energy-consuming in 2014
Total amount is 42.6 hundred million tons of standard coals, increases by 2.2% on a year-on-year basis.Wherein, consumption of coal accounts for the 66.0% of total energy consumption, on year-on-year basis
Decline 2.9%；Amount of Consumption of Crude Oil increases by 5.9%, and Natural Gas Consumption Using increases by 8.6%；Water power, wind-powered electricity generation, nuclear power, natural gas etc. are clear
Clean energy consumption accounts for the 16.9% of total energy consumption.
In addition, being announced according to General Administration of Customs, 3.1 hundred million tons of China's imported crude oil in 2014, crude oil external dependence degree is 59.6%,
57% compared with 2013 rises 2.6%.The portion issued according to China Petroleum and chemical industry federation《China's natural gas develops
The uncertain factor faced》Report display, China's natural gas Apparent con- sumption is 1800 billion cubic meters within 2014, is increased by a year-on-year basis
7.4%, wherein 580 billion cubic meter of inlet natural gas, external dependence degree is up to 32.2%.In Copenhagen in December, 2009 world gas
It waits in conference, Chinese Government promises to undertake, arrives the year two thousand twenty, and per GDP CO2 emission declined 40~45% than 2005.
Crude oil in China and natural gas external dependence degree are excessively high, seriously threaten the energy security in China, and consumption of coal accounts for
The proportion of total energy consumption figure is excessive, and prodigious pressure is brought to the environmental protection in China, there is an urgent need to actively develop it is clean, can
Regenerate the exploitation of the gentle fluid fuel of liquid.Wherein, biomass energy can pass through as unique storable carbon source in regenerative resource
Different technological means generates liquid or gaseous fuel, therefore the exploitation of biomass energy is for improving cleaning, regenerative resource
Using proportion, mitigates environmental protection pressure etc. and be of great significance.
Biomass-pyrolysis can improve the energy density of biomass, reduce cigarette ash and dust emission, realize agriculture
The recycling scientific utilization of woods waste.Biomass through pyrolysis is a complicated thermochemical study process, including molecular link
Reactions, the principal elements for influencing thermal cracking final product and its distribution such as fracture, isomerization, small molecule polymerization have biomass material
Characteristic (type and granular size), reaction temperature, heating rate, gas phase residence time, catalyst and reaction pressure etc..Wherein,
Catalyst can change activation energy when biomass through pyrolysis, the fracture location of increase biomass macromolecular, therefore catalyst
There is vital effect using for improving heat scission reaction condition.
Biomass fast pyrolysis technology refers in moderate temperature (400~600 DEG C) and the high rate of heat addition (103~104℃/
S under), in anaerobic or anaerobic environment, biomass macromolecule is cracked into low molecular organic steam and solid carbon, wherein organic
For object steam through being quickly cooled down under extremely short gas residence time (being less than 2S), condensable part generates bio oil, not condensable
Gas it is purified after be discharged into the process of air, wherein bio oil is as major cleavage products (yield can reach 50~70%).
The basic physical properties parameter of bio oil made from herbaceous plant and xylophyta slightly has difference, but difference is not very
Greatly, such as the bio oil that agricultural crop straw is obtained by biomass fast pyrolysis technology (not adding catalyst in preparation process), contain
Water rate 15~30%, 1~1.3g/cm of density3, 15~20MJ/kg of higher calorific value, viscosity (50 DEG C) 40~80mPas, pH value 2
~5,0.2~l% of mass fraction of solids, volatilize residue 45~55%, oxygen content 35~40%.In addition, thermal cracking temperature is not
Together, the physical parameter of bio oil can also be had an impact.In short, preparation process does not add the oxygen-containing of prepared by catalyst bio oil
Measure it is relatively high, it is acid strong, it is difficult to directly to light and property is unstable, be unfavorable for storing.
During Biomass Fast Pyrolysis for Bio-oil Production, catalyst appropriate is added, bio oil can be improved
Yield, reduce the heat scission reaction temperature of maximum biological oily yield, promote the decomposition of macromolecular substances, reduce the acid of bio oil
Degree, moisture content and oxygen content obtain the lightweight bio oil (aqueous biochemical more convenient for utilizing so as to improve the quality of bio oil
Oil), so as to avoid the follow-up refinement treatments such as the catalytic hydrogenation to bio oil, catalytic pyrolysis, reduce producing into for bio oil
This.Therefore, the reasonable selection of catalyst is the emphasis and key of biomass catalyzing heat scission reaction.
Being presently used for common catalyst during biomass through pyrolysis has zeolite molecular sieve, dolomite, lime stone, nickel
Base catalyst, zinc oxide etc..It is proposed in CN201410003977.9 a kind of for the liquefied catalysis of biomass fast pyrolysis
Agent preparation method, carrier are pyrolytic carbon, and active component is transition metal, can be any one of Pd, Pt, Ni or Rh.Activity
Part is loaded to by infusion process on carrier, and the orientation regulation and control of biomass fast pyrolysis liquefaction process may be implemented.
The problem of ZSM-5 molecular sieve is easy coking is then directed in CN201410019929.9, it is proposed that a kind of anti-coking changes
Property method.ZSM-5 molecular sieve is added to by certain solid-to-liquid ratio in macromolecular chelating agent modified solution, is filtered by vacuum after the completion,
Using ion water washing, after drying up to modified ZSM-5 molecular sieve, the coking process of the catalyst surface can be slowed down,
Prolong the service life.
CN201310277862.4 discloses a kind of load-type solid M/ γ-Al2O3Catalyst (M Ca, Mg, Na, K)
Preparation method, choose magnesium nitrate, calcium nitrate, sodium carbonate, potassium carbonate it is any, be dissolved in the metal salt that water is made into suitable concentration
Solution, by γ-Al2O3In carrier impregnation to metal salt solution, drying is to get the support type cracked to biomass vacuum after suction filtration
Solid base catalyst.
CN200910025061.2 discloses a kind of catalyst for microwave ultraviolet catalysis treatment of biomass and preparation
Method, active ingredient are transition metal oxide MxOy、CeO2、ZrO2、γ-Al2O3、TiO2、SiO2According to proportioning, through ball milling
Mixing, shaping and drying and calcining and activating form, and biomass difficult to degrade is handled for microwave electrodeless ultraviolet light catalysis.
A large amount of tar are generated otherwise for gasification of biomass, both reduce fuel gases calorific value, has and is easy obstruction gas pipeline
Problem, CN201410114626.5 propose a kind of preparation method of biomass char oil-breaking catalyst.By HZSM-5 molecules
Sieve is added in aluminium oxide mixture, and pore creating material and extrusion aid is added, through kneading, roll it is agglomerating after, then extruded moulding, drying, roasting
Burning obtains catalyst carrier；And catalyst is by the material composition of following weight percent：RuO20.1-1%, NiO 5-15%,
CuO 1-6%, CeO25-20%.Metallic element is loaded on a catalyst support with saturation infusion method, then through drying, roasting
Fire to obtain required catalyst.
It is to sum up known, zeolite molecular sieve and various noble metal catalysts to the catalytic effect of biomass through pyrolysis generally compared with
Good, the catalyst for being widely studied and applied, but preparing often higher price is easy during heat scission reaction
Carbon distribution coking, be easy to cause catalyst inactivation.Therefore try to explore Cheap highly effective, the biomass suitable for large-scale industrial production
The catalyst of thermal cracking processes is highly desirable.
CN201280012385.2 discloses a kind of composition system based on phyllosilicate for catalytic pyrolysis of biomass
Preparation Method, the modification of phyllosilicate include calcine the clay of leaching with sour or aqueous slkali leaching clay to form clay-ware, and
So that processed clay is contacted with the suspension containing metal ion and forms modified phyllosilicate with exchange ion.To gained
Phyllosilicate product be spray-dried, with formed be suitable for biomass catalyzing cracking microsphere particle.
Many natural inorganic materials, as dolomite, lime stone, diatomite, kaolin, olivine, cordierite, montmorillonite,
Hydrotalcite, carnallite, beryl, celestine, gypsum etc., have in nature large storage capacity, be easy to get, be cheap etc. it is excellent
Gesture when as catalyst during biomass pyrolysis for liquid production, or can improve the yield of product liquid, reduce charcoal
Generation；Or reaction condition can be improved, reduce production cost；Or product liquid distribution can be regulated and controled, increase high value component
Generation the effects that, and have many advantages, such as to be not easy coking in biomass catalyzing thermal cracking processes.But above-mentioned natural inorganic material
Expect that the mechanical strength of (calling natural inorganic catalyst in the following text) is not generally high, in biomass catalyzing thermal cracking liquefaction process, due to anti-
Answer area's temperature higher, and the movement of inside reactor particle is fierce, be easy to cause being seriously worn for natural inorganic catalyst, even
Broken, the fine dusts of formation are easily fluidized gas and carry out outside reactor, influence the Multiphase Flow in reactor and catalyst
Catalytic effect.
Therefore, there is the low deficiency of mechanical strength for natural inorganic catalyst, how to develop with high catalytic efficiency,
It is urgent to become biomass catalyzing thermal cracking liquefaction technology large-scale application for the improved catalysts that service life is long, cost price is low
Need the critical issue solved.
Invention content
The object of the present invention is to provide a kind of high mechanical properties for biomass catalyzing thermal cracking liquefaction process are functional
Porous ceramics, and the preparation method of porous ceramics is provided；Porous ceramics obtained is used as urging for biomass pyrolysis for liquid production process
When agent, activity can be shown to biomass through pyrolysis process, the yield that bio oil can be improved, the quality for improving bio oil, drop
Low biomass through pyrolysis reaction condition.Meanwhile porous ceramics can also be as the heat carrier of inside reactor.
The technical solution that the present invention specifically uses is as follows：
A kind of biomass catalyzing and liquefying porous ceramics supported catalyst, characterized in that the catalyst activity component is
Natural inorganic catalyst, natural inorganic catalyst mix after crushing, grinding, screening with ceramic aggregate, pore creating material, binder,
It is processed into porous ceramics blank, then porous ceramics blank drying, sintering, activation procedure are process, wherein the activity
Component be dolomite, lime stone, diatomite, kaolin, olivine, cordierite, montmorillonite, hydrotalcite, carnallite, beryl,
Celestine, the combination of gypsum any one or more of, preferably dolomite or montmorillonite；Wherein, natural inorganic catalyst, ceramics
Aggregate, pore creating material, binder 30~40：40~50：5~10：10~15 quality proportioning is mixed.
The ceramic aggregate is high temperature resistant, wear-resistant, impact resistance and the small material of coefficient of thermal expansion, such as silica, nitrogen
One kind or its any mixture of SiClx, aluminium oxide, silicon carbide, corundum, aluminium nitride, serpentine, hard bit stone, to make processing
Porous ceramics internal component distribution afterwards is uniform as possible, and ceramic aggregate filters out 180-400 mesh as more after attrition grinding
Hole ceramic batch uses.
Wherein, the binder is glass powder, bentonite, aluminum phosphate, waterglass, paraffin, spent pulping liquor, calcium sulfate, carboxylic
One kind in methylcellulose, polyvinyl alcohol, boric acid, stearic acid, Brazil wax, dextrin, polyvinyl butyral resin or
Its any mixture, main function, which is it, makes natural inorganic catalyst and ceramic aggregate be bonded together, convenient for molding.
Wherein, the pore creating material is powdered carbon, biomass powder, starch, ammonium hydrogen carbonate, plant fiber, molding powder, oyster shell whiting
A kind of or its any mixture, preferably biomass powder or ammonium hydrogen carbonate.
Further include fluxing agent, plasticizer, one kind of dispersant or arbitrary group in the preparation of above-mentioned porous ceramic catalyst
It closes, three is not indispensable.
Wherein, the fluxing agent fusion temperature is lower than the fusion temperature of ceramic aggregate, is zinc borate, boron oxide, fluorination
One kind or its any mixture of aluminium, calcirm-fluoride, lead oxide, copper oxide, sodium sulphate, preferably zinc borate.Additive amount is according to matter
Amount is than natural inorganic catalyst：Fluxing agent is 20~50：5~15.
Wherein, the plasticizer have the effects that enhancing, plasticising, absorption, bond, lubrication, be in order to using slip casting at
In type or extrusion forming process, conveniently stripped, reduction porous ceramics blank breakage, and reduce the cracking of porous ceramics, deformation
Etc. purposes, can be bentonite, paraffin, sodium humate, polyvinyl alcohol, one kind in gelatine or its any mixture, it is preferably swollen
Profit soil.Additive amount is according to quality than natural inorganic catalyst：Plasticizer is 20~50：1~5.
Wherein, the dispersant be in order to it is rapid, thoroughly disperse all kinds of ceramic slurries, allow ceramic slurry to have good
Dispersion flows, and its moisture content can be reduced, can be NH4OH, sodium metasilicate, sodium tripolyphosphate, calgon, stearic acid
One in sodium, sodium citrate, polyacrylic acid and its esters, alkenoic acid sodium, polyvinyl alcohol, fish oil, aliphatic acid, silane, organic titanium
Kind or its any mixture, preferably silane.Additive amount is according to quality than natural inorganic catalyst：Dispersant is 20~50：1~
5。
Above-mentioned porous ceramic catalyst can be microspheric, cylinder, cuboid or other arbitrary solid forms.It is porous
Ceramics selection criteria after molding is as follows：1. as needed, determining porous ceramics shape (microspheric, cylinder, the length used
Cube or other arbitrary solid forms), preferable shape is unified, rule microparticle, can be the sphere of 1~2mm, can be 2~
The sphere of 3mm can be the sphere of 3~4mm；2. preferential porous ceramics of the selection with certain mechanical strength and thermal stability, with
Ensure that porous ceramics supported catalyst has the performances such as preferable wear-resisting, pressure-resistant, cracking resistance during biomass through pyrolysis；3. excellent
First select the complete porous ceramics of overall structure, not cracked, local defect；4. on the basis of meeting first three condition,
The high porous ceramics of preferential selection porosity height, even aperture distribution, thermal coefficient, with enhancing and the contact of biomass powder particle
With heat transfer, and have higher catalysis response area.
A kind of biomass catalyzing and liquefying preparation method of porous ceramics supported catalyst, includes the following steps：
1) natural inorganic catalyst and ceramic aggregate are crushed respectively, is then placed in grinder and grinds 30~40min, so
The powder for screening out 180~400 mesh afterwards is spare；
2) by natural inorganic catalyst, ceramic aggregate, pore creating material, fluxing agent according to 20~50：30~60：5~15：5~
15 quality proportioning is mixed, and the water of said mixture and infiltration amount is put into blender and is sufficiently mixed, and the time is
Porous ceramics pug is made in 20~30min；
3) by porous ceramics pug after sufficiently mixing, using injection forming, extrusion forming, plastic molding, 3D printing,
Or pan-pelletizer rolling technique, prepare the base of satisfactory microspheric, cylinder, cuboid or other arbitrary solid forms
Material, referred to as " porous ceramics blank "；
4) porous ceramics blank obtained is firstly placed on natural air drying 12~24 hours at shady and cool ventilation, is then put again
Processing is dried in the drying box that temperature is 102~108 DEG C, processing time is 8~12 hours；
5) porous ceramics blank after drying is placed in calcination equipment (such as Muffle furnace, tunnel oven, shuttle kiln),
It is fired by the way of temperature programming.Incipient stage rises to 500~600 DEG C with the heating rate of 80~120 DEG C/h, and
1 hour is kept the temperature at a temperature of this, the moisture in ceramic batch is vapored away completely.Using slow heating mode of heating, can effectively reduce
Or prevent because in porous ceramics blank moisture and organic matter volatilize rapidly due to cause the generation of crackle or defect.Then proceed to
Temperature is risen to 1000~1400 DEG C of firing temperature, and keeps the temperature 2~3 hours by the heating rate of 80~120 DEG C/h；
6) for the catalytic performance of enhancing natural inorganic catalyst, the porous ceramics to sintering processes are completed carries out at activation
The temperature of calcination equipment (such as Muffle furnace, tunnel oven, shuttle kiln) is down to 800~1000 DEG C, and keeps the temperature 7~9 hours by reason；
7) after completing step (7), turn off the power supply of calcination equipment, after so that temperature is down to environment temperature naturally, take out and be made
Porous ceramics supported catalyst, and be put into hermetic bag.
Further include by water-soluble binder, plasticizer and dispersant, first by water-soluble binder, plasticizer and dispersion
Agent is according to 2~6：1~5：1~5 quality proportioning mixing, then by above-mentioned three kinds of mixture add water be configured to 5~8% it is molten
Liquid；Then according to mass ratio natural inorganic catalyst：Ceramic aggregate：Pore creating material：Fluxing agent：Mixed aqueous solution (binder, increasing
Mould agent, aqueous dispersant)=15~45：25~50：3~10：3~10：20~40, it is put into blender and fully mix
It closes, porous ceramics pug is made.
Alternatively, further include nonaqueous binders, plasticizer and dispersant, according to mass ratio natural inorganic catalyst,
Ceramic aggregate, pore creating material, fluxing agent, binder, plasticizer and dispersant are 20~50：30~60：5~15：5~15：2~6：
1~5：1~5 quality proportioning is mixed, and then said mixture and water are according to 100：40~50 quality proportioning, which is put into, to be stirred
It mixes in machine and is sufficiently mixed, porous ceramics pug is made.
The beneficial effects of the present invention are：
1. solving natural inorganic catalyst low mechanical strength, deficiency easy to wear, porous ceramic catalyst Yin Qitao
There is porcelain body frame high temperature resistant, wear-resistant, impact resistance, the small advantage of coefficient of thermal expansion ensure that porous ceramic catalyst in high temperature
Stronger impact and long-term vibration can be born in biomass through pyrolysis reactor；
2. the active part of porous ceramics supported catalyst is evenly dispersed in table in the outer surface and hole of porous ceramics
On face, with prodigious specific surface area, it can be achieved that abundant making contact with biomass powder, achievees the purpose that catalytic pyrolysis；
3. compared with biological particles, the thermal capacity and thermal coefficient of porous ceramics supported catalyst are larger, can be simultaneously
As the hot carrier in reactor, by constantly rubbing, rolling, collide, guarantee heat scission reaction regional temperature is relatively uniform,
And be sufficiently mixed with biomass powder, reach the technology requirement of the high heating rate of fast pyrolysis；
4. convenient for change porous ceramics supported catalyst in each component content, and with the entity ceramic product phase of same size
Than with the small advantage of bulk density；
5. compared with the biomass through pyrolysis process for being added without catalyst, urged using porous ceramics produced by the present invention load
Agent, can with or the yield (lightweight biology oily yield improve 10~25%) of liquid product can be improved, or reduce biomass hot tearing
Reaction condition (the corresponding temperature of maximum biology oily yield reduces by 10~35%) is solved, or (oxygen content drops the quality of improvement bio oil
Low 15~40%；Acidity reduces by 15~35%；Moisture content reduces by 13~25%；Stability improves 50~250%；Higher calorific value carries
High 15~55%) produce cost to reduce bio oil, the catalytic hydrogenation to bio oil, catalytic pyrolysis etc. are reduced or avoided
Follow-up refinement treatment.
Specific implementation mode
In order to vivider illustrate the preparation of biomass catalyzing and liquefying porous ceramics supported catalyst in the invention, and
A kind of porous ceramics load is given below in catalytic action of the porous ceramics supported catalyst obtained to biomass pyrolysis for liquid production
The preparation process of catalyst, and its shown in the catalytic effect of corn stalk powder fast pyrolysis preparing bio-oil.
Embodiment 1
The average grain diameter of porous ceramic ball obtained be 2mm, produce porous ceramic ball base material composition and its quality (i.e.
Formula) it is as follows：
Natural inorganic catalyst chooses dolomite, quality 1.2kg；Ceramic Balls aggregate selection quartz sand, quality are
2.8kg；Powdered carbon is pore creating material, quality 0.3kg；Zinc borate is fluxing agent, quality 0.3kg；Carboxymethyl cellulose is to bond
Agent, quality 0.1kg are made into a concentration of 5% solution for standby with water.
In above-mentioned raw materials in quartz sand silica content >=99%, CaO, MgO, CO in dolomite2Quality percentage
Than being respectively 30%, 22%, 48%, the chemical molecular formula of zinc borate is 2ZnO3B2O3·3.5H2O, fixed carbon in powdered carbon
Content >=95% is this carbon residue of laboratory corn stalk powder in recirculating fluidized bed after thermal cracking, has in carboxymethyl cellulose
Imitate ingredient >=99%.
Biomass through pyrolysis is with the machining process of porous ceramic ball supported catalyst：It, will be big according to above-mentioned formula
The quartz sand and dolomite of particle crush respectively, are then placed in grinder and grind 30min, then screen out 180~240 purposes
Powder is spare；By the above-mentioned 2.8kg quartz sands filtered out, the boric acid of the dolomite of 1.2kg and the powdered carbon of 0.3kg and 0.3kg
Zinc is mixed, and said mixture is put into the cmc soln matched in blender and is sufficiently stirred 25min, is obtained
Porous ceramics pug；Porous ceramics pug is put into pan-pelletizer, rolling obtains " porous ceramic ball base "；By porous ceramics obtained
Ball base is firstly placed on natural air drying 15 hours at shady and cool ventilation, then places it in the drying box that temperature is 105 DEG C and is done again
Dry processing, processing time are 10 hours；Porous ceramic ball base after drying is placed in Muffle furnace, using temperature programming
Mode is fired.Incipient stage rises to 500 DEG C with the heating rate of 100 DEG C/h, and keeps the temperature 1 hour at this temperature, will make pottery
Moisture in porcelain ball base vapors away completely, then proceedes to the heating rate of 100 DEG C/h, and temperature is risen to firing temperature 1200
DEG C, and keep the temperature 3 hours；Porous ceramic ball to sintering processes are completed carries out activation process, and the temperature of Muffle furnace is down to 900
DEG C, and keep the temperature 9 hours；The power supply for finally turning off Muffle furnace after so that temperature is down to environment temperature naturally, takes out porous pottery obtained
Porcelain ball supported catalyst, and be put into hermetic bag.
Embodiment 2
The average grain diameter of porous ceramic ball obtained be 3mm, produce porous ceramic ball base material composition and its quality (i.e.
Formula) it is as follows：Natural inorganic catalyst chooses olivine, quality 1.6kg；Ceramic Balls aggregate selection aluminium nitride, quality are
2.4kg；Corn flour is pore creating material, quality 0.4kg；Sodium sulphate is fluxing agent, quality 0.3kg；Spent pulping liquor is binder,
Quality is 0.2kg, and a concentration of 8% solution is made into water.
Machining process is：According to above-mentioned formula, the olivine of bulky grain and blocky aluminium nitride are crushed respectively, then
It is put into grinder and grinds 30min, the powder for then screening out 180~240 mesh is spare；By the above-mentioned 24kg nitridations filtered out
Aluminium, the olivine of 1.6kg are mixed with the sodium sulphate of the corn flour of 0.4kg and 0.3kg, by said mixture with
Spent pulping liquor solution, which is put into blender, is sufficiently stirred 25min, obtains porous ceramics pug；Porous ceramics pug is put into balling-up
Disk, rolling obtain " porous ceramic ball base "；Porous ceramic ball base obtained is firstly placed on natural air drying 15 hours at shady and cool ventilation,
Then it places it in again in the drying box that temperature is 105 DEG C and processing is dried, processing time is 10 hours；It will after drying
Porous ceramic ball base is placed in Muffle furnace, is fired by the way of temperature programming.Incipient stage is with the heating of 80 DEG C/h
Rate rises to 500 DEG C, and keeps the temperature 1 hour at this temperature, and the moisture in porous ceramic ball base is vapored away completely, is then proceeded to
With the heating rate of 80 DEG C/h, temperature is risen into 1100 DEG C of firing temperature, and keep the temperature 3 hours；To the more of sintering processes are completed
Hole Ceramic Balls carry out activation process, the temperature of Muffle furnace are down to 800 DEG C, and keep the temperature 8 hours；Finally turn off the electricity of Muffle furnace
Porous ceramic ball supported catalyst obtained after so that temperature is down to environment temperature naturally, is taken out, and be put into hermetic bag in source.
Embodiment 3
Using extrusion forming process, the porous ceramics size that cuboid is made is 2 × 2 × 4mm, material composition and its quality
(being formulated) is as follows：Natural inorganic catalyst chooses lime stone, quality 1.4kg；Ceramic aggregate selection quartz sand, quality are
2.6kg；Starch is pore creating material, quality 0.3kg；Copper oxide is fluxing agent, quality 0.3kg；Plasticizer is bentonite, quality
For 0.1kg；Silane is dispersant, and addition quality is 0.05kg；Carboxymethyl cellulose is binder, and quality 0.2kg will be bonded
Agent and dispersant are made into 8% solution for standby with water.
Machining process is：According to above-mentioned formula, the quartz sand of bulky grain and lime stone are crushed respectively, are then placed in
30min is ground in grinder, the powder for then screening out 200~240 mesh is spare；By the above-mentioned 2.6kg quartz sands filtered out,
The dolomite of 1.4kg is mixed with the bentonite of the starch of 0.3kg, the copper oxide of 0.3kg, 0.1kg, by said mixture with
With silane and cmc soln be put into blender and be sufficiently stirred 25min, obtain porous ceramics pug；It will be porous
Ceramic material is put into van-type hydraulic pressure automatic pressure filter and is dehydrated, and the moisture content of pug is made to reach 20~25%；By porous pottery
Porcelain pug is added in ceramic extrusion-molded equipment, obtains " the porous ceramics base " of 2 × 2 × 4mm cuboids；By porous pottery obtained
Porcelain billet is placed on natural air drying 12 hours at shady and cool ventilation, then places it in the drying box that temperature is 105 DEG C and is dried again
Processing, processing time are 8 hours；Porous ceramics base after drying is placed in Muffle furnace, by the way of temperature programming
It is fired.Incipient stage rises to 450 DEG C with the heating rate of 90 DEG C/h, and keeps the temperature 1 hour at this temperature, by porous ceramics
Moisture in base vapors away completely, then proceedes to the heating rate of 90 DEG C/h, temperature is risen to 1400 DEG C of firing temperature, and protect
Temperature 3 hours；Porous ceramics to sintering processes are completed carries out activation process, the temperature of Muffle furnace is down to 950 DEG C, and keep the temperature
9 hours；The power supply for finally turning off Muffle furnace after so that temperature is down to environment temperature naturally, takes out porous ceramics load obtained and urges
Agent, and be put into hermetic bag.
Embodiment 4
Using slip-casting shaping process, a diameter of 3mm is made, is highly the cylinder porous ceramics of 2mm, and on internal holes are
It communicates below, porous ceramics material composition and its quality (being formulated) are as follows：Natural inorganic catalyst chooses kaolin, quality
For 1.8kg；Ceramic aggregate selects hard bit stone, quality 2.0kg；Flaxen fiber is pore creating material；Zinc borate is fluxing agent, quality
For 0.3kg；Plasticizer is sodium humate, quality 0.1kg；Sodium metasilicate is dispersant, and addition quality is 0.05kg；Boric acid is viscous
Tie agent, quality 0.2kg.Sodium humate, sodium metasilicate, boric acid and water are made into 8% solution for standby.
Machining process is：According to above-mentioned formula grinder is put into after kaolin and hard bit stone preliminary crushing
Interior grinding 30min, the powder for then screening out 200~240 mesh are spare；By the above-mentioned 2.0kg hard bit stone filtered out,
The kaolin of 1.8kg is mixed with the copper oxide of 0.3kg；By said mixture and the sodium humate matched, sodium metasilicate, boric acid
Solution, which is put into blender, is sufficiently stirred 25min, obtains porous ceramics pug；Flaxen fiber is placed in the mold of a diameter of 3mm,
And be uniformly dispersed as possible, porous ceramics pug is then injected into mold, there are certain apopore in mold, convenient for will be extra
Moisture is discharged, and can suitably add certain pressure in mold side, convenient for the manufacture higher cylinder porous ceramics of compactness；It will be made
Cylinder porous ceramics base cut, be then placed on natural air drying 12 hours at shady and cool ventilation, then place it in temperature and be
Processing is dried in 105 DEG C of drying box, processing time is 10 hours；Porous ceramics base after drying is placed on Muffle
In stove, it is fired by the way of temperature programming.Incipient stage rises to 500 DEG C with the heating rate of 100 DEG C/h, and warm herein
The lower heat preservation of degree 1.5 hours, the moisture in ceramic blank is vapored away completely, is then proceeded to the heating rate of 80 DEG C/h, by temperature
1100 DEG C of firing temperature is risen to, and keeps the temperature 3 hours；Porous ceramics to sintering processes are completed carries out activation process, by Muffle
The temperature of stove is down to 900 DEG C, and keeps the temperature 8 hours；The power supply for finally turning off Muffle furnace, after so that temperature is down to environment temperature naturally,
Porous ceramics supported catalyst obtained is taken out, and is put into hermetic bag.
Embodiment 5
To examine physical arrangement, mechanics and the catalytic performance of the porous ceramics supported catalyst prepared using this patent method
The physical property of cuboid porous ceramics obtained in embodiment 3 is detected by effect.Show that its average apparent porosity is
37.8%, bulk density 0.8527g/cm3, compression strength 14.94MPa, at 400 DEG C thermal shock resistance be 6.95MPa, it is swollen
Swollen coefficient is 14.51 × 10-6, the porous ceramics of preparation has small high mechanical strength, density, large specific surface area, high temperature resistant, heat resistanceheat resistant
The advantages that pinking is good is significantly improved compared with the mechanical property of natural inorganic catalyst.
During porous ceramics supported catalyst obtained in embodiment 3 is used for biomass pyrolysis for liquid production, wherein adopting
Biomass is the corn stalk powder after crushing, and it is spare to filter out 20-80 mesh.Before biomass through pyrolysis experiment, by corn
Straw powder is placed at 105 DEG C drying 12 hours in vacuum drying box, ensures that moisture content is less than 10%.Biomass through pyrolysis reactor
For diameter 100mm, the fluidized-bed reactor of high 1200mm, fluidizing gas is the flue gas after coal combustion, into flue gas when fluidized bed
Temperature is about 450 DEG C, and flue gas rate is 30m3/h.Resistance wire is wound on reactor outer wall as reaction zone auxiliary thermal source, to lead to
Crossing temperature controller makes reaction zone temperature be set in 475 DEG C.Porous ceramics supported catalyst made from embodiment 3 is put into fluid bed
Interior, the static height of bed is selected as 80mm, and the rate that corn stalk powder enters fluidized-bed reactor through scroll feeder is 8kg/h.Corn
After entering reaction zone heat scission reaction generation Pyrolysis Gas From Biomass, Pyrolysis Gas From Biomass and thermal cracking carbon residue occur for straw powder
It is fluidized gas together to carry out outside fluid bed, after two stage cyclone separator, is effectively separated, obtains with thermal cracking carbon residue
Purified Pyrolysis Gas From Biomass body, the condenser zone for being 20 DEG C subsequently into temperature, obtains bio oil, no through rapid condensation
Condensable gases are discharged into air after burning or adsorption treatment.
Under same biomass heat scission reaction process conditions, with grain size be 2mm quartz sand alternative embodiment 3 made from
Porous ceramics supported catalyst can equally be worth product liquid --- bio oil.By bio oil obtained under the conditions of two kinds into
Row detection comparison, compared with quartz sand is as the bed material of fluid bed, made from embodiment 3 when porous ceramics supported catalyst,
It was found that：The yield of bio oil increases to 52.3% from 45.2%, improves 15.7%；The yield of lightweight bio oil increases from 28.4%
To 35.6%, 25.4% is improved；The moisture content of bio oil is reduced to 40.4% from 47.3%, reduces by 14.6%；Lightweight bio oil
Higher calorific value increases to 10.2MJ/kg from 8.7MJ/kg, 17.2% is improved, it can be seen that the quality of bio oil obtains obviously
It improves.
In addition, using the freshly prepared porous ceramics supported catalyst of embodiment 3 as the bed material of fluid bed, through 8 hours biologies
After the experiment of matter heat scission reaction, the mass loss rate of porous ceramics is 5.3%, has compared with natural inorganic catalyst and obviously changes
It is kind.And continue with biomass through pyrolysis reaction, the mass loss rate of porous ceramics can constantly reduce, and tend to one
Smaller value.Usually, after biomass through pyrolysis reaction test in 400 hours, it is necessary to replace porous ceramics supported catalyst with
Keep the catalytic effect of catalyst.
Claims (5)
1. a kind of biomass catalyzing and liquefying porous ceramics supported catalyst, characterized in that the catalyst activity component is day
Right organic catalyst, natural inorganic catalyst mix with ceramic aggregate, pore creating material, binder, add after crushing, grinding, screening
Work is process at porous ceramics blank, then porous ceramics blank drying, sintering, activation procedure, wherein the activearm
It is dolomite or montmorillonite to divide；Wherein, natural inorganic catalyst, ceramic aggregate, pore creating material, binder 30~40：40~50：5
~10：10~15 quality proportioning is mixed；
Wherein, the activation procedure is：Porous ceramics to sintering processes are completed carries out activation process, by the temperature of calcination equipment
Degree is down to 800~1000 DEG C, and keeps the temperature 7~9 hours.
2. biomass catalyzing and liquefying according to claim 1 porous ceramics supported catalyst, characterized in that further include helping
Flux, the fluxing agent be zinc borate, boron oxide, aluminum fluoride, calcirm-fluoride, lead oxide, copper oxide, sodium sulphate one kind or its
Meaning mixture, additive amount is according to quality than natural inorganic catalyst：Fluxing agent is 20~50：5~15.
3. biomass catalyzing and liquefying according to claim 1 porous ceramics supported catalyst, characterized in that further include increasing
Agent is moulded, the plasticizer is bentonite, paraffin, sodium humate, polyvinyl alcohol, one kind in gelatine or its any mixture, is added
Dosage is according to quality than natural inorganic catalyst：Plasticizer is 20~50：1~5.
4. biomass catalyzing and liquefying according to claim 1 porous ceramics supported catalyst, characterized in that further include point
Powder, the dispersant are NH4OH, sodium metasilicate, sodium tripolyphosphate, calgon, odium stearate, sodium citrate, polypropylene
Acid and its esters, alkenoic acid sodium, polyvinyl alcohol, fish oil, aliphatic acid, silane, one kind in organic titanium or its any mixture, add
Dosage is according to quality than natural inorganic catalyst：Dispersant is 20~50：1~5.
5. biomass catalyzing and liquefying according to claim 1 porous ceramics supported catalyst, characterized in that the ceramics
Aggregate is 180-400 mesh, and the pore creating material is biomass powder or ammonium hydrogen carbonate.
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| CN111574203A (en) * | 2020-05-18 | 2020-08-25 | 江苏省宜兴非金属化工机械厂有限公司 | Porous ceramic material and preparation method thereof |
| CN111763523A (en) * | 2020-06-09 | 2020-10-13 | 华中科技大学 | Rotary continuous pyrolysis reaction furnace and pyrolysis method for molten salt heat exchange |
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| CN115364852B (en) * | 2022-07-26 | 2023-08-01 | 杭州洛奇亚环保科技有限公司 | Porous ceramic loaded with nano noble metal oxide catalyst and preparation method and application thereof |
| CN116459843B (en) * | 2023-04-27 | 2024-03-05 | 江苏大学 | 3D prints NiMo/Al 2 O 3 MMT composite integral hydrogenation catalyst and preparation method and application thereof |
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