CN102010184B - Ceramic powder composition and slurry, catalyst and carrier as well as preparation method and application - Google Patents
Ceramic powder composition and slurry, catalyst and carrier as well as preparation method and application Download PDFInfo
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Abstract
The invention provides a ceramic power composition, which comprises 55-95% of alumina and further comprises one or more the following components: 5-35% of feldspar powder, 5-35% of kaolin, 5-25% of zirconia, 1-10% of titanium oxide and 0.5-5% of calcium oxide. The invention further provides ceramic slurry, a ceramic catalyst carrier prepared from the slurry and application of the carrier and the catalyst in a high-viscosity reaction system. The invention overcomes the defects of poor stability, serious inactivation phenomenon, low reaction conversion rate and the like of the traditional catalyst in the reaction of the high-viscosity system, the aperture ratio of the ceramic catalyst carrier is greatly improved compared with the prior art and can even reach a millimeter scale, and meanwhile, the ceramic catalyst carrier can be maintained with higher specific surface area inside, has the properties of uniform pore opening, high porosity, heat and shock resistance, high-temperature resistance and chemical corrosion resistance, as well as excellent mechanical strength and adsorption property, can be maintained with high stability in a reaction process, can improve the conversion rate in the reaction, and is particularly suitable for the high-viscosity reaction system.
Description
Technical field
The present invention relates to a kind of ceramic powder composition and ceramic size thereof, the invention still further relates to ceramic catalyst carrier that this ceramic size of a kind of use makes and preparation method thereof, and the catalyst and the application thereof that are made by this ceramic catalyst carrier.
Background technology
Since the nearly century, synthesized polymer material has obtained huge development, and plays an important role in national economy, high-tech sector and daily life.Occupy in these macromolecular materials market 70% share be mainly polyethylene (PE), polypropylene (PP), polystyrene (PS) and polyvinyl chloride (PVC).Yet these cheap polymer can not satisfy in multiple fields such as resource, the energy, manufacturing industry, information and environment the demand to the material combination property fully.If synthesize the macromolecular material of high comprehensive performance by the method for synthetic new monomer, technological process is long, and cost is high.By polymer is modified, modification is an extraordinary effective way to having now, wherein the polymer catalytic hydrogenation is one of important channel of polymers function, high performance.
In addition, along with crude oil increasingly heaviness and in poor quality and people to the increase day by day of light Fuel oil product consumption, its quality requirement is also improved day by day, the lighting processing of heavy oil and residual oil has become the hot subject of petroleum refining industry circle and academia's common concern.Therefore, the residual oil catalytic pyrolysis is key subjects of current crude oil working research.
At first, in the catalyst that the residual oil catalytic pyrolysis generally adopts, main component is zeolite, and it is a kind ofly to obtain by Y zeolite is material derived.Y zeolite is prepared into the form (NaY) of sodium salt.Sodium in NaY can also exchange with hydrogen, obtains HY.The HY zeolite obtained overstable gamma zeolite with its part dealuminzation before entering cracking unit be USY.Due to the higher silica alumina ratio of USY, therefore it has the internal structure more more stable than traditional zeolite.But when using USY, have two problems to need to pay close attention to: the one, because the regeneration temperature of residual oil processing is higher, so the catalysqt deactivation phenomenon is serious; The 2nd, because the carbon residue of residual oil raw material is high, coking trend is large.
The patents such as US4758338, EP0788270, CN97116404.5 use amorphous silicon aluminium and aluminium oxide jointly as catalyst carrier, but its pore structure and surface acidity are not suitable for hydrotreatment machine and the hydrogen conversion process of mink cell focus and residual oil.
The disclosed residual oil hydrocatalysts of patent such as CN1098433A, CN1253854A, CN98121076.7, add the auxiliary agent of regulating acidity of catalyst in catalyst preparation process, the catalyst performance aspect shows that the activity stability aspect is relatively poor, wherein the aperture of the first two patent is less, is about 6～8nm.
Result of study of the prior art shows, the aperture that increases catalyst is conducive to improve the performance of Resid Fcc Catalyst.But pore volume and aperture are subject to the restriction of synthetic method and raw material can not arbitrarily be regulated, and has the relation of restriction mutually between each structural parameters such as the distribution of catalyst mesoporous, pore volume.That is to say, the pore structure of catalyst and hole parameter have greatly dependence to raw materials used and preparation condition, and the change of raw material and preparation condition tends to all pore structure parameters to catalyst, exert an influence simultaneously as aperture, pore volume, pore size distribution and specific surface etc., its consequence is that a certain parameter in independent adjusting hole structure will become very difficult.The root that causes this situation is in traditional preparation carrier technique, the adjusting hole structure is normally started with from adjustment primary particle size, increase the primary particle size and will enlarge the aperture, meanwhile must cause the drawdown ratio surface area, and specific area directly has influence on catalyst activity.Therefore, in prior art, be limited for the actual margin of the pore structure parameter adjustment of the catalyst of same composition, same procedure preparation.
For example, the CN200510082624 patent has prepared a kind of nanometer-submicron level catalyst carrier take polystyrene as template.This patent has increased the adjustable macropore (5-2000nm) of size in right amount, to reduce the resistance to mass tranfer in course of reaction.The introducing of polystyrene moulding agent has increased the aperture of catalyst to a certain extent, can also partly prevent micropore in catalyst because the effect of capillary force is caved in, and makes volume and the specific area of micropore part in catalyst that certain increase also arranged.Compare with traditional catalyst, the conversion ratio of this catalyst towards heavy oil has raising clearly, and liquid product yield has had obvious increase.But the raising at this catalyst mesoporous remains very limited, the maximum gauge of its so-called macropore is still below 2 μ m, make in the sticking system of height conversion ratio still not ideal enough, the flow resistance of highly viscous fluid between hole is large, hole easily stops up, catalyst active center is capped, causes active decline.
At present for the more research of being prepared with of ceramic catalyst carrier, US 20030125594A1 adopts diatomite and phosphate to prepare ceramic catalyst, CN 200510119023.5 by molten ceramic raw material, injecting gas foaming, mould extrusion molding, leash pull out cooling and shaping, post processing obtains porous foam ceramic.But its pore size differs, and porosity is difficult to control, and mechanical strength is inhomogeneous.CN200710168480.2, CN00136037.X, CN00136040.X fire a kind of foamed ceramics catalyst carrier for the vehicle exhaust processing with organosilicon or organic metal salt, tourmaline, clay and foam stabilizer.But it is mainly used in gas phase catalytic reaction, and the application of reacting for the high viscosity liquid-phase catalysis has limitation.
Summary of the invention
Technical problem to be solved by this invention is to have overcome existing residual oil catalytic pyrolysis and the contour sticking system reacting middle catalyst poor stability of modified-high polymer reaction, deactivation phenomenom is serious, reaction conversion ratio is low, be not suitable for the defectives such as amplitude that high sticking reaction system and ceramic catalyst carrier aperture and specific area improve simultaneously is limited, provide a kind of ceramic powder composition and ceramic size and the new ceramic catalyst carrier made with this slurry and its production and use.The aperture ratio prior art of ceramic catalyst carrier of the present invention has had significantly raising, even can reach grade, kept simultaneously the higher interior specific area of carrier, and have that perforate is even, the porosity is high, anti-thermal shock, high temperature resistant, the performance of resistance to chemical attack and good mechanical strength and absorption property, can keep high stability in course of reaction, can improve the conversion ratio of reaction, be specially adapted to high sticking reaction system.
The present invention solves the problems of the technologies described above by following technical proposals.
The invention provides a kind of ceramic powder composition, it comprises aluminium oxide 55～95%, and better is 60～80%, and it also comprises one or more in following component: feldspar powder 5～35%, and better is 10～25%, better is 15～20%; Kaolin 5～35%, better is 10～25%, better is 12～15%; Zirconia 5～25%, better is 10～20%, better is 10～15%; Titanium oxide 1～10%, better is 2～8%, better is 2.5～5%; Calcium oxide 0.5～5%, better is 1～3%, better is 1.5～2.5%; Described percentage is the percentage with respect to described ceramic powder composition quality.
In the better embodiment of the present invention one, described ceramic powder composition is comprised of 55～95% aluminium oxide and one or more in following component: 5～35% feldspar powder, 5～35% kaolin, 5～25% zirconia, 1～10% titanium oxide and 0.5～5% calcium oxide.What wherein, described aluminium oxide was better is 60～80%; What described feldspar powder was better is 10～25%, and better is 15～20%; What described kaolin was better is 10～25%, and better is 12～15%; What described zirconia was better is 10～20%, and better is 10～15%; What described titanium oxide was better is 2～8%, and better is 2.5～5%; What described calcium oxide was better is 1～3%, and better is 1.5～2.5%; Described percentage is the percentage with respect to the ceramic powder composition quality.
In another better embodiment of the present invention, described ceramic powder composition can comprise aluminium oxide, feldspar powder, titanium oxide and calcium oxide; Or comprise aluminium oxide, kaolin, zirconia and titanium oxide; Or comprise aluminium oxide, feldspar powder, zirconia and titanium oxide; Or comprise aluminium oxide, feldspar powder, kaolin and titanium oxide; Or comprise aluminium oxide, feldspar powder, kaolin, zirconia, titanium oxide and calcium oxide; Described each constituent content is the same.
In the embodiment of the present invention's one the best, described ceramic powder composition comprises 92% aluminium oxide, 5% feldspar powder, 2% titanium oxide and 1% calcium oxide; Or comprise 68% aluminium oxide, 20% kaolin, 10% zirconia and 2% titanium oxide; Or comprise 80% aluminium oxide, 14% feldspar powder, 5% zirconia and 1% titanium oxide; Or comprise 71% aluminium oxide, 20% feldspar powder, 8% zirconia and 1% titanium oxide; Or comprise 75% aluminium oxide, 12% feldspar powder, 10% kaolin and 3% titanium oxide; Or comprise 59% aluminium oxide, 8% feldspar powder, 25% kaolin and 8% titanium oxide; Or comprise 55% aluminium oxide, 14% feldspar powder, 8% kaolin, 18% zirconia, 2% titanium oxide and 3% calcium oxide; Or comprise 58% aluminium oxide, 15% feldspar powder, 12% kaolin, 10% zirconia, 3% titanium oxide and 2% calcium oxide; Described percentage is the percentage with respect to the ceramic powder composition quality.
The preparation method of ceramic powder composition of the present invention be preferably with each component simply mechanical mixture evenly get final product.
The present invention also provides a kind of ceramic size, and it comprises ceramic powder composition of the present invention, solvent, binding agent, dispersant and defoamer, preferably also can comprise levelling agent.
In the better embodiment of the present invention one, described ceramic size is comprised of described ceramic powder composition, solvent, binding agent, dispersant, defoamer and levelling agent.
Wherein, described solvent is solvent commonly used when being used in this area that ceramic powder is modulated into slurry; because ceramic powder composition of the present invention is polar substances; for making it fully wetting and consider the problem of environmental protection and cost economy; preferred water and/or absolute ethyl alcohol, what described water was better is deionized water.Those skilled in the art can select the content of described solvent according to the rheological behaviour of the slurry that obtains, better is 50～80% of described ceramic powder composition gross weight, and better is 55～70%.
Wherein, described binding agent can be selected all kinds of binding agents commonly used in the ceramic size of this area, and the present invention is polyvinyl alcohol adhesive and/or polyacrylamide bonding agent particularly preferably.Wherein, the molecular weight of described polyvinyl alcohol can be selected the conventional molecular weight of the polyvinyl alcohol that uses as binding agent in this area, and better is number-average molecular weight 20,000～250, and 000, better is 20,000～200,000; The molecular weight of described polyacrylamide can be selected the conventional molecular weight of the polyacrylamide that uses as binding agent in this area, and better is number-average molecular weight 10,000～150, and 000, better is 10,000～100,000.The content of described binding agent can be selected according to this area general knowledge, and better is 1～8% of described ceramic powder composition gross weight, and better is 2～5%.
Wherein, described dispersant can be selected all kinds of dispersants commonly used in the ceramic size of this area, is generally surfactant, to reduce the interfacial tension effect, prevents the powder cohesion, makes dispersion be in stable state.One or more in the better anionic of described dispersant, cationic, nonionic and high molecular type surfactant, better is anionic and/or cationic surface-active, especially one or more that better is in carboxylate, sulfuric acid, sulfonate, phosphate ester salt, amino propylamine dioleate and quaternary surfactant, one or more that best is in tetramethyl oxyammonia, lauryl sodium sulfate, DTAC and hexadecanol phosphate sodium.Wherein, the content of described dispersant can be selected according to this area general knowledge, and better is 0.5～3% of described ceramic powder composition gross weight, and better is 1～2%.
Wherein, described defoamer can be selected each defoamer commonly used in the ceramic size of this area.Preferred alcohols of the present invention is defoamer, and better is the monohydric alcohol of carbon number 2～8, particularly preferably n-octyl alcohol and/or absolute ethyl alcohol.Wherein, the content of described defoamer can be selected according to this area general knowledge, and better is 0.5～3% of described ceramic powder composition gross weight, and better is 0.5～2%.
Wherein, when described ceramic size comprised levelling agent, described levelling agent can be selected all kinds of levelling agents commonly used in the ceramic size of this area, and the present invention is polyurethanes levelling agent and/or esters of acrylic acid levelling agent particularly preferably.Wherein, described esters of acrylic acid levelling agent can be selected in this area one or more in the Voncoat R 3310, acrylate copolymer of the various routines that can use as levelling agent and they polymer-modified.The molecular weight of described esters of acrylic acid levelling agent can be selected the conventional molecular weight of this type of levelling agent, and better is number-average molecular weight 4,000～10, and 000.Described polyurethanes levelling agent can be selected the polyurethanes levelling agent of the various routines of using as levelling agent in this area.Wherein, the content of described levelling agent can be selected according to this area general knowledge, and better is below 3% of described ceramic powder composition gross weight, but does not comprise 0%; Better is 0.15～1.5%.
Wherein, also can add in this area conventional add in described ceramic size, other conventional additives except binding agent, dispersant, defoamer and levelling agent, the kind of other conventional additives and consumption can be selected according to this area general knowledge.
What wherein, the pH value of described ceramic size was better is 9～11.The pH value of described slurry can adopt this area conventional method to regulate, and the present invention preferably adopts pH adjusting agent, stirs under normal temperature and pressure conditions 2～4 hours as ammoniacal liquor, ethylenediamine or polyhydric alcohol amine.
The preparation method of ceramic size of the present invention comprises the steps: ceramic powder composition of the present invention and solvent, binding agent, dispersant, defoamer and levelling agent are mixed, and after also can adding other conventional additives when needing, is mixed together evenly.Preferably, mix the described pH adjusting agent of rear use pH is adjusted to 9～11.
The present invention also provides a kind of preparation method of ceramic catalyst carrier, and it comprises the steps:
Step (1): described ceramic size is mixed with template, make the carrier blank; Described template is hard mould agent and soft template;
Step (2): sintering after dry above-mentioned carrier blank gets final product; Described being sintered to from room temperature is warming up to 1500～1600 ℃.
In step (1), described hard mould agent can be selected various hard mould agents commonly used in this area, better is that size range is at 0.5 μ m～5mm, not with ceramic size generation chemical reaction, and can decompose and not discharge the material of toxic gas fully under 400～600 ℃, one or more that better is in polyurethane flexible foam, carbon black, string and synthetic fibers.What described string was better is peanut shell, bagasse or wood fiber.What described synthetic fibers were better is polypropylene fibre and/or polyacrylonitrile fibre.The molecular weight of described polypropylene or polyacrylonitrile can be selected the various molecular weight that can make fiber according to this area general knowledge.Described polyurethane flexible foam can be selected the polyurethane flexible foam of all size, as long as it has open-celled structure, and the duct interconnects, and can decompose to get final product fully before ceramic post sintering, and better is the polyurethane flexible foam of 10～70PPI.PPI (Pixels per inch) refers to the number in sponge hole in an inch.10PPI is for there being per square inch 10 * 10, sponge hole.The large hole dimension that the polyurethane flexible foam percent opening produces between the polyurethane flexible foam of 10～70PPI is at 0.5 μ m～5mm.
In step (1), described soft template can be selected various soft templates commonly used in this area, be chosen in the present invention and can form the number nanometer in water to the material of tens nanometer micella or glue rod, be generally ionic and/or nonionic surface active agent, one or more that better is in neopelex, dodecyl phenenyl sulfate, shitosan, softex kw, PEG123 and PEG127.
In the better embodiment of the present invention one, step (1) adopts any the carrying out in following manner:
Mode 1, described ceramic size is mixed with template except polyurethane flexible foam, be pressed into the carrier blank in mould;
Mode 2, with described ceramic size with after template except polyurethane flexible foam mixes, flood described polyurethane flexible foam, make the carrier blank.
Wherein, what the mixing quality of described ceramic size and soft template was better is 20: 1～0.2: 1, and what the mixing quality of described ceramic size and the hard mould agent except polyurethane flexible foam was better is 10: 1～0.5: 1.
Drying described in step (2) can adopt the method for this area routine to carry out, preferably ventilation natural air drying 10～36 hours.
Sintering described in step (2) is preferably undertaken by follow procedure: the speed with 0.5～5 ℃/min is warming up to 400～600 ℃ from room temperature, then is warming up to 1500～1600 ℃ with the speed of 2～12 ℃/min, and is incubated 1～5 hour at this temperature; Better sintering procedure is: the speed with 0.5～2.5 ℃/min is warming up to 450～550 ℃ from room temperature, then is warming up to 1500～1600 ℃ with the speed of 5～10 ℃/min, and is incubated 2～4 hours at this temperature.
Preferably, before the described ceramic catalyst carrier of preparation, described hard mould agent is carried out pretreatment, to remove the impurity of surface attachment.Described pretreatment can select the preprocess method of this area routine to carry out, the preprocess method of wherein said polyurethane flexible foam, carbon black and synthetic fibers is preferably with its ultrasonic processing 20～60min in absolute ethyl alcohol, dry getting final product under 70～80 ℃.The preprocess method of described string is preferably for after flooding 1～8 hour with string in mass concentration is 5～15% salpeter solution, to neutral, dry under 90～110 ℃ with washed with de-ionized water.
The present invention also provides a kind of ceramic catalyst carrier that is made by above-mentioned preparation method thus.Ceramic catalyst carrier of the present invention has macropore and mesoporous hierarchical porous structure.Wherein, described macropore diameter is more than 10 μ m, is preferably 40 μ m～5mm; Described mesoporous aperture is 2～50nm, is preferably 5～25nm.The having significantly of aperture ratio prior art of macropore mentioned, and is more conducive to mobile mass transfer and the heat transfer of highly viscous fluid, mesoporously provides abundant specific area to be beneficial to macromolecular reaction, can improve the reaction system conversion ratio.What the porosity of described ceramic catalyst carrier was better is 66～94%; That total pore volume is better is 0.34～0.8ml/g; Total specific area is 4.3～20.9m
2/ g.
The present invention also provides a kind of catalyst, and it comprises ceramic catalyst carrier of the present invention and is carried on metal active composition on this carrier.Wherein, described metal active composition can be selected in catalytic hydrogenation the conventional various metal active compositions that use, one or more that better is in Fe, Co, Ni, Cu, Pd, Pt, Ru, Rh and Mo etc.In addition, described metal active composition preferably also comprises La and/or Ce.Described metal active composition can simple metal, the form of oxide, sulfide and the nitride of metal is carried on this carrier.
Wherein, the content of described metal active composition can be selected according to this area general knowledge, and better is 0.5～10% of total catalyst weight.
The present invention also provides a kind of preparation method of described catalyst, it can be prepared according to the preparation method of existing similar catalyst, preferred following preparation method in the present invention: with the solution impregnation ceramic catalyst carrier of the present invention of the salt of described metal active composition, roasting after oven dry, with the reducing agent reduction, get final product.
Wherein, the salt of described metal active composition is better is one or more in chloride, nitrate and the acetate etc. of this metal active composition.Described solution can be the aqueous solution or organic solution.The concentration of described solution can be selected according to this area normal concentration, generally adopts the saturated solution of salt or a little less than the solution of saturated solution concentration.
Preferably, described roasting is preferably carried out in nitrogen atmosphere or air atmosphere.Sintering temperature can be selected according to this area general knowledge, and better is 300～500 ℃.Commonly used reducing agent when described reducing agent is reducing metal, this area, one or more that better is in hydrogen, ethanol, formaldehyde and sodium borohydride etc.
Use the catalyst that ceramic catalyst carrier of the present invention prepares to have equally foramen magnum-mesoporous hierarchical porous structure, therefore be easy to separate with highly viscous fluid, thereby save the separation link, saving resource is enhanced productivity.These premium properties make catalyst of the present invention be applicable to various reaction systems, are particularly useful for high sticking system, as the polymer catalytic hydrogenation in polymer modification processing and residual oil catalytic cracking reaction or heavy oil lighting reaction.
Therefore, the present invention also provides described catalyst or the application of ceramic catalyst carrier in the reaction of the sticking system of height, especially the application in polymer catalytic hydrogenation, residual oil catalytic cracking reaction or heavy oil lighting reaction.
Room temperature described in the present invention refers to 15～40 ℃.
The present invention's raw material, reagent and equipment used is commercially available getting all.
In the present invention, but above-mentioned optimum condition any combination on the basis that meets this area general knowledge namely gets the preferred embodiments of the invention.
Positive progressive effect of the present invention is:
1, the invention provides a kind of ceramic powder composition, said composition with can make ceramic catalyst carrier have the wide-aperture while after template of the present invention coordinates, still have good meso-hole structure, improve the specific area of ceramic catalyst carrier inside.
2, the present invention has successfully made and has been difficult to the ceramic catalyst carrier that the pore volume that makes and specific area all significantly improve in the prior art always, this carrier has hierarchical porous structure, large bore dia reaches grade, perforate is even, the mobility of high adhesive aggregation compound be can guarantee, the mobile mass transfer of highly viscous fluid and the carrying out of heat transfer and reaction are beneficial to; Mesoporously provide sufficient specific area for catalyst, be beneficial to macromolecular reaction, can improve the reaction system conversion ratio, make carrier of the present invention be specially adapted to the modified-reaction of cracking reaction and the polymer catalytic hydrogenation of heavy oil lighting and the contour sticking system of slag oil crack.
3, ceramic catalyst carrier of the present invention has enough mechanical strengths, can guarantee load and the catalyst integrity in use of catalyst, anti-thermal shock, high temperature resistant, resistance to chemical attack also have good mechanical strength and absorption property, can not affect catalyst activity, physicochemical property is good, non-environmental-pollution, preparation technology is simple, and production cost is low.
4, the catalyst for preparing with ceramic catalyst carrier of the present invention is easy to separate with highly viscous fluid, can save the separation link, saving resource is enhanced productivity, and makes catalyst of the present invention be applicable to polymer modification processing, heavy oil lighting and residual oil processing technology.
The specific embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described further, but the present invention is not limited.
Table 1
| Embodiment | Aluminium oxide | Feldspar powder | Kaolin | Zirconia | Titanium oxide | Calcium oxide | Total umber |
| 1 | 92 parts | 5 parts | \ | \ | 2 parts | 1 part | 100 parts |
| 2 | 68 parts | \ | 20 parts | 10 parts | 2 parts | \ | 100 parts |
| 3 | 80 parts | 14 parts | \ | 5 parts | 1 part | \ | 100 parts |
| 4 | 75 parts | 12 parts | 10 parts | \ | 3 parts | \ | 100 parts |
| 5 | 71 parts | 20 parts | \ | 8 parts | 1 part | \ | 100 parts |
| 6 | 59 parts | 8 parts | 25 parts | \ | 8 parts | \ | 100 parts |
| 7 | 55 parts | 14 parts | 8 parts | 18 parts | 2 parts | 3 parts | 100 parts |
| 8 | 58 parts | 15 parts | 12 parts | 10 parts | 3 parts | 2 parts | 100 parts |
Umber in table 1 is weight portion.
Table 2
Percentage in table 2 is the mass percent with respect to the ceramic powder composition gross mass.
The preparation method of the polyacrylate flow agent in table 2 is:
By butyl acrylate and GMA radical polymerization preparation, the mass ratio of butyl acrylate and GMA is 1: 1.4.Polymerization initiator is benzoyl peroxide, and initiator amount is 0.015wt%, and solvent is toluene.Polymerization temperature is 130 ℃, and polymerization time is 2h, stops reacting the final vacuum drying.
The preparation method of polyurethane levelling agent is:
Mass ratio is that the toluene di-isocyanate(TDI) of 3: 1 and number-average molecular weight are 1000 adipic acid-1,4 butanediol polyester-diol reactions, catalyst is dibutyl tin laurate, catalyst amount 0.02wt%, reaction temperature is 80 ℃, the reaction time is 5h, the dihydromethyl propionic acid chain extension that adds 3wt% after reaction finishes, 20% acetone diluted, temperature keeps 50-60 ℃, stirs 2h final vacuum drying acetone is steamed.
Embodiment 1
(1) ceramic powder composition
According to the formula of table 1, will get ceramic powder composition after the simple mixing of each composition.
(2) ceramic size
According to the formula of table 2 with ceramic powder composition and binding agent, dispersant, defoamer and solvent in step (1) after, regulate pH value to 11, stirring 3h makes ceramic size.
(3) ceramic catalyst carrier
Select the polyurethane soft foamed plastics of 32PPI, be processed into 5 * 5 * 5mm size, be placed on ultrasonic processing 50min in absolute ethyl alcohol, take out after dry 2h under 70 ℃ as hard mould agent.
Choosing neopelex is soft template, and ceramic size is mixed with soft template, and ceramic size is 20: 1 with the mixing quality ratio of soft template, mixes to get mixture.Polyurethane soft foamed plastics is placed in this mixture floods 20min, constantly extruding makes it dipping fully, extrudes at last unnecessary slurry, makes the carrier blank, natural drying approximately 24h.
The carrier blank of drying is put into high temperature furnace, speed with 1.5 ℃/min rises to 500 ℃ under room temperature condition, then is warming up to 1550 ℃ with the speed of 8 ℃/min, and is incubated 4h at this temperature, take out after naturally cooling to room temperature, can obtain ceramic catalyst carrier.Adopt mercury injection apparatus to measure pore-size distribution and the specific area of ceramic catalyst carrier.The porosity that records ceramic catalyst carrier reaches 90%, and wherein macropore diameter is 400-550 μ m, and mesoporous aperture is 10-25nm, and total pore volume is 0.56ml/g, and the pore volume major part is provided by the micron hole, and total specific area is 5.53m
2/ g, 60% specific area is provided by mesoporous.
Embodiment 2
(1) ceramic powder composition
According to the formula of table 1, will get ceramic powder composition after the simple mixing of each composition.
(2) ceramic size
According to the formula of table 2 with ceramic powder composition and binding agent, dispersant, defoamer, levelling agent and solvent in step (1) after, regulate pH value to 11, stirring 3h makes ceramic size.
(3) ceramic catalyst carrier
Choosing dodecyl phenenyl sulfate is soft template, and ceramic size is mixed with soft template, and ceramic size is 15: 1 with the mixing quality ratio of soft template, mixes to get mixture.
Select the carbon black of 50 μ m as hard mould agent, carbon black is put in ultrasonic processing 30min in absolute ethyl alcohol, take out stand-by after dry 3h under 70 ℃.
Carbon black is mixed with said mixture, and mixed proportion is: the mass ratio of ceramic size and hard mould agent is 3: 1, after mixing, is placed in mould and makes the carrier blank, natural drying approximately 48h.
The carrier blank of drying is put into high temperature furnace, speed with 1 ℃/min rises to 450 ℃ under room temperature condition, then is warming up to 1600 ℃ with the speed of 5 ℃/min, and is incubated 3h at this temperature, take out after naturally cooling to room temperature, can obtain ceramic catalyst carrier.Adopt mercury injection apparatus to measure pore-size distribution and the specific area of ceramic catalyst carrier.Recording porosity is 72%, and wherein macropore diameter is 40-50 μ m, and mesoporous aperture is 8-20nm, and total pore volume is 0.39ml/g, and the pore volume major part is provided by the micron hole, and total specific area is 4.29m
2/ g, 55% specific area is provided by mesoporous.
Embodiment 3
(1) ceramic powder composition
According to the formula of table 1, will get ceramic powder composition after the simple mixing of each composition.
(2) ceramic size
According to the formula of table 2 with ceramic powder composition and binding agent, dispersant, defoamer, levelling agent and solvent in step (1) after, regulate pH value to 11, stirring 3h makes ceramic size.
(3) ceramic catalyst carrier
Choosing shitosan is soft template, and ceramic size is mixed with soft template, and ceramic size is 8: 1 with the mixing quality ratio of soft template, mixes to get mixture.
Selecting polypropylene fibre (Mn=250000) is hard mould agent, mixes with said mixture, and mixed proportion is: the mass ratio of ceramic size and polypropylene fibre is 5: 1, mixes to be placed on and makes the carrier blank in mould, natural drying approximately 48h.
The carrier blank of drying is put into high temperature furnace, speed with 0.5 ℃/min rises to 600 ℃ under room temperature condition, then is warming up to 1500 ℃ with the speed of 10 ℃/min, and is incubated 4h at this temperature, take out after naturally cooling to room temperature, can obtain ceramic catalyst carrier.Adopt mercury injection apparatus to measure pore-size distribution and the specific area of ceramic catalyst carrier.Recording porosity is 66%, and wherein macropore diameter is 30-70 μ m, and mesoporous aperture is 5-20nm, and total pore volume is 0.58ml/g, and the pore volume major part is provided by the micron hole, and total specific area is 6.22m
2/ g, 64% specific area is provided by mesoporous.
Embodiment 4
(1) ceramic powder composition
According to the formula of table 1, will get ceramic powder composition after the simple mixing of each composition.
(2) ceramic size
According to the formula of table 2 with ceramic powder composition and binding agent, dispersant, defoamer, levelling agent and solvent in step (1) after, regulate pH value to 10, stirring 3h makes ceramic size.
(3) ceramic catalyst carrier
Choosing softex kw is soft template, and ceramic size is mixed with soft template, and ceramic size is 4: 1 with the mixing quality ratio of soft template, mixes to get mixture.
Preferred dimension is the wood fiber of 70 μ m approximately, be placed in 10% salpeter solution after dipping 4h, after cleaning with deionized water after dry 2h under 110 ℃ as hard mould agent.
Hard mould agent is mixed with said mixture, and mixed proportion is: the mass ratio of ceramic size and wood fiber is 2: 1, after mixing, makes the carrier blank in mould, natural drying approximately 48h.
The carrier blank of drying is put into high temperature furnace, speed with 1 ℃/min rises to 550 ℃ under room temperature condition, then is warming up to 1600 ℃ with the speed of 10 ℃/min, and is incubated 2.5h at this temperature, take out after naturally cooling to room temperature, can obtain ceramic catalyst carrier.Adopt mercury injection apparatus to measure pore-size distribution and the specific area of ceramic catalyst carrier.Recording porosity is 79%, and wherein macropore diameter is 50-70 μ m, and mesoporous aperture is 10-20nm, and total pore volume is 0.67ml/g, and the pore volume major part is provided by the micron hole, and total specific area is 7.29m
2/ g, 76% specific area is provided by mesoporous.
Embodiment 5
(1) ceramic powder composition
According to the formula of table 1, will get ceramic powder composition after the simple mixing of each composition.
(2) ceramic size
According to the formula of table 2 with ceramic powder composition and binding agent, dispersant, defoamer, levelling agent and solvent in step (1) after, regulate pH value to 11, stirring 3h makes ceramic size.
(3) ceramic catalyst carrier
Choosing PEG123 is soft template, and ceramic size is mixed with soft template, and ceramic size is 3: 1 with the mixing quality ratio of soft template, mixes to get mixture.
Select the bagasse fibre of 100 μ m as hard mould agent, soak after 4h ultrasonic processings 40min in absolute ethyl alcohol in 10% nitric acid, taking-up after dry 3h under 70 ℃ as hard mould agent.
Bagasse fibre is mixed with said mixture, and mixed proportion is: the mass ratio of ceramic size and bagasse fibre is 3: 1, after mixing, is placed in mould and makes the carrier blank, natural drying approximately 48h.
The carrier blank of drying is put into high temperature furnace, speed with 1.5 ℃/min rises to 500 ℃ under room temperature condition, then is warming up to 1550 ℃ with the speed of 8 ℃/min, and is incubated 4h at this temperature, take out after naturally cooling to room temperature, can obtain ceramic catalyst carrier.Adopt mercury injection apparatus to measure pore-size distribution and the specific area of ceramic catalyst carrier.Recording porosity is 83%, and wherein macropore diameter is 80-150 μ m, and mesoporous aperture is 10-20nm, and total pore volume is 0.45ml/g, and the pore volume major part is provided by the micron hole, and total specific area is 6.69m
2/ g, 65% specific area is provided by mesoporous.
Embodiment 6
(1) ceramic powder composition
According to the formula of table 1, will get ceramic powder composition after the simple mixing of each composition.
(2) ceramic size
According to the formula of table 2 with ceramic powder composition and binding agent, dispersant, defoamer, levelling agent and solvent in step (1) after, regulate pH value to 9, stirring 3h makes ceramic size.
(3) ceramic catalyst carrier
Choosing PEG127 is soft template, and ceramic size is mixed with soft template, and ceramic size is 4: 1 with the mixing quality ratio of soft template, mixes to get mixture.
Select polypropylene fibre (Mn=180000) to mix with said mixture for hard mould agent, mixed proportion is: the ratio of ceramic size and polypropylene fibre is 4: 1, mixes to be placed on and makes the carrier blank in mould, natural drying approximately 48h.
The carrier blank of drying is put into high temperature furnace, speed with 1 ℃/min rises to 550 ℃ under room temperature condition, then is warming up to 1500 ℃ with the speed of 10 ℃/min, and is incubated 4h at this temperature, take out after naturally cooling to room temperature, can obtain ceramic catalyst carrier.Adopt mercury injection apparatus to measure pore-size distribution and the specific area of ceramic catalyst carrier.Recording porosity is 74%, and wherein macropore diameter is 50-100 μ m, and mesoporous aperture is 8-20nm, and total pore volume is 0.58ml/g, and the pore volume major part is provided by the micron hole, and total specific area is 6.42m
2/ g, 70% specific area is provided by mesoporous.
Embodiment 7
(1) ceramic powder composition
According to the formula of table 1, will get ceramic powder composition after the simple mixing of each composition.
(2) ceramic size
According to the formula of table 2 with ceramic powder composition and binding agent, dispersant, defoamer, levelling agent and solvent in step (1) after, regulate pH value to 11, stirring 3h makes ceramic size.
(3) ceramic catalyst carrier
Choosing PEG127 is soft template, and ceramic size is mixed with soft template, and ceramic size is 6: 1 with the mixing quality ratio of soft template, mixes to get mixture.
Select the polyurethane soft foamed plastics of the carbon black of 50 μ m and 75PPI as hard mould agent.Carbon black is put in ultrasonic processing 30min in absolute ethyl alcohol, takes out stand-by after dry 3h under 70 ℃.Select the polyurethane soft foamed plastics of 100PPI, be processed into 5 * 5 * 5mm size, be placed on ultrasonic processing 40min in absolute ethyl alcohol, take out stand-by after dry 2h under 70 ℃.
Carbon black is mixed with said mixture, and mixed proportion is: the mass ratio of ceramic size and carbon black is 3: 1, mixes.
Polyurethane soft foamed plastics is placed in the slurry that mixes floods 30min, constantly extruding makes it dipping fully, extrudes at last unnecessary slurry, makes the carrier blank, natural drying approximately 24h.
The carrier blank of drying is put into high temperature furnace, speed with 1 ℃/min rises to 550 ℃ under room temperature condition, then is warming up to 1500 ℃ with the speed of 10 ℃/min, and is incubated 4h at this temperature, take out after naturally cooling to room temperature, can obtain ceramic catalyst carrier.Adopt mercury injection apparatus to measure pore-size distribution and the specific area of ceramic catalyst carrier.Recording porosity is 94%, and wherein macropore diameter is 50-100 μ m, and mesoporous aperture is 8-20nm, and total pore volume is 0.34ml/g, and the pore volume major part is provided by the micron hole, and total specific area is 3.76m
2/ g, 65% specific area is provided by mesoporous.
Embodiment 8
(1) ceramic powder composition
According to the formula of table 1, will get ceramic powder composition after the simple mixing of each composition.
(2) ceramic size
According to the formula of table 2 with ceramic powder composition and binding agent, dispersant or soft template, defoamer, levelling agent and solvent in step (1) after, regulate pH value to 10, stirring 3h makes ceramic size.
(3) ceramic catalyst carrier
Choosing PEG123 is soft template, and ceramic size is mixed with soft template, and ceramic size is 5: 1 with the mixing quality ratio of soft template, mixes, and gets mixture 1.
Preferred dimension approximately the polyurethane soft foamed plastics of the wood fiber of 70 μ m and 100PPI as hard mould agent.Wood fiber is placed in 10% salpeter solution after dipping 4h, after cleaning with deionized water after dry 2h under 110 ℃ as hard mould agent.With polyurethane soft foamed plastics, be processed into 5 * 5 * 5mm size, be placed on ultrasonic processing 40min in absolute ethyl alcohol, take out stand-by after dry 2h under 70 ℃.
Wood fiber is mixed with said mixture 1, and mixed proportion is: the mass ratio of ceramic size and wood fiber is 3: 1, mixes, and gets mixture 2.
Polyurethane soft foamed plastics is placed in mixture 2 floods 30min, constantly extruding makes it dipping fully, extrudes at last unnecessary slurry, makes the carrier blank, natural drying approximately 24h.
This carrier blank is put into high temperature furnace, rise to 600 ℃ with the speed of 1 ℃/min under room temperature condition, then be warming up to 1600 ℃ with the speed of 8 ℃/min, and be incubated 2h at this temperature, take out after naturally cooling to room temperature, can obtain ceramic catalyst carrier.Adopt mercury injection apparatus to measure pore-size distribution and the specific area of ceramic catalyst carrier.Recording porosity is 93%, and wherein macropore diameter is 250-360 μ m, and mesoporous aperture is 8-20nm, and total pore volume is 0.78ml/g, and the pore volume major part is provided by the micron hole, and total specific area is 20.88m
2/ g, 89% specific area is provided by mesoporous.
Effect embodiment 1
One, the reduced crude catalytic cracking activity is estimated
1, Kaolinite Preparation of Catalyst B
Adopt the CN200510082624 patent take polystyrene as template, preparation submicron order catalyst carrier.Getting 2.851 gram lauryl sodium sulfate, 1.63 gram n-amyl alcohols, 100 milliliters of styrene and 840 ml waters joins in the reactor that band stirs; The temperature that makes reactor that heats while stirring is raised to 83 ℃ of left and right.After temperature of charge is stable, add the initiation reaction of 0.80g potassium persulfate, reaction was carried out 3 hours, obtained the polystyrene moulding micelle.The water intaking glass solution (contains SiO
226.3w%) 60.12g, USY molecular sieve 3.92g, water 43ml mixes, and the polystyrene moulding micelle is added in above-mentioned system.Through aging 48h post-drying, obtain catalyst B.
2, Kaolinite Preparation of Catalyst A
Take the technical grade ammonium tetramolybdate and (be equivalent to 82w%MoO
3), adding density is 0.950g/cm
3The ammoniacal liquor stirring and dissolving, make solution.Spray solution on the catalyst carrier of embodiment 1, is namely got catalyst A in 500 ℃ of lower roasting 2h after oven dry.
3, RFCC active appraisal experiment
Be raw material with reduced crude, measure respectively the activity of catalyst A and B on catalytic cracking fixed bed activity experiment device.Catalyst A or B loadings are 5.00g, and catalyst A or B and residual oil mass ratio are 3: 1,550 ℃ of reaction temperatures, feed time 70s.Product liquid is analyzed with Varian 3800 type gas chromatographs (fid detector).Table 3 is the physical parameter table of reduced crude, and test result sees Table 4.
Table 3
| Performance indications | Reduced crude |
| Density (20 ℃), g/cm 3 | 0.9069 |
| Kinematic viscosity (100 ℃), mm 2/s | 28.9 |
| Carbon residue, wt% | 4.3 |
| Mean molecule quantity | 577 |
| Hydrogen content, wt% | 13.11 |
| Carbon content, wt% | 86.52 |
| The H/C atomic ratio | 1.82 |
| Saturated component, wt% | 57.08 |
| Fragrance divides, wt% | 27.61 |
| Resin and asphalt, wt% | 15.31 |
Table 4
By as seen from Table 4, compare with existing catalyst B, use catalyst A of the present invention to carry out the RFCC reaction, the gained conversion ratio significantly improves, and gasoline yield also improves a lot, and amount of coke reduces, and diesel yield also descends to some extent.This is mainly that catalyst activity is higher because the channel diameter of catalyst A is larger, and intermediate species diesel oil can continue cracking and generate the less material (gasoline, liquefied gas etc.) of molecular weight, and amount of coke is reduced.
Two, the vacuum gas oil (VGO) catalytic cracking activity is estimated
Be raw material with vacuum gas oil (VGO), measure respectively the activity of catalyst A and catalyst B on catalytic cracking fixed bed activity experiment device.Loaded catalyst is 5.00g, and catalyst and residual oil mass ratio are 3: 1,550 ℃ of reaction temperatures, feed time 70s.Product liquid is analyzed with Varian 3800 type gas chromatographs (fid detector).Table 5 is the physical parameter table of vacuum gas oil (VGO), and test result sees Table 6.
Table 5
| Performance indications | Vacuum gas oil (VGO) |
| Density (20 ℃), g/cm 3 | 0.9221 |
| Kinematic viscosity (100 ℃), mm 2/s | 106.0 |
| Carbon residue, wt% | 8.80 |
| Mean molecule quantity | 895 |
| Hydrogen content, wt% | 12.78 |
| Carbon content, wt% | 86.93 |
| The H/C atomic ratio | 1.76 |
| Saturated component, wt% | 42.91 |
| Fragrance divides, wt% | 34.53 |
| Resin and asphalt, wt% | 22.56 |
Table 6
By as seen from Table 6, compare with existing catalyst B, use catalyst A of the present invention to carry out the RFCC reaction, the gained conversion ratio significantly improves, and gasoline yield also improves a lot, and amount of coke reduces, and diesel yield also descends to some extent.This is mainly that catalyst activity is higher because the channel diameter of catalyst A is larger, so intermediate species diesel oil can continue cracking and generate the less material of molecular weight, makes amount of coke reduce.
Effect embodiment 2
One, Kaolinite Preparation of Catalyst C
Take PtCl
2(contain PtCl
299%), add dissolving with hydrochloric acid to be configured to solution.Impregnation of catalyst carriers in embodiment 2 in this solution, through 110 ℃ of dry 3h, is reduced 5h under 400 ℃ of hydrogen atmospheres, namely get catalyst C.
Two, polymer catalytic hydrogenation
Xylene solution and the above-mentioned catalyst C of acrylonitrile-butadiene rubber (acrylonitrile content 33%) are added in the 5L reactor, with air in high-purity hydrogen displacement still, be that 0.3% (accounting for dry glue quality), Hydrogen Vapor Pressure are to carry out the hydrogenation reaction of acrylonitrile-butadiene rubber under 1.5MPa, the condition of 145 ℃ at the catalyst quality mark after sealing.With the degree of unsaturation of solution before bromine iodine method assaying reaction and after reaction, recording degree of hydrogenation is 98.1%, has good catalytic hydrogenation effect.
Effect embodiment 3
One, the preparation of existing catalyst D
Adopt soluble barium salt Ba (NO
3)
2Prepare BaSO with the sulfuric acid reaction precipitation method
4, make BaSO
4Pore volume be 0.07cm
3/ g, the aperture is 20.9nm.
Take Pd (NO
3)
2(contain Pd (NO
3)
299%), add nitric acid dissolve to be configured to solution.With BaSO
4Carrier impregnation through 110 ℃ of dry 3h, is reduced 5h under 400 ℃ of hydrogen atmospheres in solution, namely get comparative catalyst D.
Two, the polymer catalytic hydrogenation of existing catalyst
The cyclohexane solution and the above-mentioned comparative catalyst D that with number-average molecular weight are the 10wt% of 300000 ordinary polystyrenes (GPPS) are added in the 5L reactor, with air in high-purity hydrogen displacement still, be that 7.3% (accounting for the polystyrene quality), Hydrogen Vapor Pressure are to carry out the hydrogenation reaction of polystyrene under 1.5Mpa, the condition of 150 ℃ at the catalyst quality mark after sealing.With the front phenyl ring concentration with reacting rear solution of determined by ultraviolet spectrophotometry reaction, calculating degree of hydrogenation is 68.5%.
Three, the preparation of catalyst E of the present invention
Take Pd (NO
3)
2(contain Pd (NO
3)
299%), add nitric acid dissolve to be configured to solution.Impregnation of catalyst carriers in embodiment 6 in solution, through 110 ℃ of dry 3h, is reduced 5h under 400 ℃ of hydrogen atmospheres, namely get catalyst E.
Four, the polymer catalytic hydrogenation of catalyst of the present invention
The cyclohexane solution and the above-mentioned catalyst E that with number-average molecular weight are the 10wt% of 300000 ordinary polystyrenes (GPPS) are added in the 5L reactor, with air in high-purity hydrogen displacement still, be that 7.3% (accounting for the polystyrene quality), Hydrogen Vapor Pressure are to carry out the hydrogenation reaction of polystyrene under 1.5Mpa, the condition of 150 ℃ at the catalyst quality mark after sealing.With the front phenyl ring concentration with reacting rear solution of determined by ultraviolet spectrophotometry reaction, calculating degree of hydrogenation is 96.8%, and the hydrogenation successful is better than catalyst D of the prior art.
Claims (4)
1. the preparation method of a ceramic catalyst carrier is characterized in that:
(1) after will following compositions simple the mixing ceramic powder composition: 3 parts, 55 parts, aluminium oxide, 14 parts of feldspar powders, 8 parts of kaolin, 18 parts of zirconias, 2 parts of titanium oxide and calcium oxide; Umber wherein is weight portion;
(2) with after the ceramic powder composition in step (1) and 2% binding agent, 2% dispersant, 2% defoamer, 1% levelling agent and 80% solvent, regulate pH value to 11, stir 3h, make ceramic size; Wherein, described binding agent is polyvinyl alcohol, and the Mn of described polyvinyl alcohol is 200000; Described dispersant is the tetramethyl oxyammonia; Described defoamer is absolute ethyl alcohol; Described levelling agent is the polyurethane levelling agent, and the Mn of described polyurethane levelling agent is 7000; Described solvent is deionized water; Percentage wherein is the mass percent with respect to the ceramic powder composition gross mass; The preparation method of described polyurethane levelling agent is: mass ratio is that the toluene di-isocyanate(TDI) of 3: 1 and number-average molecular weight are 1000 adipic acid-1,4 butanediol polyester-diol reactions, catalyst is dibutyl tin laurate, catalyst amount 0.02wt%, reaction temperature is 80 ℃, the reaction time is 5h, the dihydromethyl propionic acid chain extension that adds 3wt% after reaction finishes, 20% acetone diluted, temperature keeps 50-60 ℃, stirs 2h final vacuum drying acetone is steamed;
(3) choosing PEG127 is soft template, and described ceramic size is mixed with described soft template, and described ceramic size is 6: 1 with the mixing quality ratio of described soft template, mixes to get mixture;
Select the polyurethane soft foamed plastics of the carbon black of 50 μ m and 75PPI as hard mould agent; Described carbon black is put in ultrasonic processing 30min in absolute ethyl alcohol, takes out stand-by after dry 3h under 70 ℃; Select the polyurethane soft foamed plastics of 100PPI, be processed into 5 * 5 * 5mm size, be placed on ultrasonic processing 40min in absolute ethyl alcohol, take out stand-by after dry 2h under 70 ℃;
Described carbon black is mixed with described mixture, and mixed proportion is: the mass ratio of described ceramic size and described carbon black is 3: 1, mixes;
Described polyurethane soft foamed plastics is placed in the slurry that mixes floods 30min, constantly extruding makes it dipping fully, extrudes at last unnecessary slurry, makes the carrier blank, natural drying 24h;
The carrier blank of drying is put into high temperature furnace, speed with 1 ℃/min rises to 550 ℃ under room temperature condition, then is warming up to 1500 ℃ with the speed of 10 ℃/min, and is incubated 4h at this temperature, take out after naturally cooling to room temperature, can obtain ceramic catalyst carrier.
2. ceramic catalyst carrier that is made by the preparation method of claim 1.
3. the preparation method of a ceramic catalyst carrier is characterized in that:
(1) after will following compositions simple the mixing ceramic powder composition: 2 parts, 58 parts, aluminium oxide, 15 parts of feldspar powders, 12 parts of kaolin, 10 parts of zirconias, 3 parts of titanium oxide and calcium oxide; Umber wherein is weight portion;
(2) with after the ceramic powder composition in step (1) and 4% binding agent, 2% dispersant, 1.5% defoamer, 1.5% levelling agent and 60% solvent, regulate pH value to 10, stir 3h, make ceramic size; Wherein, described binding agent is polyacrylamide, and the Mn of described polyacrylamide is 80000; Described dispersant is DTAC; Described defoamer is n-octyl alcohol; Described levelling agent is polyacrylate flow agent, and the Mn of described polyacrylate flow agent is 10000; Described solvent is deionized water; Percentage wherein is the mass percent with respect to the ceramic powder composition gross mass; The preparation method of described polyacrylate flow agent is: by butyl acrylate and GMA radical polymerization preparation, the mass ratio of butyl acrylate and GMA is 1: 1.4, polymerization initiator is benzoyl peroxide, initiator amount is 0.015wt%, solvent is toluene, polymerization temperature is 130 ℃, and polymerization time is 2h, stops reacting the final vacuum drying;
(3) choosing PEG123 is soft template, and described ceramic size is mixed with described soft template, and described ceramic size is 5: 1 with the mixing quality ratio of described soft template, mixes, and gets mixture 1;
Preferred dimension approximately the polyurethane soft foamed plastics of the wood fiber of 70 μ m and 100PPI as hard mould agent; Described wood fiber is placed in 10% salpeter solution after dipping 4h, after cleaning with deionized water after dry 2h under 110 ℃ as hard mould agent; With described polyurethane soft foamed plastics, be processed into 5 * 5 * 5mm size, be placed on ultrasonic processing 40min in absolute ethyl alcohol, take out stand-by after dry 2h under 70 ℃;
Described wood fiber is mixed with described mixture 1, and mixed proportion is: the mass ratio of described ceramic size and described wood fiber is 3: 1, mixes, and gets mixture 2;
Described polyurethane soft foamed plastics is placed in described mixture 2 floods 30min, constantly extruding makes it dipping fully, extrudes at last unnecessary slurry, makes the carrier blank, natural drying 24h;
This carrier blank is put into high temperature furnace, rise to 600 ℃ with the speed of 1 ℃/min under room temperature condition, then be warming up to 1600 ℃ with the speed of 8 ℃/min, and be incubated 2h at this temperature, take out after naturally cooling to room temperature, can obtain ceramic catalyst carrier.
4. ceramic catalyst carrier that is made by the preparation method of claim 3.
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| CN104829217A (en) * | 2015-03-31 | 2015-08-12 | 苏州维泰生物技术有限公司 | Corrosion resistant alumina ceramic and preparation method thereof |
| CN107434412A (en) * | 2016-05-26 | 2017-12-05 | 苏州拜博机电科技有限公司 | The preparation method of improved ceramic powder slurry and direct write shaped three dimensional structure |
| CN108859329A (en) * | 2018-06-13 | 2018-11-23 | 九江市正达玻璃实业有限公司 | A kind of formula and preparation method thereof of combined type laminated glass |
| JP7457984B2 (en) | 2018-09-11 | 2024-03-29 | 東京都公立大学法人 | gold supported catalyst |
| CN109640563B (en) * | 2019-01-25 | 2020-12-29 | Oppo广东移动通信有限公司 | Color ceramic, shell, preparation method of color ceramic and shell, and electronic equipment |
| CN112608134B (en) * | 2020-12-10 | 2023-03-24 | 南昌大学 | Preparation method and application of porous ceramic ball catalyst |
| CN114752048A (en) * | 2022-04-11 | 2022-07-15 | 深圳光华伟业股份有限公司 | Catalyst and application of preparation method thereof in preparation of biomedical polylactic acid |
| CN114685772A (en) * | 2022-04-20 | 2022-07-01 | 深圳光华伟业股份有限公司 | Novel biomedical polylactic acid synthesis method |
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