CN105347373A - Preparation method of pseudo-boehmite - Google Patents
Preparation method of pseudo-boehmite Download PDFInfo
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- CN105347373A CN105347373A CN201510809736.8A CN201510809736A CN105347373A CN 105347373 A CN105347373 A CN 105347373A CN 201510809736 A CN201510809736 A CN 201510809736A CN 105347373 A CN105347373 A CN 105347373A
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Abstract
The invention discloses a preparation method of pseudo-boehmite. The preparation method comprises the following steps: the step of gel-forming, the step of aging, the step of separation and washing and the step of drying. During the step of gel-forming, a meta-aluminate solution and carbon dioxide gas are contacted with each other in an inorganic membrane reactor so as to form a reaction product, wherein pressure of the carbon dioxide gas is greater than or equal to 0.1 MPa. By the method of the invention, pseudo-boehmite of stable quality can be produced.
Description
Technical field
The present invention relates to a kind of preparation method of pseudo-boehmite, especially a kind of carborization produces the method for pseudo-boehmite.
Background technology
Alumina powder is often used as siccative, sorbent material, catalyzer and support of the catalyst at chemical field.But a Water oxidize aluminium of natural or artificial production and the specific surface area of alumina trihydrate is low, pore volume is little, activity is low, thus can not be used for doing siccative, sorbent material, catalyzer and support of the catalyst.Pseudo-boehmite has the features such as high-specific surface area, large pore volume, wide aperture, high reactivity, is suitable for the catalyzer and support of the catalyst etc. of doing the fields such as siccative, sorbent material and petrochemical complex, chemical fertilizer and tail gas.Therefore, need a Water oxidize aluminium or alumina trihydrate to be converted into pseudo-boehmite.
Crystallization degree of pseudo-boehmite is low, and water content, higher than boehmite, often exists with colloidal state.At present, the preparation method of pseudo-boehmite mainly comprises aluminium alcoholates hydrolysis method, acid system and alkaline process (carborization).
The key step that aluminium alcoholates hydrolysis method produces pseudo-boehmite is reacted with higher alcohols in the presence of a catalyst by metallic aluminium to generate aluminium alcoholates.The product purity of aluminium alcoholates hydrolysis method is high, but can form a large amount of waste water in production process, and Organic Alcohol recovery cost is large, causes pseudo-boehmite selling at exorbitant prices.
Acid system is with aluminium salt such as Tai-Ace S 150, aluminum nitrate, aluminum chloride for raw material, carries out neutralization reaction prepare pseudo-boehmite with the water soluble alkali such as sodium hydroxide, sodium carbonate, ammoniacal liquor, and preparation process comprises plastic, aging, washing is dry.The main drawback of acid system is that to produce the cost of pseudo-boehmite higher.
China mainly adopts carborization to produce pseudo-boehmite.The units such as department of chemistry of Tongji University, Shanghai Petroleum Chemical Engineering Institute, Wenzhou essence crystal alumina company limited have carried out deep development to alkaline process pseudo-boehmite.The basic process steps of alkaline process comprise gel, aging, to be separated and washing, dry etc.In carborization plastic process, there is NaOH and CO
2quick neutralization reaction, NaAlO
2with CO
2neutralization reaction, NaAlO
2spontaneous hydrolysis reaction, CO
2with the aluminium hydroxide (hydrated aluminum oxide) generated and Na
2cO
3complex reaction, concrete reaction equation is as follows:
2NaOH+CO
2＝Na
2CO
3+H
2O(1)
2NaAlO
2+CO
2+3H
2O＝2Al(OH)
3+Na
2CO
3(2)
NaAlO
2+2H
2O＝Al(OH)
3+NaOH(3)
Na
2CO
3+CO
2+2Al(OH)
3＝2NaAl(CO
3)(OH)
2+H
2O(4)
Reaction (2) aluminium hydroxide that generates is converted into pseudo-boehmite under optimum conditions, reacts the aluminium hydroxide that (3) generate and is then converted into gibbsite, and reaction (2) and to react (3) be parallel reactor.Therefore, in the product of carborization, pseudo-boehmite or gibbsite content depend on speed and the level of response of reaction (2) and reaction (3).
Carborization is prepared pseudo-boehmite and sintering process can be relied on to produce alumina technology, utilizes intermediate product NaAlO
2solution and CO
2as reaction raw materials, technique is simple, is the operational path that cost is minimum.Formation waste liquid in production can returning alumina Production Flow Chart recycling, and basic no waste mine is discharged, and environmental pollution is little, is a kind of method compared with competitive superiority and future.
Chinese patent literature CN1091428C discloses a kind of preparation method of pseudo-boehmite: sodium metaaluminate or sodium aluminate solution are contacted with carbonated gas, with interval or continuous print mode plastic, the aging aluminium hydroxide obtained, isolates solid product, and washing is also dry; The endpoint pH of described plastic or process pH value control in the scope of 6 ~ 9.5, time or the residence time of plastic reaction are less than 40 minutes, the temperature 10 ~ 100 DEG C of plastic reaction, plastic reaction terminates to add alkaline matter rapidly afterwards, makes the pH value of slurries rise to more than 9.5 or carry out solid-liquid separation rapidly and wash.
Chinese patent literature CN103449484A discloses a kind of method of continuous seepage pseudo-boehmite: joined continuously in reaction unit by sodium aluminate solution, pass into the mixed gas of air and carbonic acid gas simultaneously, make sodium aluminate solution form powerful liquid stream and fully mix with carbon dioxide; Control the flow of mixed gas and sodium aluminate solution, the slurry temperature that reaction is generated is 25 ~ 55 DEG C, and pH value is 9.5 ~ 11; Slip by carry out after there is the curved pipeline of multiple u-shaped aging, filter, washing and drying treatment, obtain pseudo-boehmite.
Aforesaid method adopts and directly pass into CO in reaction unit
2carry out decomposition plastic, thus there is following shortcoming: processing unit falls behind, and automatization level is low, and efficiency is low; Conventional decomposition groove is to CO
2specific absorption is low, and throughput is little; Long reaction time, quality product fluctuation is large; Production unit easily scabs, and the cycle of operation is short; More difficultly realize continuous prodution.
Therefore, in the urgent need to a kind of preparation method of pseudo-boehmite, its constant product quality, can realize continuous prodution.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of pseudo-boehmite, it can produce stay-in-grade pseudo-boehmite.Further aim of the present invention is the preparation method providing a kind of pseudo-boehmite, and it can realize continuous prodution.
Present inventor has carried out studying with keen determination, finds that following technical scheme can realize above-mentioned purpose.
A preparation method for pseudo-boehmite, described preparation method comprises plastic step: meta-aluminate solution and carbon dioxide are carried out contacting with forming reactions product in inorganic film reactor; Pressure >=the 0.1MPa of described carbon dioxide.
According to preparation method of the present invention, preferably, described inorganic film reactor comprises housing and inorganic membrane assembly, and described inorganic membrane assembly is arranged on enclosure interior; Described inorganic membrane assembly comprises mineral membrane; The shape of described mineral membrane is tubulose, hollow fiber, web-like or spirrillum; Described mineral membrane comprises matrix and is carried on the functional layer on matrix, and the material of described functional layer comprises metal, alloy, glass or pottery, and the material of described matrix comprises sintered glass, sintering metal or pottery.
According to preparation method of the present invention, preferably, the temperature of reaction of described plastic step is 20 ~ 100 DEG C, and the pH value of reaction product is 9 ~ 10.5.
According to preparation method of the present invention, preferably, in described plastic step, the average discharge of meta-aluminate solution is 150 ~ 200 ml/min, and the average discharge of carbon dioxide is 10 ~ 30 liters/min.
According to preparation method of the present invention, preferably, described meta-aluminate is the basic metal meta-aluminate of solubility; In meta-aluminate solution, be 20 ~ 50 grams per liters in the meta-aluminate concentration of aluminum oxide.
According to preparation method of the present invention, preferably, described preparation method also comprises:
Aging Step: described reaction product heat aging is obtained ageing products;
Separating, washing step: described ageing products is carried out solid-liquid separation to obtain solid matter, then adopts water to carry out washing to described solid matter and obtains washed product; With
Drying step: described washed product drying is obtained pseudo-boehmite.
According to preparation method of the present invention, preferably, in described Aging Step, aging temperature is 40 ~ 70 DEG C, and digestion time is 50 ~ 200 minutes.
According to preparation method of the present invention, preferably, in described separating, washing step, wash temperature is 20 ~ 100 DEG C, and washing times is 5 ~ 15 times; The pH value of final washes is 6.8 ~ 7.
According to preparation method of the present invention, preferably, in described drying step, drying temperature is 105 ~ 130 DEG C, and time of drying is 1 ~ 24 hour.
According to preparation method of the present invention, preferably, the pore volume of described pseudo-boehmite is 0.3 ~ 0.5 ml/g, and specific surface area is 260 ~ 500m
2/ g.
Meta-aluminate solution and carbon dioxide react by the present invention in inorganic film reactor, in inorganic film reactor, gas concentration lwevel can be effectively controlled, thus promote the neutralization reaction of meta-aluminate and carbonic acid gas and suppress meta-aluminate spontaneous hydrolysis to react, thus obtain stay-in-grade pseudo-boehmite.The present invention reacts at ambient pressure, can ensure that plastic reaction safety is carried out, be conducive to industrial applications.According to the preferred technical scheme of the present invention, adopt tubular type inorganic film reactor, hollow fiber form inorganic film reactor can realize continuous prodution.
Accompanying drawing explanation
Fig. 1 is one-tenth adhesive dispenser of the present invention.
Fig. 2 is the XRD figure of pseudo-boehmite prepared by the embodiment of the present invention 1.
Description of reference numerals is as follows:
1-meta-aluminate feed unit; 2-carbonic acid gas feed unit; 3-inorganic film reactor; 4-reaction product storage unit; 5-measures supply unit; 6-flow controlling unit.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to this.
" pseudo-boehmite " of the present invention chemical formula is (A1
2o
3xH
2o, 2>x>1), also referred to as " false boehmite ", with boehmite ((A1 in its structure
2o
3h
2o) similar, but its degree of crystallinity is very low, and close to gelinite, its crystallization water yield is higher than boehmite (see " chemical encyclopedia, Beijing: Chemical Industry Press, the 10th volume, the 938th page in 1998 ").
" 1atm " of the present invention is a standard atmospheric pressure, due to the difference of height above sea level, fluctuates 10% all belong to scope of the present invention at 1atm." 1atm " of the present invention is intended to represent normal pressure, does not namely control especially gaseous tension.
" wt% " of the present invention represents weight percentage.
The preparation method of pseudo-boehmite of the present invention comprises plastic step.Optionally, the preparation method of pseudo-boehmite of the present invention can also comprise Aging Step, separating, washing step and drying step.
< plastic step >
Plastic step of the present invention for carry out contacting with forming reactions product by meta-aluminate solution and carbon dioxide in inorganic film reactor.
In the present invention, described inorganic film reactor can be selected from tubular type inorganic film reactor or hollow fiber form inorganic film reactor.Tubular type described here, hollow fiber form all refer to the shape of mineral membrane.As preferably, inorganic film reactor of the present invention is tubular type inorganic film reactor or hollow fiber form inorganic film reactor.
In the present invention, described inorganic film reactor comprises housing and inorganic membrane assembly, and described inorganic membrane assembly is arranged on enclosure interior.In the present invention, described housing and inorganic membrane assembly are tightly connected, and the method for this area routine can be adopted to seal, repeat no more here.The structure of inorganic film reactor of the present invention can be known in the art those, repeat no more here.
Inorganic membrane assembly of the present invention comprises mineral membrane.Mineral membrane of the present invention comprises metallic membrane, alloy film, ceramic membrane or glassy membrane; Be preferably ceramic membrane or glassy membrane; Be more preferably ceramic membrane.The shape of mineral membrane of the present invention can be tubulose, hollow fiber, web-like or spirrillum.Mineral membrane of the present invention can be the ceramic membrane of tubulose or hollow fiber, the glassy membrane of tubulose or hollow fiber, web-like or spiral helicine metallic membrane, or is web-like or spiral helicine alloy film.As preferably, mineral membrane of the present invention can be the ceramic membrane of tubulose or hollow fiber.It has been generally acknowledged that, tubulose, hollow fiber, web-like or spiral helicine mineral membrane are not suitable for the continuous seepage of pseudo-boehmite; The present invention then finds the mineral membrane of above-mentioned shape, especially the ceramic membrane of tubulose or hollow fiber, may be used for the continuous seepage of pseudo-boehmite.
Mineral membrane of the present invention comprises matrix and is carried on the functional layer on matrix, and the material of described functional layer comprises metal, alloy, glass or pottery, and the material of described matrix comprises sintered glass, sintering metal or pottery.Functional layer of the present invention is preferably glass material or stupalith, is more preferably stupalith; Matrix of the present invention is preferably glass material or stupalith, is more preferably stupalith.Metal membrane material of the present invention can be 304,304L, 316,316L, Ni-Cu alloy, Hastelloy, nickelalloy, titanium metal etc.The specific examples of metallic membrane of the present invention includes but not limited to the product of Nanjing University of Technology's Laboratory Production.Metallic membrane membrane pore size of the present invention can be 0.1 ~ 200 μm, is preferably 1 ~ 100 μm.Ceramic membrane materials of the present invention can be α-Al
2o
3, ZrO
2or TiO
2, be preferably α-Al
2o
3.Ceramic membrane membrane pore size of the present invention is 0.004 ~ 3 μm, is preferably 0.01 ~ 2 μm, is more preferably 0.1 ~ 0.5 μm.The specific examples of ceramic membrane of the present invention includes but not limited to the product that Nanjing Ai Yu Qi Mo Science and Technology Ltd. produces.
In the present invention, the temperature of reaction of described plastic step can be 20 ~ 100 DEG C, is preferably 20 ~ 70 DEG C, is more preferably 25 ~ 50 DEG C.In the present invention, the pH value of the reaction product of described plastic step can be 9 ~ 10.5, is preferably 9.2 ~ 10.2, is more preferably 9.5 ~ 10.
In the present invention, the pH value of described meta-aluminate solution is 10 ~ 14, is preferably 12 ~ 14.Meta-aluminate solution of the present invention comprises meta-aluminate, water and pH adjusting agent.Meta-aluminate of the present invention can be the basic metal meta-aluminate of solubility, such as sodium metaaluminate or potassium metaaluminate etc., is preferably sodium metaaluminate.PH adjusting agent of the present invention can be sodium hydroxide, potassium hydroxide or ammoniacal liquor etc., is preferably sodium hydroxide.In meta-aluminate solution of the present invention, be 20 ~ 50 grams per liters in the meta-aluminate concentration of aluminum oxide, be preferably 30 ~ 40 grams per liters, be more preferably 33 ~ 35 grams per liters.In the present invention, the average discharge of the meta-aluminate solution in described plastic step is 150 ~ 200 ml/min, is preferably 160 ~ 180 ml/min, is more preferably 165 ~ 175 ml/min.
In the present invention, the average discharge of the carbon dioxide in described plastic step can be 10 ~ 30 liters/min, is preferably 15 ~ 25 liters/min, is more preferably 20 ~ 23 liters/min.Pressure >=the 0.1MPa of the carbon dioxide in described plastic step can be 1 ~ 1.3atm, is preferably normal pressure.
< Aging Step >
Aging Step of the present invention is for obtain ageing products by above-mentioned reaction product heat aging.In the present invention, aging temperature can be 40 ~ 70 DEG C, is preferably 45 ~ 65 DEG C, is more preferably 50 ~ 60 DEG C; Digestion time can be 50 ~ 200 minutes, is preferably 55 ~ 180 minutes, is more preferably 60 ~ 90 minutes.
< separating, washing step >
Separating, washing step of the present invention, for described ageing products is carried out solid-liquid separation to obtain solid matter, then adopts water to carry out washing to described solid matter and obtains washed product.In the present invention, the method for solid-liquid separation can comprise filtration, centrifugal etc., is preferably and filters.The operational condition of solid-liquid separation of the present invention can use known in the art those, repeat no more here.In the present invention, wash temperature can be 20 ~ 100 DEG C, is preferably 25 ~ 80 DEG C, is more preferably 30 ~ 50 DEG C; Washing times can be 5 ~ 15 times, is preferably 8 ~ 10 times.In the present invention, the total amount of bath water is 10 ~ 30 liters, is preferably 13 ~ 20 liters; Each water consumption can be the same or different, preferably identical water consumption.In the present invention, the pH value of final washes is 6.8 ~ 7, is preferably 7.
< drying step >
Drying step of the present invention is for obtain pseudo-boehmite by described washed product drying.In the present invention, drying temperature can be 105 ~ 130 DEG C, is preferably 108 ~ 120 DEG C, is more preferably 110 ~ 118 DEG C; Time of drying can be 1 ~ 24 hour, is preferably 2 ~ 15 hours, is more preferably 3 ~ 10 hours.
< pseudo-boehmite >
The pore volume V of pseudo-boehmite of the present invention is 0.3 ~ 0.5 ml/g, is preferably 0.35 ~ 0.45 ml/g; Specific surface area S is 260 ~ 500m
2/ g, is preferably 280 ~ 450m
2/ g.
Pseudo-boehmite of the present invention may be used for producing activated alumina, and then as siccative, sorbent material, catalyzer and support of the catalyst.
< testing method >
Specific surface area, pore volume adopt nitrogen absorption under low temperature BET method to measure (-196 DEG C, the NOVA4000e type specific surface of Kang Ta instrument company of the U.S. and lacunarity analysis instrument).
XRD figure spectrum adopts the X'pert-MPD type X-ray diffractometer (CuK α, λ=0.154nm, sweep limit 5-80 °, sweep velocity 4 °/min) of Dutch PHILIPS Co. to measure.
The ceramic membrane used in following examples is: ceramic membrane materials α-Al
2o
3, membrane pore size is 0.3 μm, Nanjing Ai Yu Qi Mo Science and Technology Ltd. product.
embodiment
Below with reference to accompanying drawing, the present invention will be described in more detail.Fig. 1 is that one-tenth adhesive dispenser of the present invention comprises meta-aluminate feed unit 1, carbonic acid gas feed unit 2, inorganic film reactor 3, reaction product storage unit 4, metering supply unit 5 and flow controlling unit 6.Meta-aluminate feed unit 1 (liquid phase feed unit) is connected with inorganic film reactor 3, for supplying meta-aluminate solution to inorganic film reactor 3 quantitatively through metering supply unit 5; Carbonic acid gas feed unit 2 is connected with inorganic film reactor 3 by flow controlling unit 6, for supplying carbonic acid gas to inorganic film reactor 3 quantitatively.Reaction product storage unit 4 is connected with inorganic film reactor 3 by pipeline, for holding reaction product.
In meta-aluminate feed unit 1, sodium metaaluminate stoste (alumina content: 200 grams per liters) thin up is formed sodium aluminate solution.The sodium aluminate solution (liquid phase) of meta-aluminate feed unit 1 is delivered to inorganic film reactor 3 through metering supply unit 5.Carbon dioxide in carbonic acid gas feed unit 2 is delivered to inorganic film reactor 3 through flow controlling unit 6.In inorganic film reactor 3, carbon dioxide (gas phase) diffuses to sodium aluminate solution through inorganic membrane assembly (ceramic film component), and the concurrent solution plastic reaction forming reactions product estranged of the two contact, wherein comprises aluminium hydroxide.Described reaction product is delivered to reaction product storage unit 4.Through aging, to filter and washing, dry (device is not shown) obtain pseudo-boehmite.
Other processing condition of embodiment 1 ~ 5 are see table 1, and the performance perameter of gained pseudo-boehmite is see table 2.The XRD figure of pseudo-boehmite prepared by embodiment 1 is see Fig. 2.
Table 1
Table 2
| Performance perameter | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Pore volume V (ml/g) | 0.35 | 0.40 | 0.41 | 0.42 | 0.45 |
| Specific surface area (m 2/g) | 440.50.33 | 387.80 | 347.56 | 303.33 | 280.87 |
The performance parameter variations of embodiment 1 ~ 5 gained pseudo-boehmite is very little, and this shows that method of the present invention can obtain stay-in-grade pseudo-boehmite product.
In addition, embodiment 1 ~ 5 repeated 5 times respectively, the performance parameter variations scope of gained pseudo-boehmite is less than 3%, and this shows that method of the present invention is reproducible.
The present invention is not limited to above-mentioned embodiment, and when not deviating from flesh and blood of the present invention, any distortion that it may occur to persons skilled in the art that, improvement, replacement all fall into scope of the present invention.
Claims (10)
1. a preparation method for pseudo-boehmite, is characterized in that, described preparation method comprises plastic step: meta-aluminate solution and carbon dioxide are carried out contacting with forming reactions product in inorganic film reactor; Pressure >=the 0.1MPa of described carbon dioxide.
2. preparation method according to claim 1, is characterized in that: described inorganic film reactor comprises housing and inorganic membrane assembly, and described inorganic membrane assembly is arranged on enclosure interior; Described inorganic membrane assembly comprises mineral membrane; The shape of described mineral membrane is tubulose, hollow fiber, web-like or spirrillum; Described mineral membrane comprises matrix and is carried on the functional layer on matrix, and the material of described functional layer comprises metal, alloy, glass or pottery, and the material of described matrix comprises sintered glass, sintering metal or pottery.
3. preparation method according to claim 1, is characterized in that: the temperature of reaction of described plastic step is 20 ~ 100 DEG C, and the pH value of reaction product is 9 ~ 10.5.
4. preparation method according to claim 1, is characterized in that: in described plastic step, and the average discharge of meta-aluminate solution is 150 ~ 200 ml/min; The average discharge of carbon dioxide is 10 ~ 30 liters/min.
5. preparation method according to claim 1, is characterized in that: described meta-aluminate is the basic metal meta-aluminate of solubility; In meta-aluminate solution, be 20 ~ 50 grams per liters in the meta-aluminate concentration of aluminum oxide.
6. preparation method according to claim 1, is characterized in that, described preparation method also comprises:
Aging Step: described reaction product heat aging is obtained ageing products;
Separating, washing step: described ageing products is carried out solid-liquid separation to obtain solid matter, then adopts water to carry out washing to described solid matter and obtains washed product; With
Drying step: described washed product drying is obtained pseudo-boehmite.
7. preparation method according to claim 6, is characterized in that: in described Aging Step, and aging temperature is 40 ~ 70 DEG C, and digestion time is 50 ~ 200 minutes.
8. preparation method according to claim 6, is characterized in that: in described separating, washing step, and wash temperature is 20 ~ 100 DEG C, and washing times is 5 ~ 15 times; The pH value of final washes is 6.8 ~ 7.
9. preparation method according to claim 8, is characterized in that: in described drying step, and drying temperature is 105 ~ 130 DEG C, and time of drying is 1 ~ 24 hour.
10. preparation method according to claim 6, is characterized in that: the pore volume of described pseudo-boehmite is 0.3 ~ 0.5 ml/g, and specific surface area is 260 ~ 500m
2/ g.
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| CN111823678A (en) * | 2020-07-17 | 2020-10-27 | 枣庄市聚信新材料科技有限公司 | Pesticide slow-release film based on polyvinyl alcohol and preparation method thereof |
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| CN101657384A (en) * | 2007-03-27 | 2010-02-24 | 美铝澳大利亚有限公司 | Method for precipitating boehmite |
| CN101928029A (en) * | 2010-09-08 | 2010-12-29 | 苏州创元投资发展(集团)有限公司 | Method for preparing aluminum oxide sol |
| CN103172097A (en) * | 2013-04-11 | 2013-06-26 | 北京化工大学 | Pseudo-boehmite with large specific surface area and preparation method and application thereof |
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2015
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| CN101657384A (en) * | 2007-03-27 | 2010-02-24 | 美铝澳大利亚有限公司 | Method for precipitating boehmite |
| CN101928029A (en) * | 2010-09-08 | 2010-12-29 | 苏州创元投资发展(集团)有限公司 | Method for preparing aluminum oxide sol |
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| YUJUN WANG ET AL.: ""Preparation of Pseudoboehmite with a Large Pore Volume and a Large Pore Size by Using a Membrane-Dispersion Microstructured Reactor through the Reaction of CO2 and a NaAlO2 Solution"", 《IND. ENG. CHEM. RES.》 * |
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| CN111823678A (en) * | 2020-07-17 | 2020-10-27 | 枣庄市聚信新材料科技有限公司 | Pesticide slow-release film based on polyvinyl alcohol and preparation method thereof |
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Effective date of registration: 20170209 Address after: 100027 Beijing, Chaoyangmen, North Street, No. 22, No. Applicant after: China Petroleum Chemical Co Applicant after: SINOPEC CATALYST CO., LTD. Applicant after: Sinopec catalyst (Beijing) Co., Ltd. Address before: 102502 Fangshan District East Road, No. 24, Beijing Applicant before: Sinopec catalyst (Beijing) Co., Ltd. |
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| GR01 | Patent grant |