CN110540222A - Preparation method of high-temperature-resistant activated alumina - Google Patents
Preparation method of high-temperature-resistant activated alumina Download PDFInfo
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- CN110540222A CN110540222A CN201910817094.4A CN201910817094A CN110540222A CN 110540222 A CN110540222 A CN 110540222A CN 201910817094 A CN201910817094 A CN 201910817094A CN 110540222 A CN110540222 A CN 110540222A
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- boehmite
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- alumina
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 91
- 239000002002 slurry Substances 0.000 claims abstract description 57
- 238000003756 stirring Methods 0.000 claims abstract description 54
- 239000011148 porous material Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 28
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- 238000001694 spray drying Methods 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000007598 dipping method Methods 0.000 claims abstract description 7
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 20
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 20
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 16
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 15
- 239000012065 filter cake Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- -1 polyethylene Polymers 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 238000001223 reverse osmosis Methods 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 10
- 238000000746 purification Methods 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000007084 catalytic combustion reaction Methods 0.000 abstract description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003546 flue gas Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- 230000002572 peristaltic effect Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229910052761 rare earth metal Inorganic materials 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 238000005485 electric heating Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 7
- 150000001342 alkaline earth metals Chemical class 0.000 description 6
- 150000002910 rare earth metals Chemical class 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000001935 peptisation Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B01J35/61—
-
- B01J35/615—
-
- B01J35/635—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
- C01F7/441—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Abstract
A preparation method of high temperature resistant active alumina relates to a preparation method of high temperature resistant active alumina used in the fields of automobile exhaust purification, catalytic combustion and the like. The preparation method is characterized by comprising the following steps in sequence: (1) hot dipping pseudo-boehmite to remove impurities; (2) preparing pseudo-boehmite sol; (3) adding nitrate into the pseudo-boehmite sol, uniformly stirring, then dropwise adding ammonia water to adjust the pH value, and stirring and aging; (4) adding polyethylene glycol into the aged slurry; (5) spray drying to obtain modified pseudoboehmite; (6) calcining to obtain the high-temperature resistant activated alumina. By adopting the method, the specific surface area of the obtained high-temperature resistant activated alumina is not less than 100m2/g, and the pore volume is not less than 0.4 mL/g. The product is used as a catalyst carrier for automobile exhaust purification, petroleum hydrogenation catalysis and flue gas catalytic combustion, and has the advantages of high reaction activity, high temperature resistance, good stability and the like.
Description
Technical Field
A preparation method of high temperature resistant active alumina relates to a preparation method of high temperature resistant active alumina used in the fields of automobile exhaust purification, catalytic combustion and the like.
background
The pollution of the tail gas of the motor vehicle to the atmosphere is increasingly serious, and the high-efficiency catalyst for purifying the tail gas of the motor vehicle is very important for reducing the effect of the tail gas. The most effective way for treating the automobile exhaust is to install a three-way catalyst on the exhaust pipe to convert unsaturated hydrocarbon and oxynitride into saturated compounds. The catalyst for purifying the tail gas of the automobile mainly comprises a carrier, an active component and an auxiliary agent. The carrier has the main functions of bearing and dispersing active components and improving the mass transfer and heat transfer efficiency in the reaction, so that the carrier is required to have a certain specific surface area and proper pore volume; because the temperature of the automobile exhaust often reaches very high temperature, the surface sintering of gamma-Al 2O3 and the transformation to alpha-Al 2O3 are easy to occur, so that the surface area of Al2O3 is greatly reduced and the catalyst loses activity, and therefore, the carrier material is required to have very good high-temperature resistance. The modified activated alumina is applied due to the large specific surface area and thermal stability, and is also the main carrier of the current commercial catalyst.
The active alumina is used as a common carrier of a tail gas purification catalyst, and the specific surface, pore volume, pore size distribution, surface acidity and alkalinity, thermal stability and the like of the active alumina greatly influence the catalytic performance of the catalyst. However, the gamma-phase activated alumina is easy to undergo surface sintering under high temperature conditions and is transformed into a stable alpha-phase alumina crystal form, so that the specific surface area of the alumina is sharply reduced, and the surface-loaded active component is aggregated, so that the activity of the catalyst is reduced and even the catalyst is inactivated. A great deal of research shows that the addition of alkaline earth metal, SiO2, rare earth elements and the like in the alumina can effectively prevent the high-temperature surface sintering and the transformation to alpha phase of the activated alumina, thereby improving the high-temperature thermal stability of the activated alumina.
in recent years, with the rapid development of the automobile industry, the demand for high temperature resistant activated alumina has also increased rapidly. However, because the domestic pseudo-boehmite mostly takes sodium aluminate solution as raw material, the pseudo-boehmite is prepared by carbonation decomposition or inorganic acid neutralization method. The pseudo-boehmite produced by the two processes has small pore volume, and is mostly about 0.4 mL/g; in addition, the content of sodium oxide is higher than 0.05 percent, and the content of sodium oxide in the activated alumina prepared by roasting the precursor is higher than 0.07 percent, the content of sodium oxide is high, and the content of sodium oxide has adverse effect on the acidity and alkalinity of the surface of the catalyst, and in addition, the problems of small pore volume, uneven pore size distribution and the like exist. The surface acidity and alkalinity, pore volume, pore size distribution and the like of the catalyst affect the reaction activity of the catalyst. Therefore, the pseudoboehmite produced by adopting the sodium aluminate solution as the main raw material can not meet the requirement of automobile exhaust purification due to high sodium oxide content, small pore volume and the like.
at present, the pseudo-boehmite is mainly prepared by an alchol salt method abroad, the content of harmful impurities such as silicon, iron, sodium and the like in the product is low, the pore volume is large, and the activated alumina produced by taking the product as a raw material has good reaction activity but has extremely high selling price. In order to reduce the production cost, automobile exhaust purification catalyst manufacturers urgently hope that domestic special alumina enterprises can economically produce qualified active alumina substitutes.
In order to solve the problems of reactivity and high temperature resistance of the activated alumina, researchers at home and abroad develop various methods for improving the high temperature resistance of the activated alumina. F.oudet et al (J.Catalyst, 114, 112-120(1998)) in France impregnated pseudo-boehmite with lanthanum nitrate and calcined at 1150 ℃ for 12 hours, the specific surface area was 63m 2/g. I.M. Tijburg et Al (J.Mater.Sci., 26, 6479-. Japanese patent (JP03088713) describes that the specific surface of an alumina surface impregnated alkaline earth metal salt remains 100m2/g after calcination at 1000 ℃. French patent (FP2596397) describes that the specific surface of alumina is maintained at 50-60 m2/g after the alumina is impregnated with rare earth metal salt and calcined at 1150 ℃ for 12 hours.
The Chinese patent 'a preparation method of high-temperature-resistant high-specific surface area active alumina' (CN201210496978.2) discloses a preparation method of high-temperature-resistant high-specific surface area active alumina. The invention discloses a process for preparing high-temperature-resistant high-specific-surface-area active alumina by taking a compound H [ La (EDTA) synthesized by using an EDTA pore-expanding agent and La2O3 as heat stabilizers and 16H2O crystals as main raw materials and adopting a solid-solid mixing technology, wherein the process is stable at 1200 ℃.
The patent 'a high temperature resistant active alumina material and a preparation method thereof' (CN201110410339.5) is that macroporous pseudo-boehmite, high-viscosity pseudo-boehmite and additive are mixed with water, then the mixture is stirred uniformly at the rotating speed of 100-1000 r/min, then diluted nitric acid with the concentration of 30% is added for reaction, when the pH is in a peptization state of 2.0-5.5, the mixture is aged for 3-6 hours at the temperature of 80-100 ℃, pore-forming agent is added at room temperature and stirred uniformly, and then the mixture is pulped, sprayed and dried, and finally the mixture is roasted at the temperature of 900 ℃ to prepare alumina. The alumina material can keep the specific surface above 110m2/g for a long time at the temperature of 1000-1100 ℃.
In the patent "preparation method of high temperature resistant activated alumina" (CN200710179672.3), an aluminum salt solution with additives and surfactants is placed in an ultrasonic reactor, under the condition of continuous stirring, a precipitator is uniformly dripped, after the reaction is finished, a semitransparent pulpous suspension is obtained, a white precursor is obtained after centrifugal separation, washing, filtering and drying, and the white precursor is placed in a high temperature furnace for roasting, so that the high temperature resistant activated alumina is obtained. The patent "a preparation method of high temperature resistant large specific surface area alumina" (CN201110387242.7) is to add alkaline earth metal or rare earth element into water or ethanol water solution to prepare stabilizer solution, then add the stabilizer solution into the suspension made of pseudo-boehmite, and then prepare high temperature resistant active alumina after the procedures of dipping, evaporation to dryness, roasting and the like.
The patent "a preparation method of high temperature resistant active alumina" (CN200810011866.7), adopts the liquid phase counter-drop precipitation method, takes sodium aluminate solution and nitric acid solution as raw materials, takes organic matter as pore-enlarging agent, takes rare earth oxide as stabilizing agent, adopts the liquid phase counter-drop precipitation method to prepare alumina with large specific surface area and good high temperature resistance. The content of rare earth oxide in the aluminum oxide is 0.1-10 wt%, the aluminum oxide solid is treated in an air atmosphere at 700 ℃ for 5 hours, the specific surface area is larger than 350m2/g, the average pore volume is 0.3122mL/g, the average pore diameter is 5.23nm, and the pore size distribution range is 3-12 nm. The specific surface area is more than 150m2/g after being treated for 5h in an air atmosphere at 1100 ℃.
The method mainly adopts the steps of dipping the pseudo-boehmite or the gamma-Al 2O3 into alkaline earth metal or rare earth metal, thereby preparing the high-temperature resistant activated alumina. In the impregnation process, the addition amount of the added alkaline earth metal or rare earth metal accounts for less than 10% of the mass ratio of the activated alumina, and the impregnated alkaline earth metal or rare earth metal is segregated in the drying or roasting process, so that the alkaline earth metal or rare earth metal is unevenly distributed, and the surface acidity and alkalinity and the high temperature resistance of the catalyst are affected. Moreover, in order to maintain high reactivity, the content of alkali metals such as sodium oxide in the activated alumina is less than 0.05%, and the above documents do not mention how to reduce the content of harmful impurities such as sodium oxide in the activated alumina.
Disclosure of Invention
The invention aims to provide a preparation method of high-temperature resistant activated alumina which can effectively reduce the content of harmful impurities, has high reaction activity and good high-temperature resistant stability and is suitable for the fields of automobile exhaust purification and the like, aiming at the defects of the prior art.
the purpose of the invention is realized by the following technical scheme.
A preparation method of high temperature resistant active alumina is characterized in that pseudo-boehmite is adopted as a raw material, and the preparation process sequentially comprises the following steps:
(1) Hot dipping pseudo-boehmite to remove impurities;
(2) Preparing the pseudo-boehmite subjected to impurity removal and pure water into slurry, and adding a nitric acid solution to prepare pseudo-boehmite sol;
(3) Adding rare earth nitrate into the pseudo-boehmite sol, uniformly stirring, then dropwise adding ammonia water to adjust the pH value of the slurry to 8-9, and stirring and aging;
(4) Adding polyethylene glycol into the aged slurry, and stirring until the polyethylene glycol is completely dissolved;
(5) spray drying the slurry obtained in the step (4) to obtain modified pseudo-boehmite;
(6) And (4) roasting the modified pseudo-boehmite obtained in the step (5) to obtain the high-temperature-resistant activated alumina.
The invention relates to a preparation method of high-temperature-resistant active alumina, which is characterized in that a pseudo-boehmite raw material is adopted, the specific surface area (BET) of the pseudo-boehmite is 200-300m2/g, the pore volume is 0.4-0.7mL/g, the content of sodium oxide is less than 0.08% (wt%), the content of iron oxide is less than or equal to 0.020% (wt%), and the content of silicon dioxide is less than or equal to 0.02%.
The preparation method of the high-temperature resistant activated alumina is characterized in that the hot dipping impurity removal treatment process of the pseudo-boehmite in the step (1) is to add hot pure water into the pseudo-boehmite to prepare slurry with the solid content of 100-600 g/L; then adding nitric acid solution to adjust the pH value of the slurry to 6-7, stirring for 0.5-2 hours, and then filtering by adopting a vacuum belt filter to obtain the pseudo-boehmite filter cake with the sodium oxide content of less than 0.03 percent (wt%).
The preparation method of the high-temperature-resistant activated alumina is characterized in that the hot pure water in the step (1) is prepared by adopting a reverse osmosis process, the electric conductivity of the hot pure water is less than 100 mu S/cm, and the temperature of the hot pure water is 50-95 ℃.
The preparation method of the high-temperature resistant activated alumina is characterized in that the step (2) is to prepare the pseudo-boehmite subjected to the wet impurity removal and pure water into slurry with the solid content of 50-300L/g, and then to drop nitric acid solution until the pH value of the slurry is 3-5, so that the pseudo-boehmite is fully peptized.
The invention discloses a preparation method of high-temperature-resistant active alumina, which is characterized in that in the step (3), nitrate added into peptized pseudo-boehmite slurry is lanthanum nitrate or cerium nitrate, the addition amount of the lanthanum nitrate or the cerium nitrate is 2-5% of the mass of alumina in the pseudo-boehmite by the mass of the lanthanum oxide or the cerium oxide, and the lanthanum nitrate or the cerium nitrate is fully dissolved by stirring.
The invention relates to a preparation method of high temperature resistant active alumina, which is characterized in that the step (3) is that ammonia water with the concentration (mass percentage) of 20-25% is added into pseudo-boehmite slurry fully dissolving lanthanum nitrate or cerium nitrate, the pH of the slurry is adjusted to 8-9, then the slurry is heated, and stirred and aged for 1-3 hours at the temperature of 50-80 ℃.
The preparation method of the high-temperature-resistant activated alumina is characterized in that the step (3) is to add polyethylene glycol accounting for 5-10% of the mass ratio of alumina in the pseudo-boehmite into the pseudo-boehmite slurry after stirring and aging, wherein the molecular weight of the polyethylene glycol is 4000-10000.
The preparation method of the high-temperature-resistant activated alumina is characterized in that the step (4) is to dry the polyethylene glycol pseudo-boehmite dissolved slurry obtained in the step (3) by adopting a centrifugal spray drying tower to obtain modified pseudo-boehmite powder with the particle size of 20-80 microns.
The preparation method of the high-temperature-resistant activated alumina is characterized in that the pseudo-boehmite powder obtained in the step (4) is roasted at the roasting temperature of 550-750 ℃ for 1-4 hours, and the used calcining equipment is a tunnel kiln or a shuttle kiln.
The invention relates to a preparation method of high temperature resistant active alumina, which adopts pseudo-boehmite with low silicon content, low iron content and medium pore volume prepared by a sodium aluminate solution neutralization method as a raw material, and obtains rare earth modified low sodium pseudo-boehmite by wet impurity removal, peptization, heterogeneous precipitation coating modification, polyethylene glycol pore-expanding agent addition and aging, and the high temperature resistant active alumina is obtained after roasting, wherein the BET specific surface area is 150-200m2/g, the pore volume is more than 0.5mL/g, the sodium oxide content is less than 0.05% (wt%), the iron oxide content is less than or equal to 0.030% (wt%), and the silicon dioxide content is less than or equal to 0.03% (wt%). The high-temperature resistant activated alumina is aged for 12 hours at 1100 ℃, the surface area is not less than 100m2/g, and the pore volume is not less than 0.4 mL/g. Can be used for coating materials for automobile exhaust purification and the environmental protection fields of catalytic combustion of smoke and the like.
the method effectively overcomes the defects of the prior art, takes the pseudo-boehmite with low silicon content, low iron content and medium pore volume as the raw material, reduces the sodium oxide content in the pseudo-boehmite by wet processing to obtain the pseudo-boehmite with the sodium oxide content of less than 0.03 percent, carries out rare earth coating modification on the surfaces of the pseudo-boehmite particles by peptization and heterogeneous precipitation, adds an organic pore-expanding agent before spray drying, and obtains the high-temperature resistant active alumina with low sodium content, large pore volume and large specific surface area by roasting. The product is used as a catalyst carrier for automobile exhaust purification and flue gas catalytic combustion, and has the advantages of high reaction activity, high temperature resistance, good stability and the like. Has the characteristics of low production cost, good product activity and high temperature resistance, and the like.
Drawings
FIG. 1 is a process flow diagram of a preparation method of high temperature resistant activated alumina of the present invention.
Detailed Description
A process for preparing high-temp active alumina includes such steps as preparing the pseudoboehmite with low Si and Fe content and moderate pore volume and hot pure water (50-90 deg.C) to obtain slurry containing solid content of 600g/L, slowly dropping diluted nitric acid to regulate pH value to 6-7, stirring for 0.5-2 hr, and filtering by vacuum belt filter to obtain the pseudoboehmite filter cake with sodium oxide content less than 0.03% (wt%). The pseudo-boehmite filter cake and pure water are prepared into 50-300L/g slurry in an organic polymer stainless steel stirring tank lined with acid and alkali corrosion resistance, and dilute nitric acid with the concentration of about 30 percent (wt%) is slowly dripped to the pH value of 3-5 while stirring, so that the pseudo-boehmite is fully peptized. Adding a certain amount of lanthanum nitrate or cerium nitrate (the mass ratio of lanthanum oxide or cerium oxide in the lanthanum nitrate or cerium nitrate to aluminum oxide in the pseudo-boehmite is 2% -5%), stirring uniformly, slowly dropwise adding dilute ammonia water with the concentration of 20% -25% (wt%), and adjusting the pH value of the slurry to 8-9; heating the slurry to keep the temperature of the slurry at 50-80 ℃, and stirring and aging for 1-3 hours. Then polyethylene glycol with the molecular weight of 4000-10000 is added, and the adding amount is 5-10% of the mass of the alumina in the pseudo-boehmite. Stirring is continued to completely dissolve the polyethylene glycol, and then spray drying is carried out on the slurry to obtain the modified pseudo-boehmite powder with the particle size of 20-80 microns. The modified pseudo-boehmite powder is filled into a clean sagger and is roasted in a tunnel kiln or a shuttle kiln at the temperature of 550-750 ℃ for 1-4 hours to obtain the high-temperature-resistant active alumina, the BET specific surface area of the alumina is 150-200m2/g, the pore volume is more than 0.5mL/g, the sodium oxide content is less than 0.05 percent (wt percent), the iron oxide content is less than or equal to 0.030 percent (wt percent), and the silicon dioxide content is less than or equal to 0.03 percent (wt percent). The high-temperature resistant activated alumina is aged for 12 hours at 1100 ℃, the surface area is not less than 100m2/g, and the pore volume is not less than 0.4 mL/g.
Example 1
500L of pure water is added into a stainless steel stirring tank, stirring is carried out, 200 kg of pseudo-boehmite (BET specific surface area 313m2/g, pore volume 0.47ml/g, ignition loss 31%, SiO2 content 0.023%, Fe2O3 content 0.020%, Na2O content 0.05%) is added, the materials and water are mixed into homogeneous slurry, then 30% of dilute nitric acid is added by a peristaltic pump, and the pH value of the slurry is adjusted to 6.5. Heating the slurry to 70 ℃ by adopting electric heating, stirring for 1.5 hours, and then filtering and washing by adopting a vacuum belt filter to obtain a filter cake with the Na2O content of 0.025 percent. And transferring the filter cake into a stirring tank with 500L of pure water, stirring, adding 30% dilute nitric acid by using a peristaltic pump, adjusting the pH value of the slurry to 4.5, and heating the material to 50 ℃ by using electric heating so as to fully peptize the pseudo-boehmite. And then adding chemically pure lanthanum nitrate of which the mass of lanthanum oxide accounts for 3 percent of that of alumina in the pseudo-boehmite, and stirring for 30 minutes to fully dissolve the lanthanum nitrate. And (3) dropwise adding 25 percent (wt%) of dilute ammonia water by using a peristaltic pump to neutralize the slurry and adjust the pH value of the slurry to about 8.5, stirring and aging for 2 hours, and then adding 60006.9 kilograms of PEG accounting for 5 percent of the mass of the alumina in the pseudo-boehmite. After further stirring for 30 minutes, spray-drying with a 50 liter/h stainless steel spray tower to obtain modified pseudoboehmite with a particle size of 30 microns, and then calcining in a tunnel kiln at 600 ℃ for 3 hours to obtain high-temperature-resistant activated alumina with a BET specific surface area of 180m2/g, a pore volume of 0.55mL/g, a sodium oxide content of 0.035% (wt%), an iron oxide content of 0.030% (wt%) and a silica content of 0.032% (wt%). The high temperature resistant activated alumina is aged for 12 hours at 1100 ℃, and has the surface area of 110m2/g and the pore volume of 0.45 mL/g.
Example 2
500L of pure water is added into a stainless steel stirring tank, stirring is carried out, 300 kg of pseudo-boehmite (same as example 1) is added, the materials and the water are mixed into homogeneous slurry, then 30% of dilute nitric acid is added by a peristaltic pump, and the pH value of the slurry is adjusted to 6.5. Heating the slurry to 90 ℃ by adopting electric heating, stirring for 1 hour, and then filtering and washing by adopting a vacuum belt filter to obtain a filter cake with the Na2O content of 0.022%. And transferring the filter cake into a stirring tank with 500L of pure water, stirring, adding 30% dilute nitric acid by using a peristaltic pump, adjusting the pH value of the slurry to 4.5, and heating the material to 50 ℃ by using electric heating so as to fully peptize the pseudo-boehmite. And then adding chemically pure lanthanum nitrate of which the mass of lanthanum oxide accounts for 5 percent of that of alumina in the pseudo-boehmite, and stirring for 30 minutes to fully dissolve the lanthanum nitrate. And (3) dropwise adding 25% diluted ammonia water by using a peristaltic pump to adjust the pH value of the slurry to about 8.0, stirring and aging for 2 hours, and then adding 400016.5 kilograms of PEG accounting for 8% of the mass of the alumina in the pseudo-boehmite. After stirring for 60 minutes, the mixture was spray-dried in a 50 l/h stainless steel spray tower to obtain a modified pseudoboehmite having a particle size of 30 μm, and then calcined in a tunnel kiln at 650 ℃ for 3 hours to obtain a high-temperature-resistant activated alumina having a BET specific surface area of 200m2/g, a pore volume of 0.58mL/g, a sodium oxide content of 0.032% (wt%), an iron oxide content of 0.028% (wt%), and a silica content of 0.032% (wt%). The high temperature resistant activated alumina is aged for 12 hours at 1100 ℃, and has the surface area of 115m2/g and the pore volume of 0.48 mL/g.
Example 3
500L of pure water is added into a stainless steel stirring tank, stirring is carried out, 60 kg of pseudo-boehmite (same as example 1) is added, the materials and the water are mixed into homogeneous slurry, then 30% of dilute nitric acid is added by a peristaltic pump, and the pH value of the slurry is adjusted to 6.2. Heating the slurry to 90 ℃ by adopting electric heating, stirring for 1 hour, and then filtering and washing by adopting a vacuum belt filter to obtain a filter cake with the Na2O content of 0.022%. And transferring the filter cake into a stirring tank with 500L of pure water, stirring, adding 30% dilute nitric acid by using a peristaltic pump, adjusting the pH value of the slurry to 4.5, and heating the material to 50 ℃ by using electric heating so as to fully peptize the pseudo-boehmite. And then adding chemically pure lanthanum nitrate of which the mass of lanthanum oxide accounts for 5 percent of that of alumina in the pseudo-boehmite, and stirring for 30 minutes to fully dissolve the lanthanum nitrate. And (3) dropwise adding 25% diluted ammonia water by using a peristaltic pump to adjust the pH value of the slurry to about 8.0, stirring and aging for 2 hours, and then adding 600016.5 kilograms of PEG accounting for 8% of the mass of the alumina in the pseudo-boehmite. After further stirring for 30 minutes, spray-drying was carried out using a 50 liter/h stainless steel spray tower to obtain a modified pseudoboehmite having a particle size of 50 μm, followed by calcination at 700 ℃ for 2 hours in a tunnel kiln to obtain a high-temperature-resistant activated alumina having a BET specific surface area of 216m2/g, a pore volume of 0.67mL/g, a pore diameter of 16.53nm, an average particle size of 30 μm, a sodium oxide content of 0.032% (wt%), an iron oxide content of 0.028% (wt%), and a silica content of 0.032% (wt%). The high temperature resistant activated alumina is aged for 12 hours at 1100 ℃, and has the surface area of 115m2/g and the pore volume of 0.48 mL/g.
Example 4
500L of pure water is added into a stainless steel stirring tank, stirring is carried out, 300 kg of pseudo-boehmite (same as example 1) is added, the materials and the water are mixed into homogeneous slurry, then 30% of dilute nitric acid is added by a peristaltic pump, and the pH value of the slurry is adjusted to 6.5. Heating the slurry to 50 ℃ by adopting electric heating, stirring for 1 hour, and then filtering and washing by adopting a vacuum belt filter to obtain a filter cake with the Na2O content of 0.024%. And transferring the filter cake into a stirring tank with 500L of pure water, stirring, adding 30% dilute nitric acid by using a peristaltic pump, adjusting the pH value of the slurry to 4.5, and heating the material to 80 ℃ by using electric heating so as to fully peptize the pseudo-boehmite. And then adding chemically pure lanthanum nitrate of which the mass of lanthanum oxide accounts for 5 percent of that of alumina in the pseudo-boehmite, and stirring for 30 minutes to fully dissolve the lanthanum nitrate. And (3) dropwise adding 25% diluted ammonia water by using a peristaltic pump to adjust the pH value of the slurry to about 8.0, stirring and aging for 2 hours, and then adding 100004.2 kilograms of PEG accounting for 10% of the mass of the alumina in the pseudo-boehmite. After further stirring for 30 minutes, spray-drying was carried out using a 50 liter/h stainless steel spray tower to obtain a modified pseudoboehmite having a particle size of 25 μm, followed by calcination at 700 ℃ for 1 hour in a tunnel kiln to obtain a high-temperature-resistant activated alumina having a BET specific surface area of 180m2/g, a pore volume of 0.52mL/g, a sodium oxide content of 0.035% (wt%), an iron oxide content of 0.028% (wt%) and a silicon dioxide content of 0.032% (wt%). The high-temperature resistant activated alumina is aged for 12 hours at 1100 ℃, and has the surface area of 105m2/g and the pore volume of 0.42 mL/g.
Claims (10)
1. A preparation method of high temperature resistant active alumina is characterized in that pseudo-boehmite is adopted as a raw material, and the preparation process sequentially comprises the following steps:
(1) Hot dipping pseudo-boehmite to remove impurities;
(2) Preparing the pseudo-boehmite subjected to impurity removal and pure water into slurry, and adding a nitric acid solution to prepare pseudo-boehmite sol;
(3) Adding nitrate into the pseudo-boehmite sol, uniformly stirring, then dropwise adding ammonia water to adjust the pH value of the slurry to 8-9, and stirring and aging;
(4) Adding polyethylene glycol into the aged slurry, and stirring until the polyethylene glycol is completely dissolved;
(5) Spray drying the slurry obtained in the step (4) to obtain modified pseudo-boehmite;
(6) and (4) calcining the modified pseudo-boehmite obtained in the step (5) to obtain the high-temperature-resistant activated alumina.
2. The method as claimed in claim 1, wherein the pseudo-boehmite BET raw material has a specific surface area of 200-300m2/g, a pore volume of 0.4-0.7mL/g, a sodium oxide content of less than 0.08% (wt%), an iron oxide content of less than or equal to 0.020% (wt%), and a silicon dioxide content of less than or equal to 0.02% (wt%).
3. The method as claimed in claim 1, wherein the step (1) of hot-dipping impurity removal treatment of the pseudo-boehmite comprises adding hot pure water into the pseudo-boehmite to prepare slurry with a solid content of 100-600 g/L; then adding nitric acid solution to adjust the pH value of the slurry to 6-7, stirring for 0.5-2 hours, and then filtering by adopting a vacuum belt filter to obtain the pseudo-boehmite filter cake with the sodium oxide content of less than 0.03 percent (wt%).
4. the method according to claim 3, wherein the hot pure water of step (1) is pure water with conductivity less than 100 μ S/cm prepared by reverse osmosis process, and the temperature of the hot pure water is 50-95 ℃.
5. The method according to claim 1, wherein the step (2) comprises preparing a slurry containing 50-300L/g of pseudoboehmite obtained by removing impurities by a wet method and pure water, and adding dropwise a nitric acid solution until the pH value of the slurry is 3-5, thereby sufficiently peptizing the pseudoboehmite.
6. The method for preparing high temperature resistant activated alumina according to claim 1, wherein the nitrate added to the peptized pseudo-boehmite slurry in step (3) is lanthanum nitrate or cerium nitrate, the amount of the lanthanum nitrate or cerium nitrate added is 2% -5% of the mass of the alumina in the pseudo-boehmite, based on the mass of the lanthanum oxide or cerium oxide, and the lanthanum nitrate or cerium nitrate is fully dissolved by stirring.
7. The method according to claim 1, wherein the step (3) comprises adding aqueous ammonia having a mass concentration of 20% to 25% to a slurry of pseudo-boehmite in which lanthanum nitrate or cerium nitrate is sufficiently dissolved, adjusting the pH of the slurry to 8 to 9, heating the slurry, and aging the slurry at 50 to 80 ℃ for 1 to 3 hours with stirring.
8. The method as claimed in claim 1, wherein the step (3) is carried out by adding polyethylene glycol with molecular weight of 4000-10000 to the pseudoboehmite slurry after stirring and aging, wherein the polyethylene glycol accounts for 5-10% of the mass of alumina in the pseudoboehmite.
9. The method for preparing high temperature resistant activated alumina according to claim 1, wherein the step (4) is to dry the polyethylene glycol-dissolved pseudo-boehmite slurry obtained in the step (3) by using a centrifugal spray drying tower to obtain the modified pseudo-boehmite powder with the particle size of 20-80 microns.
10. The method for preparing high temperature resistant activated alumina as claimed in claim 1, wherein the step (5) comprises calcining the pseudoboehmite powder obtained in step (4) at a calcination temperature of 550-750 ℃ for 1-4 hours in a tunnel kiln or a shuttle kiln.
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