CN110540222B - Preparation method of high-temperature-resistant activated alumina - Google Patents
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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 95
- 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 89
- 239000002002 slurry Substances 0.000 claims abstract description 55
- 238000003756 stirring Methods 0.000 claims abstract description 55
- 239000011148 porous material Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 26
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 12
- 230000032683 aging Effects 0.000 claims abstract description 12
- 238000001694 spray drying Methods 0.000 claims abstract description 11
- 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
- 238000007598 dipping method Methods 0.000 claims abstract description 6
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 5
- 238000001354 calcination Methods 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
- 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
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 20
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [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
- 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
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- -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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 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 16
- 230000000694 effects Effects 0.000 abstract description 9
- 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
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000003546 flue gas Substances 0.000 abstract description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 12
- 230000002572 peristaltic effect Effects 0.000 description 12
- 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
- 239000011734 sodium Substances 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
- 150000002910 rare earth metals Chemical class 0.000 description 6
- 150000001342 alkaline earth metals Chemical class 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
- 239000007789 gas Substances 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
- 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
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 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
- 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
- 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 2
- 239000000654 additive Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel 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
- 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 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
- 229910052906 cristobalite 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
- 238000005470 impregnation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004537 pulping 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
- 238000005507 spraying Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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- 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
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- 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
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- 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
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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 of the invention, the specific surface area of the obtained high-temperature resistant activated alumina is not less than 100m2The 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. Catalysis for purifying automobile exhaustThe agent 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 reaches very high temperature frequently, the gamma-Al is easy to be caused2O3Surface sintering and surface orientation to alpha-Al occurs2O3Crystal transformation, thereby causing Al2O3The surface area is drastically reduced and the catalyst is deactivated, so that a good high temperature resistance of the support material is required. 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 alkaline earth metal and SiO are added into the alumina2And rare earth elements, etc., which 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 with a specific surface area of 63m2(ii) in terms of/g. I.M.Tijburg et Al, Netherlands (J.Mater.Sci., 26, 6479-2O3Then preparing high-temperature resistant activated alumina, and calcining the activated alumina prepared by the method at 1050 ℃ for 145 hours to ensure that the specific surface area of the activated alumina can be maintained at 80m2(ii) in terms of/g. Japanese patent (JP03088713) describes the maintenance of a specific surface of 100m after calcination of an alumina surface-impregnated alkaline earth metal salt at 1000 ℃2(ii) in terms of/g. French patent (FP2596397) introduces that the specific surface is kept between 50 and 60m after the surface of alumina is impregnated with rare earth metal salt and calcined at 1150 ℃ for 12 hours2/g。
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 an EDTA pore-expanding agent and La2O3Compound synthesized for thermal stabilizer H [ La (EDTA)].16H2The O crystal is used as a main raw material, and a solid-solid mixing technology is adopted to prepare the high-temperature-resistant high-specific surface area active alumina, so that the process for preparing the high-temperature-resistant high-specific surface area active alumina which is stable at 1200 ℃ is realized.
The patent "a high-temperature resistant active alumina material and its preparation method" (CN201110410339.5) is to make it be made into the form of powderMixing the porous pseudo-boehmite, the high-viscosity pseudo-boehmite and the additive with water, uniformly stirring at the rotating speed of 100-1000 r/min, adding 30% dilute nitric acid for reaction, aging at the temperature of 80-100 ℃ for 3-6 hours under stirring when the pH is in a peptization state of 2.0-5.5, adding a pore-forming agent at room temperature, uniformly stirring, pulping, spraying, drying, and roasting at 900 ℃ to obtain the alumina. The alumina material can keep the specific surface at 110m for a long time at the temperature of 1000-1100 DEG C2More than g.
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 alumina is 0.1-10 wt%, the alumina solid is treated for 5 hours in the air atmosphere at 700 ℃, and the specific surface area of the alumina solid is more than 350m2The specific structure area is as follows,/g, the average pore volume is 0.3122mL/g, the average pore diameter is 5.23nm, and the pore diameter distribution range is 3-12 nm. Treating at 1100 deg.C in air atmosphere for 5h, and its specific surface area is greater than 150m2/g。
The method mainly adopts pseudo-boehmite or gamma-Al2O3Alkaline earth metal or rare earth metal is impregnated to prepare 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 preparation method of the high-temperature resistant active alumina is characterized in that the adopted pseudoboehmite raw material has the specific surface area (BET) of 200-300m2The content of sodium oxide is less than 0.08 percent (wt%), the content of ferric oxide is less than or equal to 0.020 percent (wt%), and the content of silicon dioxide is less than or equal to 0.02 percent.
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 activated alumina, which adopts pseudo-boehmite with low silicon, low iron and medium pore volume prepared by a sodium aluminate solution neutralization method as a raw material, 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 obtains high-temperature resistant activated alumina after roasting, wherein the BET specific surface area of the high-temperature resistant activated alumina is 150-200 m-2The pore volume is more than 0.5mL/g, the content of sodium oxide is less than 0.05 percent (wt percent), the content of ferric oxide is less than or equal to 0.030 percent (wt percent), and the content of silicon dioxide is less than or equal to 0.03 percent (wt percent). The high temperature resistant activated alumina is aged for 12 hours at 1100 ℃, and the surface area is not less than 100m2The 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. Loading the modified pseudo-boehmite powder into a clean sagger, roasting in a tunnel kiln or a shuttle kiln at the temperature of 550-750 ℃ for 1-4 hours to obtain the high-temperature-resistant activated alumina with the BET specific surface area of 150-200m2The pore volume is more than 0.5mL/g, the content of sodium oxide is less than 0.05 percent (wt percent), the content of ferric oxide is less than or equal to 0.030 percent (wt percent), and the content of silicon dioxide is less than or equal to 0.03 percent (wt percent). The high temperature resistant activated alumina is aged for 12 hours at 1100 ℃, and the surface area is not less than 100m2The pore volume is not less than 0.4 mL/g.
Example 1
500L of pure water was added to a stainless steel stirring vessel, and after stirring, pseudoboehmite (BET specific surface area 313 m) was added2Per g, pore volume 0.47ml/g, ignition loss 31%, SiO2The content is 0.023%; fe2O3The content is 0.020%; na (Na)2O content 0.05%) to 200 kg, mixing the materials with water to obtain homogeneous slurry, adding 30% dilute nitric acid by a peristaltic pump, and adjusting the pH value of the slurry to 6.5. Heating the slurry to 70 deg.C by electric heating, stirring for 1.5 hr, filtering and washing with vacuum belt filter to obtain filter cake Na2The O content is 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. Continuously stirring for 30 minutes, performing spray drying by adopting a stainless steel spray tower of 50 liters/h to obtain modified pseudo-boehmite with the particle size of 30 microns, and then roasting in a tunnel kiln at 600 ℃ for 3 hours to obtain high-temperature-resistant activated alumina with the BET specific surface area of 180m2The specific surface area of the silica gel is 0.032%, and the specific surface area of the silica gel is 0.035% (wt%), 0.030% (wt%) and 0.032% (wt%). The high-temperature resistant activated alumina is aged for 12 hours at 1100 ℃, and the surface area is 110m2G, pore volume 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 deg.C by electric heating, stirring for 1 hr, filtering and washing with vacuum belt filter to obtain filter cake Na2The O content is 0.022%. Transferring the filter cake intoStirring in a stirring tank with 500L of pure water, adding 30% dilute nitric acid by a peristaltic pump, adjusting the pH value of the slurry to 4.5, and heating the material to 50 ℃ by electric heating 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. Stirring for 60 min, spray drying in a 50L/h stainless steel spray tower to obtain modified pseudoboehmite with particle size of 30 micron, and roasting in a tunnel kiln at 650 deg.c for 3 hr to obtain high temperature resistant active alumina with BET specific surface area of 200m2The content of sodium oxide is 0.032% (wt%), the content of ferric oxide is 0.028% (wt%), and the content of silicon dioxide is 0.032% (wt%). The high-temperature resistant activated alumina is aged for 12 hours at 1100 ℃, and the surface area is 115m2G, pore volume 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 deg.C by electric heating, stirring for 1 hr, filtering and washing with vacuum belt filter to obtain filter cake Na2The O content is 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. Continuously stirring for 30 minutes, carrying out spray drying by adopting a stainless steel spray tower of 50 liters/h,obtaining modified pseudo-boehmite with the granularity of 50 microns, and then roasting the pseudo-boehmite in a tunnel kiln for 2 hours at 700 ℃ to obtain high-temperature-resistant activated alumina with the BET specific surface area of 216m20.67mL/g of pore volume, 16.53nm of pore diameter, 30 μm of average particle size, 0.032% (wt%) of sodium oxide, 0.028% (wt%) of iron oxide, and 0.032% (wt%) of silicon dioxide. The high-temperature resistant activated alumina is aged for 12 hours at 1100 ℃, and the surface area is 115m2G, pore volume 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 deg.C by electric heating, stirring for 1 hr, filtering and washing with vacuum belt filter to obtain filter cake Na2The O content is 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. Stirring for 30 min, spray drying in a 50L/h stainless steel spray tower to obtain modified pseudoboehmite with particle size of 25 micron, and roasting in a tunnel kiln at 700 deg.c for 1 hr to obtain high temperature resistant active alumina with BET specific surface area of 180m2The content of sodium oxide is 0.035% (wt%), the content of ferric oxide is 0.028% (wt%) and the content of silicon dioxide is 0.032% (wt%). The high-temperature resistant activated alumina is aged for 12 hours at 1100 ℃, and the surface area is 105m2G, pore volume 0.42 mL/g.
Claims (6)
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; the process of hot dipping and impurity removing of the pseudo-boehmite is to add hot pure water into the pseudo-boehmite to prepare slurry with solid content of 100-600 g/L; adding nitric acid solution to adjust the pH value of the slurry to 6-7, stirring for 0.5-2 hours, and filtering by using a vacuum belt filter to obtain a pseudo-boehmite filter cake with the sodium oxide content of less than 0.03 percent (wt%);
(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, wherein the added nitrate is lanthanum nitrate or cerium nitrate, the addition amount of the lanthanum nitrate or the cerium nitrate is 2-5% of the mass of aluminum oxide in the pseudo-boehmite according to the mass of lanthanum oxide or cerium oxide, and stirring to fully dissolve the lanthanum nitrate or the cerium nitrate; after stirring uniformly, dropwise adding ammonia water to adjust the pH value of the slurry to 8-9, and stirring and aging;
(4) adding a polyethylene glycol pore-expanding agent which accounts for 5-10% of the mass ratio of the alumina in the pseudoboehmite into the aged pseudoboehmite slurry, wherein the molecular weight of the polyethylene glycol is 4000-10000, 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) calcining the modified pseudo-boehmite obtained in the step (5) at the roasting temperature of 550-750 ℃ for 1-4 hours in a tunnel kiln or a shuttle kiln to obtain the high-temperature-resistant activated alumina with the BET specific surface area of 150-200m2The content of sodium oxide is less than 0.05 percent (wt%), the content of ferric oxide is less than or equal to 0.030 percent (wt%) and the content of silicon dioxide is less than or equal to 0.03 percent (wt%); the high temperature resistant activated alumina is aged for 12 hours at 1100 ℃, and the specific surface area is not less than 100m2The pore volume is not less than 0.4 mL/g.
2. The method for preparing high temperature resistant activated alumina according to claim 1,the method is characterized in that the adopted pseudoboehmite raw material has the BET specific surface area of 200-300m2The 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% (wt%).
3. The method according to claim 1, 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 ℃.
4. 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.
5. 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.
6. 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.
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