CN115215360B - Method for improving load capacity of pseudo-boehmite supported catalyst - Google Patents
Method for improving load capacity of pseudo-boehmite supported catalyst Download PDFInfo
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- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 title claims abstract description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000000654 additive Substances 0.000 claims abstract description 51
- 230000000996 additive effect Effects 0.000 claims abstract description 51
- 238000001035 drying Methods 0.000 claims abstract description 33
- 239000011259 mixed solution Substances 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 30
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 24
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 22
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 21
- 239000012530 fluid Substances 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 14
- 238000011068 loading method Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000012046 mixed solvent Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 42
- 239000004408 titanium dioxide Substances 0.000 claims description 20
- 238000004321 preservation Methods 0.000 claims description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical group [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 7
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000010583 slow cooling Methods 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 5
- 230000007774 longterm Effects 0.000 claims 1
- 239000013078 crystal Substances 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 26
- 230000008569 process Effects 0.000 description 12
- 230000004048 modification Effects 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- -1 alkoxy aluminium Chemical compound 0.000 description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 3
- 159000000013 aluminium salts Chemical class 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 150000004682 monohydrates Chemical class 0.000 description 3
- 230000000877 morphologic effect Effects 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-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
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000012208 gluconic acid Nutrition 0.000 description 2
- 239000000174 gluconic acid Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 101150116295 CAT2 gene Proteins 0.000 description 1
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- PIYVNGWKHNMMAU-UHFFFAOYSA-N [O].O Chemical compound [O].O PIYVNGWKHNMMAU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012684 catalyst carrier precursor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910006636 γ-AlOOH Inorganic materials 0.000 description 1
Classifications
-
- 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
- C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides a method for improving the loading capacity of a pseudo-boehmite supported catalyst, which comprises the following steps: s1, adding aluminum salt and a first additive into a mixed solvent to obtain a mixed solution A; s2.50 ℃ magnetic stirring, dropwise adding oxalic acid solution into the mixed solution A obtained in the step S1 three times to obtain sol; s3, dissolving aluminum hydroxide in water, then adding a second additive, and continuously stirring to obtain a mixed solution B; s4, drying the sol supercritical fluid obtained in the step S2 into powder, adding the powder into the mixed solution B obtained in the step S3, uniformly stirring, and then placing the mixture into a reaction kettle for hydrothermal reaction to obtain a reaction product; s5, centrifuging, washing and calcining the reaction product obtained in the step S4 to obtain pseudo-boehmite; the specific surface area of the pseudo-boehmite obtained by the invention is not less than 400m 2 And/g, the aperture shrinkage at high temperature is within 5%.
Description
Technical Field
The invention belongs to the field of fine chemical synthesis, and particularly relates to a method for improving the loading capacity of a pseudo-boehmite supported catalyst.
Background
Pseudo-boehmite (pseudo-boehmite) is a chemical alumina with uncertain composition, incomplete crystallization and controllable performance, and has the chemical formula of gamma-AlOOH.nH 2 O (n=0.08 to 0.62). It is nontoxic, tasteless, white colloid (wet product) or powder (dry powder), has reticular space structure, large gap, developed specific surface area, thixotropic property under acidic environment, etc. At present, active alumina is used as a catalyst carrier in the petrochemical industry field, and the active alumina is mostly obtained by calcining pseudo-boehmite, so that the morphology and the particle size of the pseudo-boehmite determine the morphology and the specific surface area of the alumina.
Pseudo-boehmite as a raw material for alumina catalyst supports is generally prepared by the following method: (1) Alkali precipitation, i.e. neutralisation of an acidified aluminium salt with alkali, precipitation of oxygen monohydrate from a solution of the acidified aluminium salt with alkaliAluminum is converted, and pseudo-boehmite products are obtained through the processes of aging, washing, calcining and the like, and the method is commonly called an alkali precipitation (acid method), such as a method for neutralizing aluminum trichloride by ammonia water; (2) Acid precipitation, i.e. neutralization of aluminates with strong acids or aluminium salts of strong acids, by precipitating alumina monohydrate from the aluminate solution with acid, and then aging, washing, calcining, etc. to give pseudo-boehmite products, commonly known as acid precipitation (alkaline process), e.g. CO 2 A method for neutralizing sodium metaaluminate by gas or aluminum sulfate; (3) The hydrolysis of alkoxy aluminium is carried out on the alkoxy aluminium and water to generate alumina monohydrate, and then the alumina monohydrate is aged, filtered and dried to obtain the pseudo-boehmite product. It can be seen that the process of preparing pseudo-boehmite generally consists of the processes of grain formation (neutralization precipitation or hydrolysis process), grain growth (aging process), washing, calcination, etc. Therefore, the process conditions of grain generation and grain growth can influence the quantity and growth speed of grain generation, and the preparation processes of various pseudo-boehmite all provide respective process conditions and improved methods so as to achieve the purpose of controlling the physical properties of the product, such as pore volume, specific surface area and the like.
Specifically, as disclosed in patent CN 103787387B, a method for preparing pseudo-boehmite is disclosed, wherein stability of sodium metaaluminate solution is prolonged by using gluconic acid and alkali metal salt of gluconic acid, and specific surface area of the prepared pseudo-boehmite reaches 315m at maximum 2 And/g. Further, as disclosed in CN1861524, a process for producing pseudo-boehmite comprises adding 6-18 g of melamine (CA) as a pore-expanding agent into 60-180 g/L sodium aluminate solution containing aluminum oxide, dissolving and filtering, and gelling with 20-40 g/L acidified aluminum salt solution containing aluminum oxide; the gel forming temperature is 50-90 ℃, the gel forming pH value is 6.5-8.5, solid-liquid separation, filtering, washing, drying and adhering water, roasting and crystal transformation for 4-10 hours at 320-350 ℃, and crushing to obtain the pseudo-boehmite finished product, wherein the specific surface area is up to 331m at maximum 2 And/g. In addition, as in the preparation of pseudo-boehmite with large pore volume and high specific surface area, SB powder is used as seed crystal, and the seed crystal is added into sodium aluminate solution to make hydrothermal decomposition, and then cooled, vacuum filtered, washed to neutrality, washed with alcohol,The pseudo-boehmite is obtained after the calcination process, and the specific surface area is 176.8-213.6 m 2 And/g. Although the specific surface area of the pseudo-boehmite is improved to a certain extent, the problems that the preparation time is long, the pore size forming and the structure stability of the product are influenced by gas released by the template removal still exist.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a method for improving the loading capacity of a pseudo-boehmite supported catalyst, which can effectively improve the specific surface area and the morphological structure stability of the pseudo-boehmite, further improve the specific surface area and the morphological structure stability of the pseudo-boehmite directly used as a catalyst carrier or an alumina catalyst carrier precursor, and finally achieve the aim of improving the loading capacity.
In order to achieve the above object, the present invention provides a method for increasing the loading of a pseudo-boehmite supported catalyst, comprising the steps of:
s1, adding aluminum salt and a first additive into a mixed solvent to obtain a mixed solution A;
s2.50 ℃ magnetic stirring, dropwise adding oxalic acid solution into the mixed solution A obtained in the step S1 three times to obtain sol;
s3, dissolving aluminum hydroxide in water, then adding a second additive, and continuously stirring to obtain a mixed solution B;
s4, drying the sol supercritical fluid obtained in the step S2 into powder, adding the powder into the mixed solution B obtained in the step S3, uniformly stirring, and then placing the mixture into a reaction kettle for hydrothermal reaction to obtain a reaction product;
s5, centrifuging, washing and calcining the reaction product obtained in the step S4 to obtain the pseudo-boehmite.
According to the technical scheme, the modified seed crystal is prepared by the sol method through S1-2, the growth solution is prepared through S3, the seed crystal is dried and shaped through supercritical fluid drying, the shaped seed crystal is added into the growth solution to obtain a long and large decomposition product through hydrothermal reaction, and the pseudo-boehmite with high specific surface area and stable morphology and structure is obtained through S5 calcination and crystal transformation. Specifically, in S1, a sol method is adopted to prepare seed crystals, the raw materials are dispersed in a solvent, then the active monomers are generated through hydrolysis reaction, and the active monomers are polymerized to form a sol. Since the raw materials used in the sol method are firstly dispersed into the solvent to form a low-viscosity solution, the uniformity of the molecular level can be obtained in a short time, so that the grain size of the seed crystal obtained by the sol method is relatively uniform, and the control of the grain size uniformity of the follow-up pseudo-boehmite seed crystal is facilitated. In the step, a first additive is directly added to exert the steric hindrance effect, so that the binding force between pseudo-boehmite crystal seeds is weakened in sol, and the gap holes are enlarged, thereby generating macropores. In addition, the modified substance is added during solution preparation, and other elements are easily and uniformly and quantitatively doped through a solution reaction step, so that uniform doping on the molecular level is realized, and the modification of the specific surface area and the structural stability of the pseudo-boehmite by the modified substance is finally realized. In S2, the pH of the solution is changed by adding the oxalic acid solution three times, and the interstitial pores of the seed particles are enlarged by utilizing the pH fluctuation in the process, thereby promoting the increase of the volume of the seed particles and pores. In S4, before the hydrothermal reaction, the sol crystal seed is subjected to supercritical fluid drying and shaping, so that the crystal seed is dried when a drying medium is in a critical temperature and critical pressure state, the crystal seed cannot shrink or crack, the original structure and state can be maintained to a great extent, and agglomeration is effectively prevented. Specifically, the drying medium enters the seed crystal in the supercritical state to be subjected to mild and rapid exchange with solvent molecules to replace the solvent, and then the fluid is changed into gas from the supercritical state and released from the dried seed crystal, so that the seed crystal drying effect is achieved, and the seed crystal structure is ensured not to shrink and deform. And adding the shaped and non-agglomerated seed crystal into a growth solution, directly precipitating crystal nuclei of aluminum hydroxide in the growth solution onto the surface of the shaped seed crystal for growth, and modifying by a second additive to finally lead to easier generation of pseudo-boehmite crystal nuclei, larger generated crystal grains and uniform particle size. In S5, the crystallinity and the integrity of the pseudo-boehmite are improved through sintering, and the additive is subjected to crystal form conversion, so that the modified pseudo-boehmite with large specific surface area and stable structure is finally formed.
Further, in step S1, the aluminum salt is one of aluminum isopropoxide, aluminum hydroxide or aluminum chloride.
Further, in the step S1, the concentration of the aluminum salt is 0.5-2mol/L.
Further, in the step S1, the first additive is butyl titanate and diethanolamine which can react to generate titanium dioxide, and the concentration of the titanium dioxide is 0.1-0.5mol/L.
Further, in step S1, the molar ratio of the aluminum salt to the first additive is 10: (0.1-1).
In step S1, the mixed solvent is anhydrous ethanol and deionized water with the volume ratio of (6-10) being 1. The preferred volume ratio is 8:1.
further, in step S2, the oxalic acid solution finally adjusts the pH of the sol to 6.5-7.5.
By adopting the technical scheme, tiO is prepared by taking butyl titanate as a titanium source and diethanolamine as a hydrolysis inhibitor 2 The precursor is used for preparing the pseudo-boehmite for the first time, and the large amount of absolute ethyl alcohol in the solvent can promote the decomposition of the raw materials and the dispersion of the raw materials, so that the crystal grains are more complete and the crystallinity is higher. When oxalic acid is combined with transitional metallic titanium element, a soluble complex is formed due to the coordination effect of oxalic acid, the solubility of the complex is greatly increased, and finally, the prepared pseudo-boehmite seed crystal has large particle size, high load titanium, less surface moisture and water and difficult hard agglomeration, so that the specific surface is reduced, and the obtained modified seed crystal has large particle size and large specific surface area.
Further, in step S3, the supercritical fluid drying is high temperature supercritical organic solvent drying or low temperature supercritical CO 2 And (5) drying. Preferably low temperature supercritical CO 2 And (5) drying. Although the supercritical fluid drying process is mild, the damage to the structure of the object caused by the stress action when the object to be dried is dried can be avoided to a greater extent. But low temperature supercritical CO 2 The drying temperature is lower than that of the supercritical organic solvent, the supercritical organic solvent is close to room temperature, is nontoxic, is not flammable and explosive, and is milder and easier to dry and protect the modified seed crystal structure compared with the organic solvent which is toxic and has safety problems.
Further, in step S3, the concentration of the aluminum hydroxide in the mixed solution B is 0.2-0.4mol/L.
Further, in step S3, the second additive is thiourea or urea.
Further, in step S3, the molar ratio of the second additive to the aluminum hydroxide is (5-10): 1.
By adopting the technical scheme, the second additive is added in excess, so that one part of the second additive is used as a precipitator, and the excess part of the second additive is used as a precursor of the carbon-nitrogen modified substance. Specifically, the carbon-nitrogen modifier can be a shelf-like graphene with a stable structure, and the carbon-nitrogen modifier has the characteristic of large specific surface area due to a shelf-like multilayer structure.
Further, in the step S4, the temperature of the hydrothermal reaction is 120-180 ℃ and the time is 3 hours.
Further, in step S5, the calcination is to heat up to 500 ℃ rapidly, heat up briefly, cool down to 300 ℃ slowly, and heat up for a long time.
By adopting the technical scheme, substances such as water and the like are quickly removed through quick temperature rise, a fine and uniform pore structure is formed in the inner part, short heat preservation is beneficial to reducing grain growth and keeping a stable morphological structure, the temperature is raised to 500 ℃, and TiO is promoted under the condition that the pseudo-boehmite is ensured not to be transformed in crystal form 2 The precursor and the precursor of the carbon-nitrogen modifier are respectively oriented to TiO 2 And graphene-like conversion to ultimately form TiO 2 Pseudo-boehmite modified with graphene-like material and TiO-based material 2 And the graphene-like material has larger specific surface area under the simultaneous modification. Finally, slowly cooling and preserving heat for a long time to eliminate the tiny dehydration pore structure in the pseudo-boehmite, improve the density and further improve the structural stability.
Further, in the step S5, the rapid heating rate is 8-12 ℃/min, the short heat preservation time is 10-15min, the slow cooling rate is 1-2 ℃/min, and the long heat preservation time is 1-2h.
Compared with the prior art, the invention has the following beneficial effects:
the invention prepares the modified seed crystal with large grain diameter and large specific surface area by doping in sol by sol method and pH swing method, then dries and shapes the modified seed crystal by supercritical fluid drying, then grows by directly taking the shaped seed crystal as a nucleus in growth solution by hydrothermal method, and is modified again, finally obtains pseudo-boehmite by calcination process of rapid temperature rise, short heat preservation, slow temperature reduction and long-time heat preservation, and the specific surface area of the obtained pseudo-boehmite is not less than 400m 2 And/g, the aperture shrinkage at high temperature is within 5%.
Detailed Description
The invention is further described in connection with the following detailed description, in order to make the technical means, the creation characteristics, the achievement of the purpose and the effect of the invention easy to understand.
The invention provides a method for improving the loading capacity of a pseudo-boehmite supported catalyst, which comprises the following steps:
s1, adding aluminum salt and a first additive into a mixed solvent to obtain a mixed solution A;
s2.50 ℃ magnetic stirring, dropwise adding oxalic acid solution into the mixed solution A obtained in the step S1 three times to obtain sol;
s3, dissolving aluminum hydroxide in water, then adding a second additive, and continuously stirring to obtain a mixed solution B;
s4, drying the sol supercritical fluid obtained in the step S2 into powder, adding the powder into the mixed solution B obtained in the step S3, uniformly stirring, and then placing the mixture into a reaction kettle for hydrothermal reaction to obtain a reaction product;
s5, centrifuging, washing and calcining the reaction product obtained in the step S4 to obtain the pseudo-boehmite.
Specifically, in step S1, the aluminum salt is one of aluminum isopropoxide, aluminum hydroxide or aluminum chloride.
Specifically, in step S1, the concentration of the aluminum salt is 0.5 to 2mol/L.
Specifically, in the step S1, the first additive is butyl titanate and diethanolamine which can react to generate titanium dioxide, and the concentration of the titanium dioxide is 0.1-0.5mol/L.
Specifically, in step S1, the molar ratio of aluminum salt to the first additive is 10: (0.1-1).
Specifically, in step S1, the mixed solvent is anhydrous ethanol and deionized water with the volume ratio of (6-10): 1. The preferred volume ratio is 8:1.
specifically, in step S2, the oxalic acid solution finally adjusts the pH value of the sol to be 6.5-7.5.
Specifically, in step S3, the supercritical fluid drying is high temperature supercritical organic solvent drying or low temperature supercritical CO 2 And (5) drying. Preferably low temperature supercritical CO 2 And (5) drying.
Specifically, in step S3, the concentration of aluminum hydroxide in the mixed solution B is 0.2-0.4mol/L.
Specifically, in step S3, the second additive is thiourea or urea.
Specifically, in step S3, the molar ratio of the second additive to aluminum hydroxide is (5-10): 1.
Specifically, in step S4, the temperature of the hydrothermal reaction is 120-180 ℃ and the time is 3h.
Specifically, in step S5, calcination is performed by rapidly heating to 500 ℃ and then briefly preserving heat, and then slowly cooling to 300 ℃ and then preserving heat for a long time.
Specifically, in the step S5, the rapid heating rate is 8-12 ℃/min, the short heat preservation time is 10-15min, the slow cooling rate is 1-2 ℃/min, and the long heat preservation time is 1-2h.
Specific examples are given below:
example 1
A method for increasing the loading of a pseudo-boehmite supported catalyst comprising the steps of:
s1, adding aluminum salt and a first additive into a mixed solvent to obtain a mixed solution A;
s2.50 ℃ magnetic stirring, dropwise adding oxalic acid solution into the mixed solution A obtained in the step S1 three times to obtain sol;
s3, dissolving aluminum hydroxide in water, then adding a second additive, and continuously stirring to obtain a mixed solution B;
s4, drying the sol supercritical fluid obtained in the step S2 into powder, adding the powder into the mixed solution B obtained in the step S3, uniformly stirring, and then placing the mixture into a reaction kettle for hydrothermal reaction to obtain a reaction product;
s5, centrifuging, washing and calcining the reaction product obtained in the step S4 to obtain the pseudo-boehmite.
In this embodiment, in step S1, the aluminum salt is aluminum isopropoxide.
In this example, in step S1, the concentration of the aluminum salt was 0.8mol/L.
In this example, in step S1, the first additive is butyl titanate and diethanolamine which react to form titanium dioxide, the concentration of titanium dioxide being 0.15mol/L.
In this example, in step S1, the molar ratio of aluminum salt to the first additive is 10:0.5.
in this embodiment, in step S1, the mixed solvent is anhydrous ethanol and deionized water in a volume ratio of 8:1.
In this example, in step S2, the oxalic acid solution finally adjusts the pH of the sol to 7.
In this embodiment, in step S3, the supercritical fluid is dried to low temperature supercritical CO 2 And (5) drying.
In this example, in step S3, the concentration of aluminum hydroxide in the mixed solution B was 0.25mol/L.
In this embodiment, in step S3, the second additive is urea.
In this example, in step S3, the molar ratio of the second additive to aluminum hydroxide is 8:1.
In this example, in step S4, the hydrothermal reaction was carried out at 180℃for 3 hours.
In this embodiment, in step S5, calcination is performed by rapidly heating to 500 ℃ and then briefly maintaining the temperature, and then slowly cooling to 300 ℃ and then maintaining the temperature for a long time. The rapid heating rate is 10 ℃/min, the short heat preservation time is 10min, the slow cooling rate is 2 ℃/min, and the long heat preservation time is 2h.
Example 2
A method for increasing the loading of a pseudo-boehmite supported catalyst comprising the steps of:
s1, adding aluminum salt and a first additive into a mixed solvent to obtain a mixed solution A;
s2.50 ℃ magnetic stirring, dropwise adding oxalic acid solution into the mixed solution A obtained in the step S1 three times to obtain sol;
s3, dissolving aluminum hydroxide in water, then adding a second additive, and continuously stirring to obtain a mixed solution B;
s4, drying the sol supercritical fluid obtained in the step S2 into powder, adding the powder into the mixed solution B obtained in the step S3, uniformly stirring, and then placing the mixture into a reaction kettle for hydrothermal reaction to obtain a reaction product;
s5, centrifuging, washing and calcining the reaction product obtained in the step S4 to obtain the pseudo-boehmite.
In this embodiment, in step S1, the aluminum salt is aluminum hydroxide.
In this example, in step S1, the concentration of the aluminum salt was 0.5mol/L.
In this example, in step S1, the first additive is butyl titanate and diethanolamine which react to form titanium dioxide, the concentration of titanium dioxide being 0.1mol/L.
In this example, in step S1, the molar ratio of aluminum salt to the first additive is 10:0.1.
in the embodiment, in step S1, the mixed solvent is anhydrous ethanol and deionized water in a volume ratio of 6:1.
In this example, in step S2, the oxalic acid solution finally adjusts the pH of the sol to 6.5.
In this embodiment, in step S3, the supercritical fluid drying is a high temperature supercritical organic solvent drying.
In this example, in step S3, the concentration of aluminum hydroxide in the mixed solution B was 0.2mol/L.
In this embodiment, in step S3, the second additive is thiourea.
In this example, in step S3, the molar ratio of the second additive to aluminum hydroxide is 5:1.
In this example, in step S4, the hydrothermal reaction was carried out at 120℃for 3 hours.
In this embodiment, in step S5, calcination is performed by rapidly heating to 500 ℃ and then briefly maintaining the temperature, and then slowly cooling to 300 ℃ and then maintaining the temperature for a long time. The rapid heating rate is 8 ℃/min, the short heat preservation time is 12min, the slow cooling rate is 1.5 ℃/min, and the long heat preservation time is 1.5h.
Example 3
A method for increasing the loading of a pseudo-boehmite supported catalyst comprising the steps of:
s1, adding aluminum salt and a first additive into a mixed solvent to obtain a mixed solution A;
s2.50 ℃ magnetic stirring, dropwise adding oxalic acid solution into the mixed solution A obtained in the step S1 three times to obtain sol;
s3, dissolving aluminum hydroxide in water, then adding a second additive, and continuously stirring to obtain a mixed solution B;
s4, drying the sol supercritical fluid obtained in the step S2 into powder, adding the powder into the mixed solution B obtained in the step S3, uniformly stirring, and then placing the mixture into a reaction kettle for hydrothermal reaction to obtain a reaction product;
s5, centrifuging, washing and calcining the reaction product obtained in the step S4 to obtain the pseudo-boehmite.
In this embodiment, in step S1, the aluminum salt is aluminum chloride.
In this example, in step S1, the concentration of the aluminum salt was 2mol/L.
In this example, in step S1, the first additive is butyl titanate and diethanolamine which react to form titanium dioxide, the concentration of titanium dioxide being 0.5mol/L.
In this example, in step S1, the molar ratio of aluminum salt to the first additive is 10:1.
in the embodiment, in step S1, the mixed solvent is absolute ethanol and deionized water in a volume ratio of 10:1.
In this example, in step S2, the oxalic acid solution finally adjusts the pH of the sol to 7.5.
In this embodiment, in step S3, the supercritical fluid is dried to low temperature supercritical CO 2 And (5) drying.
In this example, in step S3, the concentration of aluminum hydroxide in the mixed solution B was 0.4mol/L.
In this embodiment, in step S3, the second additive is urea.
In this example, in step S3, the molar ratio of the second additive to aluminum hydroxide is 10:1.
In this example, in step S4, the hydrothermal reaction was carried out at 180℃for 3 hours.
In this embodiment, in step S5, calcination is performed by rapidly heating to 500 ℃ and then briefly maintaining the temperature, and then slowly cooling to 300 ℃ and then maintaining the temperature for a long time. The rapid heating rate is 12 ℃/min, the short heat preservation time is 15min, the slow cooling rate is 1 ℃/min, and the long heat preservation time is 1h.
Comparative example 1
In this comparative example, the first additive in step S1 was directly titanium dioxide powder. The other experimental procedures were exactly the same as those of example 1, except that the experimental procedure was otherwise identical.
Comparative example 2
In this comparative example, the first additive was not added in step S1. The other experimental procedures were exactly the same as those of example 1, except that the experimental procedure was otherwise identical.
Comparative example 3
In this comparative example, oxalic acid added in step S2 was added at one time. Other experimental procedures were exactly the same as those of example 1, except for the above.
Comparative example 4
In this comparative example, the second additive added in step S3 was not excessively added. Other experimental procedures were exactly the same as those of example 1, except for the above.
Comparative example 5
In this comparative example, ordinary vacuum drying was employed in step S4. Other experimental procedures were exactly the same as those of example 1, except for the above.
Comparative example 6
In this comparative example, the calcination process in step S5 was to raise the temperature to 500℃at 2℃per minute and then to keep the temperature for 2 hours. Other experimental procedures were exactly the same as those of example 1, except for the above.
Testing and analysis
The specific surface areas of the pseudo-boehmite obtained in examples 1 to 3 and comparative examples 1 to 6 were measured by a low temperature liquid nitrogen adsorption method, then the pseudo-boehmite obtained in examples 1 to 3 and comparative examples 1 to 6 was subjected to high temperature calcination heat treatment at 800℃for 10 hours and at 900℃for 10 hours, respectively, and the specific surface areas of the pseudo-boehmite after the high temperature calcination heat treatment was measured again by a low temperature liquid nitrogen adsorption method, and the pore shrinkage after calcination at 800℃and at 900℃was calculated by the change of the specific surface areas, respectively, and the test results are shown in Table 1.
TABLE 1 test results for examples 1-3 and comparative examples 1-6
As can be seen from Table 1, the pseudo-boehmite obtained in examples 1-3 has a specific surface area of not less than 400m 2 And/g, the aperture shrinkage rate at high temperature is within 5%, and the structural stability is good. As can be seen from comparison of examples 1-3 and comparative examples 1 and 2, comparative example 1 directly adds titanium dioxide for modification of titanium dioxide, comparative example 2 does not use a first additive, only uses a second additive for modification of graphene-like material, and the increase of specific surface area of pseudo-boehmite is limited, which also shows that examples 1-3 add titanium dioxide raw materials in solution preparation by a sol method, and the titanium dioxide raw materials are easy to uniformly and quantitatively dope through a solution reaction step, so that uniform doping preparation on molecular level is realized, and when oxalic acid is combined with transitional metallic titanium element after oxalic acid is added dropwise, a soluble complex is formed, the solubility of the complex is increased, and finally the beneficial effect of increasing the specific surface area of pseudo-boehmite is realized. By comparison with comparative example 3, it can be seen that the number of times of dropping oxalic acid, specific surface area of pseudo-boehmiteThe more the number of dropping times is, the more pH variation is easily caused, the solubility of the complex after the oxalic acid and the transitional metallic titanium element are combined is increased more and more, the clearance holes of the seed crystal particles are increased more and more, and the increase of the volume of the seed crystal particles and the hole is promoted. As can be seen by comparison with comparative example 4, comparative example 4 uses only the first additive and does not use the second additive to perform the primary titanium dioxide modification of pseudo-boehmite, and also has a limited increase in the specific surface area of pseudo-boehmite. In combination with comparative example 1, it was found that the specific surface area effect of the single titania-modified pseudo-boehmite was limited, regardless of whether the titania-modified pseudo-boehmite or the primary titania-modified pseudo-boehmite. Compared with the single graphene-like modified pseudo-boehmite of comparative example 2, the effect of increasing the specific surface area by the independent titanium dioxide modification is not as good as that by the independent graphene-like modification, but the high-temperature aperture shrinkage rate of the pseudo-boehmite after the independent graphene-like modification is not as good as that of the pseudo-boehmite after the independent titanium dioxide modification, which indicates that the structural stability of the pseudo-boehmite modified by the independent titanium dioxide is better. As can be seen from comparison with comparative examples 5 and 6, comparative example 5 uses ordinary drying, comparative example 6 uses calcination with slow temperature rise and long time heat preservation, and the obtained pseudo-boehmite has a large specific surface area through two modifications, but the aperture shrinkage rate is large at high temperature, which indicates that the drying and calcination modes have a critical effect on the structural stability of the pseudo-boehmite with large specific surface area.
While the fundamental and principal features of the invention and advantages of the invention have been shown and described, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (8)
1. A method for increasing the loading of a pseudo-boehmite supported catalyst, comprising the steps of:
s1, adding aluminum salt and a first additive into a mixed solvent to obtain a mixed solution A;
s2.50 ℃ magnetic stirring, dropwise adding oxalic acid solution into the mixed solution A obtained in the step S1 three times to obtain sol;
s3, dissolving aluminum hydroxide in water, then adding a second additive, and continuously stirring to obtain a mixed solution B;
s4, drying the sol supercritical fluid obtained in the step S2 into powder, adding the powder into the mixed solution B obtained in the step S3, uniformly stirring, and then placing the mixture into a reaction kettle for hydrothermal reaction to obtain a reaction product;
s5, centrifuging, washing and calcining the reaction product obtained in the step S4 to obtain pseudo-boehmite;
wherein:
in the step S1, the first additive is butyl titanate and diethanolamine which can react to generate titanium dioxide;
in the step S3, the second additive is thiourea or urea, and the molar ratio of the second additive to the aluminum hydroxide is (5-10): 1;
in the step S5, the calcination is to quickly raise the temperature to 500 ℃ and then keep the temperature for a short time, and then slowly lower the temperature to 300 ℃ and keep the temperature for a long time; the rapid heating rate is 8-12 ℃/min.
2. The method for increasing the loading of a pseudo-boehmite supported catalyst according to claim 1 wherein in step S1, the concentration of titania is 0.1 to 0.5mol/L.
3. The method of claim 1, wherein in step S1, the molar ratio of the aluminum salt to the first additive is 10: (0.1-1).
4. The method according to claim 1, wherein in the step S1, the mixed solvent is anhydrous ethanol and deionized water with a volume ratio of (6-10): 1.
5. The method for increasing the loading of a pseudo-boehmite supported catalyst according to claim 1 wherein in step S2, the oxalic acid solution is finally adjusted to a pH of 6.5-7.5.
6. The method according to claim 1, wherein in step S3, the supercritical fluid drying is high temperature supercritical organic solvent drying or low temperature supercritical CO 2 And (5) drying.
7. The method for increasing the loading of a pseudo-boehmite supported catalyst according to claim 1 wherein in step S4, the hydrothermal reaction is performed at a temperature of 120-180 ℃ for 3 hours.
8. The method for increasing the loading of a pseudo-boehmite supported catalyst according to claim 1, wherein in step S5, the short-term heat preservation time is 10-15min, the slow cooling rate is 1-2 ℃/min, and the long-term heat preservation time is 1-2h.
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