CN114506866B - Preparation method for continuously preparing silicon-containing pseudo-boehmite - Google Patents
Preparation method for continuously preparing silicon-containing pseudo-boehmite Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 82
- 239000010703 silicon Substances 0.000 title claims abstract description 82
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000011148 porous material Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000011734 sodium Substances 0.000 claims abstract description 35
- 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 claims abstract description 33
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 140
- 239000002002 slurry Substances 0.000 claims description 126
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 98
- 230000032683 aging Effects 0.000 claims description 51
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 49
- 239000001569 carbon dioxide Substances 0.000 claims description 49
- 239000012670 alkaline solution Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 38
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 20
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 14
- 235000019353 potassium silicate Nutrition 0.000 claims description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- 239000004115 Sodium Silicate Substances 0.000 claims description 10
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 claims description 9
- 239000003518 caustics Substances 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 230000002431 foraging effect Effects 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 3
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 3
- 238000010924 continuous production Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 18
- 238000004458 analytical method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000001035 drying Methods 0.000 description 6
- 239000000499 gel Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 229910001679 gibbsite Inorganic materials 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910018104 Ni-P Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910018536 Ni—P Inorganic materials 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 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 1
- 238000001354 calcination Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 239000002351 wastewater Substances 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
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
- C01F7/141—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent
- C01F7/142—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent with carbon dioxide
-
- 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/615—
-
- B01J35/638—
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
-
- 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
-
- 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
- C01P2006/14—Pore volume
-
- 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
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The invention discloses a method for continuously preparing silicon-containing pseudo-boehmite. The silicon-containing pseudo-boehmite prepared by the method has stable property, has the characteristics of high silicon oxide content, larger pore diameter, pore volume and the like, can meet the requirements of hydrogenation catalyst carriers, can adopt sodium metaaluminate raw materials with higher alumina concentration, can realize continuous production, greatly improves the production efficiency, and has simple process and easy operation.
Description
Technical Field
The invention relates to a method for preparing pseudo-boehmite, in particular to a method for continuously preparing silicon-containing pseudo-boehmite.
Background
The introduction of the auxiliary agent silica into the alumina can effectively modulate the surface acidity of the alumina carrier and improve the strong interaction between the active component and the alumina carrier. Meanwhile, the silicon-containing aluminum oxide has higher specific surface area, better sintering resistance and certain acid catalytic activity.
At present, the preparation methods of the silicon-containing alumina mainly comprise a precipitation method, a mixing method and an impregnation method. The precipitation method is prepared by a method of neutralizing and precipitating alkali metal silicate (or water glass) and aluminum-containing salt to form gel; the mixing method is to mix SiO 2 Hydrogels and Al 2 O 3 Directly kneading the hydrogel to form silica-alumina gel, and then washing, drying, forming and roasting to prepare the silica-alumina gel; the impregnation method is to impregnate the silicic acid hydrogel or the dry with aluminum salt solutionAfter the gel, the gel is prepared by evaporation and drying, wherein the precipitation method is the most common.
However, the silicon source introduced in the process of preparing the silicon-containing aluminum oxide by the precipitation method is mainly sodium silicate or silica sol, the sodium silicate is selected as the silicon source, a large amount of water is consumed for washing to ensure that the product has low sodium content, the waste water generated by washing also causes environmental pollution, and the silica sol is selected as the silicon source, so that the raw material cost is greatly increased.
CN1448215A discloses a siliceous aluminum hydroxide and a preparation method thereof, which comprises the steps of reacting a sodium metaaluminate solution with the alumina concentration of 5 g/L-60 g/L, a sodium silicate solution with the silica concentration of 5 g/L-40 g/L and a carbon dioxide mixed gas with the volume ratio of 10v% to 50v% under the stirring condition, stopping the reaction when the pH value of the cement slurry is 9-12, aging for 10-60 minutes, filtering, pulping a filter cake, adding the rest sodium silicate solution, aging for 10-120 minutes at 20-35 ℃, washing for 3-5 times at 20-40 ℃, and drying at 100-150 ℃ to obtain the siliceous aluminum oxide. The method requires adding silicon source water glass for multiple times, so that the morphology of silicon oxide in the synthesized silicon-containing aluminum oxide is inconsistent, and the operation process is complicated due to the multiple addition of the silicon source and multiple ageing.
In addition, the prior preparation of the silicon-containing alumina adopts kettle type intermittent production, so the problems of low production efficiency, high energy consumption, poor product stability and the like are also existed.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a method for continuously preparing the silicon-containing pseudo-boehmite, which has the characteristics of stable property, high silicon oxide content, larger pore diameter, larger pore volume and the like, can meet the requirements of hydrogenation catalyst carriers, can adopt sodium metaaluminate raw materials with higher alumina concentration, can realize continuous production, greatly improves the production efficiency, and has simple process and easy operation.
The invention provides a method for continuously preparing silicon-containing pseudo-boehmite, which comprises the following steps:
(1) Mixing the first alkaline solution and the mixed gas I containing carbon dioxide, continuously adding the mixed gas I into a first reaction kettle, reacting, and controlling the pH value of slurry in the first reaction kettle by adjusting the flow of the mixed gas I;
(2) Continuously adding a second alkaline solution from the bottom of the second reaction kettle, continuously introducing a mixed gas II containing carbon dioxide from the bottom of the second reaction kettle to react, and controlling the pH value of slurry in the second reaction kettle by adjusting the flow of the mixed gas II;
(3) When the slurry in the first reaction kettle and the second reaction kettle reach or are higher than the overflow port of the first reaction kettle and the second reaction kettle, the two slurries flow into the third reaction kettle in parallel to react, and the pH value of the slurry in the third reaction kettle is controlled;
(4) When the slurry in the third reaction kettle reaches or is higher than the overflow port of the third reaction kettle, the slurry enters an aging tank for aging, filtering is carried out after the aging is finished, and the obtained filter cake is washed and dried to obtain the silicon-containing pseudo-boehmite;
wherein the second alkaline solution is a mixed solution of an aluminum-containing alkaline solution and a silicon-containing alkaline solution.
Wherein in the step (1), the first alkaline solution is an aluminum-containing alkaline solution, and is one or more of sodium metaaluminate solution or potassium metaaluminate solution, preferably sodium metaaluminate solution; the concentration of the first alkaline solution is Al 2 O 3 And is preferably from 150 to 350g/L, more preferably from 160 to 250g/L.
In the step (1), the mixture of the first alkaline solution and the mixed gas I containing carbon dioxide is preferably mixed in a gas-liquid mixing pump; the gas-liquid mixing pump is one of a dissolved air pump, a gas-water mixing pump, a gas-mixing pump and a gas-liquid pump; the mixed gas I containing carbon dioxide can be mixed gas of carbon dioxide and air; the volume fraction of carbon dioxide in the mixed gas I containing carbon dioxide is 30-60%.
In the step (1), after gas-liquid mixing, the mixture is continuously added into a first reaction kettle from the bottom of the first reaction kettle.
In the step (1), the pH value of the slurry in the first reaction kettle after the reaction is 9.5-11.5.
In the step (1), the initial reaction temperature of the reaction is generally 15-65 ℃, the reaction is exothermic, the temperature of the system is gradually increased, the whole reaction process does not need to be cooled to keep low temperature, and the temperature of the slurry is generally 40-75 ℃ at the end of the reaction.
In the step (2), the second alkaline solution is a mixed solution of an aluminum-containing alkaline solution and a silicon-containing alkaline solution, wherein the aluminum-containing alkaline solution is one or more of a sodium metaaluminate solution or a potassium metaaluminate solution, preferably a sodium metaaluminate solution, and the silicon-containing alkaline solution is water glass. The caustic ratio of the sodium metaaluminate solution or the potassium metaaluminate solution is 1.15-1.35, preferably 1.25-1.35, and the modulus of the water glass is 2.8-3.2.
In the mixed solution, the concentration of sodium metaaluminate and/or potassium metaaluminate is calculated as Al 2 O 3 Is 1 to 30g Al 2 O 3 L, preferably 5 to 25g Al 2 O 3 Concentration of sodium silicate in terms of SiO 2 5-95 g SiO 2 L, preferably 10 to 90g SiO 2 /L。
The flow rate of the second alkaline solution is 20 mL/min-50 mL/min, preferably 25 mL/min-45 mL/min; the carbon dioxide-containing gas II can be a mixed gas of carbon dioxide and air; the volume fraction of carbon dioxide in the mixed gas II containing carbon dioxide is 50-90%.
In the step (2), the pH value of the slurry in the second reaction kettle is controlled to be 2.0-4.0.
In the step (3), the bottom water is added into the third reaction kettle before the slurry in the first reaction kettle and the slurry in the second reaction kettle enter the third reaction kettle, and the adding amount of the bottom water is 1/10-1/5 of the volume of the reaction kettle.
In step (3), the temperature of the reaction is 40 to 70 ℃, preferably 45 to 65 ℃.
In step (3), the reaction is carried out with stirring.
In the step (3), the pH value of the slurry in the reaction kettle is controlled to be 8.5-9.5 by adjusting the flow rate of the slurry in the step (1).
In the step (4), the aging tanks are preferably more than two aging tanks connected in parallel, when one aging tank collects the slurry, the aging is started, and the slurry is collected by the other aging tank.
In the step (4), the aging conditions are as follows: the temperature is 50-95 ℃ and the time is 30-120 min.
In the step (4), the washing can be performed by a washing method conventional in the art, and washing water is preferably deionized water at 50-80 ℃.
In the step (4), the drying conditions are as follows: the temperature is 100-150 ℃ and the time is 6-10 hours.
In the process of preparing the silicon-containing pseudo-boehmite, one or more auxiliary agents such as P, B or Ti can be added according to the requirement, and the mass content of the auxiliary agents is 0-6% of that of the pseudo-boehmite obtained by oxide.
The second aspect of the invention provides the silicon-containing pseudo-boehmite prepared by the method, which is roasted to obtain silicon-containing aluminum oxide, and the obtained silicon-containing aluminum oxide has the following properties: siO based on the weight of silicon-containing aluminum oxide 2 The content is 5-85%, the pore volume is more than or equal to 1.0mL/g, and the specific surface area is 280-360 m 2 /g; the ratio of the amount of the acid B to the amount of the acid L (C) is not less than 0.40mmol/g B /C L )≥0.05。
Preferably, the silicon-containing alumina has the following properties: siO based on the weight of silicon-containing aluminum oxide 2 The content is 15-65%, the pore volume is 1.0-2.0 mL/g, and the specific surface area is 300-360 m 2 /g; the ratio C of the amount of B acid to the amount of L acid is more than or equal to 0.40 to 0.50mmol/g B /C L ) 0.05 to 0.06.
The pore distribution of the silicon-containing aluminum oxide is as follows: the pore volume of the pores with the pore diameter smaller than 6nm accounts for less than Kong Rong percent of the total pore volume, the pore volume of the pores with the pore diameter of 6-15 nm accounts for 70-85 percent of the total pore volume, and the pore volume of the pores with the pore diameter larger than 15nm accounts for 10-25 percent of the total pore volume.
The roasting conditions are as follows: roasting for 3-6 hours at 500-700 ℃.
The third aspect of the invention provides the use of the silicon-containing pseudo-boehmite. The application is specifically to prepare a residual oil hydrogenation catalyst, in particular to prepare a residual oil hydrodesulfurization catalyst.
The method of the invention has the following advantages:
(1) The first alkaline solution is preferably firstly fed into the gas-liquid mixing pump before being fed into the reactor, and meanwhile, the suction inlet of the gas-liquid mixing pump utilizes the negative pressure to suck the mixed gas II containing carbon dioxide, the impeller of the pump rotating at high speed mixes the liquid with the gas, stirs and pressurizes the mixed gas to fully mix the gas with the liquid, so that the high-solubility solution is prepared, the pressure is rapidly reduced after the mixed gas enters the reactor, and the mixed gas is released for rapid carbonization reaction, so that the hydrolysis reaction of sodium metaaluminate can be obviously reduced to reduce the generation of alumina trihydrate even under the condition of higher temperature, and the crystallinity of the synthetic silicon-containing pseudo-boehmite is improved;
(2) The preparation method of the invention comprises the steps of reacting the second alkaline solution with the mixed gas containing carbon dioxide, and adjusting the pH value of the system to be acidic to enable Na in the water glass in the second alkaline solution + In a free state, the precursor of the silicon dioxide is combined with or adsorbed on the pseudo-boehmite crystal grain, so that the subsequent reaction of Na + Washing is easier and saves washing water.
(3) According to the invention, the first alkaline solution is firstly reacted with the mixed gas containing carbon dioxide quickly, the pH value of the obtained slurry is controlled, then the reacted slurry reacts with the second alkaline solution, and the generated crystal grains are used as primary particles generated by the absorption of crystal nucleus of parallel flow reaction, so that the prepared silicon-containing pseudo-boehmite crystal grains are large, full and complete, and larger pore volume and proper pore distribution are formed;
(4) Compared with the prior art, the silicon-containing pseudo-boehmite has high silicon content, low mass content of gibbsite and high crystallinity, and the silicon-containing aluminum oxide obtained by roasting has larger pore volume and pore diameter, stronger acidity and higher B acid content, thereby meeting the requirements of hydrogenation catalyst carriers;
(5) The preparation method overcomes the defects that the quality of the product is greatly influenced by the environment, the raw material concentration is low and the production efficiency is low in the process of preparing the silicon-containing pseudo-boehmite by the traditional method, and has simple process and easy operation.
Drawings
Figure 1 is a process flow diagram of the continuous preparation of silicon-containing pseudo-boehmite according to an embodiment of the invention,
wherein, 1 is first reation kettle, 2 is the second reation kettle, 3 is the third reation kettle, 4 is ageing jar, 5 is the mixed gas I entry that contains carbon dioxide, 6 is first alkaline solution entry, 7 is gas-liquid mixing pump, 8 is first alkaline solution entry, 9 is the mixed gas II entry that contains carbon dioxide, 10 is the agitator, 11 is the thick liquid export after ageing.
Detailed Description
The following describes the technical scheme of the present invention in detail with reference to examples.
In the invention, the pore distribution and the specific surface area are analyzed by adopting a low-temperature liquid nitrogen adsorption method; the amount of infrared acid was measured using a Nicolet 870 Fourier transform infrared spectrometer from Nicolet corporation of America.
The specific process flow of the invention is as follows:
(1) The mixed gas I of carbon dioxide and the first alkaline solution enter a gas-liquid mixing pump 7 from inlets 5 and 6 respectively to be mixed with gas-liquid, then enter the first reaction kettle 1 from the bottom of the first reaction kettle 1 to react, the slurry in the reaction kettle is controlled to reach the required pH value by adjusting the flow of the mixed gas I of carbon dioxide, and after the slurry in the first reaction kettle 1 reaches an overflow port, the slurry enters a third reaction kettle 3 from the overflow port;
(2) Simultaneously, the second alkaline solution and the mixed gas II containing carbon dioxide respectively enter the second reaction kettle 2 from inlets 8 and 9 at the bottom of the second reaction kettle 2 at a certain flow rate to react, and the pH value of the slurry in the second reaction kettle 2 is reduced to a required pH value by adjusting the flow of the mixed gas II containing carbon dioxide;
(3) When the slurry in the second reaction kettle 2 reaches an overflow port, the slurry enters a third reaction kettle 3 which is added with bottom water, heated to a required temperature and started with a stirrer 10 from the overflow port to react with the slurry which is added into the first reaction kettle 1 in the step (1) in parallel flow, and the pH value of the slurry in the third reaction kettle 3 is controlled by adjusting the flow rate of the slurry in the step (1);
(4) When the slurry in the third reaction kettle 3 reaches or is higher than the overflow port of the third reaction kettle, the slurry enters an aging tank 4 for slurry collection, the aging tank for collecting the slurry starts aging, and the slurry is collected by another aging tank; and (3) after the aging is finished, the slurry flows out from the slurry outlet 11, and the obtained filter cake is washed and dried to obtain the silicon-containing pseudo-boehmite.
Example 1
(1) Mixed gas with 50 percent of carbon dioxide by volume percentage and Al with the temperature of 25 DEG and the concentration 2 O 3 The sodium metaaluminate solution with the concentration of 200g/L is respectively and continuously fed into the gas pump from the gas inlet and the liquid inlet of the gas pump to be mixed, the mixed gas and liquid are fed into the first reaction kettle from the bottom of the first reaction kettle to be reacted, the pH value of the slurry in the first reaction kettle is controlled to be 10.5 by adjusting the flow of the carbon dioxide mixed gas, the temperature of the slurry is 45 ℃, and the slurry enters the third reaction kettle from the overflow port after the slurry in the first reaction kettle reaches the overflow port.
(2) Simultaneously, a mixed solution (sodium metaaluminate solution and water glass solution, wherein the caustic ratio of the sodium metaaluminate solution is 1.30, the modulus of the water glass is 3.0) continuously enters the second reaction kettle from the inlet at the bottom of the second reaction kettle at the flow rate of 35mL/min, and the concentration of the sodium metaaluminate in the mixed solution is equal to Al 2 O 3 20g/L, and the concentration of sodium silicate in the mixed solution is calculated as SiO 2 50g/L is calculated, and simultaneously, mixed gas with the volume fraction of 60 percent of carbon dioxide is introduced from the bottom of the second reaction kettle to react, the pH value of the slurry in the second reaction kettle is controlled to be 3.5 by adjusting the flow of the mixed gas of the carbon dioxide, and when the slurry in the second reaction kettle reaches an overflow port, the slurry enters a third reaction kettle from the overflow port.
(3) When the slurry in the second reaction kettle reaches the overflow port, the slurry enters a 10000mL third reaction kettle which is added with 1000mL of bottom water, has the temperature of 60 ℃ and starts a stirrer from the overflow port to react with the slurry flowing in the step (1), the pH value of the slurry in the third reaction kettle is controlled to be 9.0 by adjusting the flow rate of the slurry in the step (1), and the temperature of the slurry in the third reaction kettle is kept constant at 60 ℃.
(4) When the slurry in the third reaction kettle reaches or is higher than the overflow port, the slurry enters an aging tank for slurry collection, the aging tank for collecting the slurry starts aging, and the slurry is collected by another aging tank; the aging temperature is controlled to be 90 ℃ for 90min, and the product is washed by deionized water with the temperature of 70 ℃ which is 25 times of the product after the aging is finished, and then the product is dried for 8 hours at 120 ℃. The result of analysis of the triple water content of the silicon-containing pseudo-boehmite A-1 of the invention is shown in Table 1.
The obtained silicon-containing pseudo-boehmite A-1 was calcined at 600℃for 3 hours to obtain silicon-containing alumina a-1, whose pore properties and infrared acid analysis results are shown in Table 1.
Example 2
Otherwise as in example 1, except that the sodium silicate is added to the mixed solution of step (2) in a concentration of SiO 2 Calculated as 70g/L, the concentration of sodium metaaluminate is calculated as Al 2 O 3 The volume fraction of carbon dioxide in the mixed gas of the carbon dioxide and the air which is calculated as 12g/L is 45%, and the silicon-containing pseudo-boehmite A-2 is obtained, and the analysis result of the content of gibbsite is shown in Table 1.
The obtained silicon-containing pseudo-boehmite A-2 was further calcined at 600℃for 3 hours to obtain silicon-containing alumina a-2, whose pore properties and infrared acid properties are shown in Table 1.
Example 3
Otherwise as in example 1, except that the sodium metaaluminate solution concentration in step (1) is at a concentration of Al 2 O 3 Counting to be 230g/L; in the step (4), the silicon-containing pseudo-boehmite A-3 is obtained by washing with 38 times of deionized water at 60 ℃, and the analysis result of the gibbsite content is shown in Table 1.
The obtained silicon-containing pseudo-boehmite A-3 was further calcined at 600℃for 3 hours to obtain silicon-containing alumina a-3, whose pore properties and infrared acid properties are shown in Table 1.
Example 4
The same as in example 1 except that the flow rate in the step (3) was changed to 40mL/min, and the initial temperature of the third reaction kettle was 70 ℃; the pH value of the slurry in the third reaction kettle is controlled to be 9.4, and the silicon-containing pseudo-boehmite A-4 is obtained, and the analysis result of the three water content is shown in Table 1.
The obtained silicon-containing pseudo-boehmite A-4 was further calcined at 600℃for 3 hours to obtain silicon-containing alumina a-4, whose pore properties and infrared acid properties are shown in Table 1.
Example 5
(1) Mixing gas with 40% carbon dioxide by volume fraction, mixing gas with concentration of Al at 30deg.C 2 O 3 The sodium metaaluminate solution with the concentration of 170g/L is respectively and continuously fed into the gas pump from the gas inlet and the liquid inlet of the gas pump to be mixed, the mixed gas and liquid are fed into the first reaction kettle from the bottom of the first reaction kettle to be reacted, the pH value of the slurry in the first reaction kettle is controlled to be 11.0 by adjusting the flow of the carbon dioxide mixed gas, the temperature of the slurry is 55 ℃, and the slurry enters the third reaction kettle from the overflow port after the slurry in the first reaction kettle reaches the overflow port.
(2) Simultaneously, the mixed solution (sodium metaaluminate solution and water glass solution, wherein the caustic ratio of the sodium metaaluminate solution is 1.32, the modulus of the water glass is 2.8) continuously enters the second reaction kettle from the inlet at the bottom of the second reaction kettle at the flow rate of 25mL/min, wherein the concentration of the sodium metaaluminate in the mixed solution is equal to Al 2 O 3 10g/L, and the concentration of sodium silicate in the mixed solution is calculated as SiO 2 And the concentration is 35g/L, and simultaneously, mixed gas with the volume fraction of 65% of carbon dioxide is introduced from the bottom of the second reaction kettle to react, the pH value of the slurry in the second reaction kettle is controlled to be 3.0 by adjusting the flow of the mixed gas of carbon dioxide, and when the slurry in the second reaction kettle reaches an overflow port, the slurry enters the third reaction kettle from the overflow port.
(3) When the slurry in the second reaction kettle reaches the overflow port, the slurry enters a 10000mL third reaction kettle, to which 1500mL of bottom water is added, the temperature is 65 ℃ and a stirrer is started, from the overflow port to react with the slurry flowing in the step (1), the pH value of the slurry in the third reaction kettle is controlled to be 8.7 by adjusting the flow rate of the slurry in the step (1), and the temperature of the slurry in the third reaction kettle is kept constant at 65 ℃.
(4) When the slurry in the third reaction kettle reaches or is higher than the overflow port, the slurry enters an aging tank for slurry collection, the aging tank for collecting the slurry starts aging, and the slurry is collected by another aging tank; the aging temperature is controlled to be 90 ℃ for 90min, and after the aging is finished, the product is washed by deionized water with the temperature of 70 ℃ which is 20 times that of the prepared product, and then the product is dried for 8 hours at 120 ℃. The result of analysis of the triple water content of the silicon-containing pseudo-boehmite A-5 is shown in Table 1.
The obtained silicon-containing pseudo-boehmite A-5 was calcined at 600℃for 3 hours to obtain silicon-containing alumina a-5, whose pore properties and infrared acid analysis results are shown in Table 1.
Comparative example 1
(1) Mixed gas with 50 percent of carbon dioxide by volume percentage and Al with the temperature of 25 DEG and the concentration 2 O 3 The sodium metaaluminate solution with the concentration of 200g/L is respectively and continuously fed into the gas pump from the gas inlet and the liquid inlet of the gas pump to be mixed, the mixed gas and liquid are fed into the first reaction kettle from the bottom of the first reaction kettle to be reacted, the pH value of the slurry in the first reaction kettle is controlled to be 10.5 by adjusting the flow of the carbon dioxide mixed gas, the temperature of the slurry is 45 ℃, and the slurry enters the third reaction kettle from the overflow port after the slurry in the first reaction kettle reaches the overflow port.
(2) Simultaneously, a mixed solution (sodium metaaluminate solution and water glass solution, wherein the caustic ratio of the sodium metaaluminate solution is 1.30, the modulus of the water glass is 3.0) continuously enters the second reaction kettle from the inlet at the bottom of the second reaction kettle at the flow rate of 35mL/min, and the concentration of the sodium metaaluminate in the mixed solution is equal to Al 2 O 3 20g/L, and the concentration of sodium silicate in the mixed solution is calculated as SiO 2 50g/L is calculated, and simultaneously, mixed gas with the volume fraction of 60 percent of carbon dioxide is introduced from the bottom of the second reaction kettle to react, the pH value of the slurry in the second reaction kettle is controlled to be 6.5 by adjusting the flow of the mixed gas of the carbon dioxide, and when the slurry in the second reaction kettle reaches an overflow port, the slurry enters a third reaction kettle from the overflow port.
(3) When the slurry in the second reaction kettle reaches the overflow port, the slurry enters a 10000mL third reaction kettle which is added with 1000mL of bottom water, has the temperature of 60 ℃ and starts a stirrer from the overflow port to react with the slurry flowing in the step (1), the pH value of the slurry in the third reaction kettle is controlled to be 9.0 by adjusting the flow rate of the slurry in the step (1), and the temperature of the slurry in the third reaction kettle is kept constant at 60 ℃.
(4) When the slurry in the third reaction kettle reaches or is higher than the overflow port, the slurry enters an aging tank for slurry collection, the aging tank for collecting the slurry starts aging, and the slurry is collected by another aging tank; the aging temperature is controlled to be 90 ℃ for 90min, and the product is washed by deionized water with the temperature of 70 ℃ which is 25 times of the product after the aging is finished, and then the product is dried for 8 hours at 120 ℃. The result of analysis of the triple water content of the silicon-containing pseudo-boehmite F-1 is shown in Table 1.
The obtained silicon-containing pseudo-boehmite F-1 was calcined at 600℃for 3 hours to obtain silicon-containing alumina F-1, whose pore properties and infrared acid analysis results are shown in Table 1.
Comparative example 2
(1) The preparation modulus is 3.0, the concentration is SiO 2 Calculated as 50g/L and the concentration is calculated as Al 2 O 3 The total weight of the aluminum sulfate mixed solution is 20g/L for standby.
(2) Mixed gas with 50 percent of carbon dioxide by volume percentage and Al with the temperature of 25 DEG and the concentration 2 O 3 The sodium metaaluminate solution with the concentration of 200g/L is respectively and continuously fed into the gas pump from the gas inlet and the liquid inlet of the gas pump to be mixed, the mixed gas and liquid are fed into the first reaction kettle from the bottom of the first reaction kettle to be reacted, the pH value of the slurry in the first reaction kettle is controlled to be 10.5 by adjusting the flow of the carbon dioxide mixed gas, the temperature of the slurry is 45 ℃, and the slurry enters the third reaction kettle from the overflow port after the slurry in the first reaction kettle reaches the overflow port.
(3) Adding 1000mL of bottom water into 10000mL of a third reaction kettle, starting a stirring and heating device, adding a mixed solution into the third reaction kettle at a flow rate of 35mL/min when the temperature reaches 60 ℃, simultaneously adding the slurry in the step (2) in parallel to react, controlling the pH value of the slurry in the third reaction kettle to 9.0 by adjusting the flow rate of the slurry in the step (2), and keeping the temperature of the slurry in the third reaction kettle to be constant at 60 ℃.
(4) When the slurry in the third reaction kettle reaches or is higher than the overflow port, the slurry enters an aging tank for slurry collection, the aging tank for collecting the slurry starts aging, and the slurry is collected by another aging tank; the aging temperature is controlled to be 90 ℃ for 90min, and the product is washed by deionized water with the temperature of 70 ℃ which is 25 times of the product after the aging is finished, and then the product is dried for 8 hours at 120 ℃. The result of analysis of the triple water content of the silicon-containing pseudo-boehmite F-2 is shown in Table 1.
The obtained silicon-containing pseudo-boehmite F-2 was calcined at 600℃for 3 hours to obtain silicon-containing alumina F-2, whose pore properties and infrared acid analysis results are shown in Table 1.
Comparative example 3
(1) Caustic ratio of 1.30, concentration of Al 2 O 3 Sodium metaaluminate solution with a modulus of 3.0 and a concentration of SiO of 20g/L 2 The water glass mixed solution with the flow rate of 50g/L continuously enters the second reaction kettle from the inlet at the bottom of the second reaction kettle at the flow rate of 35mL/min, meanwhile, mixed gas with the volume fraction of 60 percent of carbon dioxide is introduced from the bottom of the second reaction kettle for reaction, the pH value of slurry in the second reaction kettle is controlled to be 3.5 by adjusting the flow rate of the mixed gas of the carbon dioxide, and when the slurry in the second reaction kettle reaches the overflow port, the slurry enters the third reaction kettle from the overflow port.
(2) When the slurry in the second reaction kettle reaches the overflow port, the slurry enters a 10000mL third reaction kettle with 1000mL of bottom water, 60 ℃ temperature and started stirrer from the overflow port, and simultaneously, al with the concentration is added in parallel flow 2 O 3 The pH value of the slurry in the third reaction kettle is controlled to be 9.0 by adjusting the flow rate of the sodium metaaluminate solution, and the temperature of the slurry in the third reaction kettle is kept constant at 60 ℃.
(3) When the slurry in the third reaction kettle reaches or is higher than the overflow port, the slurry enters an aging tank for slurry collection, the aging tank for collecting the slurry starts aging, and the slurry is collected by another aging tank; the aging temperature is controlled to be 90 ℃ for 90min, and the product is washed by deionized water with the temperature of 70 ℃ which is 25 times of the product after the aging is finished, and then the product is dried for 8 hours at 120 ℃. The result of analysis of the triple water content of the silicon-containing pseudo-boehmite F-3 is shown in Table 1.
The obtained silicon-containing pseudo-boehmite F-3 was calcined at 600℃for 3 hours to obtain silicon-containing alumina F-3, whose pore properties and infrared acid analysis results are shown in Table 1.
Example 6
150g of silicon-containing pseudo-boehmite prepared in example 1 was weighed, 3g of sesbania powder, 4.5g of 65% nitric acid and 270g of deionized water were added, kneaded, extruded, shaped, dried at 120℃for 6 hours, and calcined at 700℃for 3 hours to obtain a catalyst carrier.
Soaking the carrier in Mo-Ni-P solution, drying at 120deg.C for 6 hr, and roasting at 450deg.C for 3 hr to obtain catalyst A C Catalyst properties are shown in Table 2 and catalyst evaluation results are shown in Table 4.
Example 7
Catalyst A was obtained in the same manner as in example 6 except that the silicon-containing pseudo-boehmite prepared in example 5 was changed to silicon-containing pseudo-boehmite C The properties of-5 are shown in Table 2, and the results of the catalyst evaluation are shown in Table 4.
Comparative example 4
150g of silicon-containing pseudo-boehmite prepared in comparative example 1 was weighed, 3g of sesbania powder, 4.5g of 65% nitric acid and 270g of deionized water were added, kneaded, extruded, molded, dried at 120℃for 6 hours, and calcined at 700℃for 3 hours to obtain a catalyst carrier.
Soaking the carrier in Mo-Ni-P solution, drying at 120deg.C for 6 hr, and calcining at 450deg.C for 3 hr to obtain catalyst F C Catalyst properties are shown in Table 2 and catalyst evaluation results are shown in Table 4.
Comparative example 5
Catalyst F was obtained in the same manner as in comparative example 4 except that the silicon-containing pseudo-boehmite was changed to the silicon-containing pseudo-boehmite prepared in comparative example 2 C The properties of-2 are shown in Table 2, and the results of the catalyst evaluation are shown in Table 4.
Comparative example 6
Catalyst F was obtained in the same manner as in comparative example 4 except that the silicon-containing pseudo-boehmite was changed to the silicon-containing pseudo-boehmite prepared in comparative example 3 C The properties of-3 are shown in Table 2, and the results of the catalyst evaluation are shown in Table 4.
TABLE 1 analysis of pseudo-boehmite and alumina
Table 2 properties of the catalysts prepared in examples and comparative examples
| Catalyst numbering | A C -1 | A C -5 | F C -1 | F C -2 | F C -3 |
| Pore volume, mL/g | 0.645 | 0.652 | 0.503 | 0.508 | 0.509 |
| Specific surface area, m 2 /g | 188 | 190 | 212 | 192 | 189 |
| Average pore diameter, nm | 13.7 | 13.7 | 9.5 | 10.6 | 10.8 |
| Pore distribution, percent | |||||
| <6.0nm | 4.8 | 4.3 | 19.7 | 15.4 | 23 |
| 6.0-15.0nm | 79.4 | 80.3 | 61.2 | 66.4 | 59.9 |
| >15.0nm | 15.8 | 15.4 | 19.1 | 18.2 | 17.1 |
| Metal content, wt% | |||||
| MoO 3 | 16.5 | 16.3 | 16.4 | 16.6 | 16.4 |
| NiO | 4.1 | 4.0 | 4.0 | 4.1 | 3.9 |
The prepared catalyst was subjected to activity evaluation on a medium residue hydrotreater, wherein properties and evaluation conditions of the residue are shown in table 3, and evaluation results are shown in table 4.
TABLE 3 Properties of raw oil and evaluation conditions
TABLE 4 evaluation results of catalysts prepared in examples and comparative examples of the present invention
| Catalyst numbering | A C -1 | A C -5 | F C -1 | F C -2 | F C -3 |
| Removal rate, wt% | |||||
| Desulfurization rate | 82.7 | 82.5 | 73.3 | 74.4 | 75.2 |
| Carbon residue removal rate | 60.1 | 59.7 | 48.6 | 48.9 | 49.7 |
| Ni+V removal rate | 63.7 | 63.5 | 52.3 | 52.8 | 52.9 |
Claims (14)
1. A method for continuously preparing pseudo-boehmite, comprising the steps of:
(1) Mixing the first alkaline solution and the mixed gas I containing carbon dioxide in a gas-liquid mixing pump, continuously adding the mixed gas I into a first reaction kettle, reacting, and controlling the pH value of slurry in the first reaction kettle by adjusting the flow of the mixed gas I;
(2) Continuously adding a second alkaline solution from the bottom of the second reaction kettle, continuously introducing a mixed gas II containing carbon dioxide from the bottom of the second reaction kettle to react, and controlling the pH value of slurry in the second reaction kettle by adjusting the flow of the mixed gas II;
(3) When the slurry in the first reaction kettle and the second reaction kettle reach or are higher than the overflow port of the first reaction kettle and the second reaction kettle, the two slurries flow into the third reaction kettle in parallel to react, and the pH value of the slurry in the third reaction kettle is controlled;
(4) When the slurry in the third reaction kettle reaches or is higher than the overflow port of the third reaction kettle, the slurry enters an aging tank for aging, filtering is carried out after the aging is finished, and the obtained filter cake is washed and dried to obtain the silicon-containing pseudo-boehmite;
wherein in the step (1), the first alkaline solution is an aluminum-containing alkaline solution, and the concentration of the first alkaline solution is Al 2 O 3 Counting to 150-350 g/L;
in the step (1), the pH value of the slurry in the first reaction kettle after the reaction is 9.5-11.5;
in step (2), theThe second alkaline solution is a mixed solution of an aluminum-containing alkaline solution and a silicon-containing alkaline solution, wherein the concentration of the aluminum-containing alkaline solution in the second alkaline solution is Al 2 O 3 Is 1 to 30g Al 2 O 3 L; concentration of the alkaline solution containing silicon as SiO 2 5-95 g SiO 2 /L；
In the step (2), the pH value of the slurry in the second reaction kettle is controlled to be 2.0-4.0.
2. A method according to claim 1, characterized in that: in the step (1), the first alkaline solution is one or more of sodium metaaluminate solution or potassium metaaluminate solution; the concentration of the first alkaline solution is Al 2 O 3 The total weight is 160-250 g/L.
3. A method according to claim 1, characterized in that: in the step (1), the mixed gas I containing carbon dioxide is a mixed gas of carbon dioxide and air; the volume fraction of carbon dioxide in the mixed gas I containing carbon dioxide is 30-60%.
4. A method according to claim 1, characterized in that: in the step (2), the aluminum-containing alkaline solution is one or more of sodium metaaluminate solution and potassium metaaluminate solution, and the silicon-containing alkaline solution is water glass.
5. The method of claim 4, wherein: in the step (2), the caustic ratio of the sodium metaaluminate solution or the potassium metaaluminate solution is 1.15-1.35, and the modulus of the water glass is 2.8-3.2.
6. The method according to claim 5, wherein: in the step (2), the caustic ratio of the sodium metaaluminate solution or the potassium metaaluminate solution is 1.25-1.35.
7. The method of claim 4, wherein: in step (2), sodium metaaluminate and/or in the second alkaline solutionConcentration of potassium metaaluminate as Al 2 O 3 5-25 gAl 2 O 3 L; in the second alkaline solution, the concentration of sodium silicate is SiO 2 Is 10 to 90g SiO 2 /L。
8. A method according to claim 1, characterized in that: in the step (2), the gas II containing carbon dioxide is a mixed gas of carbon dioxide and air; the volume fraction of carbon dioxide in the mixed gas II containing carbon dioxide is 50-90%.
9. A method according to claim 1, characterized in that: in the step (3), the temperature of the reaction is 40-70 ℃.
10. The method according to claim 9, wherein: in the step (3), the temperature of the reaction is 45-65 ℃.
11. A method according to claim 1, characterized in that: in the step (3), the pH value of the slurry in the reaction kettle is controlled to be 8.5-9.5 by adjusting the flow rate of the slurry in the step (1).
12. A method according to claim 1, characterized in that: in the step (4), the aging conditions are as follows: the temperature is 50-95 ℃ and the time is 30-120 min.
13. A silicon-containing pseudoboehmite prepared according to any one of claims 1-12 characterized in that: the silicon-containing pseudo-boehmite is roasted to obtain silicon-containing aluminum oxide, and the obtained silicon-containing aluminum oxide has the following properties: siO based on the weight of silicon-containing aluminum oxide 2 The content is 5-85%, the pore volume is more than or equal to 1.0mL/g, and the specific surface area is 280-360 m 2 /g; the infrared acid amount is more than or equal to 0.40mmol/g, and the ratio of the acid amount of B acid to the acid amount of L acid is more than or equal to 0.05;
the pore distribution of the silicon-containing aluminum oxide is as follows: the pore volume of the pores with the pore diameter smaller than 6nm accounts for less than 5 percent of the total pore volume, the pore volume of the pores with the pore diameter of 6-15 nm accounts for 70-85 percent of the total pore volume, and the pore volume of the pores with the pore diameter larger than 15nm accounts for 10-25 percent of the total pore volume.
14. Use of a silicon-containing pseudoboehmite prepared according to any one of claims 1-12 or a silicon-containing pseudoboehmite according to claim 13 in the preparation of a residuum hydrogenation catalyst.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6518219B1 (en) * | 1999-10-14 | 2003-02-11 | China Petrochemical Corporation | Catalyst for hydrorefining fraction oils, its carrier and preparation |
| CN1552526A (en) * | 2003-05-31 | 2004-12-08 | 中国石油化工股份有限公司 | Silicon-phosphorus contained aluminum hydrate and its preparation |
| CN101322949A (en) * | 2008-07-18 | 2008-12-17 | 山西大学 | Alumina supporter and preparation method thereof |
| CN102139204A (en) * | 2010-02-03 | 2011-08-03 | 中国石油天然气股份有限公司 | Pseudo-boehmite containing amorphous silica alumina and preparation method thereof |
| RU2014139759A (en) * | 2014-09-30 | 2016-04-20 | Федеральное государственное бюджетное учреждение науки Институт химии нефти Сибирского отделения Российской академии наук (ИХН СО РАН) | The method of hydrotreating diesel fractions |
| CN106807352A (en) * | 2015-12-01 | 2017-06-09 | 中国石油化工股份有限公司 | A kind of active mesoporous Si-Al catalysis material |
| CN111377472A (en) * | 2018-12-27 | 2020-07-07 | 中国石油化工股份有限公司 | Preparation method of pseudo-boehmite and alumina prepared by same |
| CN111592023A (en) * | 2020-05-19 | 2020-08-28 | 大连众智创新催化剂有限公司 | Preparation method of boron-containing pseudo-boehmite |
-
2020
- 2020-10-29 CN CN202011182287.6A patent/CN114506866B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6518219B1 (en) * | 1999-10-14 | 2003-02-11 | China Petrochemical Corporation | Catalyst for hydrorefining fraction oils, its carrier and preparation |
| CN1552526A (en) * | 2003-05-31 | 2004-12-08 | 中国石油化工股份有限公司 | Silicon-phosphorus contained aluminum hydrate and its preparation |
| CN101322949A (en) * | 2008-07-18 | 2008-12-17 | 山西大学 | Alumina supporter and preparation method thereof |
| CN102139204A (en) * | 2010-02-03 | 2011-08-03 | 中国石油天然气股份有限公司 | Pseudo-boehmite containing amorphous silica alumina and preparation method thereof |
| RU2014139759A (en) * | 2014-09-30 | 2016-04-20 | Федеральное государственное бюджетное учреждение науки Институт химии нефти Сибирского отделения Российской академии наук (ИХН СО РАН) | The method of hydrotreating diesel fractions |
| CN106807352A (en) * | 2015-12-01 | 2017-06-09 | 中国石油化工股份有限公司 | A kind of active mesoporous Si-Al catalysis material |
| CN111377472A (en) * | 2018-12-27 | 2020-07-07 | 中国石油化工股份有限公司 | Preparation method of pseudo-boehmite and alumina prepared by same |
| CN111592023A (en) * | 2020-05-19 | 2020-08-28 | 大连众智创新催化剂有限公司 | Preparation method of boron-containing pseudo-boehmite |
Non-Patent Citations (1)
| Title |
|---|
| 连续碳化法制备拟薄水铝石;王晶晶等;《工业催化》;第27卷(第1期);33-37 * |
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Effective date of registration: 20231226 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |