CN112138642A - Preparation method and application of cracking catalyst - Google Patents
Preparation method and application of cracking catalyst Download PDFInfo
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- CN112138642A CN112138642A CN202011029284.9A CN202011029284A CN112138642A CN 112138642 A CN112138642 A CN 112138642A CN 202011029284 A CN202011029284 A CN 202011029284A CN 112138642 A CN112138642 A CN 112138642A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 238000005336 cracking Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910052796 boron Inorganic materials 0.000 claims abstract description 27
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 25
- 239000004327 boric acid Substances 0.000 claims description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- 239000004202 carbamide Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 150000003754 zirconium Chemical class 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 150000003608 titanium Chemical class 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 238000006317 isomerization reaction Methods 0.000 claims description 2
- 239000002159 nanocrystal Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 239000000725 suspension Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000012545 processing Methods 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 28
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 18
- 230000000694 effects Effects 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 11
- 238000012986 modification Methods 0.000 description 10
- 230000004048 modification Effects 0.000 description 10
- 239000000295 fuel oil Substances 0.000 description 9
- 229910052750 molybdenum Inorganic materials 0.000 description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 5
- 239000011280 coal tar Substances 0.000 description 5
- 238000002715 modification method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 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
- 239000000571 coke Substances 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 229910003130 ZrOCl2·8H2O Inorganic materials 0.000 description 2
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- -1 boron modified zirconium Chemical class 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000012072 active phase Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J21/066—Zirconium or hafnium; 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/082—Decomposition and pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/04—Oxides
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- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention relates to a preparation method of a cracking catalyst, which comprises the steps of hydrothermal reaction, dipping, alcohol washing, drying, roasting and the like to prepare a boron modified nano oxide catalyst which can be used in the production and processing of a suspended bed cracking catalyst. The invention is obtained by at least the following raw materials: the catalyst can effectively solve the problems of poor cracking capability, harsh reaction conditions, high catalyst addition and the like caused by the fact that the traditional catalyst is not suitable for use in the suspension bed hydrocracking process and depends on high-temperature cracking mainly, poor catalyst dispersibility and the like.
Description
Technical Field
The invention relates to a method for modifying oxide by boron, a cracking catalyst obtained by modification, and belongs to the field of petrochemical industry.
Background
Petroleum resources are a major energy source required for the economic development of the world. With the great progress of society and the rapid development of world economy, the demand of people for petroleum energy is increasing day by day. Although countries in the world try to gradually adjust energy consumption structures, fossil fuels such as petroleum still occupy a main position for a long time in the future from the present point of view, and provide main power for the development of the world economy. Various hydrocracking reactor technologies have been used for the treatment of low quality heavy oils, such as fixed bed, ebullated bed, moving bed, and suspended bed reactors.
The hydrocracking of heavy oil mainly aims at producing light fraction, middle fraction or heavy oil modification, and compared with other heavy oil hydrogenation processes in the prior various heavy oil processing technologies, the suspension bed hydrocracking has unique advantages: high liquid yield and conversion rate, low coking rate, contribution to reducing the loss of oil and stronger adaptability to the oil. Besides being embodied in the equipment, the suspension bed hydrogenation technology has the advantages that the advantages are mainly influenced by the catalyst. At present, the suspension bed catalyst mainly comprises two types of heterogeneous catalysts and homogeneous catalysts, wherein the heterogeneous catalysts are mainly solid particles or additive catalysts, but the dispersibility of solid powder in oil is not good, the addition amount is large, the hydrogenation activity ratio is low, the solid powder is easy to become a carrier for carbon deposition, and simultaneously, tail oil contains a large amount of solid particles and is difficult to treat and utilize. The homogeneous catalyst has two main types, including water soluble catalyst and oil soluble catalyst, and the water soluble catalyst is easy to dehydrate and deactivate, the oil soluble catalyst is well dispersed in oil, and has large specific surface area, high catalytic activity and excellent performance, thus being an ideal catalyst. At present, the research of hydrogenation catalysts mainly focuses on the aspects of adding ligands to improve the dispersibility of the hydrogenation catalysts in oil products, changing the vulcanization degree of active phases of the hydrogenation catalysts, or adding other elements and auxiliaries to protect the catalysts from inactivation and the like, and the cracking capability of the hydrogenation catalysts mainly depends on the high temperature of a reaction system. However, as a catalyst for treating heavy oil in a suspension bed, the catalyst not only has high hydrogenation activity, but also has strong cracking capability, so that the heavy oil can be cracked into low molecular weight compounds at a lower reaction temperature, and simultaneously hydrogenated, thereby improving the yield of light liquid oil and reducing the reaction severity.
The oxide with a pore channel structure is used as a carrier, and the traditional cracking catalyst loaded with metals such as Mo, Co, Ni, Fe and the like is widely used, but the acid strength, the acid type and the acid site number of the carrier are difficult to regulate, the pore channel of the carrier is easily blocked by a high molecular weight substance in an oil product, the surface lacks acid sites, the cracking capability is poor, the dispersity in the oil product is also poor, and the carrier is easy to become a coking carrier. In the prior art, in the process of hydrocracking of an oil product suspension bed, the traditional cracking catalyst has the problems of poor dispersity in the oil product, difficult regulation and control of acidity, easy deposition, reduced cracking effect, easy coke generation, and difficult utilization of a large amount of solid particles contained in tail oil and harsh reaction conditions of a reaction system.
Disclosure of Invention
The invention aims to provide a preparation method and application of a cracking catalyst. The invention prepares small-particle nano oxides by a hydrothermal method, and prepares a series of cracking catalysts with different boron contents by modifying boron. The crystal form, particle size, crystal grain size, surface hydroxyl and acidity of the catalyst can be regulated, so that the catalyst is improved in dispersity in an oil phase, and richer in active sites, and further has better cracking performance in the process of treating heavy oil in a suspension bed.
In order to achieve the purpose, the invention adopts the following technical scheme:
a process for preparing a cracking catalyst comprising the steps of:
(1) adding an oxide precursor and urea into a hydrothermal kettle to perform simple hydrothermal preparation of oxide nanocrystals, and performing water washing or alcohol washing, suction filtration and drying;
(2) modifying the oxide obtained in the step (1) by using a boron-containing compound by adopting an isometric immersion method or a crosslinking method, washing, filtering, drying, and roasting in a muffle furnace at different temperatures to finally obtain the modified cracking catalyst.
Wherein, the oxide precursor in the step (1) is a metal salt which is fully dissolved in distilled water or alcohol, and more preferably a zirconium salt or an aluminum salt or a titanium salt.
Wherein, the concentration of the oxide precursor added in the hydrothermal process in the step (1) is 0.1-2.0 mol/L, preferably 0.3-1.0 mol/L (based on the concentration of zirconium, aluminum and titanium).
Wherein the mass ratio of the urea in the step (1) to the cation M in the metal salt is 0.1-3.0, preferably 1.0-2.0.
Wherein, the hydrothermal temperature in the step (1) is 120-190 ℃ and the time is 6-96 h.
Wherein, the boron-containing compound in the step (2) is boric acid or borate. The mass concentration of the boron-containing compound is 0.2-20 wt%.
The drying temperature of the steps (1) and (2) is 90-150 ℃, and the drying time is 2-10 h.
Wherein, the roasting temperature in the step (2) is 340-700 ℃, and the roasting time is 2-6 h.
The nano cracking catalyst obtained by the modification method is used as a hydrocracking and isomerization catalyst for oil products.
The method for modifying the nano oxide by the boron has the advantages that:
(1) according to the method for modifying the nano oxide by the boron, raw materials required by modification comprise: the oxide precursor is zirconium salt, aluminum salt or titanium salt which can be fully dissolved in distilled water or alcohol, and the surface hydroxyl, crystal form, grain size and the like of the nano oxide can be regulated and controlled by controlling crystallization temperature and time in the hydrothermal process, so that the dispersion degree of the catalyst in an oil phase is improved, active sites are richer, and the catalyst has better cracking performance in the process of treating heavy oil in a suspension bed.
(2) In the invention, the nano oxide is prepared by the hydrothermal reaction based on urea and modified by boron modification. The precursor concentration is 0.1-2.0 mol/L based on metal cation, because the size of nano oxide is controlled. The mass concentration of the dipped boric acid solution is 0.3-20 wt%. The reason is that the nano-oxide is suitably acidic and needs to contain boron sufficient to bind with the metal cation. Boron is an electron-deficient structure, in the process of combining with the nano oxide, chemical bonds of B-O-Zr, B-O-Ti and B-O-Al can be formed, association of hydrogen bonds can exist on the surface of the oxide, and the processes have electron transfer, so that acidity is changed, and abundant acidic sites are generated.
(3) In the process of modifying nano oxide, boric acid or borate simultaneously has boron-oxygen triangular unit [ BO ]3]And boron-oxygen tetrahedral unit [ BO4]The oxides also have different coordination modes and valence changes, and the combination of the two can generate abundant structural changes.
Drawings
FIG. 1 is a XRD spectrum of a boron-modified zirconium-based nano-oxide according to the present invention;
FIG. 2 shows an IR spectrum of a boron-modified zirconium-based nano-oxide according to the present invention;
FIG. 3 is a graph showing the conversion of the product in examples and comparative examples according to the present invention.
Detailed Description
In order to facilitate understanding of the present invention, the technical solutions of the present invention are further described below with reference to the accompanying drawings and the detailed description.
Example 1
The modification scheme described in this example was prepared from the following raw materials:
zirconium oxychloride ZrOCl2·8H2O
Boric acid, H3BO3
Urea, CO (NH)2)2
Wherein, the zirconium oxychloride accounts for 10.312 g, and the urea accounts for 6.20 g. The mass concentration of the dipped boric acid solution is 0.8 wt%
The modification method in this example is:
(1) 10.312 g of zirconium oxychloride and 6.20 g of urea are dissolved in 80 mL of deionized water, and the mixture is fully stirred to be dissolved;
(2) transferring the solution into a hydrothermal kettle to perform hydrothermal reaction at constant temperature of 150 ℃ for 10 hours;
(3) cooling the reaction kettle, taking out the solid-liquid mixture obtained in the step (2), centrifuging, filtering, washing with deionized water to remove impurities, washing with ethanol, and drying at 120 ℃ for 9 hours;
(4) immersing the product obtained in the step (3) in 0.8 wt% boric acid solution for 4 h in the same volume;
(5) and (4) taking out the product obtained in the step (4), washing with alcohol, drying at 120 ℃ for 9 h, and roasting in a muffle furnace at 450 ℃ for 6 h.
(6) The modified catalyst was obtained by grinding and was reported as 150 Zr-0.8B-450.
Example 2
The modification scheme described in this example was prepared from the following raw materials:
aluminum sulfate, Al2(SO4)·18H2O
Boric acid, H3BO3
Urea, CO (NH)2)2
Wherein the aluminum sulfate is 21.3254g, the urea is 6.20 g, and the mass concentration of the dipped boric acid solution is 0.8 wt%.
The modification method in this example is:
(1) 21.3254g of aluminum sulfate and 6.20 g of urea are dissolved in 80 mL of deionized water, and the mixture is fully stirred to be dissolved;
(2) transferring the solution into a hydrothermal kettle to perform hydrothermal reaction at constant temperature of 150 ℃ for 10 hours;
(3) cooling the reaction kettle, taking out the solid-liquid mixture obtained in the step (2), centrifuging, filtering, washing with deionized water to remove impurities, washing with ethanol, and drying at 120 ℃ for 9 hours;
(4) immersing the product obtained in the step (3) in 0.8 wt% boric acid solution for 4 h in the same volume;
(5) and (4) taking out the product obtained in the step (4), washing with alcohol, drying at 120 ℃ for 9 h, and roasting in a muffle furnace at 450 ℃ for 6 h.
(6) The modified catalyst was obtained by grinding and was noted as 150 Al-0.8B-450.
Example 3
The modification scheme described in this example was prepared from the following raw materials:
tetra-n-butyl titanate, C16H36O4Ti
Boric acid, H3BO3
Urea, CO (NH)2)2
Wherein the tetrabutyl titanate is 10.892 g, the urea is 6.20 g, and the mass concentration of the dipped boric acid solution is 0.8 wt%.
The modification method in this example is:
(1) 10.892 g of tetra-n-butyl titanate and 6.20 g of urea are dissolved in 80 mL of absolute ethyl alcohol, and are fully stirred to be dissolved;
(2) transferring the solution into a hydrothermal kettle to perform hydrothermal reaction at constant temperature of 150 ℃ for 10 hours;
(3) cooling the reaction kettle, taking out the solid-liquid mixture obtained in the step (2), centrifuging, filtering, washing with deionized water to remove impurities, washing with ethanol, and drying at 120 ℃ for 9 hours;
(4) immersing the product obtained in the step (3) in 0.8 wt% boric acid solution for 4 h in the same volume;
(5) and (4) taking out the product obtained in the step (4), washing with alcohol, drying at 120 ℃ for 9 h, and roasting in a muffle furnace at 450 ℃ for 6 h.
(6) The modified catalyst was obtained by grinding and was noted as 150 Ti-0.8B-450.
Example 4
The modification scheme described in this example was prepared from the following raw materials:
zirconium oxychloride ZrOCl2·8H2O
Boric acid, H3BO3
Urea, CO (NH)2)2
Wherein, the mass concentration of the zirconium oxychloride is 10.312 g, the mass concentration of the urea is 6.20 g, and the mass concentration of the dipped boric acid solution is 0.4 wt percent.
The modification method in this example is:
(1) 10.312 g of zirconium oxychloride and 6.20 g of urea are dissolved in 80 mL of deionized water, and the mixture is fully stirred to be dissolved;
(2) transferring the solution into a hydrothermal kettle to perform hydrothermal reaction at constant temperature of 150 ℃ for 10 hours;
(3) cooling the reaction kettle, taking out the solid-liquid mixture obtained in the step (2), centrifuging, filtering, washing with deionized water to remove impurities, washing with ethanol, and drying at 120 ℃ for 9 hours;
(4) immersing the product obtained in the step (3) in 0.4 wt% boric acid solution for 4 h in the same volume;
(5) and (4) taking out the product obtained in the step (4), washing with alcohol, drying at 120 ℃ for 9 h, and roasting in a muffle furnace at 450 ℃ for 6 h.
(6) The modified catalyst was obtained by grinding and was reported as 150 Zr-0.4B-450.
Examples of the experiments
According to the four experimental schemes in the embodiment, molybdenum isooctanoate is added into the boron modified oxide catalyst for activity test, the addition amount of medium-low temperature coal tar is 45.0 g, the addition amount of molybdenum isooctanoate is 600ppm (based on the addition mass of oil), and the mass ratio of the addition amount of the boron modified oxide to the residual oil is 0.02, namely 0.90 g. The results are described as Experimental example 1, Experimental example 2, Experimental example 3 and Experimental example 4.
Comparative example 1
Molybdenum isooctanoate alone was added as catalyst, noted as 0B.
Comparative example 2
The experiment was carried out with the addition of commercial alumina and molybdenum isooctanoate purchased as a comparison and is noted CAl-0B.
1. XRD spectrogram of modified nano oxide
Taking a boron modified zirconium nano oxide catalyst as an example, the modification is carried out according to the above examples and the numbering is as follows:
(1) marking the nano oxide prepared by hydrothermal at 150 ℃ as 150 Zr-450;
(2) the 0.4 wt% boric acid (based on the mass of the impregnated zirconia) modified nano-oxide catalyst of example 4 is reported as 150 Zr-0.4B-450;
(3) the 0.8 wt% boric acid (based on the mass of the impregnated zirconia) modified nano-oxide catalyst from example 1 was reported as 150 Zr-0.8B-450.
As can be seen from the XRD spectrum of FIG. 1, the zirconium-based nano-oxide exists mainly in the form of monoclinic phase zirconia, and no crystal B is found at 2 theta of 14.2 DEG and 27.6 DEG2O3 Diffraction peaks and other boron phase diffraction peaks, which show that boron is uniformly dispersed on the surface of the nano zirconia and forms a stronger effect with the zirconia.
2. Modified nano oxide infrared spectrum
Taking a boron modified zirconium nano oxide catalyst as an example, the modification is carried out according to the above examples and the numbering is as follows:
(1) marking the nano oxide prepared by hydrothermal at 150 ℃ as 150 Zr-450;
(2) marking the 0.4 wt% boric acid modified nano-oxide catalyst in example 4 as 150 Zr-0.4B-450;
(3) the 0.8 wt% boric acid (based on the mass of the impregnated zirconia) modified nano-oxide catalyst from example 1 was reported as 150 Zr-0.8B-450.
The IR spectrogram of the boron-modified zirconium nano oxide catalyst is shown in figure 2, and the catalyst with the number of 150Zr-0.4B-450 and the number of 150Zr can be seenCatalyst concentration of-0.8B-450 at 1290cm-1The diffraction peak of B-O stretching vibration appears, the diffraction peak is more obvious along with the increase of the boron content, which indicates that boron is well introduced and can be expressed as [ BO ] on the surface of the nano oxide3]And increases with increasing boron content. Both were also found at 1630cm-1Diffraction peaks were present, but no diffraction peaks were evident in the 150Zr-450 catalyst, indicating that the incorporation of boron may form Zr-O-B bonds with zirconia via oxygen bridges.
3. Application of modified nano oxide in activity test of suspension bed hydrocracking reaction
The activity test conditions of the catalyst in this experimental example are as follows. Raw materials: 45.0 g of medium-low temperature coal tar, 12 MPa of reaction pressure, 400 ℃ of reaction temperature, 600ppm of added molybdenum (based on the added mass of the oil), 0.02 mass ratio of the added amount of the boron modified oxide to the oil, namely 0.90 g, and 2 h of reaction time.
The four catalysts prepared in the examples were tested for activity against the comparative example, the molybdenum sources added were all molybdenum isooctanoate, the contents were all 600ppm (based on the added mass of oil), and the results were as follows:
from the above table, it can be seen that the nano-oxide is modified by adding boron according to the method described herein, and is used for medium and low temperature coal tar suspension bed hydrocracking experiments, compared with commercial oxide carrier, the liquid yield and light oil yield of the catalyst can be obviously improved, and the coking rate, residual oil yield and gas yield are reduced. Among them, the nano zirconia catalyst modified with 0.4 wt% boric acid in example 4 can obtain the highest light oil yield and the lowest coke rate, and has the best hydrocracking effect in medium and low temperature coal tar.
It can also be seen from the conversion chart of the product of fig. 3 that the 0.4 wt% boric acid-modified nano-zirconia catalyst of example 4 has the lowest coke formation rate, the highest liquid yield and light oil yield, and also generates less gas, having the best activity in the activity test.
4. Dispersion test of modified oxide catalyst in oil
The four catalysts applied to the medium-low temperature coal tar suspension bed hydrocracking reaction are taken out after the reaction, cleaned and dried, and subjected to a laser particle size test, wherein the determination result is as follows:
as can be seen from the above table, the average particle size of the boron-modified zirconia is relatively reduced and is slightly lower than the particle size of the oil-soluble molybdenum after vulcanization, which indicates that the catalyst has good dispersibility in oil products.
Although the present invention has been described in detail with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims.
Claims (10)
1. A preparation method of a cracking catalyst is characterized by comprising the following steps:
(1) adding an oxide precursor and urea into a hydrothermal kettle to perform simple hydrothermal preparation of oxide nanocrystals, and performing water washing or alcohol washing, suction filtration and drying;
(2) modifying the oxide obtained in the step (1) by using a boron-containing compound by adopting an isometric immersion method or a crosslinking method, washing, filtering, drying, and roasting in a muffle furnace at different temperatures to finally obtain the modified cracking catalyst.
2. The method of claim 1, wherein the oxide precursor in step (1) is a metal salt substantially soluble in distilled water or alcohol.
3. The method of claim 2, wherein the metal salt is one of a zirconium salt, an aluminum salt, and a titanium salt.
4. The method of claim 2, wherein the oxide precursor is added to the hydrothermal process in step (1) at a concentration of 0.1-2.0 mol/L.
5. The process of claim 2, wherein the mass ratio of urea to cation M in the metal salt in step (1) is 0.1-3.0.
6. The method as claimed in claim 2, wherein the hydrothermal temperature of step (1) is 190 ℃ and the hydrothermal time is 6-96 h.
7. The process for preparing a cracking catalyst according to claim 2, wherein the boron-containing compound in the step (2) is boric acid or a borate; the mass concentration of the boron-containing compound during the impregnation is 0.2-20 wt%.
8. The method for preparing a cracking catalyst according to claim 2, wherein the drying temperature in steps (1) and (2) is 90-150 ℃, and the drying time is 2-10 h; the roasting temperature in the step (2) is 340-700 ℃, and the roasting time is 2-6 h.
9. A cracking catalyst obtainable by the preparation according to any one of claims 1 to 8.
10. Use of the cracking catalyst obtained by the preparation according to any one of claims 1 to 8 in oil hydrocracking and isomerization reactions.
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| CN113634247A (en) * | 2021-08-31 | 2021-11-12 | 福州大学 | Deoxygenation and isomerization catalyst, and preparation method and application thereof |
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