CN116328784A - Oil refining catalyst and preparation method thereof - Google Patents
Oil refining catalyst and preparation method thereof Download PDFInfo
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- CN116328784A CN116328784A CN202310590869.5A CN202310590869A CN116328784A CN 116328784 A CN116328784 A CN 116328784A CN 202310590869 A CN202310590869 A CN 202310590869A CN 116328784 A CN116328784 A CN 116328784A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 238000007670 refining Methods 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 48
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- IOGARICUVYSYGI-UHFFFAOYSA-K azanium (4-oxo-1,3,2-dioxalumetan-2-yl) carbonate Chemical compound [NH4+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O IOGARICUVYSYGI-UHFFFAOYSA-K 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 34
- 239000006185 dispersion Substances 0.000 claims abstract description 26
- 238000005470 impregnation Methods 0.000 claims abstract description 25
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- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 23
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 23
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 17
- 238000000227 grinding Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000003292 glue Substances 0.000 claims abstract description 15
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- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 16
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 16
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- KVFVBPYVNUCWJX-UHFFFAOYSA-M ethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)C KVFVBPYVNUCWJX-UHFFFAOYSA-M 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 57
- 238000009826 distribution Methods 0.000 abstract description 33
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 239000003921 oil Substances 0.000 description 40
- 230000000052 comparative effect Effects 0.000 description 27
- 239000000243 solution Substances 0.000 description 27
- 238000003756 stirring Methods 0.000 description 26
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 20
- 239000002585 base Substances 0.000 description 19
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
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Images
Classifications
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- 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
-
- 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
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/0207—Pretreatment of the support
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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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0209—Impregnation involving a reaction between the support and a fluid
-
- 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
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- B01J37/088—Decomposition of a metal salt
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- 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
- C10G45/06—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 containing nickel or cobalt metal, or compounds thereof
- C10G45/08—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 containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The application relates to the technical field of oil refining catalysts, and particularly discloses an oil refining catalyst and a preparation method thereof. A method for preparing an oil refining catalyst, comprising the following steps: s1: taking aluminum hydroxide dry glue, pore-forming agent and acid solution according to the mass ratio of (20-30) to (80-100) to (60-90), uniformly mixing to obtain plastic, and then processing and forming to obtain blank; the pore-forming agent is prepared by a method comprising the following steps: 1) Uniformly mixing carboxymethyl cellulose, alkyl quaternary ammonium base and water to obtain an intermediate solution; 2) Adding ammonium aluminum carbonate into the intermediate liquid, and uniformly dispersing to obtain a dispersion liquid; 3) Placing the dispersion liquid into a hot water bath for regeneration to obtain coarse materials, drying, crushing and grinding to obtain the coarse materials; s2: drying and heat-treating the blank material to obtain a carrier; s3: and (3) placing the carrier in impregnating solution for impregnation treatment, and drying and roasting after the carrier is impregnated uniformly. The oil refining catalyst prepared by the method has the advantages of good pore size distribution state and high catalytic effect.
Description
Technical Field
The application relates to the technical field of oil refining catalysts, in particular to an oil refining catalyst and a preparation method thereof.
Background
Currently, hydrotreating catalysts used in the oil refining industry are mostly supported catalysts, and generally adopt an impregnation production process. To a certain extent, the nature of the support determines the dispersion state of the active components of the catalyst, the surface properties of the catalyst and the service life of the catalyst, so that the selection and modification of the support are important to the development of the technicians.
Alumina has become a common carrier for hydrotreating catalysts in industry due to its good dispersion on metal components, high mechanical strength and thermal stability, and certain acidity. For alumina carriers, the pore structure mainly affects the diffusion behavior of reactants on the surface of the catalyst, if the pore structure is smaller, the reactants cannot or are not easy to enter the inner surface of the catalyst, and metal impurities and scales in heavy oil and residual oil raw materials are also easy to deposit to cause pore opening blockage, so that the activity of the catalyst is finally reduced. If the pore structure is large, the specific surface area of the catalyst is reduced, and the catalytic effect is also deteriorated, so that the distribution states of the two types of pore structures need to be balanced.
For the above problems, chinese patent application publication No. CN106582515a discloses a carbon-coated alumina carrier with a bimodal pore structure and a preparation method thereof, and the method comprises the following steps: (1) Mixing hydrated alumina and aluminum ammonium carbonate, kneading the mixture with a carbon precursor to form a plastic body, and obtaining a formed product by a physical forming method, wherein the weight ratio of the hydrated alumina to the aluminum ammonium carbonate is 1:9-9:1, and the ratio of the sum of the weights of the hydrated alumina and the aluminum ammonium carbonate to the carbon precursor is 7:3-19:1; (2) Drying the formed product in the step (1) at 50-100 ℃, and then carrying out heat treatment in an oxygen-free atmosphere to obtain the carbon-coated alumina carrier with a bimodal pore structure.
In the above document, the bimodal pore structure is manufactured by utilizing the ammonium aluminum carbonate to self-heat and explain the overflow of a large amount of gas, and the diffusion resistance of macromolecules is reduced by combining the bimodal pore structure with the macropores and the pinholes, so that the catalytic effect and the stability of the catalyst are improved. However, in the pore-forming process adopted in the above document, the decomposition process of ammonium aluminum carbonate is in an uncontrollable state, the gas production speed cannot be well regulated, and the pore size distribution form of the finally produced bimodal pore structure is not good enough, so that the catalytic efficiency of the catalyst is affected.
Disclosure of Invention
In order to further improve the pore channel structure distribution form of the catalyst and improve the catalytic efficiency of the catalyst, the application provides an oil refining catalyst and a preparation method thereof.
In a first aspect, the present application provides a method for preparing an oil refining catalyst, which adopts the following technical scheme:
a method for preparing an oil refining catalyst, comprising the following steps:
s1: taking aluminum hydroxide dry glue, pore-forming agent and acid solution according to the mass ratio of (20-30) to (80-100) to (60-90), uniformly mixing to obtain plastic, and then processing and forming to obtain blank;
the pore-forming agent is prepared by a method comprising the following steps:
1) Uniformly mixing carboxymethyl cellulose, alkyl quaternary ammonium base and water to obtain an intermediate solution;
2) Adding ammonium aluminum carbonate into the intermediate liquid, and uniformly dispersing to obtain a dispersion liquid;
3) Placing the dispersion liquid into a hot water bath for regeneration to obtain coarse materials, drying, crushing and grinding to obtain the coarse materials;
s2: drying and heat-treating the blank material to obtain a carrier;
s3: and (3) placing the carrier in impregnating solution for impregnation treatment, and drying and roasting after the carrier is impregnated uniformly.
By adopting the technical scheme, firstly, the aluminum hydroxide dry glue, the pore-forming agent and the acid solution are uniformly mixed according to a proper proportion, and the powdery particle raw materials are uniformly gathered together by utilizing the surface tension of water and the aluminum sol generated in an acidic environment, so that the plastic which is easy to process is prepared, and green body materials with different shapes and specifications are prepared through a physical forming process. And then, removing excessive moisture in the blank material through drying treatment, so that the blank material has a certain degree of mechanical strength, and is convenient for subsequent processing treatment.
And carrying out heat treatment on the dried blank at high temperature, removing part of structural water in the blank, and simultaneously changing the crystal morphology to form a stable framework structure. In addition, the pore canal structure is gradually formed by utilizing the decomposition gas production effect of the pore-forming agent while the framework structure is formed. The applicant finds that when conventional single pore formers such as ammonium aluminum carbonate, activated carbon, starch and the like are adopted, the gas production speed is not easy to control along with the continuous increase of the temperature, and the distribution state of the pore structure is not in a preferred state as a whole even if a bimodal pore structure is produced and is not controllable in the gas production process.
In this regard, the pore-forming agent is prepared by adopting a special preparation process, and the carboxymethyl cellulose, the alkyl quaternary ammonium base and the water are uniformly mixed to form an intermediate liquid in a semi-derivatization homogeneous gel state, and then the aluminum ammonium carbonate is dispersed into a gel system of the intermediate liquid. Then the dispersion liquid is subjected to hot water bath regeneration treatment, drying and crushing and grinding to prepare the pore-forming agent, wherein the pore-forming agent is composite micro-nano particles which take carboxymethyl cellulose as a coating main body, ammonium aluminum carbonate as a star-shaped distribution core and a trace amount of alkyl quaternary ammonium hydroxide as a cross-linking body between the coating main body and the distribution core.
In the whole heat treatment process, the outer layer of the pore-forming agent wrapping main body is decomposed firstly, and if intervention treatment holes are formed in the framework structure, the subsequent gas is conveniently discharged and dissipated. Along with the increase of the heat treatment temperature and the increase of the treatment time, the inner layer of the wrapping main body and part of aluminum ammonium carbonate begin to be decomposed simultaneously, and as the decomposition process is carried out simultaneously, two gas generating components play a complementary role to a certain extent, a better pore structure distribution form can be obtained while a bimodal pore structure is formed, the problems of overlarge diffusion resistance of the oil component in the pore structure of the catalyst and catalyst activity reduction caused by the deposition of harmful metal impurities are solved, and thus the catalytic effect of the catalyst is improved.
In addition, the trace alkyl quaternary ammonium base in the wrapping main body and the distribution core can improve the quantity of polar groups such as hydroxyl on the surface of the pore canal structure to a certain extent, can enhance the interaction between the carrier and metal components such as W, ni and Mo in the subsequent impregnation treatment process, improves the distribution uniformity and the combination quantity of the metal components, and further improves the catalytic effect of the catalyst.
Preferably, in the step S2, the heat treatment is divided into a first stage and a second stage, and the fitting equation of the temperature rise control curve in the first stage is y= (0.28-a) x + (2.5-b) x+112; the fitting equation of the temperature rise control curve in the second stage is y= - (0.02-m) x+ (5.1-n) x+221; wherein the ordinate is temperature (. Degree.C.) and the abscissa is time (min); the starting point of the abscissa of the first stage is set to be 0min, the ending point is set to be 90-120min, the starting point of the ordinate is set to be 120-150 ℃, and the ending point is set to be 230-260 ℃; the starting point of the abscissa of the second stage is set to be 90-120min, the end point is set to be 240-270min, the starting point of the abscissa is set to be 220-250 ℃, and the end point is set to be 550-600 ℃.
By adopting the technical scheme, on the basis of wrapping the main body-distribution core, a two-stage heat treatment process is adopted, firstly, in the low-temperature stage, the temperature rising speed is firstly high and then low, a proper decomposition environment is provided for the composite micro-nano particles, the disintegration speed of the outer layer of the wrapping main body is in a proper state, the internal structure is gradually exposed, and preparation is made for the subsequent decomposition process. And then in the high-temperature stage, on the basis of the pore-forming structure in the low-temperature stage, the inner layer of the wrapping main body and the residual distribution core are completely decomposed, and finally, the pore canal structure with double peaks and better pore size distribution state is formed.
Preferably, a ranges from 0.053 to 0.085 and b ranges from 1.19 to 1.26; m ranges from 0.0012 to 0.0038, and n ranges from 0.2 to 0.43.
By adopting the technical scheme, the parameter size of a, b, m, n is optimized and adjusted, and the fitting trend state of a heating curve is further finely adjusted, so that the decomposition and gas production process of the composite micro-nano particles is better regulated and controlled, and the better pore size distribution form is obtained.
Preferably, R of the first stage fitting equation 2 In the range of 0.5-0.65, R of the second stage fitting equation 2 Ranging from 0.8 to 0.92.
By adopting the technical scheme, the R square of the first-stage fitting equation and the second-stage fitting equation is controlled, the fitting degree of the temperature control curve is adjusted to a certain extent, the occurrence of disordered and uncontrollable decomposition processes is reduced, and the probability of defects such as defective holes, interpenetrating and the like of the carrier pore channel structure is reduced.
Preferably, in the step S1, the mass ratio of the carboxymethyl cellulose, the alkyl quaternary ammonium base and the aluminum ammonium carbonate is (10-20): 1-1.5): 3-5.
By adopting the technical scheme, when the carboxymethyl cellulose is excessively introduced, the pore size distribution is slightly good, but the reaming effect is poor, and the pore distribution is easy to disperse. The introduction of too much alkyl quaternary ammonium base results in a decrease in carrier acidity, while too little alkyl quaternary ammonium base does not perform a corresponding crosslinking action, and the number of polar groups inside the carrier is insufficient. The introduction amount of the ammonium aluminum carbonate can influence the formation of a bimodal pore structure, so that the mass ratio of the carboxymethyl cellulose, the alkyl quaternary ammonium base and the ammonium aluminum carbonate is optimized and adjusted, the pore channel structure distribution state of the carrier is further improved, and a better catalytic effect is obtained.
Preferably, the alkyl quaternary ammonium base is one or more of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide and trimethyl ethyl ammonium hydroxide.
Through adopting above-mentioned technical scheme, the molecular constitution of alkyl quaternary ammonium base is by long-chain alkyl and the quaternary ammonium cation that is located the center constitutes, and wherein the length of long-chain alkyl has decided steric hindrance and the size of cationic activity, and experimental and screening alkyl quaternary ammonium base's kind is constituteed for gel system hold effect and to wrap up main part and distribution core's crosslinking effect better.
In particular, the alkyl quaternary ammonium bases listed in the application can achieve corresponding technical effects.
Preferably, the alkyl quaternary ammonium base consists of tetrabutylammonium hydroxide and tetramethylammonium hydroxide according to the mass ratio of (2.6-3) to 1.
By adopting the technical scheme, the tetrabutylammonium hydroxide has large steric hindrance, and an entanglement structure is formed between the alkyl chain and other components and between the alkyl chain and the alkyl chain, so that a stable crosslinking system is formed. The tetramethyl ammonium hydroxide has stronger reactivity, can promote the formation of a gel system, and further optimize and adjust the composition ratio of the alkyl quaternary ammonium base, thereby forming the composite micro-nano particles with more uniform and stable structure.
Preferably, the average particle size of the pore-forming agent is 35-60 μm.
By adopting the technical scheme, the too large particle size of the pore-forming agent can cause too slow disintegration of the wrapping main body, and the subsequent pore-forming process can be limited under the influence of the heat transfer speed. Pore formers with excessively small particle size can cause unbalance and runaway of the gas production process and cause transition of pore distribution from double peaks to single peaks or irregular forms, and the pore formers with proper particle size range are selected, so that the pore structure state of the carrier can be further improved.
Preferably, in the step 3), the hot water bath regeneration process includes the steps of:
a) Placing the dispersion liquid into a hot water bath at 50-65 ℃ for presetting to obtain a semi-solid preset material;
b) Heating the hot water bath to 80-95 ℃, and performing high-frequency oscillation treatment on the gelatinous pre-formed material to obtain coarse material.
By adopting the technical scheme, the dispersion liquid is preformed in a hot water bath at 50-65 ℃, water molecules can permeate into partial areas in a gel system, so that the carboxymethyl cellulose and the ammonium aluminum carbonate molecules form pre-crosslinking and shaping, and the molecules are limited by intermolecular acting force, so that the ammonium aluminum carbonate molecules are in a semi-anchoring state.
Then heating the hot water bath and performing high-frequency oscillation treatment, under the free diffusion action and the high-frequency oscillation action of molecules, the aluminum ammonium carbonate molecules in the semi-anchoring state can form a star-shaped distribution form, and simultaneously, the permeation and the quality changing action of water molecules are also enhanced, so that the cross-linking between the carboxymethyl cellulose and the aluminum ammonium carbonate molecules in the star-shaped distribution form is stabilized, the aluminum ammonium carbonate is converted from the semi-anchoring state to the full-anchoring state, and in addition, the cross-linking is formed between the carboxymethyl cellulose and the aluminum ammonium carbonate along with the migration and the quality changing of alkyl quaternary ammonium hydroxide, and finally, the pore-forming agent in the composite micro-nano particle state is formed under the combined action of the three.
In a second aspect, the present application provides a refinery catalyst, which is prepared by the above preparation method of the refinery catalyst.
In summary, the present application has the following beneficial effects:
1. according to the preparation method, the composite micro-nano particles prepared from carboxymethyl cellulose, alkyl quaternary ammonium base and ammonium aluminum carbonate through a special preparation method are used as pore-forming agents, and a bimodal pore channel structure with better morphology can be formed at a more proper decomposition speed in a heat treatment stage, so that the prepared catalyst has a better catalytic effect.
2. In the application, a more matched heat treatment process is preferably adopted, and the decomposition and gas production processes of the composite micro-nano particles are more stable and are not easy to generate instability through the regulation and control of the temperature rise control curves of the first stage and the second stage, so that the distribution state of the obtained pore channel structure is better.
3. The oil refining catalyst prepared by the preparation method has a good catalytic effect.
Drawings
Fig. 1-15: pore size distribution curves for examples 1-10 and comparative examples 1-5 of the present application are schematically shown.
Fig. 16: schematic illustrations of the catalytic effects of examples 1-10 and comparative examples 1-5 of the present application.
Detailed Description
The present application is described in further detail below with reference to examples.
The raw materials of the examples and comparative examples herein are commercially available in general unless otherwise specified.
Examples
Example 1
The preparation method of the oil refining catalyst of the embodiment comprises the following steps:
s1: weighing 20g of aluminum hydroxide dry glue and 80g of pore-forming agent for standby, firstly uniformly mixing the aluminum hydroxide dry glue and the pore-forming agent in a stirring kettle, then dissolving 2ml of 65% nitric acid in 57g of water to obtain an acid solution, then adding the acid solution into the stirring kettle under continuous stirring, then kneading by a double-screw extruder to obtain a plastic, and finally extruding and molding by using a pore plate with the diameter of 1.5mm to obtain a blank;
s2: placing the blank material in an oven, setting a drying temperature of 120 ℃ and drying for 3 hours; the dried green body material is sent into a roasting furnace for heat treatment to obtain a carrier, the heat treatment temperature is raised to 550 ℃ from room temperature, the heating speed is 9 ℃/min, and the heat treatment time is 4 hours;
s3: adding 30ml of 80% phosphoric acid, 600ml of deionized water, 100g of molybdenum trioxide and 35g of basic nickel carbonate into a three-neck flask, heating and stirring to completely dissolve the molybdenum trioxide, adding 60g of ammonium metatungstate into the three-neck flask, and concentrating to 200ml after the ammonium metatungstate is completely dissolved to prepare an impregnating solution; and (3) carrying out impregnation treatment on the equal volume of carrier and the impregnation liquid, putting the impregnated carrier and the impregnation liquid into an oven for drying for 4 hours at the temperature of 120 ℃, putting the dried carrier and the impregnation liquid into a muffle furnace for roasting for 4 hours at the temperature of 500 ℃ to obtain the finished product.
The pore-forming agent of the embodiment is prepared by a method comprising the following steps:
1) 150g of carboxymethyl cellulose, 50ml of 40% tetraethylammonium hydroxide and 100ml of deionized water are placed in an open flask with magnetic stirring and uniformly mixed to prepare an intermediate solution;
2) Heating the intermediate liquid to 40 ℃, slowly adding 50g of ammonium aluminum carbonate into the intermediate liquid under the condition of continuous stirring, and uniformly dispersing to obtain a dispersion liquid;
3) Injecting the dispersion liquid into a hot water bath at 90 ℃ by using an injection pump and a spray head to regenerate to obtain coarse materials, controlling the injection speed to be 10ml/min, controlling the aperture of the outlet of the spray head to be 0.5mm, washing the coarse materials by using deionized water, drying, and then crushing and grinding to obtain the pore-forming agent with the average particle diameter of 20 mu m after grinding.
Wherein, the main components of the aluminum hydroxide dry glue are as follows: 97.68% of alumina, 0.08% of silicon dioxide, 2.15% of sulfate and the balance of other impurities.
The oil refining catalyst of this example was prepared by the preparation method described above.
Example 2
The preparation method of the oil refining catalyst of the embodiment comprises the following steps:
s1: weighing 30g of aluminum hydroxide dry glue and 100g of pore-forming agent for standby, firstly uniformly mixing the aluminum hydroxide dry glue and the pore-forming agent in a stirring kettle, then dissolving 2ml of 65% nitric acid in 87g of water to obtain an acid solution, then adding the acid solution into the stirring kettle under continuous stirring, then kneading by a double-screw extruder to obtain a plastic, and finally extruding and molding by using a pore plate with the diameter of 1.5mm to obtain a blank;
s2: placing the blank material in an oven, setting a drying temperature of 120 ℃ and drying for 3 hours; the dried green body material is sent into a roasting furnace for heat treatment to obtain a carrier, the heat treatment temperature is raised to 550 ℃ from room temperature, the heating speed is 9 ℃/min, and the heat treatment time is 4 hours;
s3: adding 30ml of 80% phosphoric acid, 600ml of deionized water, 100g of molybdenum trioxide and 35g of basic nickel carbonate into a three-neck flask, heating and stirring to completely dissolve the molybdenum trioxide, adding 60g of ammonium metatungstate into the three-neck flask, and concentrating to 200ml after the ammonium metatungstate is completely dissolved to prepare an impregnating solution; and (3) carrying out impregnation treatment on the equal volume of carrier and the impregnation liquid, putting the impregnated carrier and the impregnation liquid into an oven for drying for 4 hours at the temperature of 120 ℃, putting the dried carrier and the impregnation liquid into a muffle furnace for roasting for 4 hours at the temperature of 500 ℃ to obtain the finished product.
The pore-forming agent of the embodiment is prepared by a method comprising the following steps:
1) 200g of carboxymethyl cellulose, 50ml of 40% tetramethyl ammonium hydroxide and 100ml of deionized water are placed in an open flask with magnetic stirring and uniformly mixed to prepare an intermediate solution;
2) Heating the intermediate liquid to 40 ℃, slowly adding 30g of ammonium aluminum carbonate into the intermediate liquid under the condition of continuous stirring, and uniformly dispersing to obtain a dispersion liquid;
3) Injecting the dispersion liquid into a hot water bath at 90 ℃ by using an injection pump and a spray head to regenerate to obtain coarse materials, controlling the injection speed to be 10ml/min, controlling the aperture of the outlet of the spray head to be 0.5mm, washing the coarse materials by using deionized water, drying, and then crushing and grinding to obtain the pore-forming agent with the average particle diameter of 35 mu m after grinding.
Wherein, the main components of the aluminum hydroxide dry glue are as follows: 97.68% of alumina, 0.08% of silicon dioxide, 2.15% of sulfate and the balance of other impurities.
The oil refining catalyst of this example was prepared by the preparation method described above.
Example 3
The preparation method of the oil refining catalyst of the embodiment comprises the following steps:
s1: weighing 28g of aluminum hydroxide dry glue and 95g of pore-forming agent for standby, firstly uniformly mixing the aluminum hydroxide dry glue and the pore-forming agent in a stirring kettle, then dissolving 2ml of 65% nitric acid in 87g of water to obtain an acid solution, then adding the acid solution into the stirring kettle under continuous stirring, then kneading by a double-screw extruder to obtain a plastic, and finally extruding and molding by using a pore plate with the diameter of 1.5mm to obtain a blank;
s2: placing the blank material in an oven, setting a drying temperature of 120 ℃ and drying for 3 hours; the dried green body material is sent into a roasting furnace for heat treatment to obtain a carrier, the heat treatment temperature is raised to 550 ℃ from room temperature, the heating speed is 9 ℃/min, and the heat treatment time is 4 hours;
s3: adding 30ml of 80% phosphoric acid, 600ml of deionized water, 100g of molybdenum trioxide and 35g of basic nickel carbonate into a three-neck flask, heating and stirring to completely dissolve the molybdenum trioxide, adding 60g of ammonium metatungstate into the three-neck flask, and concentrating to 200ml after the ammonium metatungstate is completely dissolved to prepare an impregnating solution; and (3) carrying out impregnation treatment on the equal volume of carrier and the impregnation liquid, putting the impregnated carrier and the impregnation liquid into an oven for drying for 4 hours at the temperature of 120 ℃, putting the dried carrier and the impregnation liquid into a muffle furnace for roasting for 4 hours at the temperature of 500 ℃ to obtain the finished product.
The pore-forming agent of the embodiment is prepared by a method comprising the following steps:
1) 100g of carboxymethyl cellulose, 50ml of 40% tetrabutylammonium hydroxide and 100ml of deionized water are taken and placed in an open flask with magnetic stirring, and are uniformly mixed to prepare an intermediate solution;
2) Heating the intermediate liquid to 40 ℃, slowly adding 45g of ammonium aluminum carbonate into the intermediate liquid under the condition of continuous stirring, and uniformly dispersing to obtain a dispersion liquid;
3) Injecting the dispersion liquid into a hot water bath at 90 ℃ by using an injection pump and a spray head to regenerate to obtain coarse materials, controlling the injection speed to be 10ml/min, controlling the aperture of the outlet of the spray head to be 0.5mm, washing the coarse materials by using deionized water, drying, and then crushing and grinding to obtain the pore-forming agent with the average particle size of 60 mu m after grinding.
Wherein, the main components of the aluminum hydroxide dry glue are as follows: 97.68% of alumina, 0.08% of silicon dioxide, 2.15% of sulfate and the balance of other impurities.
The oil refining catalyst of this example was prepared by the preparation method described above.
Example 4
The preparation method of the oil refining catalyst of this example is different from that of example 3 in that: in the step S2, the heat treatment is carried out in a roasting furnace with a microcomputer temperature control system, the heat treatment is divided into a first stage and a second stage, and the fitting equation of a temperature rise control curve in the first stage is y= (0.28-a) x+ (2.5-b) x+112; the fitting equation of the temperature rise control curve in the second stage is y= - (0.02-m) x+ (5.1-n) x+221; wherein the ordinate is temperature (. Degree.C.) and the abscissa is time (min); the starting point of the abscissa of the first stage is set to be 0min, the ending point is set to be 90min, the starting point of the ordinate is set to be 120 ℃, and the ending point is set to be 260 ℃; the start point of the abscissa of the second stage was set to 90min, the end point was set to 270min, the start point of the abscissa was set to 250℃and the end point was set to 600℃and the rest was the same as in example 3.
Wherein a is 0.053, b is 1.26, m is 0.0038, and n is 0.2. R of first stage fitting equation 2 0.85, R of the second stage fitting equation 2 0.6. The temperature control accuracy in the heat treatment process is 0.5 ℃.
The oil refining catalyst of this example was prepared by the preparation method described above.
Example 5
The preparation method of the oil refining catalyst of this example is different from that of example 3 in that: in the step S2, the heat treatment is carried out in a roasting furnace with a microcomputer temperature control system, the heat treatment is divided into a first stage and a second stage, and the fitting equation of a temperature rise control curve in the first stage is y= (0.28-a) x+ (2.5-b) x+112; the fitting equation of the temperature rise control curve in the second stage is y= - (0.02-m) x+ (5.1-n) x+221; wherein the ordinate is temperature (. Degree.C.) and the abscissa is time (min); the starting point of the abscissa of the first stage is set to be 0min, the ending point is set to be 120min, the starting point of the ordinate is set to be 150 ℃, and the ending point is set to be 230 ℃; the start point of the abscissa of the second stage was set to 120min, the end point was set to 240min, the start point of the abscissa was set to 220℃and the end point was set to 550℃and the rest was the same as in example 3.
Wherein a is 0.085, b is 1.19, m is 0.0012, and n is 0.43. R of first stage fitting equation 2 0.5, R of the second stage fitting equation 2 0.92. The temperature control accuracy in the heat treatment process is 0.5 ℃.
The oil refining catalyst of this example was prepared by the preparation method described above.
Example 6
The preparation method of the oil refining catalyst of this example is different from that of example 3 in that: in the step S2, the heat treatment is carried out in a roasting furnace with a microcomputer temperature control system, the heat treatment is divided into a first stage and a second stage, and the fitting equation of a temperature rise control curve in the first stage is y= (0.28-a) x+ (2.5-b) x+112; the fitting equation of the temperature rise control curve in the second stage is y= - (0.02-m) x+ (5.1-n) x+221; wherein the ordinate is temperature (. Degree.C.) and the abscissa is time (min); the starting point of the abscissa of the first stage is set to be 0min, the end point is set to be 100min, the starting point of the ordinate is set to be 150 ℃, and the end point is set to be 230 ℃; the start point of the abscissa of the second stage was set to 100min, the end point was set to 260min, the start point of the abscissa was set to 220℃and the end point was set to 550℃and the rest was the same as in example 3.
Wherein a is 0.065, b is 1.23, m is 0.0032, and n is 0.38. R of first stage fitting equation 2 0.65, the second stageR of fitting equation 2 0.8. The temperature control accuracy in the heat treatment process is 0.5 ℃.
The oil refining catalyst of this example was prepared by the preparation method described above.
Example 7
The preparation method of the oil refining catalyst of this example is different from that of example 6 in that: in step S1, the alkyl quaternary ammonium base consists of tetrabutylammonium hydroxide and tetramethylammonium hydroxide according to the mass ratio of 2.6:1, and the rest is the same as in example 6.
The oil refining catalyst of this example was prepared by the preparation method described above.
Example 8
The preparation method of the oil refining catalyst of this example is different from that of example 6 in that: in step S1, the alkyl quaternary ammonium base consists of tetrabutylammonium hydroxide and tetramethylammonium hydroxide according to the mass ratio of 3:1, and the rest is the same as in example 6.
The oil refining catalyst of this example was prepared by the preparation method described above.
Example 9
The preparation method of the oil refining catalyst of this example is different from that of example 8 in that:
in the preparation method of the pore-forming agent of the embodiment, the hot water bath regeneration process comprises the following steps:
a) Injecting the dispersion liquid into a hot water bath at 50 ℃ by using an injection pump and a spray head for presetting, controlling the injection speed to be 15ml/min, and controlling the aperture of an outlet of the spray head to be 0.5mm to obtain a semi-solid preset material;
b) Heating the hot water bath to 80 ℃, and simultaneously carrying out high-frequency oscillation treatment on the semi-solid pre-formed material to obtain coarse material, wherein the high-frequency oscillation treatment adopts an ultrasonic process, the ultrasonic power is 350W, then washing the coarse material with deionized water, drying, and then crushing and grinding to obtain the pore-forming agent with the average particle diameter of 600 mu m.
The remainder was the same as in example 8.
Example 10
The preparation method of the oil refining catalyst of this example is different from that of example 8 in that:
in the preparation method of the pore-forming agent of the embodiment, the hot water bath regeneration process comprises the following steps:
a) Injecting the dispersion liquid into a hot water bath at 65 ℃ by using an injection pump and a spray head for presetting, controlling the injection speed to be 15ml/min, and controlling the aperture of an outlet of the spray head to be 0.5mm to obtain a semi-solid preset molding material;
b) Heating the hot water bath to 95 ℃, and simultaneously carrying out high-frequency oscillation treatment on the semi-solid pre-formed material to obtain coarse material, wherein the high-frequency oscillation treatment adopts an ultrasonic process, the ultrasonic power is 350W, then washing the coarse material with deionized water, drying, and then crushing and grinding to obtain the pore-forming agent with the average particle diameter of 600 mu m.
The remainder was the same as in example 8.
Comparative example
Comparative example 1
The preparation method of the oil refining catalyst of the comparative example comprises the following steps:
s1: weighing 30g of aluminum hydroxide dry glue and 80g of carboxymethyl cellulose for standby, firstly uniformly mixing the aluminum hydroxide dry glue and the carboxymethyl cellulose in a stirring kettle, then dissolving 2ml of 65% nitric acid in 57g of water to obtain an acid solution, then adding the acid solution into the stirring kettle under continuous stirring, then kneading by a double-screw strip extruder to obtain a plastic, and finally extruding and molding by a pore plate with the diameter of 1.5mm to obtain a blank;
s2: placing the blank material in an oven, setting a drying temperature of 120 ℃ and drying for 3 hours; the dried green body material is sent into a roasting furnace for heat treatment to obtain a carrier, the heat treatment temperature is raised to 550 ℃ from room temperature, the heating speed is 9 ℃/min, and the heat treatment time is 4 hours;
s3: adding 30ml of 80% phosphoric acid, 600ml of deionized water, 100g of molybdenum trioxide and 35g of basic nickel carbonate into a three-neck flask, heating and stirring to completely dissolve the molybdenum trioxide, adding 60g of ammonium metatungstate into the three-neck flask, and concentrating to 200ml after the ammonium metatungstate is completely dissolved to prepare an impregnating solution; and (3) carrying out impregnation treatment on the equal volume of carrier and the impregnation liquid, putting the impregnated carrier and the impregnation liquid into an oven for drying for 4 hours at the temperature of 120 ℃, putting the dried carrier and the impregnation liquid into a muffle furnace for roasting for 4 hours at the temperature of 500 ℃ to obtain the finished product.
The oil refining catalyst of the comparative example was prepared by the above preparation method.
Comparative example 2
The preparation method of the oil refining catalyst of the comparative example comprises the following steps:
s1: weighing 30g of aluminum hydroxide dry gel and 80g of aluminum ammonium carbonate for standby, firstly uniformly mixing the aluminum hydroxide dry gel and the aluminum ammonium carbonate in a stirring kettle, then dissolving 2ml of 65% nitric acid in 57g of water to obtain an acid solution, then adding the acid solution into the stirring kettle under continuous stirring, then kneading by a double-screw extruder to obtain a plastic, and finally extruding and molding by a pore plate with the diameter of 1.5mm to obtain a blank;
s2: placing the blank material in an oven, setting a drying temperature of 120 ℃ and drying for 3 hours; the dried green body material is sent into a roasting furnace for heat treatment to obtain a carrier, the heat treatment temperature is raised to 550 ℃ from room temperature, the heating speed is 9 ℃/min, and the heat treatment time is 4 hours;
s3: adding 30ml of 80% phosphoric acid, 600ml of deionized water, 100g of molybdenum trioxide and 35g of basic nickel carbonate into a three-neck flask, heating and stirring to completely dissolve the molybdenum trioxide, adding 60g of ammonium metatungstate into the three-neck flask, and concentrating to 200ml after the ammonium metatungstate is completely dissolved to prepare an impregnating solution; and (3) carrying out impregnation treatment on the equal volume of carrier and the impregnation liquid, putting the impregnated carrier and the impregnation liquid into an oven for drying for 4 hours at the temperature of 120 ℃, putting the dried carrier and the impregnation liquid into a muffle furnace for roasting for 4 hours at the temperature of 500 ℃ to obtain the finished product.
The oil refining catalyst of the comparative example was prepared by the above preparation method.
Comparative example 3
The preparation method of the oil refining catalyst of this comparative example is different from that of example 1 in that:
the pore-forming agent of the comparative example was prepared by a method comprising the steps of:
1) Placing 150g of carboxymethyl cellulose and 100ml of deionized water into an open flask with magnetic stirring, and uniformly mixing to obtain an intermediate solution;
2) Heating the intermediate liquid to 40 ℃, slowly adding 50g of ammonium aluminum carbonate into the intermediate liquid under the condition of continuous stirring, and uniformly dispersing to obtain a dispersion liquid;
3) Drying the dispersion liquid, and then crushing and grinding to obtain the pore-forming agent with the average particle diameter of 200 mu m after grinding.
The remainder was the same as in example 1.
Comparative example 4
The preparation method of the oil refining catalyst of this comparative example is different from that of example 1 in that:
the pore-forming agent of the comparative example was prepared by a method comprising the steps of:
1) Placing 150g of carboxymethyl cellulose, 50ml of 40% sodium hydroxide solution and 100ml of deionized water into an open flask with magnetic stirring, and uniformly mixing to obtain an intermediate solution;
2) Heating the intermediate liquid to 40 ℃, slowly adding 50g of ammonium aluminum carbonate into the intermediate liquid under the condition of continuous stirring, and uniformly dispersing to obtain a dispersion liquid;
3) Injecting the dispersion liquid into a dilute sulfuric acid solution at 90 ℃ by using an injection pump and a spray head, neutralizing by acid and alkali, regenerating to obtain coarse materials, controlling the injection speed to be 10ml/min, controlling the aperture of an outlet of the spray head to be 0.5mm, washing the coarse materials by using deionized water, drying, and then crushing and grinding to obtain the pore-forming agent with the average particle size of 200 mu m after grinding.
The remainder was the same as in example 1.
Comparative example 5
The preparation method of the oil refining catalyst of this comparative example is different from that of example 1 in that:
the pore-forming agent of the comparative example was prepared by a method comprising the steps of:
1) Placing 150g of active carbon, 50ml of chitosan gel and 100ml of deionized water into an open flask with magnetic stirring, and uniformly mixing to obtain an intermediate solution;
2) Heating the intermediate liquid to 40 ℃, slowly adding 50g of ammonium aluminum carbonate into the intermediate liquid under the condition of continuous stirring, and uniformly dispersing to obtain a dispersion liquid;
3) The dispersion liquid is pre-dried to be semi-solid, then the semi-solid is extruded to obtain strip coarse material, the coarse material is further dried in an oven, and then the coarse material is crushed and ground to obtain the pore-forming agent with the average particle size of 200 mu m.
The remainder was the same as in example 1.
Performance test
1. Pore size analysis
The refining catalysts of examples 1 to 10 and comparative examples 1 to 5 were analyzed by mercury intrusion, and the pore size distribution was evaluated by a pore size distribution curve, and the test results are shown in FIGS. 1 to 15 (FIG. 1 corresponds to example 1, and so on).
2. Catalytic effect
2.1 main component composition parameters of raw oil for experiment: reduced pressure wax oil 87.75%, coker wax oil 12.56%, and other components.
The main property parameters of the experimental raw oil are as follows:
density 0.902g/cm (20 ℃ C.);
0.53 percent (W%) of carbon residue;
distillation range (ASTM-D1160/. Degree.C.);
IBM/10%/50%90%/FBP295/350/436/535/612；
S22189（μg/g）；
N1758（μg/g）；
Fe3.22（μg/g）；
Ni0.28（μg/g）；
V0.67（μg/g）；
saturation fraction 59.13;
fragrance fraction 30.06;
gum 10.81.
2.2 Experimental apparatus: the method is carried out on a 100ml fixed bed hydrogenation evaluation device and comprises a feed pump, a heating furnace, a reactor main body, an air flow meter and a temperature indicator, wherein the reactor main body is made of stainless steel, and has the specification of 150cm in length, 1.5cm in outer diameter and 1cm in inner diameter; the catalyst loading is 100ml, the bed layer height is 24cm, 15ml of protective agent is filled at the top, the air tightness is tested, and the catalyst is subjected to presulfiding treatment for standby after being qualified.
2.3 evaluation conditions: the reaction pressure is 10MPa and the space velocity is 1.5h -1 The temperature is 380 ℃, and the hydrogen-oil ratio is 700:1.
The refinery catalysts of examples 1 to 10 and comparative examples 1 to 5 were tested for catalytic effect according to the above experimental parameters, and the results of the tests are shown in fig. 16, using desulfurization rate (HDS%) as an evaluation index.
As can be seen from analysis examples 1-3 and fig. 1-3, the preparation method adopts the compound use of carboxymethyl cellulose and ammonium aluminum carbonate to prepare the composite micro-nano particle pore-forming agent with a special package structure, can obtain a stable and adaptive decomposition process and gas production speed in a heat treatment stage, can form a pore channel structure with better distribution state, and ensures that the diffusion and mass transfer efficiency of reactants on a catalyst is higher in the use process, thereby improving the catalytic effect of the catalyst.
As can be seen from analysis of examples 4-6 and combining fig. 4-6, by adopting the synergistic effect of two heating processes and matching with a proper heating control curve, the matching performance of the overlapping gas production stage and the independent gas production stage of the decomposition of the outer layer substance and the inner layer substance of the pore-forming agent is better, so that a more perfect pore channel structure is formed, and as can be seen from the analysis of example 6, the pore size distribution is slightly dispersed, the pore size distribution in the range of 10-15nm is more, the pore-forming agent has a more moderate macroporous structure, and the overall catalytic effect is better.
As can be seen from the analysis of examples 7-8 and examples 9-10 in combination with fig. 7-10, further optimization and adjustment of the type composition of the alkyl quaternary ammonium base can improve the bonding strength between the package main body and the distribution core and the modification degree of the polarity of the surface of the pore structure, thereby improving the catalytic effect. In addition, by adopting a hot water bath injection molding process, the formed long cylindrical semi-solid pre-molded material can form an alkyl quaternary ammonium base migration concentration gradient along the diameter direction in a regeneration stage, so that alkyl quaternary ammonium base molecules are in dynamic balance of crosslinking, dissociation and diffusion, and meanwhile, ultrasonic treatment with proper power is further carried out, so that concentration polarization effect is not easy to form at a solid-liquid interface of the semi-solid pre-molded material, the structural state of the pore-forming agent is further improved, a better decomposition gas production effect is obtained, and a more perfect pore size distribution state is formed.
As can be seen from analysis of example 1 and comparative examples 1-6 in combination with FIGS. 1 and 11-15, the comparative example 1 uses carboxymethyl cellulose as pore-forming agent, which has a somewhat unbalanced ratio between the large pores and the small pores, and has poor overall catalytic efficiency. When aluminum ammonium carbonate was used as the pore-forming agent in comparative example 2, the overall pore size distribution was slightly better than that in comparative example 1. In comparative example 3, carboxymethyl cellulose and ammonium aluminum carbonate are directly mixed for use, so that a corresponding inclusion structure cannot be formed, disordered decomposition is easy to occur in the heat treatment stage, the state of a pore channel structure is poor, an invalid pore structure with oversized is generated, and the catalytic effect is reduced more. In comparative examples 4 and 5, inorganic alkali and chitosan gel are adopted to replace alkyl quaternary ammonium alkali respectively, so that complete and uniform inclusion structures cannot be formed, the integral decomposition pore-forming process is not easy to regulate and control, and the distribution form of the produced pore channel structure is poor.
In a comprehensive view, the catalyst with good pore structure distribution state can be obtained by adopting the special composite micro-nano particle pore-forming agent in combination with a temperature rise control curve with good suitability, and has a very good catalytic effect, and the desulfurization rate is more than 90%.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (10)
1. A method for preparing an oil refining catalyst, which is characterized by comprising the following steps:
s1: taking aluminum hydroxide dry glue, pore-forming agent and acid solution according to the mass ratio of (20-30) to (80-100) to (60-90), uniformly mixing to obtain plastic, and then processing and forming to obtain blank;
the pore-forming agent is prepared by a method comprising the following steps:
1) Uniformly mixing carboxymethyl cellulose, alkyl quaternary ammonium base and water to obtain an intermediate solution;
2) Adding ammonium aluminum carbonate into the intermediate liquid, and uniformly dispersing to obtain a dispersion liquid;
3) Placing the dispersion liquid into a hot water bath for regeneration to obtain coarse materials, drying, crushing and grinding to obtain the coarse materials;
s2: drying and heat-treating the blank material to obtain a carrier;
s3: and (3) placing the carrier in impregnating solution for impregnation treatment, and drying and roasting after the carrier is impregnated uniformly.
2. The method for preparing a refinery catalyst according to claim 1, wherein in the step S2, the heat treatment is divided into a first stage and a second stage, and the fitting equation of the temperature rise control curve of the first stage is y= (0.28-a) x, + (2.5-b) x+112; the fitting equation of the temperature rise control curve in the second stage is y= - (0.02-m) x+ (5.1-n) x+221; wherein the ordinate is temperature (. Degree.C.) and the abscissa is time (min); the starting point of the abscissa of the first stage is set to be 0min, the ending point is set to be 90-120min, the starting point of the ordinate is set to be 120-150 ℃, and the ending point is set to be 230-260 ℃; the starting point of the abscissa of the second stage is set to be 90-120min, the end point is set to be 240-270min, the starting point of the abscissa is set to be 220-250 ℃, and the end point is set to be 550-600 ℃.
3. The method for preparing a catalyst for oil refining according to claim 2, wherein a ranges from 0.053 to 0.085 and b ranges from 1.19 to 1.26; m ranges from 0.0012 to 0.0038, and n ranges from 0.2 to 0.43.
4. The method for preparing a refinery catalyst according to claim 2, wherein the temperature rise control curve of the first stage is R of the fitting equation 2 In the range of 0.5-0.65, R of the fitting equation of the temperature rise control curve of the second stage 2 Ranging from 0.8 to 0.92.
5. The method for preparing a catalyst for oil refining according to claim 1, wherein in the step S1, the mass ratio of carboxymethyl cellulose, alkyl quaternary ammonium base and aluminum ammonium carbonate is (10-20): 1-1.5): 3-5.
6. The method for preparing a refinery catalyst according to claim 1, wherein the alkyl quaternary ammonium base is one or more of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide and trimethyl ethyl ammonium hydroxide.
7. The method for preparing a catalyst for oil refining according to claim 6, wherein the alkyl quaternary ammonium base consists of tetrabutylammonium hydroxide and tetramethylammonium hydroxide according to the mass ratio of (2.6-3): 1.
8. The method for preparing a catalyst for oil refining according to claim 1, wherein the average particle size of the pore-forming agent is 35-60 μm.
9. The method for preparing a catalyst for oil refining according to claim 1, wherein in the step 3), the hot water bath regeneration process comprises the steps of:
a) Placing the dispersion liquid into a hot water bath at 50-65 ℃ for presetting to obtain a semi-solid preset material;
b) Heating the hot water bath to 80-95 ℃, and performing high-frequency oscillation treatment on the gelatinous pre-formed material to obtain coarse material.
10. A refinery catalyst prepared by the process for preparing a refinery catalyst as recited in claim 1.
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