CN113786859A - Hydrocracking catalyst, and preparation method and application thereof - Google Patents
Hydrocracking catalyst, and preparation method and application thereof Download PDFInfo
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- CN113786859A CN113786859A CN202111229679.8A CN202111229679A CN113786859A CN 113786859 A CN113786859 A CN 113786859A CN 202111229679 A CN202111229679 A CN 202111229679A CN 113786859 A CN113786859 A CN 113786859A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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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
- 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
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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
- 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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- 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
- C10G47/06—Sulfides
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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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
- C10G47/26—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries
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Abstract
The invention discloses a hydrocracking catalyst and a preparation method and application thereof, wherein the catalyst comprises a hydrogenation active component and a cracking active component, the hydrogenation active component is an oil-soluble ionic liquid containing active metal, the active metal is selected from one or more of VIB and VIII group metals and plays a role in catalytic hydrogenation, the cracking active component is an amorphous composite oxide taking silicon dioxide as a matrix and doped with a modifier, and the modifier is one or more of IIIB, IVB and IIIA group metals and plays a role in catalytic cracking. The invention also provides a preparation method of the hydrocracking catalyst, which is characterized in that the oil-soluble ionic liquid and the composite oxide are dispersed in the solvent, and the catalyst can be prepared after in-situ vulcanization, and the preparation process is simple and convenient to operate. The catalyst provided by the invention is suitable for a poor-quality oil suspension bed hydrogenation process, plays a role in mutual synergy of catalytic hydrogenation and cracking, and has the characteristics of high conversion rate, high yield of light components and low coking rate.
Description
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a hydrocracking catalyst and a preparation method and application thereof.
Background
The deep processing of poor oil is an important means for obtaining light fuel oil. At present, although the processing technology of the inferior oil at home and abroad is various, the processing technology can be mainly classified into a decarburization technical route and a hydrogenation technical route. The former mainly comprises the technologies of heavy oil catalytic cracking, delayed coking, solvent deasphalting and the like; the latter is mainly various hydrotreating processes including fixed bed, moving bed, fluidized bed, suspended bed, etc. Compared with the decarburization technical route which has more low-value byproducts and longer process route, the hydrogenation technical route has the advantages of higher conversion depth of inferior oil, high light oil yield, high resource utilization rate and the like, and is more and more widely applied to the aspect of deep processing of the inferior oil in the future. The suspension bed hydrogenation process has the advantages of strong raw material adaptability, simple process, flexible operation, high conversion rate and the like, and is a better choice under the hydrogenation route compared with the fixed bed, boiling bed and moving bed hydrogenation processes in the aspects of raw material diffusion, pressure drop, mass transfer and easy inactivation of a catalyst, and is an inferior oil hydrogenation conversion technology with a very good application prospect.
The suspension bed hydrogenation process is a hydro-thermal cracking hydrogenation reaction under the working conditions of high temperature and high hydrogen pressure, and poor-quality oil hydrocarbon molecules are hydro-thermal cracked under the conditions of high temperature and high pressure to generate hydrocarbon radicals; the catalyst is used for adsorbing hydrogen and activating the hydrogen into hydrogen free radicals, and the hydrogen free radicals can capture hydrocarbon free radicals formed by thermal cracking and carry out hydrogenation passivation on the hydrocarbon free radicals so as to inhibit the hydrocarbon free radicals from being over-cracked and carrying out condensation coking reaction. Thus, the core of the suspension bed hydrogenation process is the catalyst. The catalyst of the existing suspension bed hydrogenation process is divided into a heterogeneous catalyst and a homogeneous catalyst according to solubility and state, and further, the homogeneous catalyst can be divided into a water-soluble catalyst and an oil-soluble catalyst according to the difference of hydrophilic and lipophilic characteristics. The heterogeneous catalyst is convenient to source and low in cost, but the catalyst generally has the problem of poor dispersibility and low catalytic activity; the precursor of the water-soluble catalyst is easy to aggregate when water is rapidly evaporated, so that finally formed large-size particles are difficult to achieve nano-size dispersion in inferior oil, and the catalytic activity is low; the oil-soluble catalyst is easy to achieve uniform dispersion of molecular level in an oil phase due to the fact that the oil-soluble catalyst contains a lipophilic ligand, and shows high catalytic hydrogenation and coke inhibition activities. However, the currently reported oil-soluble catalysts generally have the defects of complex synthetic route, high cost and the like, and limit further industrial application of the catalysts. Meanwhile, only polycyclic aromatic hydrocarbon can be hydrogenated and saturated by a single hydrogenation catalyst to generate cycloparaffin, and the added value of the product is low.
Disclosure of Invention
The invention aims to solve the problems of poor dispersity, complex synthetic route, high cost and single performance of a suspension bed hydrogenation process catalyst, and provides a novel hydrocracking catalyst and a preparation method thereof by combining an oil-soluble ionic liquid with hydrogenation activity and a composite oxide with cracking activity.
The invention adopts the following technical scheme:
a hydrocracking catalyst comprises a hydrogenation active component and a cracking active component, wherein the hydrogenation active component is an oil-soluble ionic liquid containing active metals, the cracking active component is an amorphous composite oxide which takes silicon dioxide as a matrix and is doped with a modifier, and the mass ratio of the hydrogenation active component to the cracking active component in the catalyst is (0.003-6) in terms of the mass of the active metals: 1.
the cation in the hydrogenation active component is one of quaternary ammonium, imidazole, pyridine or pyrrole organic cations containing long-chain alkyl, and the anion is an inorganic anion containing active metal, wherein the active metal is selected from one or more of VIB and VIII group metals.
Preferably, the active metal is one of molybdenum or tungsten.
The modifier in the cracking active component is one or more of IIIB, IVB and IIIA group metals, wherein the ratio of the number of silicon atoms in the matrix to the number of modifier metal atoms is 1 (0.05-1).
Preferably, the modifier is one or more of Zr, Ce, Ti and Al.
A preparation method of a hydrocracking catalyst comprises the steps of dispersing oil-soluble ionic liquid and composite oxides in a solvent, adding a vulcanizing agent, and carrying out in-situ vulcanization by the vulcanizing agent to obtain the target catalyst.
The solvent is one or a mixture of naphtha and vacuum gas oil.
The mass ratio of a mixture formed by the oil-soluble ionic liquid and the composite oxide to the solvent is (0.01-1): 1.
the vulcanizing agent is additionally added sublimed sulfur powder or organic sulfide contained in reaction raw materials; the content of the vulcanizing agent enables the ratio of the number of sulfur atoms to the number of active metal atoms in the ionic liquid to be (2-10): 1.
the vulcanizing agent is vulcanized in situ at the temperature of 200-350 ℃ for 30-120 min.
An application of a hydrocracking catalyst in a poor-quality oil suspension bed hydrogenation process comprises the following steps:
s1, weighing the prepared hydrocracking catalyst, adding the hydrocracking catalyst into the inferior oil, and shearing and homogenizing the hydrocracking catalyst by using a high-speed shearing machine to obtain a mixture of the catalyst and the inferior oil;
and S2, inputting the mixture obtained in the step S1 into a suspension bed reactor by using a feed pump, filling hydrogen, and passing the mixture through the reactor from bottom to top in a gas-liquid-solid three-phase slurry mode to perform catalytic hydrocracking reaction on the poor oil.
The mass ratio of the hydrocracking catalyst added in the step S1 to the inferior oil is (0.01-2): 1.
The reaction temperature in the step S2 is 350-450 ℃, the reaction pressure is 10-25 MPa, and the hydrogen-oil ratio is 300-2000.
The technical scheme of the invention has the following advantages:
A. the hydrogenation active component in the hydrocracking catalyst provided by the invention is oil-soluble ionic liquid, the long-chain alkyl group contained in the cation of the hydrogenation active component has good oil solubility, and can be highly dispersed in poor oil, so that the dispersibility of active metal contained in the anion is improved, and the hydrogenation active component is subjected to in-situ vulcanizationThe nano-scale active phase is formed, and the catalytic hydrogenation performance is excellent; the cracking active component has amorphous crystal phase characteristics and mesoporous texture characteristics, is beneficial to the approach of reactant molecules to active sites, has proper acid site quantity and strength, particularly has the interaction between silicon atoms and modified metals, and generates at a silicon-oxygen metal bridge bond
The acidic site is beneficial to the catalytic cracking reaction of reactant molecules such as isomerization, ring-opening cracking and the like, and the economic value of the product is improved.
B. The hydrocracking catalyst provided by the invention has a catalytic action mechanism of mutual synergy of catalytic hydrogenation and catalytic cracking, can be used for a poor-quality oil suspension bed hydrocracking process, and has the advantages of high conversion rate, high yield of light components and low coking rate.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a hydrocracking catalyst, which comprises a hydrogenation active component and a cracking active component, wherein the hydrogenation active component is oil-soluble ionic liquid containing active metal, the cation in the hydrogenation active component is one of quaternary ammonium, imidazole, pyridine or pyrrole organic cations containing long-chain alkyl, the anion is inorganic anion containing active metal, and the active metal is selected from one or more of VIB and VIII group metals, preferably one of molybdenum or tungsten; the cracking active component is an amorphous composite oxide which takes silicon dioxide as a matrix and is doped with a modifier, wherein the modifier is one or more of IIIB, IVB and IIIA group metals, preferably one or more of Zr, Ce, Ti and Al, and the ratio of the number of silicon atoms in the matrix to the number of modifier metal atoms is 1 (0.05-1). The mass ratio of the hydrogenation active component to the cracking active component in the catalyst is (0.003-6) in terms of the mass of the active metal: 1.
the invention also provides a preparation method of the hydrocracking catalyst, which comprises the steps of dispersing the oil-soluble ionic liquid and the composite oxide in a solvent, adding a vulcanizing agent, and carrying out in-situ vulcanization for 30-120 min by the vulcanizing agent at the temperature of 200-350 ℃ to obtain the target catalyst. The solvent is one or a mixture of naphtha and vacuum gas oil, and the mass ratio of the mixture formed by the added oil-soluble ionic liquid and the composite oxide to the solvent is (0.01-1): 1. the vulcanizing agent is additionally added sublimed sulfur powder or organic sulfide contained in reaction raw materials, and the content of the vulcanizing agent enables the ratio of the number of sulfur atoms to the number of active metal atoms in the ionic liquid to be (2-10): 1.
in addition, the invention also provides an application of the hydrocracking catalyst in the inferior oil suspension bed hydrogenation process, which comprises the following steps:
s1, weighing the prepared hydrocracking catalyst, adding the hydrocracking catalyst into the inferior oil, and shearing and homogenizing the hydrocracking catalyst by using a high-speed shearing machine to obtain a mixture of the catalyst and the inferior oil; the mass ratio of the hydrocracking catalyst to the inferior oil is (0.01-2) to 1.
And S2, inputting the mixture obtained in the step S1 into a suspension bed reactor by using a feed pump, filling hydrogen, and passing the mixture through the reactor from bottom to top in a gas-liquid-solid three-phase slurry mode, wherein the hydrogen-oil ratio is 300-2000, and the poor-quality oil catalytic hydrocracking reaction is carried out at the temperature of 350-450 ℃ and the reaction pressure of 10-25 MPa.
The hydrogenation active component in the hydrocracking catalyst provided by the invention is oil-soluble ionic liquid, and the long-chain alkyl group contained in the cation of the hydrogenation active component has good oil solubility and can be highly dispersed in inferior oil, so that the dispersibility of active metal contained in the anion is improved, and a nanoscale active phase is formed after in-situ vulcanization, and the hydrogenation catalyst has excellent catalytic hydrogenation performance; the cracking active component has amorphous crystal phase characteristic and mesoporous texture characteristic, is favorable for reactant molecules to approach active sites, has proper acid site number and strength, particularly has interaction between silicon atoms and modified metal, and is applied to siliconOxygen metal bridge bond formation
The acidic site is beneficial to the catalytic cracking reaction of reactant molecules such as isomerization, ring-opening cracking and the like, and the economic value of the product is improved.
The present invention will be described in detail below by way of specific examples.
Hydrocracking catalyst and preparation method thereof
Example 1:
in a 300 ml autoclave, 120 g of naphtha was charged, and 4500ppm of Mo equivalent tributylmethylammonium molybdate ionic liquid and 15 g of SiO were sequentially added2-ZrO2The composite oxide and 1.8 g of L-sulphur powder, wherein the ratio of the number of silicon atoms to the number of zirconium atoms in the composite oxide is 1:0.1, and the ratio of the number of sulfur atoms to the number of active metal Mo atoms in the ionic liquid is 10. After the addition, the reaction kettle nut is locked and checked to confirm that the sealing performance is good. And (3) raising the temperature of the reaction kettle to 350 ℃ in a hydrogen atmosphere for in-situ vulcanization, wherein the vulcanization time is 120min, and the molybdenum-based catalytic hydrocracking catalyst A is prepared.
Example 2:
120 g of vacuum gas oil is added into a 300 ml high-pressure reaction kettle, and 4500ppm W equivalent trioctyl methyl ammonium tungstate ionic liquid and 15 g of SiO are added in sequence2-CeO2The composite oxide and 0.94 g L of sulphur powder, wherein the ratio of the number of silicon atoms to the number of cerium atoms in the composite oxide is 1:0.2, and the ratio of the number of sulphur atoms to the number of active metal W atoms in the ionic liquid is 10. After the addition, the reaction kettle nut is locked and checked to confirm that the sealing performance is good. And (3) raising the temperature of the reaction kettle to 350 ℃ in a hydrogen atmosphere for in-situ vulcanization, wherein the vulcanization time is 100min, and thus obtaining the tungsten-based catalytic hydrocracking catalyst B.
Example 3:
50 g of naphtha and 70 g of vacuum gas oil are added into a 300 ml high-pressure reaction kettle, and 4500ppm of Mo equivalent 1-hexyl-3-methylimidazole phosphomolybdate ionic liquid and 15 g of SiO2-TiO2Composite oxide and 144 g of sulphur powder, wherein the ratio of the number of silicon atoms to the number of titanium atoms in the composite oxide is 1:0.05, and the ratio of the number of sulphur atoms to the number of Mo atoms in the active metal in the ionic liquid is 8. After the addition, the reaction kettle nut is locked and checked to confirm that the sealing performance is good. And (3) raising the temperature of the reaction kettle to 320 ℃ in a hydrogen atmosphere for in-situ vulcanization, wherein the vulcanization time is 80min, and thus obtaining the molybdenum-based catalytic hydrocracking catalyst C.
Example 4:
adding 120 g of naphtha into a 300 ml high-pressure reaction kettle, and adding 4500ppm of Mo equivalent 1-octyl-3-methylimidazole molybdate ionic liquid and 15 g of SiO2-ZrO2-Al2O3The composite oxide and 0.9 g of sulfur powder, wherein the atomic ratio of Si/(Zr + Al) in the composite oxide is 1:0.5, and the ratio of the number of sulfur atoms to the number of active metal Mo atoms in the ionic liquid is 5. After the addition, the reaction kettle nut is locked and checked to confirm that the sealing performance is good. And (3) raising the temperature of the reaction kettle to 250 ℃ in a hydrogen atmosphere for in-situ vulcanization for 30min to prepare the molybdenum-based catalytic hydrocracking catalyst D.
Example 5:
120 g of vacuum gas oil is added into a 300 ml high-pressure reaction kettle, and 4500ppm of Mo equivalent N-decyl pyridine molybdate ionic liquid and 15 g of SiO are added in sequence2-ZrO2-TiO2The composite oxide and 1.08 g liter of sulphur powder, wherein the atomic ratio of Si/(Zr + Ti) in the composite oxide is 1:0.6, and the ratio of the number of sulphur atoms to the number of active metal Mo atoms in the ionic liquid is 6. After the addition, the reaction kettle nut is locked and checked to confirm that the sealing performance is good. And (3) raising the temperature of the reaction kettle to 200 ℃ in a hydrogen atmosphere for in-situ vulcanization, wherein the vulcanization time is 60min, and the molybdenum-based catalytic hydrocracking catalyst E is prepared.
Example 6:
adding 120 g of naphtha into a 300 ml high-pressure reaction kettle, and adding 4500ppm W equivalent N, N-dodecyl-methyl pyrrole phosphotungstate ionic liquid and 15 g of SiO2-TiO2-Al2O3A composite oxide and 0.75 g L of sulphur powder, wherein Si/(Ti + Al) in the composite oxide is originalThe sub ratio is 1:1, and the ratio of the number of sulfur atoms to the number of active metal W atoms in the ionic liquid is 8. After the addition, the reaction kettle nut is locked and checked to confirm that the sealing performance is good. And (3) raising the temperature of the reaction kettle to 300 ℃ in a hydrogen atmosphere for in-situ vulcanization, wherein the vulcanization time is 60min, and the molybdenum-based catalytic hydrocracking catalyst F is prepared.
The following two comparative experiments were designed on the basis of example 6, with the difference that the catalyst in the comparative example contains only the hydrogenation active component or the cracking active component of example 6.
Comparative example 1:
adding 120 g of naphtha into a 300 ml high-pressure reaction kettle, and sequentially adding 4500ppm W equivalent N, N-dodecyl-methyl pyrrole phosphotungstate ionic liquid and 0.75 g liter of sulphur powder, wherein the ratio of the number of sulphur atoms to the number of active metal W atoms in the ionic liquid is 8. After the addition, the reaction kettle nut is locked and checked to confirm that the sealing performance is good. And (3) raising the temperature of the reaction kettle to 300 ℃ in a hydrogen atmosphere for in-situ vulcanization, wherein the vulcanization time is 60min, and the molybdenum-based catalytic hydrocracking catalyst G is prepared.
Comparative example 2:
in a 300 ml autoclave, 120 g of naphtha were charged, and 15 g of SiO were added in this order2-TiO2-Al2O3The composite oxide and 0.75 g of sulfur powder, wherein the atomic ratio of Si/(Ti + Al) in the composite oxide is 1: 1. After the addition, the reaction kettle nut is locked and checked to confirm that the sealing performance is good. And (3) raising the temperature of the reaction kettle to 300 ℃ in a hydrogen atmosphere for in-situ vulcanization, wherein the vulcanization time is 60min, and the molybdenum-based catalytic hydrocracking catalyst H is prepared.
Second, application example of hydrocracking catalyst
The hydrocracking catalysts prepared in examples 1 to 6 and comparative examples 1 to 2 are respectively used for the suspension bed catalytic hydrocracking evaluation of the atmospheric residue, and the experimental steps are as follows:
and mixing the hydrocracking catalyst with the atmospheric residue oil, and shearing and homogenizing by using a high-speed shearing machine to obtain a mixture of the catalyst and the atmospheric residue oil, wherein the mass ratio of the added hydrocracking catalyst to the inferior oil is 1: 10. The mixture is input into a suspension bed reactor by a feed pump, the mixture and hydrogen gas pass through the suspension bed reactor from bottom to top in a gas-liquid-solid three-phase slurry mode, and the atmospheric residue catalytic hydrocracking reaction is carried out under the conditions that the reaction temperature is 430 ℃, the reaction pressure is 15MPa and the hydrogen-oil ratio is 1200.
After the reaction is finished, collecting the product, carrying out reduced pressure distillation by using a reduced pressure distillation instrument, and collecting fractions with different temperatures, wherein the fractions comprise light oil (less than 350 ℃), vacuum gas oil (350-524 ℃) and residual oil (more than 524 ℃); the distillation residue was washed with toluene, centrifuged, dried and weighed to calculate the coke rate. The conversion rate of inferior oil, liquid yield, gas yield and coking rate of examples and comparative examples were calculated according to the following formulas, respectively, and the results are shown in Table 1.
Conversion (wt.%) is (m)Residual oil in feedstock-mPost-reaction residual oil)/mResidual oil in feedstock×100％
Liquid yield (wt.%) is (m)Light oil+mVacuum gas oil+mResidual oil)/mRaw oil×100％
Coking rate (wt.%) mResidue of rice/mRaw oil×100％
Gas yield (wt.%) was (1-liquid yield-coking rate) × 100%
TABLE 1 comparison of catalytic hydrocracking Performance of atmospheric resids
As can be seen from table 1, the hydrocracking catalyst suitable for the suspension bed process provided by the present invention has excellent catalytic performance. Compared with the hydrocracking catalyst F, the catalyst G only containing the hydrocracking active component has lower conversion rate, the catalyst H only containing the cracking active component has obviously reduced liquid yield and sharply increased gas yield and coking rate, and the hydrocracking catalyst provided by the invention has the synergistic catalytic action and has the advantages of high conversion rate, high yield of light components and low coking rate.
Nothing in this specification is said to apply to the prior art.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are intended to be within the scope of the invention.
Claims (13)
1. The hydrocracking catalyst is characterized by comprising a hydrogenation active component and a cracking active component, wherein the hydrogenation active component is an oil-soluble ionic liquid containing active metals, the cracking active component is an amorphous composite oxide which takes silicon dioxide as a matrix and is doped with a modifier, and the mass ratio of the hydrogenation active component to the cracking active component in the catalyst is (0.003-6): 1.
2. the hydrocracking catalyst according to claim 1, wherein the cation in the hydrogenation active component is one of quaternary ammonium, imidazole, pyridine or pyrrole organic cations containing long-chain alkyl, and the anion is an inorganic anion containing active metal, and the active metal is one or more selected from VIB and VIII group metals.
3. The hydrocracking catalyst of claim 2, wherein the active metal is one of molybdenum or tungsten.
4. The hydrocracking catalyst of claim 1, wherein the modifier in the cracking active component is one or more of group IIIB, group IVB and group IIIA metals, and the ratio of the number of silicon atoms in the matrix to the number of modifier metals is 1 (0.05-1).
5. The hydrocracking catalyst of claim 4, wherein the modifier is one or more of Zr, Ce, Ti and Al.
6. The process for preparing a hydrocracking catalyst according to any one of claims 1 to 5, wherein the target catalyst is prepared by dispersing an oil-soluble ionic liquid and a composite oxide in a solvent, adding a vulcanizing agent, and vulcanizing with the vulcanizing agent in situ.
7. The method of claim 6, wherein the solvent is one of naphtha and vacuum gas oil or a mixture of both.
8. The preparation method of the hydrocracking catalyst according to claim 6, wherein the mass ratio of the mixture of the oil-soluble ionic liquid and the composite oxide to the solvent is (0.01-1): 1.
9. the method for producing a hydrocracking catalyst according to claim 6, wherein the sulfiding agent is additionally added sublimed sulfur powder or organic sulfide contained in the reaction raw material; the content of the vulcanizing agent enables the ratio of the number of sulfur atoms to the number of active metal atoms in the ionic liquid to be (2-10): 1.
10. the preparation method of the hydrocracking catalyst according to claim 6, wherein the vulcanizing agent in-situ vulcanization temperature is 200 to 350 ℃ and the vulcanization time is 30 to 120 min.
11. The application of the hydrocracking catalyst in the poor oil suspension bed hydrogenation process is characterized by comprising the following steps:
s1, weighing the prepared hydrocracking catalyst, adding the hydrocracking catalyst into the inferior oil, and shearing and homogenizing the hydrocracking catalyst by using a high-speed shearing machine to obtain a mixture of the catalyst and the inferior oil;
and S2, inputting the mixture obtained in the step S1 into a suspension bed reactor by using a feed pump, filling hydrogen, and passing the mixture through the reactor from bottom to top in a gas-liquid-solid three-phase slurry mode to perform catalytic hydrocracking reaction on the poor oil.
12. The application of the hydrocracking catalyst in the hydrogenation process of the inferior oil suspension bed according to claim 11, wherein the mass ratio of the hydrocracking catalyst added in the step S1 to the inferior oil is (0.01-2): 1.
13. The application of the hydrocracking catalyst in the poor oil suspension bed hydrogenation process according to claim 11, wherein the reaction temperature in the step S2 is 350-450 ℃, the reaction pressure is 10-25 MPa, and the hydrogen-oil ratio is 300-2000.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6139723A (en) * | 1996-02-23 | 2000-10-31 | Hydrocarbon Technologies, Inc. | Iron-based ionic liquid catalysts for hydroprocessing carbonaceous feeds |
| CN1446888A (en) * | 2003-04-07 | 2003-10-08 | 石油大学(华东) | Suspension bed hydrocracking technique for producing gasoline with high octane number and diesel oil with high cetane number simultaneously |
| CN1459487A (en) * | 2002-05-23 | 2003-12-03 | 中国石油天然气股份有限公司 | Dispersion technology for online dispersing liquid catalyst in viscous raw oil |
| CN105498806A (en) * | 2014-09-25 | 2016-04-20 | 中国科学院大连化学物理研究所 | Surface-amphiphilic nano tungsten molybdenum sulfide hydrogenation catalyst, preparation method and application thereof |
| CN108264934A (en) * | 2016-12-30 | 2018-07-10 | 北京华石联合能源科技发展有限公司 | A kind of suspension bed hydrogenation process for handling heavy oil |
| CN111420670A (en) * | 2020-05-11 | 2020-07-17 | 太原理工大学 | Hydrogenation catalyst, preparation method and application thereof |
| CN111468097A (en) * | 2020-03-24 | 2020-07-31 | 福州大学化肥催化剂国家工程研究中心 | Catalytic cracking catalyst, preparation method and application thereof |
| CN112791741A (en) * | 2019-11-14 | 2021-05-14 | 中国石油天然气股份有限公司 | Preparation method of hydrocracking catalyst |
| CN112916041A (en) * | 2021-01-29 | 2021-06-08 | 福州大学化肥催化剂国家工程研究中心 | Oil-soluble molybdenum-based ionic liquid catalyst and preparation method and application thereof |
| CN112934245A (en) * | 2021-01-29 | 2021-06-11 | 福州大学 | Oil-soluble molybdenum-based composite hydrogenation catalyst, and preparation method and application thereof |
-
2021
- 2021-10-21 CN CN202111229679.8A patent/CN113786859A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6139723A (en) * | 1996-02-23 | 2000-10-31 | Hydrocarbon Technologies, Inc. | Iron-based ionic liquid catalysts for hydroprocessing carbonaceous feeds |
| CN1459487A (en) * | 2002-05-23 | 2003-12-03 | 中国石油天然气股份有限公司 | Dispersion technology for online dispersing liquid catalyst in viscous raw oil |
| CN1446888A (en) * | 2003-04-07 | 2003-10-08 | 石油大学(华东) | Suspension bed hydrocracking technique for producing gasoline with high octane number and diesel oil with high cetane number simultaneously |
| CN105498806A (en) * | 2014-09-25 | 2016-04-20 | 中国科学院大连化学物理研究所 | Surface-amphiphilic nano tungsten molybdenum sulfide hydrogenation catalyst, preparation method and application thereof |
| CN108264934A (en) * | 2016-12-30 | 2018-07-10 | 北京华石联合能源科技发展有限公司 | A kind of suspension bed hydrogenation process for handling heavy oil |
| CN112791741A (en) * | 2019-11-14 | 2021-05-14 | 中国石油天然气股份有限公司 | Preparation method of hydrocracking catalyst |
| CN111468097A (en) * | 2020-03-24 | 2020-07-31 | 福州大学化肥催化剂国家工程研究中心 | Catalytic cracking catalyst, preparation method and application thereof |
| CN111420670A (en) * | 2020-05-11 | 2020-07-17 | 太原理工大学 | Hydrogenation catalyst, preparation method and application thereof |
| CN112916041A (en) * | 2021-01-29 | 2021-06-08 | 福州大学化肥催化剂国家工程研究中心 | Oil-soluble molybdenum-based ionic liquid catalyst and preparation method and application thereof |
| CN112934245A (en) * | 2021-01-29 | 2021-06-11 | 福州大学 | Oil-soluble molybdenum-based composite hydrogenation catalyst, and preparation method and application thereof |
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