CN108816279B - Preparation method of normal paraffin hydroisomerization catalyst - Google Patents
Preparation method of normal paraffin hydroisomerization catalyst Download PDFInfo
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
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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
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
Abstract
The invention discloses a preparation method of a normal alkane hydroisomerization catalyst, which is prepared by kneading, extruding and granulating one or more one-dimensional ten-membered ring mesoporous molecular sieves and then loading one or more VIII group metals. According to the preparation method, in the catalyst roasting stage, wet air containing 1-10 wt% of water is used as a medium, so that the problem that the selectivity of the catalyst isoparaffin is reduced due to halogen residues caused by using halogen-containing metal salt when the metal is loaded is solved. Compared with the catalyst prepared by the traditional roasting method, the long-chain normal paraffin hydroisomerization catalyst prepared by the method can improve the yield of an isomerization product by more than 5 percent while maintaining the catalytic activity, and is convenient to operate and easy to control.
Description
The present application is a priority application of the following applications
Application No. of the original application: 201810498744.9
Application date of the original application: 2018-5-23
The invention name of the original application: a preparation method of a normal paraffin hydroisomerization catalyst.
Technical Field
The invention belongs to the technical field of preparation of hydrogenation catalysts, and particularly relates to a preparation method of a normal paraffin hydroisomerization catalyst.
Background
In recent years, with the rapid development of modern industries, the quality requirement of lubricating oil on base oil is increasing. Early solvent dewaxing and catalytic dewaxing have not been able to meet the requirements for high quality lubricant base oils. The heterogeneous pour point depression technology which arose in the 80 s of the 20 th century shows special advantages in preparing base oil with low pour point and high viscosity index in high yield. The isomerization pour point depressing technique is to hydroisomerize non-ideal macromolecule normal paraffin into isoparaffin with the same molecular weight under the action of catalyst, thereby achieving the purpose of depressing the pour point, obviously depressing the pour point of the dewaxed oil and having higher yield and viscosity index of the lube base oil. The heterogeneous pour point depressing lubricating oil base oil has the advantages that the product structure can be flexibly adjusted according to market demands, and the diversified production is met.
In order to meet the requirements of the isomerization and pour point depression process, the key point of the technology is to develop a high-efficiency bifunctional catalyst with noble metal supported by an acidic carrier, wherein active metal in the catalyst plays a role in dehydrogenation/hydrogenation, and the acidic carrier provides a proper acidic site for isomerization. The organic combination of the active metal and the acidic support will play a crucial role in the catalytic performance of the catalyst.
Patents USP5135638, USP5149421, USP5246556, CNP1703497A, CNP1762594A sequentially report the use of molecular sieves containing one-dimensional ten-membered ring structure loaded with noble metal elements for alkane hydroisomerization reactions, the preparation process can be roughly described as: one or more one-dimensional ten-membered ring structure molecular sieves or other acidic carriers are selected to be mixed with an adhesive to be extruded into strips for molding, active metal is loaded on the molded carrier by an isometric impregnation method, and the isomerization catalyst is obtained by roasting in the air after drying. The molecular sieve with one-dimensional ten-membered ring structure comprises SAPO-11, MAPO-11, H-Beta, ZSM-22, SSZ-32X, SSZ-32, ZSM-23, SAPO-31, SAPO-41, ZSM-12, ZSM-48, EU-1, NU-10, and the loaded active metal comprises a group VI metal, a group VIII metal or a mixture thereof. These reports all used a similar approach, i.e. the sample was calcined in air after loading to give the final catalyst. In the preparation method, the supported active metal is often a halogen-containing metal salt, and the halogen remained on the surface of the catalyst cannot be completely removed by roasting in the air atmosphere, so that the selectivity and yield of the isomerization product on the bifunctional isomerization catalyst are reduced, and the activity and service life of the catalyst are influenced. For the catalytic reaction affected by halogen, methods such as water washing, alkali washing and the like are commonly adopted in the preparation process of the catalyst.
The literature (Applied catalysis A: General 2006, 298, 57) reports washing Au/Al with dilute aqueous ammonia solutions2O3The catalyst improves the catalytic activity of the catalyst in CO oxidation; the use of HAuCl has been reported in the literature (Journal of Catalysis 2006, 237, 190)4Preparation of Au/TiO2Catalyst, use of dilute ammonia gas on Au/TiO2And (4) treating to improve the catalytic activity of the catalyst to achieve the effect of removing residual chlorine. However, these methods consume water and energy, and are prone to introduce other contaminants, which cause secondary damage to the active metal and the support, contamination, and even a decrease in the catalytic performance of the catalyst.
Disclosure of Invention
The invention aims to provide a preparation method of a normal paraffin hydroisomerization catalyst aiming at the defects of the prior art. Compared with the catalyst prepared by the traditional roasting method, the normal paraffin hydroisomerization catalyst prepared by the invention can improve the yield of an isomerization product by more than 5 percent while maintaining the catalytic activity, and is convenient to operate and easy to control.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a normal paraffin hydroisomerization catalyst specifically comprises the following steps:
(1) roasting the molecular sieve for 4 hours at 550 ℃ in a muffle furnace air atmosphere, and removing the residual template agent;
(2) uniformly mixing the molecular sieve treated in the step (1) with an adhesive, adding nitric acid and deionized water with the concentration of 0.5-5 wt%, uniformly kneading, extruding to form a cylindrical carrier with the diameter of 2.0 mm, drying at room temperature for 24 hours, and roasting in an air atmosphere; drying the roasted carrier at 120 ℃ for 12 hours, and cooling to room temperature;
(3) adding VIII group metal salt into 2 wt% nitric acid, and stirring until the solid is completely dissolved to obtain an impregnation liquid;
(4) soaking the carrier obtained in the step (2) in the soaking solution obtained in the step (3) by adopting an isometric soaking method for 1 hour, airing overnight, and then drying at 120 ℃ for 8 hours;
(5) and (4) roasting the impregnated carrier in the step (4) in an air atmosphere to obtain the catalyst.
The molecular sieve in the step (1) is a hydrogen type molecular sieve, and comprises one or more of SAPO-11, MAPO-11, H-Beta, ZSM-22, SSZ-32X, SSZ-32, ZSM-23, SAPO-31, SAPO-41, ZSM-12, ZSM-48, EU-1 and NU-10.
The adhesive in the step (2) comprises any one of pseudo-boehmite, diatomite and amorphous silica-alumina.
According to the dry basis mass percentage, the proportion of the molecular sieve to the adhesive in the step (2) is (60-80%): (20% -40%).
The VIII metal salt in the step (3) is H2PtCl6Metal salt, H2PtBr6Metal salt, PdCl2Metal salt, Pt (NH)3)2Cl2Metal salt and Pt (NH)3)2Br2One or more of metal salts.
In the prepared catalyst, the content of the supported VIII group metal in the catalyst is 0.1 wt% -3.0 wt%.
The roasting process in the step (2) and the step (5) is specifically as follows: two-stage gradient roasting is adopted, and in the first stage, the temperature is raised from room temperature to 150 ℃ at the speed of 2 ℃/min and is kept for 2 hours; and in the second stage, raising the temperature to 500 ℃ at the speed of 2 ℃/min, introducing wet air with the water content of 1-10 wt%, and keeping the air flow rate at 50-200 ml/min for 4 hours at 500 ℃ until the end.
The invention has the beneficial effects that: compared with the catalyst prepared by the traditional roasting method, the normal paraffin hydroisomerization catalyst prepared by the invention can improve the yield of an isomerization product by more than 5 percent while maintaining the catalytic activity, and is convenient to operate and easy to control.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.
A preparation method of a normal paraffin hydroisomerization catalyst specifically comprises the following steps:
(1) roasting the molecular sieve for 4 hours at 550 ℃ in a muffle furnace air atmosphere, and removing the residual template agent;
(2) mixing the molecular sieve treated in the step (1) and a binder according to a dry basis mass ratio of (60-80%): (20% -40%) for 15 minutes, adding nitric acid and deionized water with the concentration of 0.5-5 wt%, kneading uniformly, extruding to form a cylindrical carrier with the diameter of 2.0 mm, drying at room temperature for 24 hours after drying, and then roasting in an air atmosphere; drying the roasted carrier at 120 ℃ for 12 hours, and cooling to room temperature;
(3) adding VIII group metal salt into 2 wt% nitric acid, and stirring until the solid is completely dissolved to obtain an impregnation liquid;
(4) soaking the carrier obtained in the step (2) in the soaking solution obtained in the step (3) by adopting an isometric soaking method for 1 hour, airing overnight, and then drying at 120 ℃ for 8 hours;
(5) and (3) roasting the impregnated carrier in the step (4) in an air atmosphere to obtain the catalyst, wherein the content of the supported VIII group metal in the catalyst is 0.1-3.0 wt%.
The molecular sieve in the step (1) is a hydrogen type molecular sieve, and comprises one or more of SAPO-11, MAPO-11, H-Beta, ZSM-22, SSZ-32X, SSZ-32, ZSM-23, SAPO-31, SAPO-41, ZSM-12, ZSM-48, EU-1 and NU-10.
The adhesive in the step (2) comprises any one of pseudo-boehmite, diatomite and amorphous silica-alumina.
The VIII metal salt in the step (3) is H2PtCl6Metal salt, H2PtBr6Metal salt, PdCl2Metal salt, Pt (NH)3)2Cl2Metal salt and Pt (NH)3)2Br2One or more of metal salts.
The roasting process in the step (2) and the step (5) is specifically as follows: two-stage gradient roasting is adopted, and in the first stage, the temperature is raised from room temperature to 150 ℃ at the speed of 2 ℃/min and is kept for 2 hours; and in the second stage, raising the temperature to 500 ℃ at the speed of 2 ℃/min, introducing wet air with the water content of 1-10 wt%, and keeping the air flow rate at 50-200 ml/min for 4 hours at 500 ℃ until the end.
Example 1
(1) Roasting the SAPO-11 molecular sieve for 4 hours at 550 ℃ in the air atmosphere of a muffle furnace to remove the residual template agent;
(2) the SAPO-11 molecular sieve treated in the step (1) and pseudo-boehmite are mixed according to the mass ratio of dry basis of 75%: mixing 25% of the raw materials for 15 minutes until the raw materials are uniform, adding nitric acid and deionized water with the concentration of 3 wt%, uniformly kneading, extruding to form a cylindrical carrier with the diameter of 2.0 mm, drying at room temperature for 24 hours after drying, and then roasting in an air atmosphere; drying the roasted carrier at 120 ℃ for 12 hours, and cooling to room temperature;
(3) h is to be2PtCl6Adding metal salt into 2 wt% nitric acid, and stirring until the solid is completely dissolved to obtain Pt-containing impregnation liquid;
(4) soaking the carrier obtained in the step (2) in the Pt-containing soaking solution obtained in the step (3) for 1 hour by adopting an isometric soaking method, airing the carrier overnight, and then drying the carrier for 8 hours at 120 ℃;
(5) roasting the impregnated carrier in the step (4) in an air atmosphere to prepare an isodewaxing catalyst, which is recorded as Pt/SAPO-11/AL-w-1, wherein the content of the loaded Pt metal in the catalyst is 0.5 wt%; the product is tabletted and crushed into 20-40 meshes for use.
The roasting process in the step (2) and the step (5) is specifically as follows: two-stage gradient roasting is adopted, and in the first stage, the temperature is raised from room temperature to 150 ℃ at the speed of 2 ℃/min and is kept for 2 hours; in the second stage, the temperature is raised to 500 ℃ at the speed of 2 ℃/min, wet air with the water content of 5 wt% is introduced, the air flow rate is 120 ml/min, and the temperature is kept for 4 hours at 500 ℃ until the end.
Example 2
(1) Roasting the SAPO-11 molecular sieve for 4 hours at 550 ℃ in the air atmosphere of a muffle furnace to remove the residual template agent;
(2) the SAPO-11 molecular sieve treated in the step (1) and pseudo-boehmite are mixed according to the mass ratio of dry basis of 75%: mixing 25% of the raw materials for 15 minutes until the raw materials are uniform, adding nitric acid and deionized water with the concentration of 3 wt%, uniformly kneading, extruding to form a cylindrical carrier with the diameter of 2.0 mm, drying at room temperature for 24 hours after drying, and then roasting in an air atmosphere; drying the roasted carrier at 120 ℃ for 12 hours, and cooling to room temperature;
(3) h is to be2PtBr6Adding metal salt into 2 wt% nitric acid, and stirring until the solid is completely dissolved to obtain Pt-containing impregnation liquid;
(4) soaking the carrier obtained in the step (2) in the Pt-containing soaking solution obtained in the step (3) for 1 hour by adopting an isometric soaking method, airing the carrier overnight, and then drying the carrier for 8 hours at 120 ℃;
(5) roasting the impregnated carrier in the step (4) in an air atmosphere to prepare an isodewaxing catalyst, which is marked as Pt/SAPO-11/AL-w-2, wherein the content of the loaded Pt metal in the catalyst is 0.5 wt%; the product is tabletted and crushed into 20-40 meshes for use.
The roasting process in the step (2) and the step (5) is specifically as follows: two-stage gradient roasting is adopted, and in the first stage, the temperature is raised from room temperature to 150 ℃ at the speed of 2 ℃/min and is kept for 2 hours; in the second stage, the temperature is raised to 500 ℃ at the speed of 2 ℃/min, wet air with the water content of 5 wt% is introduced, the air flow rate is 120 ml/min, and the temperature is kept for 4 hours at 500 ℃ until the end.
Example 3
(1) Roasting the SAPO-11 molecular sieve for 4 hours at 550 ℃ in the air atmosphere of a muffle furnace to remove the residual template agent;
(2) the SAPO-11 molecular sieve treated in the step (1) and pseudo-boehmite are mixed according to the mass ratio of dry basis of 75%: mixing 25% of the raw materials for 15 minutes until the raw materials are uniform, adding nitric acid and deionized water with the concentration of 3 wt%, uniformly kneading, extruding to form a cylindrical carrier with the diameter of 2.0 mm, drying at room temperature for 24 hours after drying, and then roasting in an air atmosphere; drying the roasted carrier at 120 ℃ for 12 hours, and cooling to room temperature;
(3) PdCl2Adding metal salt into 2 wt% nitric acid, and stirring until the solid is completely dissolved to obtain Pd-containing impregnation liquid;
(4) soaking the carrier obtained in the step (2) in the Pd-containing soaking solution obtained in the step (3) by adopting an isometric soaking method for 1 hour, airing the carrier overnight, and then drying the carrier for 8 hours at 120 ℃;
(5) roasting the impregnated carrier in the step (4) in an air atmosphere to prepare an isodewaxing catalyst, which is recorded as Pd/SAPO-11/AL-w, wherein the content of the loaded Pd metal in the catalyst is 0.5 wt%; the product is tabletted and crushed into 20-40 meshes for use.
The roasting process in the step (2) and the step (5) is specifically as follows: two-stage gradient roasting is adopted, and in the first stage, the temperature is raised from room temperature to 150 ℃ at the speed of 2 ℃/min and is kept for 2 hours; in the second stage, the temperature is raised to 500 ℃ at the speed of 2 ℃/min, wet air with the water content of 5 wt% is introduced, the air flow rate is 120 ml/min, and the temperature is kept for 4 hours at 500 ℃ until the end.
Example 4
(1) Roasting the SAPO-11 molecular sieve for 4 hours at 550 ℃ in the air atmosphere of a muffle furnace to remove the residual template agent;
(2) the SAPO-11 molecular sieve treated in the step (1) and pseudo-boehmite are mixed according to the mass ratio of dry basis of 75%: mixing 25% of the raw materials for 15 minutes until the raw materials are uniform, adding nitric acid and deionized water with the concentration of 3 wt%, uniformly kneading, extruding to form a cylindrical carrier with the diameter of 2.0 mm, drying at room temperature for 24 hours after drying, and then roasting in an air atmosphere; drying the roasted carrier at 120 ℃ for 12 hours, and cooling to room temperature;
(3) mixing Pt (NH)3)2Cl2Adding metal salt into 2 wt% nitric acid, and stirring until the solid is completely dissolved to obtain Pt-containing impregnation liquid;
(4) soaking the carrier obtained in the step (2) in the Pt-containing soaking solution obtained in the step (3) for 1 hour by adopting an isometric soaking method, airing the carrier overnight, and then drying the carrier for 8 hours at 120 ℃;
(5) roasting the impregnated carrier in the step (4) in an air atmosphere to prepare an isodewaxing catalyst, which is marked as N-Pt/SAPO-11/AL-w-1, wherein the content of the loaded Pt metal in the catalyst is 0.5 wt%; the product is tabletted and crushed into 20-40 meshes for use.
The roasting process in the step (2) and the step (5) is specifically as follows: two-stage gradient roasting is adopted, and in the first stage, the temperature is raised from room temperature to 150 ℃ at the speed of 2 ℃/min and is kept for 2 hours; in the second stage, the temperature is raised to 500 ℃ at the speed of 2 ℃/min, wet air with the water content of 5 wt% is introduced, the air flow rate is 120 ml/min, and the temperature is kept for 4 hours at 500 ℃ until the end.
Example 5
(1) Roasting the SAPO-11 molecular sieve for 4 hours at 550 ℃ in the air atmosphere of a muffle furnace to remove the residual template agent;
(2) the SAPO-11 molecular sieve treated in the step (1) and pseudo-boehmite are mixed according to the mass ratio of dry basis of 75%: mixing 25% of the raw materials for 15 minutes until the raw materials are uniform, adding nitric acid and deionized water with the concentration of 3 wt%, uniformly kneading, extruding to form a cylindrical carrier with the diameter of 2.0 mm, drying at room temperature for 24 hours after drying, and then roasting in an air atmosphere; drying the roasted carrier at 120 ℃ for 12 hours, and cooling to room temperature;
(3) mixing Pt (NH)3)2Br2Adding metal salt into 2 wt% nitric acid, and stirring until the solid is completely dissolved to obtain Pt-containing impregnation liquid;
(4) soaking the carrier obtained in the step (2) in the Pt-containing soaking solution obtained in the step (3) for 1 hour by adopting an isometric soaking method, airing the carrier overnight, and then drying the carrier for 8 hours at 120 ℃;
(5) roasting the impregnated carrier in the step (4) in an air atmosphere to prepare an isodewaxing catalyst, which is marked as N-Pt/SAPO-11/AL-w-2, wherein the content of the loaded Pt metal in the catalyst is 0.5 wt%; the product is tabletted and crushed into 20-40 meshes for use.
The roasting process in the step (2) and the step (5) is specifically as follows: two-stage gradient roasting is adopted, and in the first stage, the temperature is raised from room temperature to 150 ℃ at the speed of 2 ℃/min and is kept for 2 hours; in the second stage, the temperature is raised to 500 ℃ at the speed of 2 ℃/min, wet air with the water content of 5 wt% is introduced, the air flow rate is 120 ml/min, and the temperature is kept for 4 hours at 500 ℃ until the end.
Comparative example 1
The other steps are the same as the example 1, and the roasting process is different, namely the roasting process in the step (2) and the step (5) is specifically as follows: two-stage gradient roasting is adopted, and in the first stage, the temperature is raised from room temperature to 150 ℃ at the speed of 2 ℃/min and is kept for 2 hours; the second stage is raised to 500 ℃ at the speed of 2 ℃/min, and the air is kept for 4 hours at the temperature of 500 ℃ until the end; the catalyst obtained is marked as Pt/SAPO-11/AL-1.
Comparative example 2
The other steps are the same as the example 2, and the roasting process is different, namely the roasting process in the step (2) and the step (5) is specifically as follows: two-stage gradient roasting is adopted, and in the first stage, the temperature is raised from room temperature to 150 ℃ at the speed of 2 ℃/min and is kept for 2 hours; the second stage is raised to 500 ℃ at the speed of 2 ℃/min, and the air is kept for 4 hours at the temperature of 500 ℃ until the end; the catalyst obtained is marked as Pt/SAPO-11/AL-2.
Comparative example 3
The other steps are the same as the example 3, and the roasting process is different, namely the roasting process in the step (2) and the step (5) is specifically as follows: two-stage gradient roasting is adopted, and in the first stage, the temperature is raised from room temperature to 150 ℃ at the speed of 2 ℃/min and is kept for 2 hours; the second stage is raised to 500 ℃ at the speed of 2 ℃/min, and the air is kept for 4 hours at the temperature of 500 ℃ until the end; the catalyst obtained is denoted as Pd/SAPO-11/AL.
Comparative example 4
The other steps are the same as the example 4, and the roasting process is different, namely the roasting process in the step (2) and the step (5) is specifically as follows: two-stage gradient roasting is adopted, and in the first stage, the temperature is raised from room temperature to 150 ℃ at the speed of 2 ℃/min and is kept for 2 hours; the second stage is raised to 500 ℃ at the speed of 2 ℃/min, and the air is kept for 4 hours at the temperature of 500 ℃ until the end; the prepared catalyst is marked as N-Pt/SAPO-11/AL-1.
Comparative example 5
The other steps are the same as the example 5, and the roasting process is different, namely the roasting process in the step (2) and the step (5) is specifically as follows: two-stage gradient roasting is adopted, and in the first stage, the temperature is raised from room temperature to 150 ℃ at the speed of 2 ℃/min and is kept for 2 hours; the second stage is raised to 500 ℃ at the speed of 2 ℃/min, and the air is kept for 4 hours at the temperature of 500 ℃ until the end; the prepared catalyst is marked as N-Pt/SAPO-11/AL-2.
Catalyst evaluation
The n-dodecane hydroisomerization reaction was carried out in a high-pressure fixed bed reactor, and the catalyst prepared in examples 1 to 5 and comparative examples 1 to 5 was packed in a mass of 2.0 ml. Before reaction, the catalyst needs to be reduced for 2 hours at the temperature of 450 ℃ under normal pressure, and when the temperature is reduced to the reaction temperature, the raw material hydrogen is introduced to react with the n-dodecane. The reaction conditions are as follows: the reaction temperature was 318 deg.C, the reaction pressure was 3.5 MPa, the mass space velocity of the raw material was 1.0 h-1, the molar ratio of hydrogen to n-dodecane was 40:1, and the reaction results are shown in Table 1.
Wherein, the calculation formula of the n-dodecane conversion rate and the selectivity of the isomeric product is as follows:
TABLE 1 evaluation results of catalysts
Through comparing the five experiments of example 1 and comparative example 1, example 2 and comparative example 2, example 3 and comparative example 3, example 4 and comparative example 4, and example 5 and comparative example 5, it can be seen that the isomerization product yield of the catalyst in the n-dodecane hydroisomerization is obviously improved by selecting different group VIII halogen-containing metal salts and different molecular sieves to prepare the isomerization catalyst and introducing air containing 1% -10% of water vapor in the calcination stage.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (5)
1. A preparation method of a normal paraffin hydroisomerization catalyst is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) roasting the molecular sieve for 4 hours at 550 ℃ in a muffle furnace air atmosphere, and removing the residual template agent;
(2) uniformly mixing the molecular sieve treated in the step (1) with an adhesive, adding nitric acid and deionized water with the concentration of 0.5-5 wt%, uniformly kneading, extruding to form a cylindrical carrier with the diameter of 2.0 mm, drying at room temperature for 24 hours, and roasting in an air atmosphere; drying the roasted carrier at 120 ℃ for 12 hours, and cooling to room temperature;
(3) adding VIII group metal salt into 2 wt% nitric acid, and stirring until the solid is completely dissolved to obtain an impregnation liquid;
(4) soaking the carrier obtained in the step (2) in the soaking solution obtained in the step (3) by adopting an isometric soaking method for 1 hour, airing overnight, and then drying at 120 ℃ for 8 hours;
(5) roasting the impregnated carrier in the step (4) in an air atmosphere to obtain the catalyst;
the VIII metal salt in the step (3) is H2PtCl6Metal salt, H2PtBr6Metal salt, PdCl2Metal salt, Pt (NH)3)2Cl2Metal salt and Pt (NH)3)2Br2One or more of metal salts; the roasting process in the step (2) and the step (5) is specifically as follows: two-stage gradient roasting is adopted, and in the first stage, the temperature is raised from room temperature to 150 ℃ at the speed of 2 ℃/min and is kept for 2 hours; the second stage is raised to 500 ℃ at the speed of 2 ℃/min and kept for 4 hours until the end; in the roasting process, when the furnace temperature reaches 500 ℃, wet air with the water content of 1-10 wt% is introduced, and the air flow rate is 50-200 ml/min.
2. The method for preparing a normal paraffin hydroisomerization catalyst according to claim 1, wherein: the molecular sieve in the step (1) is a hydrogen type molecular sieve, and comprises one or more of SAPO-11, MAPO-11, H-Beta, ZSM-22, SSZ-32X, SSZ-32, ZSM-23, SAPO-31, SAPO-41, ZSM-12, ZSM-48, EU-1 and NU-10.
3. The method for preparing a normal paraffin hydroisomerization catalyst according to claim 1, wherein: the adhesive in the step (2) comprises any one of pseudo-boehmite, diatomite and amorphous silica-alumina.
4. The method for preparing a normal paraffin hydroisomerization catalyst according to claim 1, wherein: according to the dry basis mass percentage, the proportion of the molecular sieve to the adhesive in the step (2) is (60-80%): (20% -40%).
5. The method for preparing a normal paraffin hydroisomerization catalyst according to claim 1, wherein: in the prepared catalyst, the content of the supported VIII group metal in the catalyst is 0.1 wt% -3.0 wt%.
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| CN111185226A (en) * | 2020-03-06 | 2020-05-22 | 中化泉州石化有限公司 | Preparation method of Zn modified molecular sieve loaded Ni/W bimetal heterogeneous pour point depressing catalyst |
| CN111659462B (en) * | 2020-06-30 | 2023-10-27 | 中化泉州石化有限公司 | Preparation method of high-activity isomerism pour point depressing catalyst |
| CN114618569B (en) * | 2020-12-10 | 2023-06-06 | 中国科学院大连化学物理研究所 | Catalyst and preparation method and application thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85103199A (en) * | 1984-04-13 | 1986-10-22 | 联合碳化公司 | Molecular sieve compositions |
| CN1283587A (en) * | 1999-07-06 | 2001-02-14 | 中国石油化工集团公司 | Molecular sieve of silicon aluminium phosphate with AEL structure and its synthesis process |
| CN1380251A (en) * | 2002-05-30 | 2002-11-20 | 复旦大学 | SAPO-11 molecular sieve catalyst and its preparation method |
| CN1392099A (en) * | 2002-07-30 | 2003-01-22 | 复旦大学 | SAPO-11 molecualr sieve and its preparing method |
| CN1772611A (en) * | 2005-09-28 | 2006-05-17 | 中国科学院大连化学物理研究所 | Composite molecular sieve in ten-element cyclic structure and its synthesis process |
| ZA200509837B (en) * | 2003-07-03 | 2007-02-28 | Inst Francais Du Petrole | Process for improving the pour point of hydrocarbon charges resulting from the Fischer-Tropsch process, using a catalyst based on a mixture of zeolites |
| CN103241745A (en) * | 2013-04-16 | 2013-08-14 | 中国海洋石油总公司 | Synthesis method and application of small-particle-size SAPO-11 molecular sieve |
| CN103316710A (en) * | 2013-07-11 | 2013-09-25 | 中科合成油内蒙古有限公司 | Hydroisomerization/cracking catalyst, and preparation method and application thereof |
| CN104028297A (en) * | 2014-06-18 | 2014-09-10 | 浙江工业大学 | Preparation method of catalyst for isomerization of biological alkane |
| CN105749963A (en) * | 2014-12-16 | 2016-07-13 | 中国科学院大连化学物理研究所 | Preparation method of hydroisomerization/cracking catalyst and catalyst |
| CN107500306A (en) * | 2017-08-31 | 2017-12-22 | 江苏有容催化技术研究所有限公司 | A kind of molecular sieve catalysts of SAPO 11 and preparation method thereof |
-
2018
- 2018-06-08 CN CN201810589299.7A patent/CN108816279B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85103199A (en) * | 1984-04-13 | 1986-10-22 | 联合碳化公司 | Molecular sieve compositions |
| CN1283587A (en) * | 1999-07-06 | 2001-02-14 | 中国石油化工集团公司 | Molecular sieve of silicon aluminium phosphate with AEL structure and its synthesis process |
| CN1380251A (en) * | 2002-05-30 | 2002-11-20 | 复旦大学 | SAPO-11 molecular sieve catalyst and its preparation method |
| CN1392099A (en) * | 2002-07-30 | 2003-01-22 | 复旦大学 | SAPO-11 molecualr sieve and its preparing method |
| ZA200509837B (en) * | 2003-07-03 | 2007-02-28 | Inst Francais Du Petrole | Process for improving the pour point of hydrocarbon charges resulting from the Fischer-Tropsch process, using a catalyst based on a mixture of zeolites |
| CN1772611A (en) * | 2005-09-28 | 2006-05-17 | 中国科学院大连化学物理研究所 | Composite molecular sieve in ten-element cyclic structure and its synthesis process |
| CN103241745A (en) * | 2013-04-16 | 2013-08-14 | 中国海洋石油总公司 | Synthesis method and application of small-particle-size SAPO-11 molecular sieve |
| CN103316710A (en) * | 2013-07-11 | 2013-09-25 | 中科合成油内蒙古有限公司 | Hydroisomerization/cracking catalyst, and preparation method and application thereof |
| CN104028297A (en) * | 2014-06-18 | 2014-09-10 | 浙江工业大学 | Preparation method of catalyst for isomerization of biological alkane |
| CN105749963A (en) * | 2014-12-16 | 2016-07-13 | 中国科学院大连化学物理研究所 | Preparation method of hydroisomerization/cracking catalyst and catalyst |
| CN107500306A (en) * | 2017-08-31 | 2017-12-22 | 江苏有容催化技术研究所有限公司 | A kind of molecular sieve catalysts of SAPO 11 and preparation method thereof |
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