Reforming catalyst with high platinum dispersity and preparation method thereof
By introducing ordinary second -set metals such as zinc or tin, and adopting competitive adsorption methods, it has improved the platinum dispersality of stone brain oil catalytic reorganization catalysts, solved the dependence of existing technology to the pupae, and achieved efficient efficiency. Catalytic effect and reduction cost.
Patent Information
- Application Number
- CN202411569411.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-05
- Publication Date
- 2025-01-28
AI Technical Summary
Existing naphtha catalytic reforming catalysts rely on the rare metal rhenium, resulting in limited reserves and supply dependence, making it difficult to improve the dispersion and stability of platinum.
By introducing ordinary second -divided metals such as zinc or tin, and using competitive absorbing immersion methods, it improves the platinum scattering of catalysts and reduces the dependence on the 铼.
The reorganization catalyst with high platinum decentralization is realized. The PT decentralization of the catalyst is ≥40%, which reduces the dependence of rare metals and reduces the manufacturing cost.
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of catalysts, and in particular relates to a reforming catalyst with high platinum dispersion and a preparation method thereof. Background Art
[0002] The catalytic reforming process of naphtha is an important means to produce high-octane gasoline and BTX. It is one of the important processes in refineries and petrochemical plants around the world and has received widespread attention. As the core catalyst of catalytic reforming of naphtha, the activity and stability of catalytic reforming catalyst directly affect the operational stability and economic benefits of the process.
[0003] Reforming catalyst is a bifunctional catalyst, including isomerization acid function and hydrogenation / dehydrogenation metal function. The isomerization acid function is provided by halogen, while the hydrogenation / dehydrogenation metal function is mainly provided by the precious metal platinum on the catalyst. The dispersion of platinum on the carrier and its stability at high temperature have a decisive influence on the activity and stability of the catalyst.
[0004] In order to improve the activity and stability of reforming catalysts, the reforming catalyst commonly used in industry is Pt-Re bimetallic catalyst, which adds rhenium to improve the dispersion of platinum and the stability under harsh conditions. However, as rhenium is one of the typical rare metals, its reserves and supply are relatively limited. Therefore, it is necessary to continuously explore new naphtha catalytic reforming catalyst systems and preparation technologies to reduce dependence on rhenium. Summary of the invention
[0005] The object of the present invention is to provide a reforming catalyst with high platinum dispersion and no metal rhenium, and a preparation method thereof, by introducing a common second component metal and adopting a competitive adsorption impregnation method, the platinum dispersion of the catalyst is improved, thereby improving the activity and stability of the catalyst, so as to solve the problems existing in the above-mentioned background technology.
[0006] To achieve the above objectives, this application is implemented through the following technical solutions:
[0007] A reforming catalyst with high platinum dispersion is composed of 93-99% of a carrier, 0.1-1.0% of a noble metal, 0.01-2.0% of other metals and 0.1-4.0% of a halogen, by mass percentage, and the sum of the mass percentages of each combination is 100%. In the reforming catalyst, the dispersion of the noble metal is ≥40%.
[0008] Furthermore, the carrier is alumina beads; the noble metal is platinum; the other metal is at least one of zinc or tin; and the halogen is chlorine.
[0009] Furthermore, the alumina crystal phase is γ phase.
[0010] Furthermore, the preparation method of the alumina spheres is an oil-ammonia column molding method or an oil column molding method.
[0011] The method for preparing any of the above-mentioned reforming catalysts with high platinum dispersion comprises the following steps:
[0012] S1. Preparation of impregnation solution: mixing platinum compound, other metal compound and / or halogen compound, and competitive adsorbent according to a set ratio to prepare an impregnation solution;
[0013] S2, impregnating the carrier with the impregnation solution prepared in step S1 and then drying the carrier to obtain a reforming catalyst body;
[0014] S3. Using air containing water and halogen compounds in a set ratio to activate the reforming catalyst body of step S2 to obtain a reforming catalyst with high platinum dispersion.
[0015] Furthermore, the competitive adsorbent in step S1 is at least one of an inorganic acid or an organic acid.
[0016] Furthermore, the inorganic acid is one of hydrochloric acid and phosphoric acid, or a mixture of the two.
[0017] Furthermore, the organic acid is one of acetic acid and citric acid or a mixture of the two.
[0018] Furthermore, the pH value of the impregnation solution is 0.1-1.3.
[0019] Furthermore, in step S3, the halogen compound is hydrogen chloride or chlorine, the activation treatment temperature is 350-450°C, the time is 2-8h, and during the activation treatment, the H2O / Cl molar ratio is 5-20:1.
[0020] The beneficial effects of the present invention are:
[0021] 1. Through the above technical scheme, a naphtha reforming catalyst with high Pt dispersion can be obtained, and the Pt dispersion of the catalyst is ≥40%.
[0022] 2. The introduction of tin or Z zinc to replace the rhenium component in the traditional reforming catalyst reduces the catalyst's dependence on rare metals and reduces the catalyst manufacturing cost.
[0023] 3. The platinum dispersion of the catalyst is improved by adding a competitive adsorbent to the impregnation solution. The method is simple and convenient. DETAILED DESCRIPTION
[0024] The technical solution of the present invention is described in detail below through examples. The following examples are merely exemplary and can only be used to explain and illustrate the technical solution of the present invention, but cannot be construed as limiting the technical solution of the present invention.
[0025] Example 1
[0026] In a clean beaker, add 150 mL of deionized water, and then add 0.27 g of platinum nitrate hexahydrate and 2.95 g of tin tetrachloride pentahydrate, stir to completely dissolve, then add 1.00 g of 85% by volume phosphoric acid, adjust the pH value of the impregnation solution to 0.83, stir evenly, and the desired impregnation solution is obtained.
[0027] Place 97.25 g of γ-alumina balls in a single-necked flask of a rotary evaporator, pour in the above impregnation solution, and after rotary impregnation for 1 hour, turn on heating and vacuuming at a heating temperature of 100° C., and dry the catalyst body by rotary evaporation.
[0028] The dried catalyst body was activated with air containing water and hydrochloric acid at a temperature of 400°C for 5 hours. The molar ratio of H2O / Cl during the treatment was 5:1. The prepared catalyst was designated as 1#.
[0029] Example 2
[0030] The 2.95 g of tin tetrachloride hexahydrate in Example 1 was replaced by 4.55 g of zinc nitrate hexahydrate, the pH value of the impregnation solution was 0.62, the γ-alumina balls were changed to 98.22 g, and the other conditions were the same as in Example 1. The prepared catalyst was recorded as 2#.
[0031] Example 3
[0032] The 0.27 g of platinum nitrate hexahydrate in Example 1 was replaced with 0.53 g, the 2.95 g of tin tetrachloride hexahydrate was replaced with 2.95 g of tin tetrachloride hexahydrate + 2.28 g of tin tetrachloride hexahydrate, the 1.00 g of 85% by volume phosphoric acid was replaced with 1.00 g of 36.5% by volume hydrochloric acid, the pH value of the impregnation solution was 0.57, the γ-alumina ball was changed to 96.11 g, and the other conditions were the same as in Example 1. The prepared catalyst was recorded as 3#.
[0033] Example 4
[0034] In Example 1, 0.27 g of platinum nitrate hexahydrate was replaced by 0.53 g, 2.95 g of tin tetrachloride hexahydrate was replaced by 6.83 g of zinc nitrate hexahydrate, 1.00 g of 85% by volume phosphoric acid was replaced by 2.00 g of citric acid, the pH value of the impregnation solution was 0.73, the γ-alumina ball was changed to 97.68 g, and other conditions were the same as in Example 1. The prepared catalyst was recorded as 4#.
[0035] Example 5
[0036] In Example 1, 0.27 g of platinum nitrate hexahydrate was replaced by 0.53 g, 2.95 g of tin tetrachloride hexahydrate was replaced by 6.83 g of zinc nitrate hexahydrate, 1.00 g of 85% by volume phosphoric acid was replaced by 2.00 g of citric acid, the pH value of the impregnation solution was 1.15, the γ-alumina ball was changed to 97.68 g, and other conditions were the same as in Example 1. The prepared catalyst was recorded as 5#.
[0037] Example 6
[0038] The 0.27 g of platinum nitrate hexahydrate in Example 1 was replaced by 0.80 g, the 2.95 g of tin tetrachloride hexahydrate was replaced by 4.43 g, the pH value of the impregnation solution was 0.55, the γ-alumina ball was changed to 95.63 g, and the other conditions were the same as in Example 1. The prepared catalyst was recorded as 6#.
[0039] Example 7
[0040] In Example 1, 0.27 g of platinum nitrate hexahydrate was replaced by 0.80 g, 2.95 g of tin tetrachloride hexahydrate was replaced by 6.83 g of zinc nitrate hexahydrate, 1.00 g of 85% by volume phosphoric acid was replaced by 1.00 g of acetic acid, the pH value of the impregnation solution was 1.02, the γ-alumina ball was changed to 97.46 g, and other conditions were the same as in Example 1. The prepared catalyst was recorded as 7#.
[0041] Example 8
[0042] In Example 1, 0.27 g of platinum nitrate hexahydrate was replaced by 0.80 g, 2.95 g of tin tetrachloride hexahydrate was replaced by 2.95 g of tin tetrachloride hexahydrate + 2.28 g of tin tetrachloride hexahydrate, 1.00 g of 85% by volume phosphoric acid was replaced by 1.00 g of citric acid, the pH value of the impregnation solution was 1.04, the γ-alumina ball was changed to 96.24 g, and other conditions were the same as in Example 1. The prepared catalyst was recorded as 8#.
[0043] Example 9
[0044] In Example 1, 0.27 g of platinum nitrate hexahydrate was replaced by 1.33 g, 2.95 g of tin tetrachloride hexahydrate was replaced by 5.91 g, 1.00 g of 85% by volume phosphoric acid was replaced by 1.00 g of 36.5% by volume hydrochloric acid, the pH value of the impregnation solution was 0.75, the γ-alumina ball was changed to 96.24 g, and other conditions were the same as in Example 1. The prepared catalyst was recorded as 9#.
[0045] Example 10
[0046] In a clean beaker, add 150 mL of deionized water, and then add 2.65 g of platinum nitrate hexahydrate and 9.10 g of tin tetrachloride hexahydrate, stir to completely dissolve, then add 1.00 g of 85% by volume phosphoric acid, adjust the pH value of the impregnation solution to 0.59, stir evenly, and the desired impregnation solution is obtained.
[0047] Place 95.20 g of γ-alumina balls in a single-necked flask of a rotary evaporator, pour in the above impregnation solution, and after rotary impregnation for 1 hour, turn on heating and vacuuming at a heating temperature of 100° C., and dry the catalyst body by rotary evaporation.
[0048] The pH of the impregnation solution was adjusted to 0.94, and the dried catalyst body was immersed in the impregnation solution. After rotary impregnation for 1 hour, heating and vacuuming were started. The heating temperature was 80° C., and the catalyst was dried by rotary evaporation.
[0049] The dried catalyst was activated with air containing water and hydrochloric acid at a temperature of 400°C for 5 hours. The molar ratio of H2O / Cl during the treatment was 5:1. The prepared catalyst was designated as 1#.
[0050] Table 1 Dispersion of catalysts prepared in Examples 1-10
[0051]
[0052] Table 1
[0053]
[0054] Embodiment 11
[0055] In a clean beaker, add 150 mL of deionized water, and then add 0.80 g of platinum nitrate hexahydrate, 2.95 g of tin tetrachloride pentahydrate, and 2.28 g of zinc nitrate hexahydrate, stir to completely dissolve, then add 1.00 g of citric acid, adjust the pH value of the impregnation solution to 0.91, stir evenly, and the desired impregnation solution is obtained.
[0056] 96.24 g of γ-alumina balls were placed in a single-necked flask of a rotary evaporator, and the above impregnation solution was poured in. After rotary impregnation for 1 hour, heating and vacuuming were turned on to dry the catalyst by rotary evaporation.
[0057] The dried catalyst was activated with air containing water and hydrochloric acid at a temperature of 400°C and a H2O / Cl molar ratio of 10:1. The prepared catalyst was designated as 11#.
[0058] Example 12
[0059] The preparation of the impregnation liquid, the impregnation and the drying steps are the same as those in Example 11. The dried catalyst is then activated with air containing water and hydrochloric acid. The activation temperature is 450°C. The molar ratio of H2O / Cl during the treatment is 10:1. The prepared catalyst is designated as 12#.
[0060] Example 13
[0061] The preparation of the impregnation liquid, the impregnation and the drying steps are the same as those in Example 11. The dried catalyst is then activated with air containing water and hydrochloric acid. The activation temperature is 450°C. The H2O / Cl molar ratio during the treatment is 20:1. The prepared catalyst is designated as 13#.
[0062] Table 2 Dispersion of catalysts prepared in Examples 11-13
[0063]
[0064] The homemade catalyst and commercial reference agent were used for experimental evaluation. The composition and dispersion of the commercial reference agent are shown in Table 3.
[0065] Table 3 Dispersion of catalysts prepared in Examples 11-13
[0066]
[0067] 2 mL of catalyst was loaded on a high-pressure microreactor, and the reaction performance of the catalyst was evaluated using n-heptane as the raw material. The reaction temperature was 500 °C, the pressure was 1.0 MPa, and the volumetric space velocity when feeding the liquid was 6 h -1 , the hydrogen / hydrocarbon volume ratio is 1200:1, and the reaction results are shown in Table 4.
[0068] Table 4 Reaction results
[0069]
[0070] The above is only a preferred embodiment of the present invention, and does not limit the present invention in other forms. Any technician familiar with the profession may use the above disclosed technical content to change or modify it into an equivalent embodiment with equivalent changes. However, any simple modification, equivalent change and modification made to the above embodiment according to the technical essence of the present invention without departing from the technical solution of the present invention still belongs to the protection scope of the technical solution of the present invention.
Claims
1. A reforming catalyst with high platinum dispersion, which is composed of 93-99% of a carrier, 0.1-1.0% of a precious metal, 0.01-2.0% of other metals and 0.1-4.0% of a halogen, and the sum of the mass percentages of each combination is 100%, characterized in that: In the reforming catalyst, the dispersion of precious metals is ≥40%.
2. The reforming catalyst with high platinum dispersion according to claim 1, characterized in that: The carrier is alumina beads; the noble metal is platinum; the other metal is at least one of zinc and tin; and the halogen is chlorine.
3. The reforming catalyst with high platinum dispersion according to claim 2, characterized in that: The aluminum oxide crystal phase is a γ phase.
4. The reforming catalyst with high platinum dispersion according to claim 2, characterized in that: The preparation method of the alumina pellets is an oil-ammonia column molding method or an oil column molding method.
5. A method for preparing a reforming catalyst with high platinum dispersion according to any one of claims 1 to 4, characterized in that: The following steps are involved: S1. Preparation of impregnation solution: mixing platinum compound, other metal compound and / or halogen compound, and competitive adsorbent according to a set ratio to prepare an impregnation solution; S2, impregnating the carrier with the impregnation solution prepared in step S1 and then drying the carrier to obtain a reforming catalyst body; S3. Using air containing water and halogen compounds in a set ratio to activate the reforming catalyst body of step S2 to obtain a reforming catalyst with high platinum dispersion.
6. The method for preparing a reforming catalyst with high platinum dispersion according to claim 5, characterized in that: The competitive adsorbent in step S1 is at least one of an inorganic acid or an organic acid.
7. The method for preparing a reforming catalyst with high platinum dispersion according to claim 6, characterized in that: The inorganic acid is one of hydrochloric acid and phosphoric acid or a mixture of the two.
8. The method for preparing a reforming catalyst with high platinum dispersion according to claim 6, characterized in that: The organic acid is one of acetic acid and citric acid or a mixture of the two.
9. The method for preparing a reforming catalyst with high platinum dispersion according to claim 5, characterized in that: The pH value of the impregnation solution is 0.1-1.
3.
10. The method for preparing a reforming catalyst with high platinum dispersion according to claim 5, characterized in that: In step S3, the halogen compound is hydrogen chloride or chlorine, the activation treatment temperature is 350-450°C, the time is 2-8h, and during the activation treatment, the H2O / Cl molar ratio is 5-20:1.