CN109201105B - Preparation method of deep desulfurization catalyst - Google Patents
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/163—X-type faujasite
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
- C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/14—After treatment, characterised by the effect to be obtained to alter the inside of the molecular sieve channels
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
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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
- 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
- C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
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Abstract
本发明涉及一种用于燃料油品催化氧化深度脱硫，制备超清洁燃料油品领域的催化剂,利用改性后的分子筛负载杂多酸，制备成负载型脱硫催化剂，在保持杂多酸的高活性、高选择性的同时，提高了杂多酸的重复使用性能。本发明一方面利用强酸和强氧化剂预处理分子筛，然后利用离子交换对分子筛进行改性，使分子筛孔道内局部位置提高静电场强度，使硫化物分子被极化从而容易被吸附进而被催化；另一方面选择杂多酸为主催化剂，也使分子筛对有机硫化物的催化性能大为提高。因本该催化剂应用于生产后，脱硫率高提高、生产成本和操作费用大为降低。The invention relates to a catalyst used for the deep desulfurization of fuel oil by catalytic oxidation and the preparation of ultra-clean fuel oil. The modified molecular sieve is used to support a heteropoly acid to prepare a supported desulfurization catalyst. At the same time of activity and high selectivity, the reusability of heteropolyacids is improved. On the one hand, the present invention uses strong acid and strong oxidant to pretreat the molecular sieve, and then uses ion exchange to modify the molecular sieve, so that the local position in the molecular sieve channel increases the electrostatic field strength, so that the sulfide molecules are polarized so as to be easily adsorbed and then catalyzed; On the one hand, the selection of heteropolyacid as the main catalyst also greatly improves the catalytic performance of molecular sieves for organic sulfides. Because the catalyst is used in production, the desulfurization rate is high and the production cost and operating cost are greatly reduced.
Description
Technical Field
The invention relates to a catalyst for deep desulfurization of fuel oil products by catalytic oxidation to prepare ultra-clean fuel oil products.
Background
At present, the fuel oil hydrodesulfurization technology is widely adopted in industry, sulfides such as mercaptan, thioether and thiophene can be removed, but the deep desulfurization operation condition is harsh, the hydrogen consumption is large, the operation equipment is expensive, and especially the difficulty of hydrodesulfurization of dibenzothiophene sulfides is higher. The non-hydrodesulfurization operation condition is mild, the investment of process equipment and the operation cost are low, the environmental pollution is less, and particularly, the catalytic oxidation desulfurization technology has good effect of removing the intractable benzothiophene and the derivatives thereof, thereby being widely concerned by researchers at home and abroad. The key of the catalytic oxidation desulfurization is a catalyst with high activity, high selectivity and high reusability. The catalysts such as metal salt, metal oxide, organic acid and the like can be used for catalytic oxidation desulfurization, but the consumption of the oxidant in the process is large, and the desulfurization effect is not ideal. The heteropoly acid as super strong solid acid catalyst has unique hexagonal cage structure, unique acidity, multiple functions and 'pseudo liquid phase' behavior, different elements can show the difference between acidity and redox property, so that the catalytic performance is controllable, which is beneficial to catalyst design and widely applied in the catalytic field. But the heteropolyacid catalyst has the problems of difficult recovery and serious catalyst loss in the using process. The development of the supported heteropolyacid catalyst has important significance on the development of the deep desulfurization technology.
The supported heteropolyacid catalyst has large specific surface area, can improve the desulfurization effect and the reusability of the catalyst, and avoids the defect of great loss in the use process of the heteropolyacid.
Disclosure of Invention
The invention aims to keep the high activity and high selectivity of heteropoly acid, and simultaneously adopts a molecular sieve loading method to improve the reusability of heteropoly acid and reduce the loss of catalyst.
The purpose of the invention is realized by the following scheme, and the preparation steps are as follows:
(1) carrying out surface modification pretreatment on a 13X or ZSM-5 molecular sieve to obtain the molecular sieve as a catalyst carrier, wherein the modification treatment comprises the step of dipping the molecular sieve by using strong acid (sulfuric acid, hydrochloric acid or nitric acid) and strong oxidant (ozone or hydrogen peroxide) in a volume ratio of 1: 5-5: 1 to improve the surface performance of the molecular sieve; and then, carrying out isovolumetric impregnation on the pretreated molecular sieve by using a solution of rare earth metal ions or transition metal ions, and carrying out ion exchange to obtain a molecular sieve carrier, wherein the concentration of the rare earth metal ions or the transition metal ions is 0.05-0.8 mol/L.
(2) Taking 2g of the molecular sieve carrier, drying for 2 hours at 400 ℃, cooling, adding the molecular sieve carrier into a reactor, adding 60mL of toluene and 0.1-5 mL of silane coupling agent into the reactor, refluxing for 1-10 hours, cooling, washing with a large amount of ethanol for three times, and drying for 3 hours at 100 ℃ under reduced pressure, wherein the silane coupling agent is one of 3-aminopropyltriethoxysilane, 3- (methacryloyl chloride) propyltrimethoxysilane, KH-540, KH550, KH560, KH 580 and KH 590.
(3) And (3) adding the product obtained in the step (2), 40mL of isopropanol and 0.5-5 g of heteropolyacid into a reactor, refluxing for 2 hours, cooling, washing with a large amount of isopropanol for three times, and drying at 100 ℃ under reduced pressure for 5 hours after washing to prepare the catalyst, wherein the heteropolyacid is one or two of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, phosphomolybdotungstic acid and silicomolybdotungstic acid.
The invention has positive effects on deep desulfurization: on one hand, the molecular sieve is modified by pretreating the molecular sieve by using strong acid and a strong oxidant and realizing ion exchange, so that the intensity of an electrostatic field is improved at a local position in a pore passage of the molecular sieve, sulfide molecules are polarized and are easily adsorbed, and the catalytic conversion efficiency of organic sulfides is improved; on the other hand, the invention selects heteropoly acid as the main catalyst, and greatly improves the catalytic performance of the molecular sieve on organic sulfide. After the catalyst is applied to production, the desulfurization rate is improved, and the production cost and the operation cost are greatly reduced.
Detailed Description
The following examples were used to conduct desulfurization experiments to verify the excellent desulfurization performance of the catalytic oxidative desulfurization catalyst of the present invention.
Example 1
The preparation method of the catalyst comprises the following steps:
(1) carrying out surface modification treatment on the 13X molecular sieve to obtain a molecular sieve as a catalyst carrier, wherein the modification treatment comprises the step of pretreating the molecular sieve by using strong acid (sulfuric acid) and strong oxidant (hydrogen peroxide), and the volume ratio of the strong acid to the strong oxidant is 1:1 so as to improve the surface performance of the molecular sieve; and then, carrying out isovolumetric impregnation on the pretreated molecular sieve by using a solution of rare earth metal ions (cerium nitrate) to realize ion exchange, wherein the concentration of the rare earth metal ions is 0.1 mol/L.
(2) Taking 2g of the molecular sieve carrier, drying at 400 ℃ for 2 hours, cooling, adding the molecular sieve carrier into a reactor, adding 60mL of toluene and 0.2mL of silane coupling agent into the reactor, refluxing for 4 hours, cooling, washing with a large amount of ethanol for three times, and drying at 100 ℃ under reduced pressure for 3 hours, wherein the silane coupling agent is 3-aminopropyltriethoxysilane.
(3) And (3) adding the product obtained in the step (2), 40mL of isopropanol and 0.2g of heteropoly acid into a reactor, refluxing for 2 hours, cooling, washing with a large amount of isopropanol for three times, and drying at 100 ℃ under reduced pressure for 5 hours after washing to prepare the catalyst, wherein the heteropoly acid is phosphotungstic acid.
Evaluation of desulfurization Effect:
the evaluation test of the desulfurizing agent was carried out in a batch desulfurization apparatus, using dibenzothiophene n-heptane solution containing 500 μ g/g of sulfur as a desulfurization object of a simulated oil, taking 20mL of the simulated oil, adding 2.5mL of hydrogen peroxide (30%), 0.05g of cetyltrimethylammonium bromide and 0.05g of a desulfurization catalyst, stirring at 30 ℃ for 3 hours, measuring the sulfur content, calculating the desulfurization rate to be 95.2%, and after 3 times of repeated use, the desulfurization rate to be 90%.
Example 2
The preparation method of the catalyst comprises the following steps:
(1) carrying out surface modification treatment on the 13X molecular sieve to obtain a molecular sieve as a catalyst carrier, wherein the modification treatment comprises the step of pretreating the molecular sieve by using strong acid (hydrochloric acid) and strong oxidant (hydrogen peroxide), and the volume ratio of the strong acid to the strong oxidant is 1:2 so as to improve the surface performance of the molecular sieve; and then, carrying out isovolumetric impregnation on the pretreated molecular sieve by using a solution of transition metal ions (copper nitrate) to realize ion exchange, wherein the concentration of the transition metal ions is 0.2 mol/L.
(2) Taking 2g of the molecular sieve carrier, drying at 400 ℃ for 2 hours, cooling, adding the molecular sieve carrier into a reactor, adding 60mL of toluene and 0.3mL of silane coupling agent into the reactor, refluxing for 8 hours, cooling, washing with a large amount of ethanol for three times, and drying at 100 ℃ under reduced pressure for 3 hours, wherein the silane coupling agent is KH-540.
(3) And (3) adding the product obtained in the step (2), 40mL of isopropanol and 0.3g of heteropoly acid into a reactor, refluxing for 2 hours, cooling, washing with a large amount of isopropanol for three times, and drying at 100 ℃ under reduced pressure for 5 hours after washing to prepare the catalyst, wherein the heteropoly acid is phosphomolybdic acid.
Evaluation of desulfurization Effect:
the evaluation test of the test desulfurizing agent was carried out in a batch desulfurization apparatus, 20mL of the simulated oil was taken as a desulfurization object of the simulated oil, 2.5mL of hydrogen peroxide (30%), 0.05g of cetyltrimethylammonium bromide and 0.05g of a desulfurization catalyst were added, the sulfur content was measured after stirring for 3 hours at 30 ℃, the desulfurization rate was calculated to be 97.1%, and the desulfurization rate was 92.1% after 3 times of repeated use.
Example 3:
the preparation method of the catalyst comprises the following steps:
(1) the method comprises the following steps of carrying out surface modification treatment on a ZSM-5 molecular sieve to obtain the molecular sieve as a catalyst carrier, wherein the modification treatment comprises the step of pretreating the molecular sieve by using strong acid (hydrochloric acid) and strong oxidant (hydrogen peroxide), and the volume ratio of the strong acid to the strong oxidant is 1:1 so as to improve the surface performance of the molecular sieve; and then, carrying out isovolumetric impregnation on the pretreated molecular sieve by using a solution of transition metal ions (cobalt nitrate) to realize ion exchange, wherein the concentration of the rare earth metal ions or the transition metal ions is 0.1 mol/L.
(2) Taking 2g of the molecular sieve carrier, drying at 400 ℃ for 2 hours, cooling, adding the molecular sieve carrier into a reactor, adding 60mL of toluene and 0.4mL of silane coupling agent into the reactor, refluxing for 6 hours, cooling, washing with a large amount of ethanol for three times, and drying at 100 ℃ under reduced pressure for 3 hours, wherein the silane coupling agent is KH 560.
(3) And (3) adding the product obtained in the step (2), 40mL of isopropanol and 0.4g of heteropoly acid into a reactor, refluxing for 2 hours, cooling, washing with a large amount of isopropanol for three times, and drying at 100 ℃ under reduced pressure for 5 hours after washing to prepare the catalyst, wherein the heteropoly acid is phosphomolybdic tungstic acid.
Evaluation of desulfurization Effect:
the evaluation test of the test desulfurizing agent was carried out in a batch desulfurization apparatus, using gasoline containing dibenzothiophene of 500 μ g/g sulfur content as a desulfurization object, taking 20mL of gasoline, adding 2.5mL of hydrogen peroxide (30%), 0.05g of cetyltrimethylammonium bromide and 0.03 g of the above desulfurization catalyst, stirring at 30 ℃ for 3 hours, measuring the sulfur content, calculating the desulfurization rate to be 90.2%, and after 3 times of repeated use, the desulfurization rate to be 88.2%.
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 within the scope of the invention.
Claims (6)
1. A preparation method of a deep desulfurization catalyst for catalytic oxidation of fuel oil products comprises the following preparation steps:
(1) carrying out surface modification treatment on a 13X or ZSM-5 molecular sieve to obtain the molecular sieve as a catalyst carrier, wherein the modification treatment comprises the step of impregnating the molecular sieve with sulfuric acid, hydrochloric acid or nitric acid and ozone or hydrogen peroxide, the volume ratio of the sulfuric acid, the hydrochloric acid or the nitric acid to the ozone or the hydrogen peroxide is 1: 5-5: 1 to improve the surface performance of the molecular sieve, and then carrying out ion exchange on the pretreated molecular sieve with a solution of rare earth metal ions or transition metal ions to obtain the molecular sieve carrier;
(2) taking 2g of the molecular sieve carrier in the step (1), drying at 400 ℃ for 2 hours, cooling, adding into a reactor, adding 60mL of toluene and 0.1-5 mL of silane coupling agent, refluxing for 1-10 hours, cooling, washing with a large amount of ethanol for three times, and drying under reduced pressure at 100 ℃ for 3 hours;
(3) and (3) adding the product obtained in the step (2), 40mL of isopropanol and 0.5-5 g of heteropoly acid into a reactor, refluxing for 2 hours, cooling, washing with a large amount of isopropanol for three times, and drying at 100 ℃ under reduced pressure for 5 hours after washing to obtain the catalyst.
2. The method for preparing a desulfurization catalyst according to claim 1, characterized in that the ion exchange in step (1) in claim 1 is carried out by an equivalent-volume impregnation method.
3. The method for preparing a desulfurization catalyst according to claim 1, characterized in that the concentration of the solution of rare earth metal ions or transition metal ions in the step (1) in claim 1 is 0.05 to 0.8 mol/L.
4. The method for preparing desulfurization catalyst according to claim 1, characterized in that the silane coupling agent of step (2) in claim 1 is one of 3-aminopropyltriethoxysilane, KH-540, KH 560.
5. The method for preparing a desulfurization catalyst according to claim 1, characterized in that the heteropoly-acid of step (3) in claim 1 is one of phosphotungstic acid, phosphomolybdic acid, phosphomolybdotungstic acid.
6. The method for preparing desulfurization catalyst according to claim 1, characterized in that the solution of rare earth metal ions or transition metal ions in step (1) in claim 1 is one of cerium nitrate, copper nitrate, cobalt nitrate solutions.
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|---|---|---|---|---|
| CN102134508A (en) * | 2011-01-30 | 2011-07-27 | 山东大学 | Oxidation desulfuration method based on modified MCM-41 anchored heteropolyacid catalyst |
| CN102357366A (en) * | 2011-09-02 | 2012-02-22 | 新疆大学 | Non-mercury catalyst used for acetylene hydrochlorination |
| CN107413293A (en) * | 2017-08-09 | 2017-12-01 | 沈阳三聚凯特催化剂有限公司 | A kind of desulfurizing agent and preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134508A (en) * | 2011-01-30 | 2011-07-27 | 山东大学 | Oxidation desulfuration method based on modified MCM-41 anchored heteropolyacid catalyst |
| CN102357366A (en) * | 2011-09-02 | 2012-02-22 | 新疆大学 | Non-mercury catalyst used for acetylene hydrochlorination |
| CN107413293A (en) * | 2017-08-09 | 2017-12-01 | 沈阳三聚凯特催化剂有限公司 | A kind of desulfurizing agent and preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| Selectivity adsorption of thiophene alkylated derivatives over modified Cu+-13X zeolite;MIAO Tong et al.;《ELSEVIER》;20120831;第30卷(第8期);第808页左栏第1、2段，812页左栏第2、3段 * |
| Zeolites for adsorptive desulfurization from fuels;Roghaye Dehghan et al.;《ELSEVIER》;20170630;第167卷;第103页第3.2.1.2部分、第109页第3.4部分 * |
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