CN1151879C - Nanometer level transition metal oxide catalyst for transforming mercaptan and its prepn. - Google Patents
Nanometer level transition metal oxide catalyst for transforming mercaptan and its prepn. Download PDFInfo
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- CN1151879C CN1151879C CNB001076825A CN00107682A CN1151879C CN 1151879 C CN1151879 C CN 1151879C CN B001076825 A CNB001076825 A CN B001076825A CN 00107682 A CN00107682 A CN 00107682A CN 1151879 C CN1151879 C CN 1151879C
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Abstract
The present invention belongs to a catalyst for transforming mercaptan contained in gas or liquid petrochemical material and a preparation method of the catalyst. The active component of the catalyst is selected from 1 to 6 kinds of oxides of Co, Mn, Ni, Cu, Fe and Cr, and the catalyst is a nanometer level transition metal element oxide catalyst of which the X-ray diffraction diagram does not have the diffraction peak of the active component, and the one-time accumulation state of the active component is smaller than 5 nm. The active component is directly loaded on a carrier via an immersion method. When the catalyst is used, the catalyst has the advantages of high activity, no lye discharge and no need of activating agents, and is particularly suitable for transforming mercaptan contained in oil products.
Description
Technical Field
The invention relates to a catalyst for converting mercaptan contained in gaseous or liquid petrochemical materials and a preparation method of the catalyst.
Background
In the process of petroleum refining, hydrocarbon oils (also called oil products) such as liquefied petroleum gas, naphtha, catalytic gasoline, straight-run aviation kerosene, lamp oil, diesel oil and the like which are subjected to alkali cleaning in advance all contain a certain amount of mercaptan, are strong in corrosivity and have large odor, and are not beneficial to storage and use of materials. Mercaptan can cause the corrosion test of liquefied petroleum gas to be unqualified, so that doctor tests of gasoline and aviation kerosene cannot pass, and the quality of products is reduced or the products cannot be qualified and delivered.
The process for converting mercaptan is proposed by American Global oil products company (UOP) in 1958, and through the development of more than forty years, the technology is continuously improved, from the alkali deodorization method to the latest alkali-free deodorization method, thousands of such devices are running in the world, the current process for converting mercaptan comprises ① liquid extraction and regeneration process, the process is suitable for deodorizing the mercaptan of liquefied petroleum gas or light oil products, the most basic process of the process is that after the sodium hydroxide solution dissolves poly-phthalocyanine cobalt or sulfonated-phthalocyanine cobalt catalyst, the mixture is fully mixed and reacted with the liquefied petroleum gas or light oil products (including naphtha, catalytic gasoline, straight-run aviation kerosene, lamp oil and diesel oil) in a tower or a container, the mercaptan in the oil product reacts with the sodium hydroxide to generate sodium mercaptan, and the sodium mercaptan enters into alkali liquor, the reaction formula is:
In different use occasions, different requirements are made on the total sulfur content of gaseous or liquid petrochemical materials. For example, the total sulfur content of China to civil liquefied petroleum gas is less than or equal to 343mg/m3And the qualified requirement of the copper sheet corrosion test. Thus, when the total sulfur content is satisfactory, the relevant criteria can be met as long as the mercaptans are converted to neutral disulfides.
Disclosure of Invention
The invention aims to provide a catalyst for converting mercaptan, which has higher activity in use, does not discharge alkali liquor and does not need an activating agent, and a preparation method thereof.
The general technical idea of the invention is as follows: a catalyst for the fixed catalytic bed is disclosed, which can oxidize the thioalcohol in the petrochemical gas or liquid material passing through the catalytic bed into disulfide by oxygen and features high activity, no discharge of alkali liquid and no need of activator.
The technical scheme for providing the catalyst for converting mercaptan to realize the aim of the invention is as follows: the active component of the catalyst is selected from 1-6 oxides of transition metal elements Co, Mn, Ni, Cu, Fe and Cr, the catalyst is a nanometer transition metal oxide catalyst which does not have diffraction peaks of the active component in an X-ray diffraction pattern and has a primary accumulation state of less than 5nm, the active component is directly loaded on a carrier by an impregnation method, and the loading amount of the active component on the carrier is 1-20 wt%.
The transition metal elements in the active components can be mixed in any molar ratio.
The carrier is an aluminum-containing carrier which is roasted at 1200-1600 ℃, the carrier takes mullite, cordierite, magnesia alumina spinel or α -alumina as a main phase, and the carrier is spherical or cylindrical.
The technical scheme for realizing the preparation method of the catalyst for converting mercaptan provided by the invention is as follows: preparing an aqueous solution of transition metal salt according to the mole number required by the set active component, wherein the metal elements of the transition metal salt are 1-6 of Co, Mn, Ni, Cu, Fe and Cr; adding organic hydroxy acid, wherein the molar ratio of the total metal ions to the organic hydroxy acid is 1: 0.1-1: 2.0; uniformly mixing a transition metal salt aqueous solution and organic hydroxy acid to obtain an impregnation solution; impregnating the support with the impregnation solution; drying the carrier dipped in the impregnation liquid at 60-100 ℃, pre-roasting at 150-200 ℃ for 1-4 hours, and roasting at 300-600 ℃ for 0.5-4 hours to generate a transition metal oxide in situ on the carrier, wherein the active component is directly loaded on the carrier to obtain the catalyst; the catalyst is a nanometer transition metal oxide catalyst which does not have diffraction peaks of active components in an X-ray diffraction pattern and has an active component primary accumulation state of less than 5nm, and the loading amount of the active components on a carrier is 1-20 percent (weight).
In the metal salt aqueous solution, the total concentration of metal ions is 1.0-2.0M, the metal salt is nitrate, and the organic hydroxy acid is citric acid, tartaric acid or lactic acid.
The roasting temperature is 300-500 ℃, and the roasting time is 0.5-2 hours.
The catalyst taking the nanometer transition metal oxide as an active component is used for converting mercaptan in gaseous or liquid petrochemical materials; in particular to the transformation of mercaptan contained in liquefied petroleum gas or light oil products.
The invention has the positive effects that: (1) when the transition metal element oxide with the nano-scale particle size of the active component is used for catalyzing the oxidation of mercaptan, the transition metal element oxide plays a role of a bridge for transferring electrons. Under the participation of the catalyst, the mercapto group of the mercaptan is oxidized by oxygen, the valence bond between the sulfur in the mercapto group and hydrogen is broken, the hydrogen and the oxygen are combined to generate water, and the rest parts of two mercaptan molecules are combined to form a disulfide molecule, so that the aim of converting the mercaptan is fulfilled. The transition metal oxide with nano-grade particle size enables the active component to have larger action area and the mercaptan to have higher oxidation speed, thereby having industrial use value. (2) When the catalyst is used, the mercaptan contained in the oil product can be oxidized after the oil product passes through the catalyst bed layer on the premise that the molar concentration of oxygen is greater than that of the mercaptan. During the catalytic reaction, no activator or organic or inorganic alkali is needed, so that the true alkali-free deodorization and alkali-free slag is realizedAnd no secondary pollution. (3) The reaction speed is high in the catalytic reaction, even if the liquid space velocity is 25h-1Can still ensure the complete deodorization at high space velocity. (4) When the catalyst is used for converting mercaptan contained in light oil products such as naphtha, gasoline, aviation kerosene, lamp oil, diesel oil and the like, if the molar concentration of dissolved oxygen in the light oil products is greater than that of the mercaptan, air does not need to be introduced during the catalytic reaction; of course, in order to ensure the safety, a small amount of air or oxygen can be introduced. (5) Especially when the catalyst of the invention is used for converting mercaptan contained in liquefied petroleum gas, the mercaptan in the liquefied petroleum gas can be oxidized into disulfide only by 'dissolved oxygen' in the liquefied petroleum gas under the catalytic action. The process of deodorizing liquefied petroleum gas by alkali deodorization is fundamentally changed, the process is greatly simplified, the mercaptan is completely converted, and the problem which is solved for a long time and is not solved by people is solved. (6) Transition metal oxides are generally considered to have catalytic activity for combustion reactions of CO and hydrocarbon, and have been used for treatment of plant exhaust gas from chemical plants. However, the invention relates to the use of mercaptans for the conversion of gaseous or liquid petrochemical materials, in particular for oils.
Drawings
FIG. 1 is an X-ray diffraction pattern of a support according to a first embodiment of the present invention;
FIG. 2 is an X-ray diffraction pattern of the catalyst in the first example of the invention.
Detailed Description
The composition, preparation and effect of the catalyst of the present invention will be further described with reference to examples. The inventive content is not at all restricted thereto.
Examples 1,
Weighing 1.9 kg of talcum, 1.95 kg of kaolin, 1.15 kg of Al (OH)3Placed in a kneaderMixing, adding 0.1 kg of polyvinyl alcohol and 0.05 kg of CMC (carboxymethyl cellulose) and a proper amount of water, kneading and mixing into a paste shape, making into balls with the diameter of 5mm by using a ball forming mill, baking the balls, and roasting the baked balls at the temperature of 1000-1600 ℃ for 16 hours in a high-temperature furnace to generate a spherical carrier, wherein the carrier is identified by an X-ray diffraction phase (shown in figure 1), the main phase is cordierite, the percentage of the main phase in the weight of the carrier is 96%, and the rest of the carrier is magnesium oxide, silicon oxide, aluminum oxide and a composite compound of the oxides.
87.3 g Co (NO) are weighed out3)2·6H2O, 35.8 g 50% Mn (NO)3)2The solution and 30 g of tartaric acid were added with water to 160 ml and stirred uniformly to prepare a maceration extract. And (2) adding 320 g of the carrier into the impregnation liquid, fully impregnating, drying at the temperature of 80-120 ℃, pre-activating at the temperature of 250 ℃ for 1 hour, and roasting at the temperature of 300-500 ℃ for 2 hours to prepare the catalyst, namely a catalyst A, wherein the loading amount of the active component is 10%, and the molar ratio of manganese to cobalt is Mn: Co: 1: 3. The catalyst A was analyzed by X-ray diffraction (see FIG. 2), and it was found that only the cordierite phase was present and the diffraction intensity was reduced, but the transition metal oxide phase was not present in the diffraction pattern, and it was found that the transition metal oxide, manganese oxide and cobalt oxide, had a primary accumulation state of less than 5 nm.
The obtained catalyst A is crushed to 20-40 meshes, 10 g of the catalyst A is taken and placed in a glass chromatographic column with the diameter of 15mm, and the height-diameter ratio is about 5. Taking the catalytic gasoline which is subjected to alkaline washing and electric refining and contains about 150ppm of mixed mercaptan, and enabling the catalytic gasoline to pass through a fixed bed layer of a catalyst A, wherein the liquid state space velocity (LHSV) is 20h-1. The gasoline after passing through the catalyst bed layer does not contain mercaptan any more, and the doctor test passes, so that the copper sheet corrosion is qualified.
Examples 2,
1 kg of alumina balls with the grain diameter of 3-5 mm produced by a Shandong aluminum factory on the market are taken and roasted for 14 hours at 1200-1400 ℃, so as to prepare the alumina spherical carrier, the carrier is identified by an X-ray diffraction phase (similar to the situation shown in figure 1 and not provided), the main phase is α -alumina, and the weight percentage of the main phase in the carrier is 98%.
Weighing 24.2 gCu(NO3)2·3H2O, 71.6 g 50% by weight of Mn (NO)3)2Solution and 22.5 gThe preparation method comprises the following steps of diluting tartaric acid with water to 120 ml, uniformly stirring to prepare an impregnation solution, weighing 240 g of the prepared carrier, placing the carrier into the impregnation solution, fully impregnating, drying at the temperature of 80-100 ℃, pre-roasting at 250 ℃ for 1 hour, and then roasting at 300-500 ℃ for 2 hours to prepare a catalyst, namely a catalyst B, wherein the loading amount of an active component is 9.8%, the molar ratio of manganese to copper is Mn: Cu being 2: 1, and the catalyst B is analyzed by X-ray diffraction (similar to the situation in a figure 2, and is not provided), only has a phase of α -aluminum oxide, the diffraction intensity is reduced, but the phase of a transition metal oxide does not appear in a diffraction diagram, and the primary accumulation state of the transition metal oxide, namely manganese oxide and copper oxide is determined to be less than 5 nm.
Crushing the obtained catalyst B to 20-40 meshes, and putting 10 g of the crushed catalyst B into a glass chromatographic column with the diameter of 15mm, wherein the height-diameter ratio is about 5. Aviation kerosene containing about 80ppm of mixed mercaptan was passed through a fixed bed of catalyst B at a liquid space velocity (LHSV) of 10h-1. The aviation kerosene which passes through the catalyst bed layer does not contain mercaptan any more, and the doctor test passes, so that the copper sheet is qualified in corrosion.
Examples 3,
Weighing 1.10 kg of light magnesium oxide, 1.70 kg of Al (OH)3And 0.2 kg of polyvinyl alcohol, adding a proper amount of water, kneading, preparing pellets with the diameter of 3-5 mm, drying at 80-120 ℃, and roasting at 1200-1600 ℃ for 10-14 hours to obtain the carrier. The carrier was analyzed by polycrystalline X-ray diffraction (similar to the case of fig. 1, not shown, the same applies hereinafter), the predominant phase was magnesium aluminate spinel, and the predominant phase accounted for 96.5% by weight of the carrier, with the remainder of the carrier being magnesium oxide, silicon oxide, and a composite compound of magnesium oxide and silicon oxide.
87.2 g of Ni (NO) are weighed out3)2·6H2O, 143.2 g of 50% Mn (NO)3)2The solution and 52.5 g tartaric acid were added with water to 240 ml, and stirred uniformly to prepare a maceration extract. Weighing 490 g of the carrier, placing the carrier intoan impregnation solution, fully impregnating, drying at the temperature of 80-100 ℃, and pre-drying at the temperature of 250 DEG CRoasting for 1 hour, and then roasting for 2 hours at 300-500 ℃ to obtain the catalyst C, wherein the loading amount of the active component is 9.5%, and the molar ratio of manganese to nickel is Mn: Ni is 4: 3. The catalyst C was analyzed by X-ray diffraction (similar to the case of FIG. 2, not shown, the same applies hereinafter) and only the phase of magnesium aluminate spinel was found to have a reduced diffraction intensity, but the phase of transition metal oxide was not found in the diffraction pattern, and it was found that the primary accumulation state of transition metal oxide, manganese oxide and nickel oxide was less than 5 nm.
Crushing the obtained catalyst C to 20-40 meshes, and putting 10 g of the crushed catalyst C into a glass chromatographic column with the diameter of 15mm, wherein the height-diameter ratio is about 5. Taking the catalytic gasoline which is subjected to alkaline washing and electric refining and contains about 150ppm of mixed mercaptan, and enabling the catalytic gasoline to pass through a fixed bed layer of a catalyst C at a liquid state space velocity (LHSV) of 20h-1. The gasoline passing through the catalyst bed layer does not contain mercaptan any more, and the doctor test passes, so that the copper sheet corrosion is qualified.
Examples 4,
0.92 kg of a material containing 70% Al is weighed out2O3Of aluminum paste with 0.39 kg of a mixture containing 92% by weight of SiO2Mixing silica gel, adding 0.02 kg polyvinyl alcohol and proper amount of water, forming into mud, making into small balls with diameter of 3-5 mm with a ball forming mill, oven drying, roasting at 1000-1600 deg.C for 16 hr to obtain spherical carrier, and subjecting the carrier to X-ray diffractionAnd (3) performing projectile phase identification, wherein the main phase is mullite, the main phase accounts for 97% of the weight of the carrier, and the rest of the carrier is silicon oxide, aluminum oxide and a composite compound of the silicon oxide and the aluminum oxide.
58.18 g of Co (NO) are weighed out3)2·6H2O, 116.28 g of Ni (NO)3)2·6H2O, 144.9 g of Cu (NO)3)2.3H2O, 286.24 g of 50% by weight Mn (NO)3)2The solution and 210 g of citric acid are dissolved in water to be adjusted to 1000 ml, and the solution is stirred evenly to prepare impregnation liquid. Weighing 100 g of the carrier, putting 50 ml of impregnation liquid, fully impregnating, drying at the temperature of 80-100 ℃, pre-roasting at the temperature of 250 ℃ for 1 hour, and roasting at the temperature of 300-500 ℃ for 2 hours to obtain the carrierThe catalyst, designated catalyst D, had an active component loading of 10.2% on the support. The mol ratio of the transition metal elements of cobalt, nickel, copper and manganese is as follows: co, Ni, Cu and Mn are 1: 2: 3: 4. The catalyst D has only mullite phase and the diffraction intensity is reduced through X-ray diffraction analysis, but the phase of the transition metal oxide does not appear in a diffraction pattern, and the primary accumulation state of the transition metal oxide, namely cobalt oxide, nickel oxide, copper oxide and manganese oxide, can be determined to be less than 5 nm.
Crushing the obtained catalyst D to 20-40 meshes, putting 10 g of the crushed catalyst D into a glass chromatographic column with the diameter of 15mm, enabling the height-diameter ratio to be 5, enabling diesel oil containing about 80ppm of mixed mercaptan to pass through a fixed bed of the catalyst D, and enabling the liquid space velocity (LHSV) to be 10h-1And the diesel oil after passing through the catalyst bed layer does not contain mercaptan any more, and the doctor test passes, so that the copper sheet corrosion is qualified.
Examples 5,
Weighing 400 g Cr (NO)3)3·9H2Diluting O and 75 g tartaric acid to 500 ml with water, and stirring uniformly to prepare a steeping fluid. Weighing 750 g of the carrier prepared in the example 1, placing the carrier in an impregnation solution, fully impregnating, drying at the temperature of 80-120 ℃, pre-roasting at 250 ℃ for 1 hour, and roasting at the temperature of 300-500 ℃ for 2 hours to prepare a catalyst, namely a catalyst E, wherein the loading amount of an active component is 10.1%. The catalyst E was analyzed by X-ray diffraction, and only the cordierite phase was found, and the diffraction intensity was reduced, but the transition metal oxide phase was not found in the diffraction pattern, and it was found that the primary accumulation state of the transition metal oxide chromium oxide was less than 5 nm.
Crushing the obtained catalyst E to 20-40 meshes, putting 10 g of the crushed catalyst E into a stainless steel adsorption column with pressure and the diameter of 15mm, wherein the height-diameter ratio of a catalyst bed layer is about 5. Taking liquefied petroleum gas containing mixed mercaptan of about 100ppm, passing through a fixed bed layer of a catalyst E, and ensuring that the liquid space velocity (LHSV) is 5h-1. The liquefied petroleum gas after passing through the catalyst bed layer does not contain mercaptan any more, and the copper sheet is qualified after corrosion.
Examples 6,
87.3 g Co (NO) are weighed out3)2·6H2O and 22.5 g tartaric acid, waterWeighing 0.20 kg of the carrier prepared in the example 2, putting the carrier into the impregnation liquid, fully impregnating, drying at the temperature of80-100 ℃, pre-roasting at the temperature of 250 ℃ for 1 hour, and roasting at the temperature of 300-500 ℃ for 2 hours to prepare a catalyst, namely a catalyst F, wherein the loading amount of an active component is 10%, and the catalyst F is analyzed by X-ray diffraction, only has a phase of α -aluminum oxide, the diffraction intensity is reduced, but the phase of a transition metal oxide does not appear in a diffraction diagram, and can be used for preparing the catalystThe primary accumulation state of the transition metal oxide, cobalt oxide, was considered to be less than 5 nm.
The obtained catalyst F is crushed to 20-40 meshes, 10 g of the catalyst F is placed in a glass chromatographic column with the diameter of 15mm, and the height-diameter ratio is about 5. Naphtha containing about 80ppm of mixed mercaptans was passed over a fixed bed of catalyst F at a liquid space velocity (LHSV) of 10h-1. The naphtha after passing through the catalyst bed layer does not contain mercaptan any more, and the doctor test passes, so that the copper sheet corrosion is qualified.
Claims (9)
1. A nanometer transition metal element oxide catalyst for converting mercaptan is characterized in that active components of the catalyst are 1-6 oxides selected from transition metal elements Co, Mn, Ni, Cu, Fe and Cr, the catalyst is a catalyst which does not have diffraction peaks of the active components in an X-ray diffraction pattern and has a primary accumulation state of less than 5nm, the active components are directly loaded on a carrier through an impregnation method, the loading amount of the active components on the carrier is 1-10.2 wt%, and the carrier takes mullite, cordierite, magnesia-alumina spinel or α -alumina as a main phase.
2. The catalyst of claim 1, wherein: the transition metal elements in the active component can be mixed in any molar ratio.
3. The catalyst of claim 1, wherein: the carrier is an aluminum-containing carrier which is roasted at 1200-1600 ℃.
4. A catalyst according to any one of claims 1 to 3, characterized in that: the shape of the carrier is spherical or cylindrical.
5. A process for preparing the catalyst of claim 1, characterized in that: preparing an aqueous solution of transition metal salt according to the mole number required by the set active component, wherein the metal elements of the transition metal salt are 1-6 of Co, Mn, Ni, Cu, Fe and Cr; adding organic hydroxy acid, wherein the molar ratio of the total metal ions to the organic hydroxy acid is 1: 0.1-1: 2.0; uniformly mixing a transition metal salt aqueous solution and organic hydroxy acid to obtain an impregnation solution; impregnating the support with the impregnation solution; drying the carrier dipped in the impregnation liquid at 60-100 ℃, pre-roasting at 150-200 ℃ for 1-4 hours, and roasting at 300-600 ℃ for 0.5-4 hours to generate a transition metal oxide in situ on the carrier, wherein the active component is directly loaded on the carrier to obtain the catalyst; the catalyst is a catalyst which does not have diffraction peaks of active components in an X-ray diffraction pattern and has a primary accumulation state of the active components of less than 5nm, and the loading amount of the active components on a carrier is 1-20 percent (weight).
6. The method of claim 5, wherein: in the metal salt aqueous solution, the total concentration of metal ions is 1.0-2.0M, the metal salt is nitrate, and the organic hydroxy acid is citric acid, tartaric acid or lactic acid.
7. The method of claim 5, wherein: the roasting temperature is 300-500 ℃, and the roasting time is 0.5-2 hours.
8. Use of the catalyst according to claim 1 for the conversion of mercaptans in gaseous or liquid petrochemical materials.
9. Use of a catalyst according to claim 8, characterized in that: it is used for converting mercaptan contained in liquefied petroleum gas or light oil products.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1320958C (en) * | 2005-05-30 | 2007-06-13 | 北京三聚环保新材料有限公司 | Double-effect catalyst and its production process |
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| CN100363473C (en) * | 2005-05-30 | 2008-01-23 | 北京三聚环保新材料有限公司 | Method for converting alkyl sulfhydrate contained in liquefied petroleum gas |
| CN100376326C (en) * | 2006-03-30 | 2008-03-26 | 上海工程技术大学 | Method for preparing supported nano copper nickel catalyst and application thereof in oxidative dehydrogenation reaction of alkylol amine |
| CN101100611B (en) * | 2006-07-05 | 2013-04-24 | 中国石油化工股份有限公司 | Gasoline sulfur-reducing composition and its preparing and using method |
| CN113019390A (en) * | 2021-03-18 | 2021-06-25 | 上海大学材料基因组工程(萍乡)研究院 | Preparation method and use method of grain reversible growth catalyst |
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| CN1320958C (en) * | 2005-05-30 | 2007-06-13 | 北京三聚环保新材料有限公司 | Double-effect catalyst and its production process |
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