CN1234809C - Process for transforming thiols contained in light oil - Google Patents
Process for transforming thiols contained in light oil Download PDFInfo
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- CN1234809C CN1234809C CN 00109631 CN00109631A CN1234809C CN 1234809 C CN1234809 C CN 1234809C CN 00109631 CN00109631 CN 00109631 CN 00109631 A CN00109631 A CN 00109631A CN 1234809 C CN1234809 C CN 1234809C
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Abstract
The present invention relates to a refining method of light oil products, which uses a catalytic oxidation method with a fixed bed to make light oil products with air or oxygen pass a catalyst bed layer arranged in a fixed bed reactor; the oxidation reaction of oxygen and the thiol of the light oil products is generated to generate disulfide under the action of a catalyst; an active constituent of the catalyst is oxides of a nanometer transition metal elements, composite oxides of perovskite type rare earth or spinel type oxides. When thiol is converted with the refining method, the refining method has the advantages of high efficiency, no exhaust of alkali liquor, and no requirement to an activator; a deodorization technique of the existing light oil products is greatly simplified.
Description
Technical Field
The invention relates to a method for refining light oil.
Background
The light oil product comprises naphtha, catalytic gasoline, straight run aviation kerosene, kerosene for lamps, diesel oil and the like. In the process of the desulfurization process of the light oil product, the light oil product after the pre-alkali washing contains a certain amount of mercaptan, and at the moment, the mercaptan in the organic sulfide contained in the light oil product has strong corrosivity and large odor, which is not beneficial to the storage and use of materials, and the existence of the mercaptan can cause unqualified corrosion of a copper sheet of the light oil product, so that the doctor test of gasoline and aviation kerosene cannot pass through the mercaptan, and the product quality is reduced or the product cannot be qualified and delivered.
The most basic process of the process is that after a sodium hydroxide solution is dissolved in a poly-cobalt phthalocyanine or a sulfonated cobalt phthalocyanine catalyst, the process is fully mixed and reacted with light oil products (comprising naphtha, catalytic gasoline, straight-run aviation kerosene, lamp kerosene and diesel oil) in a tower or a container, and the mercaptan in the oil products is reacted with the sodium hydroxide to generate sodium mercaptide which enters alkali liquor, wherein the reaction formula is as follows:
③ Merox fixed bed mercaptan converting process, Urox fixed bed catalyst, with higher activity and stability, is produced by special technology and can be directly filled in reactor for use, the conversion rate is higher, called as Merox fixed bed deodorization process, the process can be divided into small amount of alkali, small amount of alkali and no alkali process (the alkali is sodium hydroxide), the small amount of alkali deodorization process with alkali injection amount of 1-5% is called as small amount of alkali deodorization process, the small amount of alkali deodorization process without activator is not injected, the activator is injected into ppm level sodium hydroxide solution and called as small amount of alkali deodorization process, the small amount of alkali deodorization process without activator is used, the waste alkali liquor dischargeis reduced, the waste alkali liquor discharge is still existed, the small amount of alkali deodorization process and no alkali deodorization process need special activator is added, the Merox fixed bed mercaptan converting process needs to inject air in operation, the required air is 200% of theoretical requirement.
The invention patent GB 2105742A of British discloses a method for removing mercaptan in oil products by catalytic oxidation of mercaptan in oil products in the presence of oxygen; the active component of the catalyst used in the method can be copper oxide. The invention patent US 3907666 a of the united states discloses a method for removing sulfur compounds (mainly mercaptans) in oil products by catalytic oxidation in the presence of oxygen; the active component of the catalyst adopted in the method can be spinel type oxide CuFe2O4。
Disclosure of Invention
The invention aims to provide a method for converting mercaptan contained in light oil, which has high conversion rate in use, no alkali liquor discharge and no need of an activating agent.
The technical scheme for realizing the purpose of the invention is as follows: a fixed bed catalytic oxidation method is adopted, so that the light oil mixed with air or oxygen passes through a catalyst bed layer arranged in a fixed bed reactor, and under the action of a catalyst, the oxygen and mercaptan contained in the light oil are subjected to oxidation reaction to generate disulfide; the active component of the catalyst is nano-grade transition metal oxide, perovskite type rare earth composite oxide or spinel type oxide. In the method, the using amount of the air or the oxygen is 1.5-2 times of the theoretical required amount. When the method is used for converting mercaptan contained in light oil products in large-scale industrial production, mercaptan oxidation is carried out at 40-60 ℃ and under the operation pressure of 0.4-0.8 MPa; the airspeed of the light oil flowing through the catalyst bed is 0.5-5 h-1The height-diameter ratio of the catalyst bed layer is 1 to 6, and the bulk density (also called bulk density) is 0.6 to 0.9g/cm3. The optimal space velocity of the light oil flowing through the catalyst bed is 1-3 h-1(ii) a The bulk density is 0.7 to 0.8g/cm3. When the method is used for converting mercaptan contained in light oil products in a laboratory, mercaptan oxidation is carried out at 40-60 ℃ and under the operation pressure of 0.3-0.5 MPa; the air speed of the light oil flowing through the catalyst bed is 3-20 h-1The height-diameter ratio of the catalyst bed layer is 3-10, and the bulk density is 0.6-0.9 g/cm3。
When the active component of the catalyst is a nanometer transition metal oxide, the active component is selected from 1-5 oxides of transition metal elements Co, Mn, Ni, Fe and Cr, the catalyst is a catalyst which has no diffraction peak 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% by weight of the carrier. The 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 d-alumina as main phases; the shape of the carrier is spherical or cylindrical.
When the catalyst is a perovskite type rare earth composite oxide as an active component, the general formula of the perovskite type rare earth composite oxide is as follows: a. the1-XA’xB1-YB’YO3The catalyst is characterized in that A represents lanthanide rare earth metal elements, A represents alkaline earth metal elements, B and B' represent transition metal elements, X is more than or equal to 0 and less than or equal to 0.9, Y is more than or equal to 0 and less than or equal to 0.9, the lanthanide rare earth elements are 1 or 2 of mixed light rare earth produced by La, Ce and Baoto rare earth companies, the alkaline earth metal elements are 1 or 2 of Ba, Sr and Ca, the transition metal elements are 2 or 1 of Fe, Co, Ni, Mn, Cu and Ti, the carrier of the catalyst is a carrier taking mullite, cordierite, magnesia alumina spinel or α -alumina as a main phase, the weight percentage of the main phase in the carrier is more than or equal to 80%, the active components are directly loaded on the carrier, the mullite is 5-15% of the weight of the carrier on the carrier, the preferred lanthanide rare earth metal elements are La, Ce, the alkaline earth metal elements are Sr and Ca, the transition metal elements are Mn, Co, Cu, Fe and Ti, and the carrier is a preferred composite chemical carrier taking the load amount of the lanthanide rare earth spinel or the cordierite as the main phase0.6Sr0.4Co0.8Ti0.2O3、La0.8Sr0.2Cu0.5Mn0.5O3、La0.8Ba0.2Fe0.8Cu0.2O3、La0.8Ce0.2Cu0.5Mn0.5O3、La0.8Ca0.2Co0.8Ti0.2O3、La0.6Ca0.4Co0.8Ti0.2O3、La0.6Sr0.4Co0.6Mn0.4O3、RE0.6Sr0.4Co0.8Ti0.2O3、RE0.8Sr0.2Cu0.5Mn0.5O3Or RE0.6Sr0.4Co0.6Mn0.4O3。
When the above-mentioned catalyst is used in which the active component is pointedIn the case of the spinel-type oxide, the spinel-type oxide has a general formula: (A)XA’1-X)(BYB’1-Y)2O4Wherein A, A 'is a metal element selected from Zn, Co, Ni, Mg, Mn, Cu and Cd, B is a metal element Fe, B' is a metal element selected from Cr, Co, Ni and Mn, X is more than or equal to 0 and less than or equal to 1, Y is more than or equal to 0.4 and less than or equal to 1.0, and the carrier of the catalyst is mullite, cordierite, magnesia-alumina spinel or α -Al2O3The carrier is a main phase, and the weight percentage of the main phase in the carrier is more than or equal to 80 percent; the active component is directly loaded on the carrier, and the loading amount of the active component on the carrier is 5-15% of the weight of the carrier. Preferred A, A' are each a metal element selected from Zn, Co, Mn; b' is a metal element Cr; the carrier of the catalyst is a carrier taking cordierite or magnesia-alumina spinel as a main phase, and the weight percentage of the main phase in the carrier is more than or equal to 80 percent. A preferred spinel-type oxide has the formula (Zn)0.8Co0.2)(Fe0.5Cr0.5)2O4、(Zn0.6Mg0.4)(Fe0.6Cr0.4)2O4、(Zn0.5Ni0.5)(Fe0.7Cr0.3)2O4、(Zn0.7Co0.3)Fe2O4、(Zn0.5Mn0.5)(Fe0.8Cr0.2)2O4Or (Zn)0.5Cd0.5)(Fe0.8Cr0.2)2O4。
The invention has the positive effects that: (1) when the method of the invention is used for catalytic reaction and transformation of mercaptan, no activator, organic base or inorganic base is needed to be added, and the mercaptan contained in the oil product can be oxidized after the oil product passes through the catalyst bed. The process is greatly simplified, the mercaptan is completely converted, and the real alkali-free deodorization, the alkali residue-free treatment and the secondary pollution-free treatment are realized. Solves the problems which people need to solve for a long time but not solve. (2) When the activity of the catalyst of the present invention is reduced or deactivatedThe surface of the catalyst is washed by hot water at the temperature of 80-90 ℃, and the activity is recovered after the catalyst is dried, so the service life is long. (3) The method of the invention adopts the catalyst with special effect on mercaptan conversion, and the reaction speed is high when the catalytic reaction is carried out, even if the liquid space velocity is 20h-1Still ensures complete conversion of mercaptan at high space velocities. (4) When the method of the invention adopts the catalyst which takes the transition metal oxide with the nanometer grain diameter as the active component, the active component plays a role of a bridge for transferring electrons. Under the participation of the catalyst, the mercapto group of the mercaptan is oxidized, the valence bond between the sulfur in the mercapto group and the hydrogen is broken, the hydrogen is combined with the oxygen to generate water, and the rest parts of the two mercaptan molecules are combined into 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. (5) When the method of the invention adopts the catalyst with the perovskite type oxide as the active component, the active component A1-XA’xB1-YB’YO3Oxide with the structure of ABO3A compound of formula (I), wherein the B or B' position is in a high valence state. The high valence state of B or B 'promotes the mercapto group of mercaptan contained in the light oil product to be oxidized by oxygen, the valence bond between sulfur and hydrogen in the mercapto group is broken, hydrogen is combined with oxygen under the participation of high valence state ions of B or B' to generate water, and the rest of two mercaptan molecules are combined into a disulfide molecule, thereby achieving the purpose of converting mercaptan. When the activity of the catalyst is reduced or the catalyst is invalid, the surface of the catalyst can be washed by hot water, and the activity is recovered after the catalyst is dried, so the service life is long. (6) When the method of the present invention uses a catalyst in which a spinel type oxide is used as an active component, the catalyst is prepared by using the active component (A)XA’1-X)(BYB’1-Y)2O4Oxide of structure AB2O4When the compound is used for converting mercaptan contained in light oil products, the mercaptan group of the mercaptan is oxidized under the bridge action of electron transfer of a catalyst, the valence bond between sulfur and hydrogen in the mercaptan group is broken, the hydrogen and 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. Also, when the catalyst activity is reduced or deactivatedThe surface of the catalyst can be washed by hot water and the activity is recovered after drying, so the service life is long.
Detailed Description
The process of the present invention for converting mercaptans contained in light oils will now be further illustrated with reference to the following examples. The inventive content is not at all restricted thereto.
(1) Preparation of the carrier: the method for preparing the carrier in the laboratory is given below, and when industrial production needs to be carried out, the method for preparing the carrier in the laboratory can be carried out by amplifying by 100-1000 times, and corresponding equipment is selected, so that the method meets the requirements of industrial production.
1. Preparing a cordierite phase carrier: weighing 1.9 kg of talcum, 1.95 kg of kaolin, 1.15 kg of Al (OH)3Putting the mixture into a kneader to be mixed evenly, adding 0.1 kg of polyvinyl alcohol, 0.05 kg of CMC (carboxymethyl cellulose) and a proper amount of water into the mixture to form a paste, preparing the mixture into small balls with the diameter of 3-5 mm by using a ball forming mill, drying the small balls, and roasting the small balls for 16 hours at the temperature of 1000-1600 ℃ in a high-temperature furnace to generate spherical carriers. The carrier is identified by X-ray diffraction phase, the main phase is cordierite, the weight percentage of the main phase in the carrier is 96%, and the rest part of the carrier is magnesia, silica and oxygenAluminum oxide and composite compounds of these oxides.
2. And (2) preparing the alumina spherical carrier, namely weighing 1 kg of gamma-alumina spheres with the diameter of 3-5 mm, which are produced by a Shandong aluminum factory on the market, and roasting for 14 hours at 1200-1600 ℃ to prepare the alumina spherical carrier, wherein the carrier is identified by an X-ray diffraction phase, the main phase is α -alumina, the weight percentage of the main phase in the carrier is 98%, and the rest of the carrier is alumina.
3. Preparing a magnesium aluminate spinel phase carrier: 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 is analyzed by polycrystalline X-ray diffraction, the main phase is magnesium aluminate spinel, and the main phaseAccounting for 96.5 percent of the weight of the carrier, and the rest part of the carrier is magnesia, silica and a composite compound of the magnesia and the silica.
4. Preparing a mullite phase carrier: 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 SiO2The silica gel is fully mixed, then 0.02 kg of polyvinyl alcohol and a proper amount of water are added to form a paste, a ball forming mill is used for preparing small balls with the diameter of 3-5 mm, the small balls are dried and are roasted for 16 hours at the temperature of 1000-1600 ℃ in a high-temperature furnace to generate a spherical carrier, the carrier is identified by an X-ray diffraction phase, the main phase is mullite, the weight percentage of the main phase in the carrier is 97%, and the rest of the carrier is silicon oxide, aluminum oxide and a composite compound of the silicon oxide and the aluminum oxide.
The carrier prepared by the method is passivated by high-temperature treatment, so that the carrier and the active component do not generate chemical reaction at the temperature of preparing the catalyst, and the function of the active component can be effectively exerted when mercaptan is converted.
(2) Preparation of the catalyst: the method for preparing the catalyst in the laboratory is given below, and when industrial production needs to be carried out, the method for preparing the catalyst in the laboratory can be carried out by amplifying by 100-1000 times, and corresponding equipment is selected, so that the method meets the requirements of industrial production.
1. Preparation of catalyst a1 whose active component is a nano-scale transition metal oxide (manganese oxide and cobalt oxide): 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. 320 g of the cordierite phase carrier is put into the impregnation liquid, after sufficient impregnation (about 0.5 hour), the obtained product is dried at the temperature of 80-120 ℃, pre-activated for 1 hour at the temperature of 250 ℃, and roasted for 2 hours at the temperature of 300-500 ℃ to prepare the catalyst, namely the catalyst A1, wherein the loading amount of the active component is 10%, and the molar ratio of manganese to cobalt is Mn: Co being 1: 3. The catalyst A1 was analyzed by X-ray diffraction, and only the cordierite phase was found to have a reduced diffraction intensity, but the transition metal oxide phase did not appear in the diffraction patternIt is considered that the primary accumulation state of the transition metal oxides, manganese oxide and cobalt oxide, is less than 5 nm.
2. Preparation of catalyst a2 whose active component is a nano-scale transition metal oxide (manganese oxide and copper oxide): 24.2 g of Cu (NO) are weighed out3)2·3H2O, 71.6 g 50% by weight of Mn (NO)3)2The solution and 22.5 g of wineWeighing 240 g of the alumina spherical carrier, putting the alumina spherical carrier into an 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 obtain a catalyst A2, wherein the loading of an active component is 9.8%, the molar ratio of manganese to copper is Mn: Cu which is 2: 1, and the catalyst A2 only has a α -aluminum oxide phase through X-ray diffraction analysis, the diffraction intensity is reduced, but the transition metal oxide phase does not appear in a diffraction diagram, and the primary accumulation state of the transition metal oxide, namely manganese oxide and copper oxide, is less than 5 nm.
3. Preparing a catalyst A3 with the active components of nano-scale transition metal element oxides (manganese oxide and nickel 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 magnesia-alumina spinel phase carrier, putting the magnesia-alumina spinel phase carrier into an impregnating solution, fully impregnating, drying at the temperature of 80-100 ℃, pre-roasting at the temperature of 250 ℃ for 1 hour, and then roasting at the temperature of 300-500 ℃ for 2 hours to prepare a catalyst, namely a catalyst A3, wherein the loading capacity of an active component is 9.5%, and the molar ratio of manganese to nickel is Mn: Ni is 4: 3. The catalyst A3 was analyzed by X-ray diffraction, 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.
4. Preparing a catalyst A4 with the active component of nano-scale transition metal element oxides (cobalt oxide, nickel oxide, copper oxide and manganese oxide): 58.18 g are weighedCo(NO3)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 mullite phase carrier, putting 50 ml of impregnation liquid, fully impregnating, drying at the temperature of 80-100 ℃, pre-roasting for 1 hour at the temperature of 250 ℃, and roasting for 2 hours at the temperature of 300-500 ℃ to obtain the catalyst, namely the catalyst A4, wherein the loading capacity of the active component on the carrier is 10.2%. 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 A4 was analyzed by X-ray diffraction, and had only a mullite phase and a reduced diffraction intensity, but the phase of the transition metal oxide did not appear in the diffraction pattern, and it was confirmed that the primary accumulation state of the transition metal oxides, cobalt oxide, nickel oxide, copper oxide and manganese oxide, was less than 5 nm.
5. Preparation of catalyst a5 whose active component is a nanoscale transition metal oxide (chromium oxide): weighing 400 g Cr (NO)3)3·9H2Diluting O and 75g tartaric acid to 500 ml with water, and stirring uniformly to prepare a steeping fluid. Weighing 750 g of the cordierite phase carrier, placing the cordierite phase carrier in an impregnation solution, fully impregnating, drying at the temperature of 80-120 ℃, pre-roasting at the temperature of 250 ℃ for 1 hour, and then roasting at the temperature of 300-500 ℃ for 2 hours to prepare a catalyst, namely a catalyst A5, wherein the loading capacity of an active component is 10.1%. The catalyst A5 was analyzed by X-ray diffraction, 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 chromium oxide had a primary accumulation state of less than 5 nm.
6. Preparation of catalyst a6 whose active component is a nanoscale transition metal oxide (cobalt oxide): 87.3 g Co (NO) are weighed out3)2·6H2O and 22.5 g of tartaric acid are diluted to 120 ml by water and stirred evenly to prepare a steeping fluid. Weighing 0.20 kg of the alumina spherical carrier, and placing in a soaking tankFully soaking in the impregnation liquid, 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 the catalyst, namely the catalyst A6, wherein the loading of the active component is 10%, and the catalyst A6 is analyzed by X-ray diffraction, only a α -aluminum oxide phase is reduced in diffraction intensity, but a transition metal oxide phase does not appear in a diffraction pattern, and the primary accumulation state of the transition metal oxide, namely cobalt oxide, is determined to be less than 5 nm.
7. Preparing a catalyst B1 with the active component being perovskite type rare earth composite oxide: 100.0 g La was weighed out2O3And putting the mixture into a 1000 ml beaker, adding 200 ml of 65-68% nitric acid, violently releasing heat and emitting gas, obtaining colorless transparent liquid after the dissolution is finished, and then adding 500 ml of distilled water. 84.7 g of Sr (NO) are weighed out separately3)2232.8 g Co (NO)3)2·6H2O and 210.0 g citric acid were added to the beaker, and 21.5 ml TiCl was added4The mixture was added to a beaker, shaken well and diluted with water to 1000 ml as a steep. Adding 200 g of the cordierite phase carrier into 100 ml of impregnation liquid, fully impregnating, drying at 80-100 ℃, roasting and activating at 300-500 ℃ for 4-12 hours to obtain a catalyst, namely a catalyst B1, wherein the loading capacity of an active component is 10.80% (based on the weight of the carrier). The chemical formula of the active component is La by element analysis0.6Sr0.4Co0.8Ti0.2O3(ii) a The phase of the active component is perovskite compound phase by X-ray diffraction analysis.
8. Preparing a catalyst B2 with the active component being perovskite type rare earth composite oxide: 133 g La was weighed2O3And putting the mixture into a 1000 ml beaker, adding 200 ml of 65-68% nitric acid, violently releasing heat and gassing, obtaining colorless transparent liquid after the dissolution is finished, and adding 500 ml of distilled water. Then 42.3 g Sr (NO) are weighed respectively3)2120.8 g of Cu (NO)3)2·3H2O, 170 g Mn (NO)3)2(50% aqueous solution) and 150.1 g tartaric acid, diluted to 1000 ml with water and mixed well to obtainAnd (4) dipping liquid. Adding 200 g of the alumina sphere carrier into 100 ml of impregnation liquid, fully impregnating, drying at 80-100 ℃, roasting at 300-500 ℃ for 4-12 hours to obtain a catalyst, namely a catalyst B2, wherein the loading capacity of the active component is 10.2% (based on the carrier quantity). The chemical formula of the active component is La by element analysis0.8Sr0.2Cu0.5Mn0.5)O3(ii) a The phase of the active component is perovskite compound phase by X-ray diffraction analysis.
9. Preparing a catalyst B3 with the active component being perovskite type rare earth composite oxide: 133 g La was weighed2O3Putting the mixture into a 1000 ml beaker, adding 200 ml of 65-68% nitric acid, obtaining colorless transparent liquid after the dissolution is finished, and then adding 500 ml of distilled water. 52.3 gof Ba (NO) were weighed out separately3)2323.2 g Fe (NO)3)3·9H2O, 48.3 g Cu (NO)3)2·3H2O and 90.1 g of lactic acid are added into a beaker, diluted to 1000 ml by water and fully stirred to obtain the steeping liquor. Adding 200 g of the magnesia-alumina spinel phase sphere carrier into 100 ml of impregnation liquid, fully impregnating, drying at 80-100 ℃, pre-roasting at 200-300 ℃ for 1-4 hours, and roasting at 300-500 ℃ for activation to 4 ℃After 12 hours, a catalyst, designated as catalyst B3, was prepared with an active component loading of 10.1% (based on the support). The chemical formula of the active component is La by element analysis0.8Ba0.2Fe0.8Cu0.2O3(ii) a The phase of the active component is perovskite compound phase by X-ray diffraction analysis.
10. Preparing a catalyst B4 with the active component being perovskite type rare earth composite oxide: 133 g La was weighed2O3And putting the mixture into a 1000 ml beaker, adding 200 ml of 65-68% nitric acid, and adding 500 ml of distilled water after dissolution. Then 86.8 g of Ce (NO) is weighed respectively3)3·6H2O, 120.8 g Cu (NO)3)2·3H2O, 179 g Mn (NO)3)2(50% aqueous solution) and 90 g lactic acid were added to a beaker and diluted to 1000 mm with waterThe mixture is fully stirred evenly to obtain the impregnation liquid. Adding 200 g of the mullite phase spherical carrier into 100 ml of impregnation liquid, fully impregnating, drying at 80-100 ℃, pre-roasting at 200-300 ℃ for 1-4 hours, roasting and activating at 300-500 ℃ for 4-12 hours to obtain a catalyst, namely a catalyst B4, wherein the loading amount of an active component is 9.8% (based on the carrier amount). The chemical formula of the active component is La by element analysis0.8Ce0.2Cu0.5Mn0.5O3(ii) a The phase of the active component is perovskite compound phase by X-ray diffraction analysis.
11. Preparing a catalyst B5 with the active component being perovskite type rare earth composite oxide: 133 g La was weighed2O3Putting the mixture into a 1000 ml beaker, adding 200 ml of 65-68% nitric acid, dissolving, and then adding 500 ml of distilled water. 47.2 g Ca (NO) are weighed out3)2·4H2O, 232.8 g Co (NO)3)2·6H2O and 210 g citric acid, and then 21.5 ml TiCl were pipetted4Adding into a beaker, diluting with water to 1000 ml, and stirring thoroughly to obtain the maceration extract. Adding 200 g of the cordierite phase carrier into 100 ml of impregnation liquid, fully impregnating, drying at 80-100 ℃, roasting and activating at 300-500 ℃ for 4-12 hours to obtain a catalyst, namely a catalyst B5, wherein the loading capacity of an active component is 9.5% (based on the carrier quantity). The chemical formula of the active component is La by element analysis0.8Ca0.2Co0.8Ti0.2O3(ii) a The phase of the active component is perovskite compound phase by X-ray diffraction analysis.
12. Preparing a catalyst B6 with the active component being perovskite type rare earth composite oxide: 100 g of La was weighed2O3Putting the mixture into a 1000 ml beaker, adding 200 ml of 65-68% nitric acid, and adding 500 ml of distilled water after dissolution. Then 94.5 g Ca (NO) are weighed respectively3)2·4H2O, 232.8 g Co (NO)3)2·6H2O and 150 g tartaric acid, and then 21.5 ml TiCl were pipetted4Adding into a beaker, diluting with water to 1000 ml, and stirring thoroughly to obtain the maceration extract. Will be provided withAdding 200 g of the alumina spherical carrier into 100 ml of impregnation liquid, fully impregnating, drying at 80-100 ℃, roasting and activating at 300-500 ℃ for 4-12 hours to obtain a catalyst, namely a catalyst B6, wherein the loading capacity of an active component is 9.9% (based on the carrier quantity). The chemical formula of the active component is La by element analysis0.6Ca0.4Co0.8Ti0.2O3(ii) a The phase of the active component is perovskite compound phase by X-ray diffraction analysis.
13. Preparing a catalyst B7 with the active component being perovskite type rare earth composite oxide: 100 g of La was weighed2O3Putting the mixture into a 1000 ml beaker, adding 200 ml of 65-68% nitric acid, dissolving, and then adding 500 ml of distilled water. Then 84.7 g of Sr (NO) are weighed respectively3)2174.6 g Co (NO)3)2·6H2O, 71.6 g Mn (NO)3)2(50% Water soluble)Liquid) and 210 g of citric acid were added to a beaker, diluted to 1000 ml with water, and sufficiently stirred to obtain a maceration extract. Adding 200 g of the magnesia-alumina spinel phase carrier into 100 ml of impregnation liquid, fully impregnating (about 0.5 hour), drying at 80-100 ℃, roasting and activating at 300-500 ℃ for 4-12 hours to obtain a catalyst, namely catalyst B7, wherein the loading capacity of the active component is 10.1% (based on the carrier quantity). The chemical formula of the active component is La by element analysis0.6Sr0.4Co0.6Mn0.4O3(ii) a The phase of the active component is perovskite compound phase by X-ray diffraction analysis.
14. Preparing a catalyst B8 with the active component being perovskite type rare earth composite oxide: weighing 100 g of mixed light rare earth oxide produced by Baotou rare earth company, putting the mixed light rare earth oxide into a 1000 ml beaker, adding 200 ml of 65-68% nitric acid, and adding 500 ml of distilled water after the mixed light rare earth oxide is dissolved. 84.7 g of Sr (NO) are weighed out3)2232.8 g Co (NO)3)2·6H2O and 210 g citric acid were added to the beaker, and 21.5 ml TiCl was added4Diluting to 1000 ml with water, and stirring thoroughly to obtain the immersion liquid. 200 g of the above-mentioned mullite phase carrier are added into 10Soaking 0 ml of the soaking solution for 0.5 hour, drying at 80-100 ℃, and roasting at 300-500 ℃ for 4-12 hours to obtain the catalyst, namely the catalyst B8, wherein the loading capacity of the active component is 9.9% (based on the carrier weight). The chemical formula of the active component is RE by element analysis0.6Sr0.4Co0.8Ti0.2O3(ii) a The phase of the active component is perovskite compound phase by X-ray diffraction analysis.
15. Preparing a catalyst B9 with the active component being perovskite type rare earth composite oxide: weighing 133 g of mixed light rare earth oxide produced by Liyang rare earth company, adding the mixed light rare earth oxide into a 1000 ml beaker, adding 200 ml of 65-68% nitric acid, and adding 500 ml of distilled water after the dissolution is completed. 42.3 g of Sr (NO) are weighed out3)2120.8 g of Cu (NO)3)2·3H2O, 179 g Mn (NO)3)2(50% aqueous solution) and 150 g tartaric acid were added to a beaker, diluted to 1000 ml with water and stirred well to obtain a steep. And (2) adding 200 g of the cordierite phase carrier into 100 ml of impregnation liquid, soaking for 0.5 hour, drying at 80-100 ℃, and roasting at 300-500 ℃ for 4-12 hours to obtain a catalyst, namely catalyst B9, wherein the loading amount of the active component is 10.5% (based on the carrier amount). The active component has a chemical formula of RE by element analysis0.8Sr0.2Cu0.5Mn0.5O3(ii) a The phase of the active component is perovskite compound phase by X-ray diffraction analysis.
16. Preparing a catalyst B10 with the active component being perovskite type rare earth composite oxide: 100 g of mixed light rare earth oxide produced by Jiangxi rare earth company is weighed and put into a 1000 ml beaker, 200 ml of 65-68% nitric acid is added, and 500 ml of distilled water is added after dissolution is completed. 84.7 g of Sr (NO) are weighed out3)2174.6 g Co (NO)3)2·6H2O, 71.6 g Mn (NO)3)2(50% aqueous solution) and 210 g of citric acid were added to a beaker, diluted to 1000 ml with water and stirred well to obtain a steep. 200 g of the alumina spherical carrier is added into 100 ml of impregnation liquid to be impregnated for 0.5 hour, and then the mixture is dried at 80-100 ℃ and is dried at 30 DEG CRoasting at 0-500 ℃ for 4-12 hours to obtain the catalyst, namely the catalyst B10, wherein the loading amount of the active component is 11% (based on the amount of the carrier). The active component has a chemical formula of RE by element analysis0.6Sr0.4Co0.6Mn0.4O3(ii) a The phase of the active component is perovskite compound phase by X-ray diffraction analysis.
17. Preparation of a catalyst with a spinel-type oxide as an active component C1: 28 g of Zn (NO) are weighed out3)2·6H2O, 6.8 g Co (NO)3)2·6H2O, 66.6 g Fe (NO)3)3·9H2O and 47.0 g Cr (NO)3)3·9H2ODissolving in water to prepare 200 ml solution, then adding 56.0 g of citric acid, stirring, dissolving and uniformly mixing to obtain the impregnation solution. And (3) adding 140 g of the cordierite phase carrier into the impregnation liquid, soaking for 0.5 hour, drying at 80-100 ℃, and roasting at 300-500 ℃ for 2 hours to prepare the catalyst, namely the catalyst C1, wherein the loading amount of the active component is 10.80% (based on the carrier amount). The chemical formula of the active component is (Zn) by element analysis0.8Co0.2)(Fe0.5Cr0.5)2O4(ii) a The phase of the active component is a spinel compound phase by X-ray diffraction analysis.
18. Preparation of a catalyst with a spinel-type oxide as an active component C2: 12.0 g of Zn (NO) are weighed out3)2·6H2O, 10.4 g Mg (NO)3)2·6H2O, 46.0 g Fe (NO)3)3·9H2O and 32.4 g Cr (NO)3)3·9H2Dissolving O in water to prepare 120 ml of solution, adding 30 g of citric acid, and uniformly stirring to obtain the impregnation liquid. 60 g of the alumina sphere carrier is taken out after being soaked for 0.5 hour, dried at the temperature of 80-100 ℃, and roasted at the temperature of 300-500 ℃ for 2 hours to prepare the catalyst, namely the catalyst C2, wherein the loading capacity of the active component is about 9.5 percent (based on the carrier quantity). The chemical formula of the active component is (Zn) by element analysis0.6Mg0.4)(Fe0.6Cr0.4)2O4(ii) a By X-ray diffraction analysis, active groupThe separated phase is a spinel compound phase.
19. Preparation of a catalyst with a spinel-type oxide as an active component C3: 14.0 g of Zn (NO) are weighed out3)2·6H2O, 3.4 g Ni (NO)3)2·6H2O, 33.3 g Fe (NO)3)3·9H2O and 23.5 g Cr (NO)3)3·9H2Dissolving O in water to prepare 100 ml of solution, adding 28 g of citric acid, and uniformly stirring to obtain the impregnation liquid. Taking 70 g of the magnesia-alumina spinel phase carrier, soaking for 0.5 hour, taking out, drying at 80-100 ℃, and roasting at 300-500 ℃ for 2 hours to prepare the catalyst, namely the catalyst C3, wherein the loading capacity of the active component is 10.1% (based on the carrier quantity). The chemical formula of the active component is (Zn) by element analysis0.5Ni0.5)(Fe0.7Cr0.3)2O4(ii) a The phase of the active component is a spinel compound phase by X-ray diffraction analysis.
20. Preparation of a catalyst with a spinel-type oxide as an active component C4: 8.0 g of Zn (NO) are weighed out3)2·6H2O, 2.0 g Co (NO)3)2·6H2O and 32.5 g Fe (NO)3)3·9H2Dissolving O in water to prepare 60 ml of solution, adding 16.0 g of citric acid, and uniformly stirring to obtain the impregnation solution. And (3) taking 30 g of the alumina spherical carrier, soaking for 0.5 hour, taking out, drying, and roasting at 300-500 ℃ for 2 hours to prepare the catalyst, namely the catalyst C4, wherein the loading amount of the active component is 9.8% (based on the carrier amount). The chemical formula of the active component is (Zn) by element analysis0.7Co0.3)Fe2O4(ii) a The phase of the active component is a spinel compound phase by X-ray diffraction analysis.
21. Preparation of a catalyst with a spinel-type oxide as an active component C5: 6.0 g of Zn (NO) are weighed out3)2·6H2O, 7.16 g Mn (NO)3)2(50% aqueous solution), 23.0 g Fe (NO)3)3·9H2O and 16.2 g Cr (NO)3)3·9H2Dissolving O in water to prepare 60 ml solutionThen, 14.5 g of citric acid was added thereto, and the mixture was stirred uniformly to obtain a dipping solution. And (3) putting 30 g of the cordierite phase carrier into an impregnation liquid, impregnating for 0.5 hour, taking out and drying, and activating at 300-500 ℃ for 2 hours to prepare the catalyst, namely the catalyst C5, wherein the loading capacity of the active component is 9.5% (based on the carrier weight). The chemical formula of the active component is (Zn) by element analysis0.5Mn0.5)(Fe0.8Cr0.2)2O4(ii) a By X-rayAnd (4) analyzing by line diffraction, wherein the phase of the active component is a spinel compound phase.
22. Preparation of a catalyst with a spinel-type oxide as an active component C6: 6.0 g of Zn (NO) are weighed out3)2·6H2O, 4.84 g Cu (NO)3)2·3H2O, 23.0 g Fe (NO)3)3·9H2O and 16.2 g Cr (NO)3)3·9H2Dissolving O in water to prepare 60 ml of solution, adding 14.5 g of citric acid, and uniformly stirring to obtain the impregnation solution. And (3) adding 30 g of the cordierite phase carrier into the impregnation liquid, impregnating for 0.5 hour, taking out and drying, and activating at 300-500 ℃ for 2 hours to prepare the catalyst, namely the catalyst C6, wherein the loading amount of the active component is 9.9% (based on the carrier amount). The chemical formula of the active component is (Zn) by element analysis0.5Cu0.5)(Fe0.8Cr0.2)2O4(ii) a The phase of the active component is a spinel compound phase by X-ray diffraction analysis.
23. Preparation of a catalyst with a spinel-type oxide as an active component C7: 6.0 g of Zn (NO) are weighed out3)2·6H2O, 6.2 g Cd (NO)3)2·4H2O, 23.0 g Fe (NO)3)3·9H2O and 16.2 g Cr (NO)3)3·9H2Dissolving O in water to prepare 60 ml of solution, adding 14.5 g of citric acid, and uniformly stirring to obtain the impregnation solution. Adding 30 g of the alumina spherical carrier into the impregnation liquid, impregnating for 0.5 hour, taking out, drying, activating for 2 hours at 300-500 ℃ to prepare the catalyst, namely the catalyst C7, wherein the loading amount of the active component is 10.1% (based on the carrier weight)As a reference). The chemical formula of the active component is (Zn) by element analysis0.5Cd0.5)(Fe0.8Cr0.2)2O4(ii) a The phase of the active component is a spinel compound phase by X-ray diffraction analysis.
(3) Examples of the conversion in the laboratory of mercaptans contained in light oils. The bulk density (also referred to as bulk density) of each catalyst was 0.75g/cm3。
Examples 1,
The obtained catalyst A1 is crushed to 20-40 meshes, 10 g of the catalyst 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 passing the catalytic gasoline through a fixed bed layer of a catalyst A1, wherein the liquid 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,
The obtained catalyst A2 is crushed into 20-40 meshes, 10 g of the catalyst is placed in a glass chromatographic column with thediameter of 15mm, and the height-diameter ratio is about 5. Aviation kerosene containing about 80ppm of mixed mercaptan was passed through a fixed bed of catalyst A2 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,
The obtained catalyst A3 is crushed into 20-40 meshes, 10 g of the catalyst is 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 passing the catalytic gasoline through a fixed bed layer of a catalyst A3, wherein the liquid space velocity (LHSV) is 20h-1. Gasoline after passing through the catalyst bed layer does not contain any moreMercaptan, doctor's test passed, the copper sheet corrodes the qualification.
Examples 4 to 5,
Respectively crushing the obtained catalysts A4 and A5 into 20-40 meshes, respectively taking 10 g of the crushed catalyst, putting the crushed catalyst into 2 glass chromatographic columns with the diameter of 15mm, respectively putting the glass chromatographic columns with the height-diameter ratio of 5, and respectively passing diesel oil containing about 80ppm of mixed mercaptan through the catalysts A4 and A5Fixed bed, liquid space velocity (LHSV) of 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 6,
The obtained catalyst A6 is crushed to 20-40 meshes, 10 g of the catalyst 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 A6 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.
Example 7,
The obtained catalyst B1 is crushed to 20-40 meshes, 10 g of the catalyst is taken and placed in a glass chromatographic column with the diameter of 15mm, and the height-diameter ratio is about 5. Taking catalytic gasoline containing about 150ppm of mixed mercaptan and subjected to alkaline washing electric refining to pass through a fixed bed layer of a catalyst B1, wherein the liquid 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 is qualified in corrosion.
Examples 8 to 9,
Respectively crushing the obtained catalysts B2 and B3 to 20-40 meshes, and respectively putting 10 g of the crushed catalysts into a corresponding glass chromatographic column with the diameter of 15mm, wherein the height-diameter ratio is about 5. Taking aviation kerosene containing about 80ppm of mercaptan, respectively passing through fixed beds of catalysts B2 and B3, wherein liquid space velocity (LHSV) is 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 10,
The obtained catalyst B4 is crushed to 20-40 meshes, 10 g of the catalyst B is placed in a glass chromatographic column with the diameter of 15mm, and the height-diameter ratio is about 5. Taking aviation kerosene containing about 80ppm of mercaptan, and passing the aviation kerosene through a fixed bed of a catalyst B4 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 11,
Crushing the obtained catalyst B5 to 20-40 meshes, taking 10 g, and placing inThe height-diameter ratio of the glass chromatographic column with the diameter of 15mm is about 5. Taking catalytic gasoline containing about 150ppm of mixed mercaptan and subjected to alkaline washing electric refining to pass through a fixed bed layer of a catalyst B5, wherein the liquid 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 is qualified in corrosion.
Examples 12,
The obtained catalyst B6 is crushed to 20-40 meshes, 10 g of the catalyst B is placed in a glass chromatographic column with the diameter of 15mm, and the height-diameter ratio is about 5. Taking aviation kerosene containing about 80ppm of mercaptan, and passing the aviation kerosene through a fixed bed of a catalyst B6 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 13,
The obtained catalyst B7 is crushed to 20-40 meshes, 10 g of the catalyst is taken and placed in a glass chromatographic column with the diameter of 15mm, and the height-diameter ratio is about 5. Taking catalytic gasoline containing about 150ppm of mixed mercaptan and subjected to alkaline washing electric refining to pass through a fixed bed layer of a catalyst B7, wherein the liquid 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 is qualified in corrosion.
Examples 14,
The obtained catalyst B8 is crushed to 20-40 meshes, 10 g of the catalyst B is placed in a glass chromatographic column with the diameter of 15mm, and the height-diameter ratio is about 5. Taking diesel oil containing about 80ppm of mercaptan, and passing the diesel oil through a fixed bed of catalyst B8, wherein the liquid space velocity (LHSV) is 10h-1. 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 15,
The obtained catalyst B9 is crushed to 20-40 meshes, 10 g of the catalyst is taken and placed in a glass chromatographic column with the diameter of 15mm, and the height-diameter ratio is about 5. Taking catalytic gasoline containing about 150ppm of mixed mercaptan and subjected to alkaline washing electric refining to pass through a fixed bed layer of a catalyst B9, wherein the liquid space velocity (LHSV) is 20h-1. The gasoline passing through the catalyst bed layer does not contain mercaptan any more, and the doctor tests show that the copper sheet is qualified in corrosion.
Examples 16,
The obtained catalyst B10 is crushed to 20-40 meshes, 10 g of the catalyst B 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 mercaptans was passed over a fixed bed of catalyst B10 at a liquidspace 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.
Examples 17,
The obtained catalyst C1 is crushed to 20-40 meshes, 10 g of the catalyst is taken and placed in a glass chromatographic column with the diameter of 15mm, and the height-diameter ratio is about 5. Taking catalytic gasoline which contains about 150ppm of mixed mercaptan and is subjected to alkaline washing and electric refining, passing the catalytic gasoline through a fixed bed layer of a catalyst C1, wherein the liquid space velocity (LHSV) is 25h-1. The catalytic 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 18,
Crushing the catalyst C2 to 20-40 meshes, putting 10 g of the crushed catalyst into a glass chromatographic column with the diameter of 15mm and the height and diameterThe ratio is about 5. Aviation kerosene containing about 80ppm of mixed mercaptans was passed through a fixed bed of catalyst C2 at a liquid space velocity (LHSV) of 20-1. No mercaptan sulfur exists in the aviation kerosene passing through the catalyst bed layer, and the copper sheet is qualified in corrosion after passing a doctor test.
Examples 19 to 20,
Respectively crushing the obtained catalysts C3 and C4 to 20-40 meshes, and respectively putting 10 g of the crushed catalysts into a corresponding glass chromatographic column with the diameter of 15mm, wherein the height-diameter ratio is about 5. Taking diesel oil containing about 80ppm of mercaptan, respectively passing through fixed beds of catalysts C3 and C4, and the liquid space velocity (LHSV) is 10h-1. 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 21,
The obtained catalyst C5 is crushed to 20-40 meshes, 10 g of the catalyst 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 mercaptans was passed over a fixed bed of catalyst C5 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.
Examples 22,
The obtained catalyst C6 is crushed to 20-40 meshes, 10 g of the catalyst is taken and placed in a glass chromatographic column with the diameter of 15mm, and the height-diameter ratio is about 5. Taking catalytic gasoline containing about 150ppm of mixed mercaptan and subjected to alkaline washing and electric refining to pass through a fixed bed layer of a catalyst C6, wherein the liquid space velocity (LHSV) is 20h-1. The catalytic 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 23,
The obtained catalyst C7 is crushed to 20-40 meshes, 10 g of the catalyst is placed in a glass chromatographic column with the diameter of 15mm, and the height-diameter ratio is about 5. Taking aviation kerosene containing about 80ppm of mercaptan, and passing the aviation kerosene through a fixed bed of a catalyst C7 at a liquid space velocity (LHSV) of 20h-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.
(4) Examples of commercial conversions of mercaptans contained in light oils.
Examples 24,
When an atmospheric and vacuum oil refining device with annual production capacity of 250 ten thousand tons operates, 20 tons of naphtha can be produced per hour, and after pre-alkali washing, H analysis is carried out2The S content is zero, the mercaptan content is 48ppm, and the doctor test is passed, so that the copper sheet fails to be corroded. On a naphtha conveying pipeline, introducing air into naphtha at the flow speed of 2-3 cubic meters per hour through a branch pipe, and allowing the naphtha mixed with the air to enter from bottom to top and pass through a fixed bed reactor at the flow rate of 27.4 cubic meters per hour. The diameter of the devulcanizer is 1.6 m, the height is 10 m, 9.65 tons of the A1 catalyst are filled in the devulcanizer, the filling height is 6.4 m, the height-diameter ratio of the catalyst bed layer is 4, and the bulk density is 0.75g/cm3Controlling the space velocity of naphtha to be 2.13h-1At a temperature of 40 deg.CThe catalytic oxidation reaction of mercaptan is carried out at 0.4 MPa.
When naphtha passes through a catalyst bed layer, mercaptan in the naphtha and oxygen in mixed air in the naphtha are subjected to oxidation reaction under the action of a catalyst to generate disulfide, the naphtha flows out of the fixed bed reactor from the upper part of the catalyst bed layer, after analysis, the naphtha contains no mercaptan and contains neutral disulfide, and the naphtha passes a doctor test, so that copper sheet corrosion is qualified.
Examples 25 to 46,
The rest is the same as the example 24 except that: the catalysts are respectively the catalysts A2-A6, B1-B10 and C1-C7.
Examples 47,
When an atmospheric and vacuum oil refining device with the annual production capacity of 300 ten thousand tons is operated, 45 tons of kerosene for lamps can be produced per hour, and after pre-alkaline washing, H analysis is carried out2The S content is zero, the mercaptan content is 66ppm, and the doctor test is passed, so that the copper sheet fails to be corroded. On a kerosene conveying pipeline for the lamp, air is introduced into the kerosene for the lamp from a branch pipe at the flow speed of 5-6 cubic meters per hour, the kerosene for the lamp mixed with the air enters a fixed bed reactor from bottom to top, and the flow rate is 53.6 cubic meters per hour. The diameter of the devulcanizer is 2.0 m, the height is 14 m, 23.24 tons of the A1 catalyst are filled in the devulcanizer, the filling height is 10 m, the height-diameter ratio of the catalyst bed layer is 5, and the bulk density is 0.74g/cm3The space velocity of kerosene for the control lamp is 1.71h-1The catalytic oxidation reaction of mercaptan was carried out at a temperature of 40 ℃ and a pressure of 0.5 MPa.
When the kerosene for the lamp passes through the catalyst bed layer, mercaptan in the kerosene for the lamp and oxygen in air mixed in the kerosene for the lamp are subjected to oxidation reaction under the action of the catalyst to generate disulfide, the kerosene for the lamp flows out of the fixed bed reactor from the upper part of the catalyst bed layer, and after analysis, the kerosene for the lamp does not contain mercaptan but contains neutral disulfide, and the copper sheet is qualified in corrosion after passing a doctor test.
Examples 48 to 69,
The rest is the same as the example 48, except that: the catalysts are respectively the catalysts A2-A6, B1-B10 and C1-C7.
Examples 70,
Atmospheric and vacuum oil refining with annual production capacity of 400 ten thousand tonsWhen the device is operated, 68 tons of No. 3 aviation kerosene can be produced per hour, and after pre-alkali washing, H analysis is carried out2The S content is zero, the mercaptan content is 112ppm, and the doctor test is passed, so that the copper sheet fails to be corroded. On a pipeline for running No. 3 aviation kerosene, air is introduced into No. 3 aviation kerosene through a branch pipe at the flow speed of 18-20 cubic meters per hour, the No. 3 aviation kerosene mixed with the air enters from bottom to top and passes through a fixed bed reactor, and the flow rate is 81 cubic meters per hour. The diameter of the devulcanizer is 2.4 meters, the height of the devulcanizer is 14 meters, 38.09 tons of the A1 catalyst are filled in the devulcanizer, the filling height of the devulcanizer is 10.8 meters, the height-diameter ratio of a catalyst bed layer is 4.5, and the bulk density of the devulcanizer is 0.78g/cm3Controlling the airspeed of No. 3 aviation kerosene to be 1.66h-1The catalytic oxidation reaction of mercaptan was carried out at a temperature of 40 ℃ and a pressure of 0.5 MPa.
When the No. 3 aviation kerosene passes through the catalyst bed layer, mercaptan in the No. 3 aviation kerosene and oxygen in air mixed in the No. 3 aviation kerosene are subjected to oxidation reaction under the action of the catalyst to generate disulfide, the No. 3 aviation kerosene flows out of the fixed bed reactor from the upper part of the catalyst bed layer, and after analysis, the No. 3 aviation kerosene does not contain mercaptan but contains neutral disulfide, and the copper sheet is qualified in corrosion after passing a doctor test.
Examples 71 to 92,
The rest is the same as example 70 except that: the catalysts are respectively the catalysts A2-A6, B1-B10 and C1-C7.
Examples 93,
When an atmospheric and vacuum oil refining device with the annual production capacity of 800 ten thousand tons operates, 120 tons of No. 3 aviation kerosene can be produced per hour, and the aviation kerosene is subjected to pre-alkali washing, stripping and H analysis2The S content is zero, the mercaptan content is 180ppm, and the doctor test is not passed, but the copper sheet corrosion test is failed. On a pipeline for running No. 3 aviation kerosene, air is introduced into No. 3 aviation kerosene through a branch pipe at the flow speed of 40-52 cubic meters per hour, the No. 3 aviation kerosene mixed with the air enters from bottom to top and passes through a fixed bed reactor, and the flow rate is 143 cubic meters per hour. The diameter of the devulcanizer is 3.0 m, the height is 13 m, 50.87 tons of the A1 catalyst are filled in the devulcanizer, the filling height is 9.0 m, the height-diameter ratio of the catalyst bed layer is 3, and the bulk density is 0.8g/cm3Control ofThe space velocity for preparing No. 3 aviation kerosene is 2.25h-1The catalytic oxidation reaction of mercaptan was carried out at a temperature of 40 ℃ and a pressure of 0.5 MPa.
When the No. 3 aviation kerosene passes through the catalyst bed layer, mercaptan in the No. 3 aviation kerosene and oxygen in air mixed in the No. 3 aviation kerosene are subjected to oxidation reaction under the action of the catalyst to generate disulfide, the No. 3 aviation kerosene flows out of the fixed bed reactor from the upper part of the catalyst bed layer, and after analysis, the No. 3 aviation kerosene does not contain mercaptan but contains neutral disulfide, and the copper sheet is qualified in corrosion after passing a doctor test.
Examples 94 to 115,
The rest is the same as example 93 except that: the catalysts are respectively the catalysts A2-A6, B1-B10 and C1-C7.
Examples 116,
When an atmospheric and vacuum oil refining device with annual production capacity of 500 ten thousand tons is operated, 75 tons of high-quality light diesel oil can be produced per hour, and after pre-alkali washing, H analysis is carried out2The S content is zero, the mercaptan content is 88ppm, and the doctor test is not passed, but the copper sheet corrosion test is failed. On a pipeline for running high-quality light diesel oil, introducing air into the high-quality light diesel oil through a branch pipe at a flow speed of 15-17 cubic meters per hour, wherein the high-quality light diesel oil mixed with the air flows into a fixed bed reactor from bottom to top, and the flow rate is 90 cubic meters per hour. The diameter of the devulcanizer is 2.4 m, the height is 12 m, 28.49 tons of the A1 catalyst are filled in the devulcanizer, the filling height is 8.4 m, the height-diameter ratio of the catalyst bed layer is 3.5, and the bulk density is 0.75g/cm3Controlling the space velocity of high-quality light diesel oil to be 2.37h-1The catalytic oxidation reaction of mercaptan was carried out at a temperature of 60 ℃ and a pressure of 0.5 MPa.
When the high-quality light diesel oil passes through the catalyst bed layer, mercaptan in the high-quality light diesel oil and oxygen in introduced air are subjected to oxidation reaction to generate disulfide, the high-quality light diesel oil flows out of the fixed bed reactor from the upper part of the catalyst bed layer, and after analysis, the high-quality light diesel oil does not contain mercaptan but contains neutral disulfide, and the copper sheet is qualified in corrosion after passing a doctor test.
Examples 117 to 138,
The rest is the same as the embodiment 116 except that: the catalysts are respectively the catalysts A2-A6, B1-B10 and C1-C7.
Example 139
When the catalytic cracking unit with annual production capacity of 80 ten thousand tons is operated, 45 tons of catalytic gasoline can be produced per hour, and after pre-alkali washing, H analysis is carried out2The S content is zero, the mercaptan content is 96ppm, and the doctor test is passed, so that the copper sheet fails to be corroded. On a pipeline for conveying catalytic gasoline, air is introduced into the catalytic gasoline through a branch pipe at the flow speed of 10-12 cubic meters per hour, the catalytic gasoline mixed with the air enters from the bottom and flows out of the fixed bed reactor from the top, and the flow rate is 62 cubic meters per hour. The diameter of the devulcanizer is 2.4 m, the height is 10 m, 20.89 tons of the Al catalyst are filled in the devulcanizer, the filling height is 6 m, the height-diameter ratio of the catalyst bed layer is 2.5, and the bulk density is 0.77g/cm3Controlling the space velocity of the catalytic gasoline to be 2.28h-1The catalytic oxidation reaction of mercaptan was carried out at a temperature of 40 ℃ and a pressure of 0.5 MPa.
When the catalytic gasoline passes through the catalyst bed layer, mercaptan contained in the catalytic gasoline and oxygen in air mixed in the catalytic gasoline are subjected to oxidation reaction under the action of the catalyst to generate disulfide, the catalytic gasoline flows out of the fixed bed reactor from the upper part of the catalyst bed layer, and after analysis, the catalytic gasoline does not contain mercaptan but contains neutral disulfide, and the copper sheet is qualified in corrosion after passing a doctor test.
Examples 140 to 161,
The rest isthe same as example 139 except that: the catalysts are respectively the catalysts A2-A6, B1-B10 and C1-C7.
Examples 162,
When a catalytic cracking unit with annual capacity of 200 ten thousand tons is operated, 120 tons of catalytic gasoline can be produced per hour, and after pre-alkali washing, H is analyzed2The S content is zero, the mercaptan content is 128ppm, and the doctor test is passed, so that the copper sheet fails to be corroded. On a pipeline for conveying catalytic gasoline, introducing air into the catalytic gasoline at a flow speed of 36-38 cubic meters per hour through a branch pipe, and mixing the airThe catalytic gasoline of the gas passes through the fixed bed reactor from bottom to top, and the flow rate is 164 cubic meters per hour. The diameter of the devulcanizer is 3.0 m, the height is 11 m, 41.20 tons of the A1 catalyst are filled in the devulcanizer, the filling height is 7.2 m, the height-diameter ratio of the catalyst bed layer is 2.4, and the bulk density is 0.81g/cm3Controlling the space velocity of the catalytic gasoline to be 3.29h-1The catalytic oxidation reaction of mercaptan was carried out at a temperature of 40 ℃ and a pressure of 0.8 MPa.
When the catalytic gasoline passes through the catalyst bed layer, mercaptan contained in the catalytic gasoline and oxygen in air mixed in the catalytic gasoline are subjected to oxidation reaction under the action of the catalyst to generate disulfide, the catalytic gasoline flows out of the fixed bed reactor from the upper part of the catalyst bed layer, and after analysis, the catalytic gasoline does not contain mercaptan but contains neutral disulfide, and the copper sheet is qualified in corrosion after passing a doctor test.
Examples 163 to 184, the rest were the same as those of example 162 except that: the catalysts are respectively thecatalysts A2-A6, B1-B10 and C1-C7.
Claims (6)
1. A method for converting mercaptan contained in light oil, which is applied to large-scale industrial production or laboratories; the method adopts a fixed bed catalytic oxidation method, the active component of the used catalyst is a nano-grade transition metal oxide, a perovskite type rare earth composite oxide or a spinel type oxide, and the using amount of air or oxygen is 1.5-2 times of the theoretical required amount; the light oil mixed with air or oxygen passes through a catalyst bed layer arranged in a fixed bed reactor, and under the action of a catalyst, the oxygen and mercaptan contained in the light oil are subjected to oxidation reaction to generate disulfide;
when the method is used for converting mercaptan contained in the light oil product in large-scale industrial production, the mercaptan is oxidized at the temperature of 40-60 ℃ and under the operation pressure of 0.4-0.8 MPa, and the airspeed of the light oil product flowing through the catalyst bed is 0.5-5 h-1The height-diameter ratio of the catalyst bed layer is 1-6, and the bulk density is 0.6-0.9 g/cm3；
When the method is used for converting mercaptan contained in light oil in a laboratory, the mercaptan is oxidized at the temperature of 40-60 ℃ and under the operation pressure of 0.3-0.5 MPa, and the airspeed of the light oil flowing through a catalyst bed is 3-20 h-1The height-diameter ratio of the catalyst bed layer is 3-10, and the bulk density is 0.6-0.9 g/cm3；
When the active component of the catalyst is a nano-scale transition metal element oxide, the active component is 1-5 oxides selected from transition metal elements Co, Mn, Ni, Fe and Cr, the catalyst is a catalyst which has no diffraction peak 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, the loading amount of the active component on the carrier is 1-20% by weight of the carrier, the metal elements in the active component can be mixed in any molar ratio, the carrier is an aluminum-containing carrier calcined at 1200-1600 ℃, the carrier takes mullite, cordierite, magnesia alumina spinel or α -alumina as a main phase, and the shape of the carrier is spherical or cylindrical;
when the active component of the catalyst used is a spinel-type oxide, the general formula of the spinel-type oxide is: (A)XA’1-X)(BYB’1-Y)2O4Wherein A, A 'is a metal element selected from Zn, Co, Ni, Mg, Mn and Cd, B is a metal element Fe, B' is a metal element selected from Cr, Co, Ni and Mn, X is more than or equal to 0 and less than or equal to 1, Y is more than or equal to 0.4 and less than or equal to 1.0, and the carrier of the catalyst is mullite, cordierite, magnesia-alumina spinel or α -Al2O3The carrier is a main phase, and the weight percentage of the main phase in the carrier is more than or equal to 80 percent; the active component is directly loaded on the carrier, and the loading amount of the active component on the carrier is 5-15% of the weight of the carrier;
when the active component of the catalyst is perovskite type rare earth composite oxide, the general formula of the perovskite type rare earth composite oxide is as follows: a. the1-XA’xB1-YB’YO3(ii) a Wherein A represents a lanthanide rare earth element; a' represents an alkaline earth metal element; b andb' represents a transition metal element; x is more than or equal to 0 and less than or equal to 0.9; y is more than or equal to 0 and less thanor equal to 0.9; the lanthanide rare earth metal elements are 1 or 2 of La and Ce; the alkaline earth metal elements are 1 or 2 of Ba, Sr and Ca; the transition metal elements are 1 or 2 of Fe, Co, Ni, Mn, Cu and Ti; the carrier of the catalyst is mullite, cordierite, magnesia-alumina spinel orα -aluminum oxide is used as a carrier of a main phase, the weight percentage of the main phase in the carrier is more than or equal to 80%, the active component is directly loaded on the carrier, and the loading amount of the active component on the carrier is 5-15% of the weight of the carrier.
2. The method of claim 1, wherein: when the method is used for converting mercaptan contained in the light oil product in large-scale industrial production, the airspeed of the light oil product flowing through the catalyst bed is 1-3 h-1(ii) a The bulk density is 0.7 to 0.8g/cm3。
3. The method of claim 1, wherein: when the active component is perovskite type rare earth composite oxide, lanthanide series rare earth metal elements limited in the general formula are La and Ce, alkaline earth metal elements are Sr and Ca, and transition metal elements are Mn, Co, Cu, Fe and Ti; the carrier is a carrier taking cordierite, magnesia-alumina spinel or mullite as a main phase.
4. The method of claim 3, wherein: the chemical formula of the perovskite type rare earth composite oxide of the active component is La0.6Sr0.4Co0.8Ti0.2O3、La0.8Sr0.2Cu0.5Mn0.5O3、La0.8Ba0.2Fe0.8Cu0.2O3、La0.8Ce0.2Cu0.5Mn0.5O3、La0.8Ca0.2Co0.8Ti0.2O3、La0.6Ca0.4Co0.8Ti0.2O3Or La0.6Sr0.4Co0.6Mn0.4O3。
5. The method according to claim 1 or 2, characterized in that: when the active component of the catalyst is spinel type oxide, A, A' in the general formula is metal elements selected from Zn, Co and Mn; b' is a metal element Cr; the catalyst carrier is a carrier taking cordierite or magnesium aluminate spinel as a main phase.
6. The method according to claim 1 or 2, characterized in that: when the active component of the catalyst used is a spinel-type oxide, the spinel-type oxide has the chemical formula of (Zn)0.8Co0.2)(Fe0.5Cr0.5)2O4、(Zn0.6Mg0.4)(Fe0.6Cr0.4)2O4、(Zn0.5Ni0.5)(Fe0.7Cr0.3)2O4、(Zn0.7Co0.3)Fe2O4、(Zn0.5Mn0.5)(Fe0.8Cr0.2)2O4Or (Zn)0.5Cd0.5)(Fe0.8Cr0.2)2O4。
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| CN100352894C (en) * | 2005-05-30 | 2007-12-05 | 北京三聚环保新材料有限公司 | Method for supplying oxygen to hydrocarbon oil |
| CN100429295C (en) * | 2005-06-21 | 2008-10-29 | 大连理工大学 | Fixed bed oxidation desulfur reaction method |
| CN100462146C (en) * | 2006-11-07 | 2009-02-18 | 北京三聚环保新材料股份有限公司 | Method for preparing catalyst for converting mercaptan in gasoline |
| CN100462145C (en) * | 2006-11-07 | 2009-02-18 | 北京三聚环保新材料股份有限公司 | Method for preparing catalyst for converting mercaptan in liquefied gas |
| MX358123B (en) | 2011-10-24 | 2018-08-06 | Aditya Birla Nuvo Ltd | An improved process for the production of carbon black. |
| US9410042B2 (en) | 2012-03-30 | 2016-08-09 | Aditya Birla Science And Technology Company Ltd. | Process for obtaining carbon black powder with reduced sulfur content |
| CN102764669B (en) * | 2012-07-19 | 2015-12-02 | 北京三聚环保新材料股份有限公司 | A kind of Catalysts and its preparation method for catalyzed conversion isomery mercaptan |
| CA2886518C (en) * | 2012-09-28 | 2021-06-08 | Aditya Birla Science And Technology Company Limited | Methods and composition for desulfurization of compositions |
| CN104549337B (en) * | 2013-10-15 | 2017-01-25 | 中国石油化工股份有限公司 | Oxidation catalyst for mercaptan in light oil, as well as preparation method and application of mercaptan oxidation catalyst |
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