CN1330127A - Process for transforming thiols contained in light oil - Google Patents
Process for transforming thiols contained in light oil Download PDFInfo
- Publication number
- CN1330127A CN1330127A CN 00109631 CN00109631A CN1330127A CN 1330127 A CN1330127 A CN 1330127A CN 00109631 CN00109631 CN 00109631 CN 00109631 A CN00109631 A CN 00109631A CN 1330127 A CN1330127 A CN 1330127A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- active component
- mercaptan
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
A process for convering the thiols contained by light oil features use catalytic oxidization method with fixed bed, that is, the light oil mixed with air or oxygen passes through the catalyst bed layer in fixed-bed reactor, where the oxygen and thiols contained in oil take part in oxidizing reaction to generate disulfides under the action of catalyst whose active components are nm-class transition metal oxide, perovskite-type composite rare-earth oxide, or spinel-type oxide. Its advantages are high efficiency, no discharge of alkali solution, and no need of activating agent.
Description
The invention relates to a method for refining light oil.
The light oil product includes naphtha, catalytic gasoline, straight run aviation kerosene, lamp oil, diesel oil, etc. 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 method for converting mercaptan contained in light oil products is firstly proposed by American Global oil products company (UOP) in 1958, and through the development of last forty years, the technology is continuously improved, the method is developed from an alkaline liquid extraction deodorization method to a fixed bed alkali-free deodorization method, thousands of devices are operated in the world, the current mercaptan conversion process comprises ① liquid extraction and regeneration processes, 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 mercaptan and the light oil products (including naphtha, catalytic gasoline, straight-run aviation kerosene, lamp oil and diesel oil) are fully mixed and reacted in a tower or a container, and the mercaptan in the oil products is reacted with the sodium hydroxide to generate sodium mercaptan which enters into an alkaline solution, and the reaction formula is as follows:
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。
The catalyst used is a catalyst whose active component is 1 to 6 oxides selected from transition metal elements Co, Mn, Ni, Cu, Fe, Cr, and which is a catalyst in which no diffraction peak of the active component appears in an X-ray diffraction pattern and the primary accumulation state of the active component is less than 5nm, the active component being directly supported on a carrier by an impregnation method,and the amount of the active component supported on the carrier by weight is 1 to 20%.
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 α -alumina as a main phase, and the carrier is spherical or cylindrical.
The catalyst is a catalyst with an active component of perovskite type rare earth composite oxide, and 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 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 metal element is La,Ce. The catalyst comprises 1 or 2 kinds of mixed light rare earth, 1 or 2 kinds of alkaline earth metal elements of Ba, Sr and Ca, 2 or 1 kinds of transition metal elements of Fe, Co, Ni, Mn, Cu and Ti, a carrier of the catalyst is a carrier taking mullite, cordierite, magnesia-alumina spinel or α -alumina as main phases, the weight percentage of the main phases in the carrier is more than or equal to 80%, active components are directly loaded on the carrier, and the loading amount of the active components on the carrier by weight is 5-15%.
Preferably, the lanthanide rare earth metal elements are La and Ce, the alkaline earth metal elements are Sr and Ca, and the 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.
The preferred active component perovskite type rare earth composite oxide has the chemical formula of 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、La0.6Ca0.4Co0.8Ti0.2O3、La0.6Sr0.4Co0.6Mn0.4O3、RE0.6Sr0.4Co0.8Ti0.2O3、RE0.8Sr0.2Cu0.5Mn0.5O3Or RE0.6Sr0.4Co0.6Mn0.4O3。
The catalyst is a catalyst with an active component of spinel oxide, and the general formula of the spinel oxide is as follows: (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% by weight.
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 cordierite or magnesia-alumina spinel as a main phase.
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)2O4、(Zn0.5Cu0.5)(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 is reduced or the catalyst is invalid, the surface of the catalyst can be washed by hot water at 80-90 ℃, and the activity is recovered after the catalyst is dried, so that 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, and the hydrogen is combined with oxygen to generate water under the participation of high valence state ions of B or B' positionThe remaining part of the two thiol molecules is then combined into one disulfide molecule for the purpose of converting the thiol. 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. Similarly, when the catalyst activity is reduced or loses efficacy, the surface of the catalyst can be washed by hot water, and the activity is recovered after drying, so the service life is long.
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 an 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, alumina and a composite compound of the 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 magnesia-alumina spinel, the weight percentage of the main phase in the carrier is 96.5%, and the rest part of the carrier is magnesia, silicon oxide and a composite compound of the magnesia and the silicon oxide.
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 carrieris 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 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.
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)2Weighing 240 g of the alumina spherical carrier, putting the alumina spherical carrier into the 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 prepare the catalyst A2, wherein the loading of active components is 9.8%, the molar ratio of manganese to copper is Mn: Cu is 2: 1, and the phase of α -aluminum oxide only is obtained by X-ray diffraction analysis of the catalyst A2The intensity was reduced, but the phase of the transition metal oxide was not present in the diffraction pattern, and it was confirmed that the primary accumulation state of the transition metal oxide, manganese oxide and copper oxide, was 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 are added with water to 240 ml and stirredMixing to obtain soaking solution. 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 is4: 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 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 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 in an impregnation solution, and fullyAnd (3) after impregnation, drying at the temperature of 80-120 ℃, pre-roasting at 250 ℃ for 1 hour, and then roasting at the temperature of 300-500 ℃ for 2 hours to obtain the catalyst, namely the catalyst A5, wherein the loading capacity of the 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, putting the alumina spherical carrier into an impregnation solution, fully impregnating, drying at the temperature of 80-100 ℃,the catalyst is prepared by pre-roasting at 250 ℃ for 1 hour and then roasting at 300-500 ℃ for 2 hours, wherein the catalyst A6 is obtained, the loading amount of an 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 cobalt oxide, a transition metal 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: 100.0g 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). Elemental analysis of the active ingredientChemical formula is La0.6Sr0.4Co0.8Ti0.2O3(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 were added to a beaker, diluted to 1000 ml with water, and mixed well to obtain a solution. 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 toobtain 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 analysis0.8Sr0.2Cu0.5Mn0.5O3(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 g of 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, roasting and activating at 300-500 ℃ for 4-12 hours to prepare a catalyst, namely a catalyst B3, wherein the loading capacity of an active component is 10.1% (by the weight of the carrier)Reference). 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 type compound by X-ray diffraction analysisAnd (4) a substance phase.
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, diluted to 1000 ml with water and stirred well to obtain a steep. 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)Quasi). 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. Adding 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% 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. Adding 200 g ofThe magnesia-alumina spinel phase carrier is added into 100 ml of impregnation liquid, fully impregnated (about 0.5 hour), dried at the temperature of 80-100 ℃, and roasted and activated at the temperature of 300-500 ℃ for 4-12 hours to prepare the catalyst, namely the catalyst B7, wherein the loading capacity of the active component is 10.1 percent (based on the carrier quantity). Elemental analysis, active groupHas the chemical formula of La0.6Sr0.4Co0.6Mn0.4O3(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. And (2) adding 200 g of the mullite 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 the catalyst, namely the catalyst B8, wherein the loading amount of the active component is 9.9% (based on the carrier amount). 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)2, 120.8 g 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 Warp beamAnd (4) analyzing by X-ray diffraction, wherein the phase of the active component is a perovskite compound phase.
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. And (2) adding 200 g of the alumina spherical 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 B10, wherein the loading amount of the active component is 11% (based on the carrier amount). 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)3·9H2O is dissolved inPreparing 200 ml of solution in water, adding 56.0 g of citric acid, stirring, dissolving and uniformly mixing to obtain the impregnation liquid. 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 spinel type oxide as active componentCatalyst 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 The phase of the active component is a spinel compound phase by X-ray diffraction analysis.
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. 30 g of the alumina spherical carrier is taken and soakedSoaking for 0.5 hour, taking out and drying, and roasting for 2 hours at 300-500 ℃ to prepare the catalyst, namely the catalyst C4, wherein the loading capacity of the active component is 9.8% (based on the carrier quantity). 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 of solution, adding 14.5 g of citric acid, and uniformly stirring to obtain the impregnation solution. 30 g of the cordierite phase carrier is taken and put into an impregnation liquid to be impregnated for 0.5 hour, the cordierite phase carrier is taken out and dried, and then is activated for 2 hours at the temperature of 300-500 ℃ to prepare the catalyst, namely the catalyst C5, wherein the loading capacity of the active component is 9.5 percent (based on the carrier weight)As a reference). The chemical formula of the active component is (Zn) by element analysis0.5Mn0.5)(Fe0.8Cr0.2)2O4(ii) a The phase of the active component is a spinel compound phase by X-ray diffraction analysis.
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 Warp beamAnd (4) analyzing by X-ray diffraction, wherein the phase of the active component is a spinel compound phase.
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. And (3) adding 30 g of the alumina spherical carrier into the impregnation liquid, impregnating for 0.5 hour, taking out, drying, and activating at 300-500 ℃ for 2 hours to prepare the catalyst, namely the catalyst C7, wherein the loading amount of the active component is 10.1% (based on the carrier amount). 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 the diameter 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,
Crushing the obtained catalyst A3 to 20-40 meshes, putting 10 g of the crushed catalyst into a glass chromatographic column with the diameter of 15mm,the aspect 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. 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 to 5,
Respectively crushing the obtained catalysts A4 andA5 to 20-40 meshes, respectively taking 10 g of the crushed catalysts, putting the crushed catalysts into 2 glass chromatographic columns with the diameter of 15mm, respectively putting the glass chromatographic columns with the height-diameter ratio of 5, respectively taking diesel oil containing about 80ppm of mixed mercaptan, respectively passing the diesel oil through fixed beds of the catalysts A4 and A5, and respectively setting 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 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, and respectively passing through catalysts B2 and B3Fixed bed, 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 10,
The obtained catalytic B4 is crushed into 20-40 meshes, 10 g of the catalytic B4 is put into 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 the 10 g into a glass chromatographic column with the diameter of 15mmThe aspect 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 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,
Crushing the obtained catalyst B8 to 20-40 meshes, taking 10 g of the crushed catalyst B and placing the crushed catalyst B in a containerThe height-diameter ratio of the glass chromatographic column with the diameter of 15mm 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 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 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 sulfur any moreAlcohol, doctor tests pass, and the copper sheet is qualified in corrosion.
Examples 18,
Crushing the catalyst C2 to 20-40 meshes, and placing 10 g of the crushed catalyst in a glass chromatographic column with the diameter of 15mm, wherein the height-diameter 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 thiol 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 and the mercaptan content is 48ppm, doctor's test failed, and the copper sheet failed to corrode. On a naphtha conveying pipeline, introducing air into naphtha at a flow speed of 2-3 cubic meters per hour through a branch pipe, and mixing the airThe gaseous naphtha was passed through the fixed bed reactor from bottom to top at a 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/cm3Controllingthe space velocity of naphtha to be 2.13h-1The catalytic oxidation reaction of mercaptan was carried out at a temperature of 40 ℃ and a pressure of 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,
When an atmospheric and vacuum oil refining device with the annual production capacity of 400 million tons operates, 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 operated by 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 hourAmong the coals, No. 3 aviation kerosene mixed with air passes through the fixed bed reactor from bottom to top, 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/cm3Controlling the space velocity of No. 3 aviation kerosene to be 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 running by high-quality light diesel oil, a branch pipe leads air to be ventilated at the flow speed of 15-17 cubic meters per hourThe high-quality light diesel oil mixed with air flows into the high-quality light diesel oil from bottom to top and passes through the fixed bed reactor, and the flow rate is 90 cubic meters per hour. The diameter of the devulcanizer is 2.4 meters, the height is 12 meters, and the inner part is28.49 tons of the A1 catalyst were loaded, the loading height was 8.4 m, the height-diameter ratio of the catalyst bed was 3.5, and the bulk density was 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.
Examples 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 A1 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 is the 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, air is introduced into the catalytic gasoline through a branch pipe at the flow speed of 36-38 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 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 is the same as the embodiment 162 except that: the catalysts are respectively the catalysts A2-A6, B1-B10 and C1-C7.
Claims (13)
1. A method for converting mercaptan contained in light oil products adopts a fixed bed catalytic oxidation method, so that the light oil products mixed with air or oxygen pass through a catalyst bed layer arranged in a fixed bed reactor, and under the action of a catalyst, the oxygen and the mercaptan contained in the light oil products 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.
2. The method of claim 1, wherein: the amount of air or oxygen is 1.5-2 times of the theoretical requirement.
3. The method of claim 1, wherein: oxidizing mercaptan 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 1-6, and the bulk density is 0.6-0.9 g/cm3。
4. The method of claim 3, wherein: the air speed 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。
5. The method of claim 1, wherein: oxidizing mercaptan 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
6. Method according to one of claims 1 to 5, characterized in that: the catalyst used is one whose active component is 1-6 oxides selected from transition metal elements Co, Mn, Ni, Cu, Fe, Cr, and is a catalyst whose primary accumulation state of the active component is less than 5nm and in which no diffraction peak of the active component appears in an X-ray diffraction pattern, and the active component is directly supported on a carrier by an impregnation method, and the supporting amount of the active component on the carrier by weight is 1-20%.
7. The method as claimed in claim 6, wherein the metal elements in the active component are 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 carrier is spherical or cylindrical.
8. Method according to one of claims 1 to 5, characterized in that: the catalyst is a catalyst with an active component of perovskite type rare earth composite oxide, and 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 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 metal elements are 1 or 2 of La, Ce and mixed light rare earth; the alkaline earth metal elements are 1 or 2 of Ba, Sr and Ca; the transition metal elements are Fe, Co, Ni,The catalyst comprises 2 or 1 of Mn, Cu and Ti, wherein carriers of the catalyst are carriers taking mullite, cordierite, magnesia-alumina spinel or α -aluminum oxide as main phases, the weight percentage of the main phases in the carriers is more than or equal to 80%, active components are directly loaded on the carriers, and the loading capacity of the active components on the carriers by weight is 5-15%.
9. The method of claim 8, wherein: the lanthanide rare earth metal elements are La and Ce, the alkaline earth metal elements are Sr and Ca, and the 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.
10. The method of claim 8, 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、La0.6Ca0.4Co0.8Ti0.2O3、La0.6Sr0.4Co0.6Mn0.4O3、RE0.6Sr0.4Co0.8Ti0.2O3、RE0.8Sr0.2Cu0.5Mn0.5O3Or RE0.6Sr0.4Co0.6Mn0.4O3。
11. Method according to one of claims 1 to 5, characterized in that: the catalyst used is a catalyst with the active component of spinel-type oxide, and the general formula of the spinel-type oxide is as follows: (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% by weight.
12. The method of claim 11, wherein: A. a' is respectively a metal element selected from Zn, Co and Mn; b' is a metal element Cr; the carrier of the catalyst is cordierite or magnesia-alumina spinel as a main phase.
13. The method of claim 11, wherein: 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)2O4、(Zn0.5Cu0.5)(Fe0.8Cr0.2)2O4Or (Zn)0.5Cd0.5)(Fe0.8Cr0.2)2O4。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00109631 CN1234809C (en) | 2000-06-16 | 2000-06-16 | Process for transforming thiols contained in light oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00109631 CN1234809C (en) | 2000-06-16 | 2000-06-16 | Process for transforming thiols contained in light oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1330127A true CN1330127A (en) | 2002-01-09 |
| CN1234809C CN1234809C (en) | 2006-01-04 |
Family
ID=4579758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00109631 Expired - Lifetime CN1234809C (en) | 2000-06-16 | 2000-06-16 | Process for transforming thiols contained in light oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1234809C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| CN102764669A (en) * | 2012-07-19 | 2012-11-07 | 北京三聚环保新材料股份有限公司 | Catalyst for catalytically converting isomercaptan and preparation method thereof |
| KR20150063510A (en) * | 2012-09-28 | 2015-06-09 | 아디트야 비를라 사이언스 앤 테크놀로지 컴퍼니 리미티드 | Methods and composition for desulfurization of compositions |
| 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 |
| 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 |
| US9873797B2 (en) | 2011-10-24 | 2018-01-23 | Aditya Birla Nuvo Limited | Process for the production of carbon black |
-
2000
- 2000-06-16 CN CN 00109631 patent/CN1234809C/en not_active Expired - Lifetime
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| US9873797B2 (en) | 2011-10-24 | 2018-01-23 | Aditya Birla Nuvo Limited | 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 |
| CN102764669A (en) * | 2012-07-19 | 2012-11-07 | 北京三聚环保新材料股份有限公司 | Catalyst for catalytically converting isomercaptan and preparation method thereof |
| CN104812481A (en) * | 2012-09-28 | 2015-07-29 | 埃迪亚贝拉科技有限公司 | Methods and compositions for desulfurization of compositions |
| JP2015532320A (en) * | 2012-09-28 | 2015-11-09 | アディティア ビルラ サイエンス アンド テクノロジー カンパニー リミテッド | Method and composition for desulfurization of a composition |
| KR20150063510A (en) * | 2012-09-28 | 2015-06-09 | 아디트야 비를라 사이언스 앤 테크놀로지 컴퍼니 리미티드 | Methods and composition for desulfurization of compositions |
| CN104812481B (en) * | 2012-09-28 | 2017-11-10 | 埃迪亚贝拉科技有限公司 | For making the method and composition of composition desulfurization |
| CN107663461A (en) * | 2012-09-28 | 2018-02-06 | 埃迪亚贝拉科技有限公司 | For making the method and composition of composition desulfurization |
| KR102125107B1 (en) * | 2012-09-28 | 2020-06-19 | 아디트야 비를라 사이언스 앤 테크놀로지 컴퍼니 프라이빗 리미티드 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1234809C (en) | 2006-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1022542C (en) | Perovskite-type rare-earth composite oxides catalyst for combustion | |
| CN1732250A (en) | Process for removing sulfide contained in hydrocarbon-containing gas | |
| CN1057211A (en) | The method of from flue gas and other air-flows, removing oxysulfide with sorbent | |
| CN108187605B (en) | A kind of highly selective gasoline adsorption deep desulfurizer of support type hydroxide and preparation method thereof | |
| CN105749863A (en) | Compound desulfurizer and preparation method thereof | |
| CN106693632A (en) | Zinc oxide based normal-temperature deep desulfurizing agent as well as preparation method and application thereof | |
| CN104624196B (en) | A kind of high-specific surface area fischer-tropsch synthetic catalyst and preparation method and application | |
| CN1234809C (en) | Process for transforming thiols contained in light oil | |
| CN1245488C (en) | Method for indudstrialized refining liquefied petrolium gas (LPG) | |
| CN1702157A (en) | Method for refining catalytic liquefied petroleum gas | |
| CN1836768A (en) | Claus tail gas hydrogenation catalyst | |
| CN108855093B (en) | Nickel-copper hydrogenation catalyst and preparation method thereof | |
| CN108641776B (en) | Method for removing sulfur in petroleum coke by using manganese powder | |
| CN1072975C (en) | Alumina-based catalyst for the treatment of gases containing sulphur compounds, use of these catalysts for the treatment and processes for treatment of the said gases | |
| SA519410261B1 (en) | Hydrotreatment of feedstock from renewable sources using catalysts with a high content of active phase | |
| CN103028363A (en) | Gas desulfurization adsorbent and preparation method thereof as well as desulfurization method for sulphur-contained gas | |
| CN1871063A (en) | Desulfurization and novel methods for same | |
| CN111056612B (en) | Treatment method and application of sulfur-containing wastewater | |
| CN1292053C (en) | Process for transforming thiols contained in liquefied petroleum gas | |
| CN1766047A (en) | Selective hydrogenation desulfuration catalyst for catalytically cracking gasoline and its preparation method | |
| CN1194077C (en) | Alkali-free refining process of liquefied petroleum gas or natural gas | |
| CN1151879C (en) | Nanometer level transition metal oxide catalyst for transforming mercaptan and its prepn. | |
| CN1314783C (en) | Catalyst of inverting thiol in liquefied gas and producing process thereof | |
| CN1147010A (en) | Process for normal temp. removal of organic sulfur from artificial coal gas | |
| CN1206031C (en) | Catalyst for converting mercaptan contained in hydrocarbon oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: BEIJING SANJU ENVIRONMENTAL PROTECTION AND NEW MAT Free format text: FORMER NAME OR ADDRESS: SANJU ENVIRONMENT PROTECTION NEW MATERIAL CO., LTD., BEIJING |
|
| CP03 | Change of name, title or address |
Address after: Beijing Haidian District people's Congress Road 33, the big line foundation building 9 floor Patentee after: Beijing Sj Environmental Protection New Material Co., Ltd. Address before: Huayuan Shilong Industrial Zone, Beijing Road, Mentougou District No. 4 Patentee before: Sanju New Environment Protection Materials Co., Ltd., Beijing |
|
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060104 |