A method for preparing a non-calcined sulfur-containing hydrorefining catalyst

Abstract

The invention discloses a method for preparing a non-calcined sulfur-containing hydrorefining catalyst. The method comprises: firstly mixing ammonium dithiocarbamate, nickel salt and / or cobalt salt, auxiliary agent and deionized water, heating and stirring, then adding ammonium tetrathiomolybdate and / or ammonium tetrathiotungstate, and adjusting the volume of the obtained sulfur-containing composite active metal precursor impregnation liquid with deionized water, and impregnating an equal volume on an alumina carrier containing a microwave sensitizer at a temperature of 50°C to 90°C, firstly using an ultrasonic treatment with a frequency of 20KHz, and then using an ultrasonic treatment with a frequency of 50KHz, and then using a microwave drying with a radiation frequency of 840MHz under nitrogen protection, and then using a microwave drying with a radiation frequency of 2450MHz, to obtain a non-calcined sulfur-containing hydrorefining catalyst. The method of the invention is efficient and simple, the active metal is evenly dispersed, the synergy between different active metals is good, the effective utilization rate of the active metal is high, and the non-calcined sulfur-containing hydrorefining catalyst has excellent hydrogenation performance.

Description

Technical Field

[0001] The invention relates to a method for preparing a non-calcined sulfur-containing hydrogenation refining catalyst. Background Art

[0002] The petroleum fraction hydrogenation process is the key technology for producing clean oil products. Among them, high-performance hydrogenation catalysts are the key to hydrogenation technology.

[0003] Traditional petroleum fraction hydrogenation catalysts are prepared by loading active components such as cobalt, nickel, tungsten and molybdenum on porous carrier materials to form supported solid catalysts. Among them, active components such as cobalt, nickel, tungsten and molybdenum exist in the form of oxides. In actual use, a sulfiding agent is used to convert the active components on the petroleum fraction hydrogenation catalyst into sulfide forms of cobalt, nickel, tungsten and molybdenum to obtain ideal hydrogenation activity and stability. Therefore, petroleum fraction hydrogenation catalysts need to be sulfurized before use.

[0004] There are two methods for sulfurization of hydrogenation catalysts: in-situ sulfurization and ex-situ sulfurization. In-situ sulfurization is to load the oxidized catalyst into the hydrogenation reactor, and introduce hydrogen and sulfurizing agent into the reactor during the heating process for pre-sulfurization. The disadvantages of this method are: special pre-sulfurization equipment is required, the sulfurization time is long, the sulfurization cost is high, the sulfurizing agent is highly toxic and flammable, and it is easy to cause pollution to people and the environment.

[0005] The ex-situ sulfidation method is to transfer the pre-sulfidation of the catalyst to a special sulfidation reaction device or the prepared catalyst is already a sulfided catalyst, so that the catalyst can be loaded into the hydrogenation reactor and used without further sulfidation. It has become the development trend of hydrogenation catalyst preparation technology in recent years. At present, the ex-situ sulfidation technology of hydrogenation catalysts with more industrial applications mainly consists of two technical routes:

[0006] (1) The first technical route is to complete the presulfurization of the catalyst in the presence of hydrogen and hydrogen sulfide or an easily decomposable organic sulfiding agent in a special presulfurization device, and then passivate it with oxygen-containing gas to produce a non-self-igniting pre-non-calcined sulfur-containing hydrorefining catalyst;

[0007] (2) The second technical route is to first introduce the sulfiding agent (composed of petroleum solvents containing olefin components, elemental sulfur, vegetable oil, organic sulfides, organic polysulfides, sulfones, sulfoxides and vulcanization accelerators) into the voids of the oxidized hydrogenation catalyst by sublimation, melting or impregnation, and then pre-sulfurize the catalyst partly by heating treatment in the presence of nitrogen. Finally, the catalyst is loaded into the hydrogenation reactor and the pre-sulfurization of the catalyst is completed during the start-up heating process and in the presence of hydrogen.

[0008] U.S. Patent No. 5,958,816 proposes the use of a fluidized bed process, in which a hydrogenation catalyst is sulfurized with H2 / H2S gas in a dedicated presulfurization reactor, and then passivated with oxygen-containing gas or air. The catalyst is directly loaded into the reactor and started in use. This patent solves the problems of high temperature and acidic water release during the sulfurization process, but the process is complicated and the processing cost is high. Sulfate is generated during the air passivation process and remains on the catalyst, affecting the service life of the catalyst.

[0009] Chinese patent application 91101805.7 discloses a method for incorporating sulfur into the pores of a hydrocarbon treatment catalyst, which is characterized by: first treating the catalyst with a solvent-diluted sulfiding agent, and then sulfiding the catalyst in the presence of water vapor at a temperature above 250°C. The sulfiding agent used is composed of elemental sulfur and an organic sulfur compound that easily decomposes hydrogen sulfide in the presence of hydrogen, and the solvent used is a solvent oil containing an olefin fraction or a vegetable oil. Chinese patent application 85107953 discloses a method for treating a hydrogenation catalyst, which mainly includes first impregnating the hydrogenation catalyst with elemental sulfur dissolved and diluted with a petroleum solvent and a variety of organic polysulfides at 50 to 150°C, then treating the catalyst at a temperature below 275°C in a hydrogen-free atmosphere, sulfiding the active metal oxide, and finally activating the catalyst at a temperature above 275°C in the presence of hydrogen. U.S. Patent No. 6365542 discloses a method for presulfiding a hydrogenation catalyst outside the device, which is characterized by first treating the oil containing elemental sulfur and olefins with nitrogen at a temperature of 100 to 300°C.

[0010] U.S. Patent No. 5,985,787 discloses a presulfurization method for a hydrogenation catalyst, which is characterized in that the vulcanizing agent is an olefin-containing oil, vegetable oil, organic sulfide, organic polysulfide, elemental sulfur, etc. diluted with a solvent, wherein there must be both sulfides with a decomposition temperature below 220°C and sulfides with a decomposition temperature above 220°C. U.S. Patent No. 5,681,782 improves the previous catalyst presulfurization technology by adding an oxygen-containing organic compound during the addition of the sulfide. Chinese Patent Application No. 98801896.9 discloses a vulcanizing agent for the ex-situ vulcanization of a hydrogenation catalyst, which is mainly composed of tertiary mercaptans of C4 to C16 and is used in combination with H2S, CS2, primary or secondary mercaptans, organic polysulfides, thiophene and its derivatives, sulfoxides, sulfones, cyclopentane, etc. Chinese patent application 00100400.X discloses an ex-situ presulfurization method for a hydrogenation catalyst, which is characterized in that an olefin-containing component, elemental sulfur and an additive are first mixed, heated at 100 to 220°C for more than 0.5 hour, and then the catalyst is impregnated with the obtained product and treated with nitrogen at a temperature of 100 to 300°C for more than 1 hour.

[0011] The patented technologies reported above are all ex-situ presulfurization technologies. Compared with in-situ sulfidation, they have the advantages of high catalyst activity, saving start-up time, simplifying start-up steps, and less pollution to people and the environment. However, the ex-situ presulfurization is the same as the in-situ presulfurization. The presulfurization process is carried out under the action of hydrogen. The oxidized catalyst may undergo hydrogenolysis reaction, and the binding force between the active component and the carrier is often too strong, so that the hydrogenation catalyst cannot be completely sulfided, resulting in the catalyst activity cannot be further improved. The catalyst is presulfurized in an oxidized state before use, which increases the production steps of the catalyst and the production cost, directly affecting the economic efficiency of the process.

[0012] In addition, in recent years, another new preparation method of non-calcined sulfur-containing hydrorefining catalyst has been reported, that is, using a sulfide precursor of Mo or W to directly prepare a non-calcined sulfur-containing hydrorefining catalyst. Chinese patent CN1569331 discloses a modified cobalt-molybdenum-based sulfide catalyst and its preparation method, by preparing an ammonium thiomolybdate solution, coprecipitating molybdenum, cobalt and a third transition metal component, and calcining under nitrogen protection to obtain a black powder catalyst. The disadvantage of this method is that it can only prepare powdered catalysts and cannot be used in large-scale fixed bed hydrogenation equipment; waste liquid is generated during the preparation process, there are environmental problems, and the preparation cost is high.

[0013] Chinese patent CN200410039449.5 discloses that the precursors of Group IVB metals Mo and W are introduced into the voids of a hydrogenation catalyst carrier by using soluble thiomolybdate and thiotungstate solutions, and converted into sulfides of Mo and W by heating treatment in nitrogen, and then a soluble salt solution of Co or Ni is introduced, and converted into sulfides of Co or Ni by heating treatment in nitrogen, thereby obtaining a non-baked sulfur-containing hydrogenation refining catalyst loaded with metal sulfides. Chinese patent CN200810228363.5 uses an impregnation solution to impregnate the required catalyst carrier, and then obtains a non-baked sulfur-containing hydrogenation refining catalyst by drying and heat treatment, characterized in that the impregnation solution contains a sulfide precursor of metal Mo or W, and also contains a complex of Ni or Co inorganic salt; the heat treatment process is to treat at 200-350°C for 1-10 hours; and drying and heat treatment do not require nitrogen protection. Summary of the invention

[0014] The purpose of the present invention is to overcome the shortcomings of the above-mentioned prior art by introducing a multifunctional complexing agent, combining hot impregnation of an alumina carrier containing a microwave sensitizer, ultrasonic treatment and microwave drying, so that the catalyst is more likely to generate a highly active metal sulfide active phase, thereby making the non-calcined sulfur-containing hydrorefining catalyst have excellent hydrogenation performance.

[0015] The present invention provides a method for preparing a non-calcined sulfur-containing hydrorefining catalyst, the preparation method comprising:

[0016] Firstly, ammonium dithiocarbamate, nickel salt and / or cobalt salt, auxiliary agent and a certain amount of deionized water are mixed, heated and stirred, and then ammonium tetrathiomolybdate and / or ammonium tetrathiotungstate are added, and the obtained sulfur-containing composite active metal precursor impregnation liquid is fixed to volume with deionized water, and is impregnated on an alumina carrier containing a microwave sensitizer at an equal volume at a temperature of 50°C to 90°C, and is firstly subjected to ultrasonic treatment with a frequency of 20KHz, and then to ultrasonic treatment with a frequency of 50KHz, and then, under nitrogen protection, is firstly subjected to microwave drying with a radiation frequency of 840MHz, and then to microwave drying with a radiation frequency of 2450MHz, to obtain a non-calcined sulfur-containing hydrogenation refining catalyst, wherein the molar amount of the ammonium dithiocarbamate used is 50% to 300% of the molar amount of the nickel salt and / or the cobalt salt; and the microwave drying temperature is 100 to 120°C.

[0017] In the method for preparing a non-calcined sulfur-containing hydrogenation refining catalyst described in the present invention, the molar amount of the ammonium dithiocarbamate used is preferably 100% to 150% of the molar amount of the nickel salt and / or the cobalt salt.

[0018] The nickel salt and / or cobalt salt is preferably selected from one or more of basic carbonates, nitrates and acetates, more preferably basic carbonates.

[0019] The auxiliary agent is preferably one or more of citric acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, ethylene glycol and ethanolamine.

[0020] The microwave sensitizer is preferably one or more of Fenton's reagent, activated carbon, graphite, conductive carbon black, semi-conductive carbon black and carbon fiber sensitizer.

[0021] The ultrasonic time is preferably 5 to 30 minutes.

[0022] The microwave drying time is preferably 30 to 120 minutes.

[0023] The non-calcined sulfur-containing hydrorefining catalyst contains 5wt% to 30wt% of molybdenum and / or tungsten, and 1wt% to 10wt% of cobalt and / or nickel, based on the weight of the final catalyst.

[0024] The present invention also provides a non-calcined sulfur-containing hydrogenation refining catalyst prepared by the above preparation method.

[0025] The non-calcined sulfur-containing hydrorefining catalyst prepared by the method of the present invention is mainly used in the oil hydrorefining process, and is suitable for treating one or more of various oil products such as coking gasoline and diesel, catalytic cracking gasoline and diesel, vacuum gas oil, thermally refined gas oil, catalytically refined gas oil, catalytically refined circulating oil, coking gas oil, deasphalted oil, etc. The raw materials are usually hydrocarbons with a boiling point of 180 to 700°C. DETAILED DESCRIPTION

[0026] The technical features of the present invention are described in detail below with specific embodiments, but the embodiments do not limit the protection scope of the present invention.

[0027] The specific preparation steps of the present invention are as follows: firstly, ammonium dithiocarbamate, nickel salt and / or cobalt salt, auxiliary agent and a certain amount of deionized water are mixed, heated and stirred, then ammonium tetrathiomolybdate and / or ammonium tetrathiotungstate are added, the obtained sulfur-containing composite active metal precursor impregnation liquid is fixed to volume with deionized water, and an equal volume is impregnated on an alumina carrier containing a microwave sensitizer at a temperature of 50° C. to 90° C., firstly ultrasonically treated with a frequency of 20 KHz, then ultrasonically treated with a frequency of 50 KHz, and then under nitrogen protection, firstly microwave dried with a radiation frequency of 840 MHz, and then microwave dried with a radiation frequency of 2450 MHz, to obtain a non-calcined sulfur-containing hydrogenation refining catalyst.

[0028] Embodiment 1:

[0029] 13 grams of ammonium dithiocarbamate, 6 grams of basic nickel carbonate, 6 grams of citric acid and 40 grams of deionized water were mixed, heated and stirred at 90°C, and then 30 grams of ammonium tetrathiomolybdate were added. The obtained sulfur-containing composite active metal precursor impregnation solution was fixed to volume with deionized water, and an equal volume was impregnated on 100 grams of alumina carrier containing 1% by weight of activated carbon at a temperature of 90°C, firstly ultrasonically treated for 3 minutes at an ultrasonic frequency of 20KHz, and then ultrasonically treated for 2 minutes at an ultrasonic frequency of 50KHz, and then, under nitrogen protection, firstly dried with microwaves with a radiation frequency of 840MHz, a microwave drying temperature of 120°C, and a drying time of 20 minutes, and then dried with microwaves with a radiation frequency of 2450MHz, a microwave drying temperature of 120°C, and a drying time of 10 minutes, to obtain a non-calcined sulfur-containing hydrorefining catalyst 1.

[0030] Embodiment 2:

[0031] 2.5 g of ammonium dithiocarbamate, 6 g of nickel nitrate, 3 g of nickel acetate, 6 g of ethylene glycol and 40 g of deionized water were mixed, heated and stirred at 50°C, and then 20 g of ammonium tetrathiotungstate was added. The obtained sulfur-containing composite active metal precursor impregnation solution was fixed to volume with deionized water, and an equal volume was impregnated on 100 g of an alumina carrier containing 2% by weight of Fenton reagent at a temperature of 50°C, firstly ultrasonically treated for 20 minutes at an ultrasonic frequency of 20 KHz, and then ultrasonically treated for 10 minutes at an ultrasonic frequency of 50 KHz, and then, under nitrogen protection, firstly dried with microwaves at a radiation frequency of 840 MHz, a microwave drying temperature of 110°C, and a drying time of 15 minutes, and then dried with microwaves at a radiation frequency of 2450 MHz, a microwave drying temperature of 110°C, and a drying time of 20 minutes, to obtain a non-calcined sulfur-containing hydrorefining catalyst 2.

[0032] Embodiment 3:

[0033] 4.5 g of ammonium dithiocarbamate, 4.5 g of nickel nitrate, 3.8 g of nickel acetate, 6 g of ethylenediaminetetraacetic acid and 40 g of deionized water were mixed, heated and stirred at 60°C, then 20 g of ammonium tetrathiomolybdate and 10 g of ammonium tetrathiotungstate were added, the obtained sulfur-containing composite active metal precursor impregnation solution was fixed to volume with deionized water, and an equal volume was impregnated on 100 g of an alumina carrier containing 2% by weight of carbon fiber at a temperature of 60°C, firstly ultrasonically treated for 15 minutes at an ultrasonic frequency of 20 KHz, then ultrasonically treated for 10 minutes at an ultrasonic frequency of 50 KHz, and then, under nitrogen protection, firstly dried with microwaves at a radiation frequency of 840 MHz, a microwave drying temperature of 100°C, and a drying time of 60 minutes, and then dried with microwaves at a radiation frequency of 2450 MHz, a microwave drying temperature of 100°C, and a drying time of 60 minutes, to obtain a non-calcined sulfur-containing hydrogenation refining catalyst 3.

[0034] Embodiment 4:

[0035] 4.5 g of ammonium dithiocarbamate, 8.4 g of nickel acetate, 5 g of ethanolamine and a certain amount of deionized water were mixed, heated and stirred at 70°C, and then 10 g of ammonium tetrathiomolybdate and 20 g of ammonium tetrathiotungstate were added. The obtained sulfur-containing composite active metal precursor impregnation solution was fixed to volume with deionized water, and impregnated in an equal volume on 100 g of an alumina carrier containing 3% by weight of conductive carbon black at 70°C, firstly ultrasonically treated for 15 minutes at an ultrasonic frequency of 20 KHz, and then ultrasonically treated for 15 minutes at an ultrasonic frequency of 50 KHz, and then, under nitrogen protection, firstly dried with microwaves at a radiation frequency of 840 MHz, a microwave drying temperature of 110°C, and a drying time of 60 minutes, and then dried with microwaves at a radiation frequency of 2450 MHz, a microwave drying temperature of 110°C, and a drying time of 60 minutes, to obtain a non-calcined sulfur-containing hydrogenation refining catalyst 4.

[0036] Embodiment 5:

[0037] 6 g of ammonium dithiocarbamate, 6 g of nickel nitrate, 3 g of cobalt nitrate, 4 g of citric acid and 40 g of deionized water were mixed, heated and stirred at 80°C for 10 minutes, then 30 g of ammonium tetrathiomolybdate was added, the obtained sulfur-containing composite active metal precursor impregnation solution was fixed to volume with deionized water, and an equal volume was impregnated on 100 g of an alumina carrier containing 1% by weight of graphite at 80°C, firstly ultrasonically treated for 10 minutes at an ultrasonic frequency of 20 KHz, then ultrasonically treated for 10 minutes at an ultrasonic frequency of 50 KHz, and then, under nitrogen protection, firstly dried with microwaves at a radiation frequency of 840 MHz, a microwave drying temperature of 100°C, and a drying time of 20 minutes, and then microwave radiation frequency of 2450 MHz, a microwave drying temperature of 100°C, and a drying time of 30 minutes, to obtain a non-calcined sulfur-containing hydrogenation refining catalyst 5.

[0038] Comparative Example 1:

[0039] Mix 6 grams of nickel nitrate, 3 grams of cobalt nitrate, 4 grams of citric acid and 40 grams of deionized water, stir at 30°C for 1 hour, then add 30 grams of ammonium tetrathiomolybdate, make up the obtained sulfur-containing composite active metal precursor impregnation solution with deionized water, impregnate an equal volume on 100 grams of alumina carrier at 30°C, let it stand for 5 hours, and dry it in an oven at 500°C for 5 hours under nitrogen protection to obtain hydrogenation refining catalyst A.

[0040] The catalyst activity evaluation conditions were as follows: mixed diesel as feedstock (Table 1), reaction pressure of 6.0 MPa, hydrogen-to-oil volume ratio of 400:1, volume space velocity of 2.0 h -1 , the reaction temperature is 320℃.

[0041] Table 1 Main properties of crude oil

[0042] project data <![CDATA[Density (20 °C), g / cm 3 > 0.8539 Distillation range, ℃ IBP / 10% 216 / 279 30％ / 50％ 294 / 308 70％ / 90％ 325 / 354 95% / EBP 367 / 373 S, μg / g 14650 N, μg / g 216

[0043] Table 2 The activity of the catalyst samples is expressed as relative hydrodesulfurization rate (with the comparative example hydrorefining catalyst A as 100)

[0044] Catalyst No. 1 2 3 4 5 A Relative hydrodesulfurization rate 151 129 145 137 142 100

[0045] It can be seen from the above results that the non-calcined sulfur-containing hydrorefining catalyst obtained by the method of the present invention has better hydrogenation performance.

Claims

1. A method for preparing a non-calcined sulfur-containing hydrorefining catalyst, characterized in that: The preparation method comprises: firstly mixing ammonium dithiocarbamate, nickel salt and / or cobalt salt, auxiliary agent and a certain amount of deionized water, heating and stirring, then adding ammonium tetrathiomolybdate and / or ammonium tetrathiotungstate, fixing the obtained sulfur-containing composite active metal precursor impregnation solution with deionized water, impregnating an equal volume on an alumina carrier containing a microwave sensitizer at a temperature of 50°C to 90°C, firstly performing ultrasonic treatment with a frequency of 20KHz, then performing ultrasonic treatment with a frequency of 50KHz, and then, under nitrogen protection, first performing microwave drying with a radiation frequency of 840MHz, then performing microwave drying with a radiation frequency of 2450MHz, to obtain a non-calcined sulfur-containing hydrogenation refining catalyst; wherein the molar amount of the ammonium dithiocarbamate used is 50% to 300% of the molar amount of the nickel salt and / or the cobalt salt; the microwave drying temperature is 100 to 120°C; and the auxiliary agent is one or more of citric acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, ethylene glycol and ethanolamine.

2. The method for preparing a non-calcined sulfur-containing hydrotreating catalyst according to claim 1, characterized in that: The molar amount of the ammonium dithiocarbamate used is 100% to 150% of the molar amount of the nickel salt and / or the cobalt salt.

3. The method for preparing a non-calcined sulfur-containing hydrorefining catalyst according to claim 1, characterized in that: The nickel salt and / or cobalt salt is selected from one or more of basic carbonate, nitrate and acetate.

4. The method for preparing a non-calcined sulfur-containing hydrorefining catalyst according to claim 1, characterized in that: The microwave sensitizer is one or more of Fenton's reagent, activated carbon, graphite, conductive carbon black, semi-conductive carbon black and carbon fiber sensitizer.

5. The method for preparing a non-calcined sulfur-containing hydrorefining catalyst according to claim 1, characterized in that: The ultrasonic time is 5 to 30 minutes.

6. The method for preparing a non-calcined sulfur-containing hydrotreating catalyst according to claim 1, characterized in that: The microwave drying time is 30 to 120 minutes.

7. The method for preparing a non-calcined sulfur-containing hydrotreating catalyst according to claim 1, characterized in that: The non-calcined sulfur-containing hydrorefining catalyst contains 5wt% to 30wt% of molybdenum and / or tungsten, and 1wt% to 10wt% of cobalt and / or nickel, based on the weight of the final catalyst.

8. A non-calcined sulfur-containing hydrorefining catalyst prepared by the preparation method according to any one of claims 1 to 7.

9. Use of the non-calcined sulfur-containing hydrorefining catalyst according to claim 8 in an oil hydrorefining process, characterized in that: The oil product is one or more of coking gasoline and diesel, catalytic cracking gasoline and diesel, vacuum gas oil, thermally refined gas oil, catalytically refined gas oil, catalytically refined circulating oil, coking gas oil and deasphalted oil.