A method for preparing a sulfur-containing hydrogenation active protection catalyst

Abstract

The invention discloses a method for preparing a sulfur-containing hydrogenation active protection catalyst. The method comprises: firstly mixing ammonium dithiocarbamate, nickel salt and / or cobalt salt, ethylenediaminetetramethylenephosphonic acid and a certain amount of deionized water, heating and stirring, then adding ammonium tetrathiomolybdate and / or ammonium tetrathiotungstate, and impregnating the obtained sulfur-containing composite active metal precursor impregnation liquid at a temperature of 50°C to 90°C in equal volume on a modified alumina carrier containing a microwave sensitizer, firstly ultrasonically treating, and then drying with a microwave having a radiation frequency of 840 MHz under nitrogen protection, and then drying with a microwave having a radiation frequency of 2450 MHz, to obtain a sulfur-containing hydrogenation active protection catalyst. The method of the invention has the characteristics of high efficiency and simplicity, uniform dispersion of active metals, good synergy between different active metals, and high effective utilization rate of active metals. The prepared catalyst has good catalytic activity, large pore volume, high specific surface area, high strength and strong hydrogenation demetallization ability, and can be widely used in oil product hydrogenation processing.

Description

Technical Field

[0001] The invention relates to a method for preparing a sulfur-containing hydrogenation active protection catalyst. Background Art

[0002] As the quality of crude oil deteriorates, the content of impurities such as colloid, asphaltene and organometallic compounds in crude oil increases. The presence of these impurities can easily cause the catalyst activity to drop rapidly and even become inactivated. An effective way to solve this problem is to load a protective agent with hydrogenation activity on the upper part of the hydrogenation catalyst bed. Hydrogenation protective catalysts with larger pore volume and pore diameter have strong metal and carbon tolerance, which can protect the downstream hydrogenation main agent and extend the service life of the main agent.

[0003] Examples of the prior art regarding hydrogenation protection catalysts and their preparation include:

[0004] CN200610113493.5 discloses a hydrogenation protective agent and its preparation, the protective agent contains one or more porous heat-resistant inorganic oxides, characterized in that the total pore volume of the protective agent is 0.3-1.5 mm / g, wherein the protective agent contains millimeter-level macropores, the diameter of the millimeter-level macropores is 0.1-1.5 microns, and the pore volume of the millimeter-level macropores is 0.05-0.7 ml / g. The preparation method of the hydrogenation protective agent comprises mixing, molding, drying and roasting one or more porous heat-resistant inorganic oxides and / or precursors of porous heat-resistant inorganic oxides with at least one organic matter, wherein the organic compound is a solid particle with a melting point between 30 and 200°C, a particle size of 0.3-2.5 mm and insoluble in water.

[0005] CN201010220850.4 discloses a method for preparing a hydroprocessing protective agent. In the method, an alumina carrier is prepared by kneading two different pseudo-boehmite dry rubber powders, and then loaded with active metals; the first pseudo-boehmite has a relatively small crystallinity and a large pore volume, and can provide pores with a pore diameter of 30nm to 100nm, and the second pseudo-boehmite has a relatively high crystallinity and can provide micron-level pores. Because of its high acidity index, it presents an extremely hard block after drying, and after being crushed, 100% of it passes through 50 mesh, which can not only increase the number of micron-level pores, but also improve the strength of the catalyst carrier. By adjusting the mixing ratio between the two, a hydroprocessing protective agent with high strength, large bulk density, large pore volume and low wear rate can be prepared.

[0006] CN98111379.6 discloses a hydrogenation protection catalyst and a preparation method thereof. The catalyst carrier is a bimodal pore with an ultra-large pore size of 0.1-30 μm, a catalyst pore volume of 0.1-0.8 mL / g, a specific surface area of ​​0.1-20 m2 / g, and contains 6.65 wt% to 20.0 wt% of VIB group metal elements and / or 8.71 wt% to 26.13 wt% of VIII group metal elements. The preparation method is to prepare an alumina carrier by a particle stacking method, and then impregnate it with an equal amount of a molybdenum-containing solution and a nickel-containing solution. The impregnated catalyst is dried at 100-120°C for 2-5 hours and roasted at 500-550°C for 2-5 hours.

[0007] CN00110019.X discloses a hydrogenation active protective agent and its preparation method. The carrier used in the protective agent contains both γ-alumina and δ-alumina. The protective agent contains 3-22m% of VIB group metal oxides and 0.5-5m% of VIII group metal oxides, 0-2m% of IA group metal oxides, 0-3m% of phosphorus, and a specific surface area of ​​100-250m2 / g. The pore volume is 0.4-0.8mL / g.

[0008] CN200910206230.2 discloses a residual oil hydrogenation protection catalyst and its application. The catalyst has large pore volume, large pore diameter, high porosity, reasonable pore distribution, large surface pore opening, good pore penetration, and contains more than 36% of pores above 1000nm. Especially when used in the residual oil fixed bed hydrogenation method, the metal removed can be uniformly precipitated in the entire catalyst bed, and the impurities vanadium and calcium can be precipitated inside the pores, thereby improving the utilization rate of the pores and maintaining long-term operation.

[0009] The above-mentioned prior art provides various solutions to the problems in the use of hydrogenation protection catalysts. It is not difficult to see that the pore properties of the carrier (including pore volume, pore size, pore distribution and other properties) directly determine the performance of such catalysts. Summary of the invention

[0010] The purpose of the present invention is to overcome the shortcomings of the above-mentioned prior art. The method of the present invention introduces a multifunctional complexing agent, combines hot impregnation, and a modified alumina carrier containing a microwave sensitizer. It is first treated with ultrasound at a frequency of 20KHz and then with ultrasound at a frequency of 50KHz. Under nitrogen protection, it is first dried with microwaves at a radiation frequency of 840MHz and then with microwaves at a radiation frequency of 2450MHz. The method provides a method for preparing a sulfur-containing hydrogenation active protected catalyst with high efficiency and simplicity, uniform dispersion of active metals, good synergy between different active metals, high effective utilization rate of active metals, good catalytic activity, large pore volume, high specific surface area, high strength and strong hydrogenation demetallization ability.

[0011] The invention discloses a method for preparing a sulfur-containing hydrogenation active protection catalyst. The method comprises: firstly mixing ammonium dithiocarbamate, nickel salt and / or cobalt salt, ethylenediaminetetramethylenephosphonic acid and a certain amount of deionized water, heating and stirring, then adding ammonium tetrathiomolybdate and / or ammonium tetrathiotungstate, and impregnating the obtained sulfur-containing composite active metal precursor impregnation liquid on a modified alumina carrier containing a microwave sensitizer at a temperature of 50°C to 90°C in equal volume, firstly performing ultrasonic treatment with a frequency of 20KHz, and then performing ultrasonic treatment with a frequency of 50KHz, and then, under nitrogen protection, first performing microwave drying with a radiation frequency of 840MHz, and then performing microwave drying with a radiation frequency of 2450MHz, to obtain a sulfur-containing hydrogenation active protection 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, preferably 100% to 150%; and the microwave drying temperature is 100 to 120°C.

[0012] In the method for preparing the sulfur-containing hydrogenation active protected catalyst of the present invention, the nickel salt and / or cobalt salt is preferably selected from one or more of basic carbonates, nitrates and acetates, and basic carbonates are further preferred.

[0013] In the method for preparing the sulfur-containing hydrogenation active protected catalyst of the present invention, 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.

[0014] In the preparation method of the above-mentioned sulfur-containing hydrogenation active protected catalyst of the present invention, the modified alumina carrier preferably contains at least two or more compounds selected from phosphorus pentoxide, silicon dioxide, zirconium dioxide, magnesium oxide, zinc oxide, potassium oxide, boron oxide and titanium dioxide, and the content is 1wt% to 20wt% of the weight of the carrier component.

[0015] In the method for preparing the sulfur-containing hydrogenation active protected catalyst of the present invention, the ultrasonic time is preferably 5 to 30 minutes.

[0016] In the method for preparing the sulfur-containing hydrogenation active protected catalyst of the present invention, the microwave drying time is preferably 30 to 120 minutes.

[0017] In the preparation method of the above-mentioned sulfur-containing hydrogenation active protected catalyst of the present invention, it is preferred that the sulfur-containing hydrogenation active protected catalyst has a total content of nickel and / or cobalt of 0.5wt% to 5wt% and a total content of molybdenum and / or tungsten of 1wt% to 15wt% based on the weight of the final catalyst.

[0018] The present invention further provides a sulfur hydrogenation activity protection catalyst prepared by the above preparation method.

[0019] The present invention further provides an application of the sulfur hydrogenation activity protection catalyst in the process of oil product hydroprocessing, especially in the process of hydroprocessing inferior oil products with high sulfur, high nitrogen and high metal content.

[0020] The method of the present invention introduces a multifunctional complexing agent, combines hot impregnation, and a modified alumina carrier containing a microwave sensitizer, first uses an ultrasonic treatment with a frequency of 20KHz, then uses an ultrasonic treatment with a frequency of 50KHz, and then uses a microwave drying with a radiation frequency of 840MHz under nitrogen protection, and then uses a microwave drying treatment with a radiation frequency of 2450MHz, to provide a method for preparing a sulfur-containing hydrogenation active protection catalyst with high efficiency and simplicity, uniform dispersion of active metals, good synergy between different active metals, high effective utilization rate of active metals, good catalytic activity, large pore volume, high specific surface area, high strength and strong hydrogenation demetallization ability. Compared with the hydrogenation protection catalyst provided by the prior art, the hydrogenation protection catalyst provided by the present invention has excellent hydrogenation demetallization activity while having the function of a conventional protective agent, can be widely used in the oil product hydrogenation process, is particularly suitable as a hydrogenation protection catalyst for inferior oil products with high sulfur, high nitrogen and high metal content, can effectively solve the problems of fouling, clogging, and forced shutdown of the catalyst bed of the industrial hydrogenation device due to excessive pressure drop, and prolongs the service life of the hydrogenation catalyst. DETAILED DESCRIPTION

[0021] 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.

[0022] The specific preparation steps of the present invention are as follows: firstly, ammonium dithiocarbamate, nickel salt and / or cobalt salt, ethylenediaminetetramethylenephosphonic acid 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 a modified alumina carrier containing a microwave sensitizer at a temperature of 50°C to 90°C, firstly ultrasonically treated with a frequency of 20KHz, and then ultrasonically treated with a frequency of 50KHz, and then under nitrogen protection, firstly microwave dried with a radiation frequency of 840MHz, and then microwave dried with a radiation frequency of 2450MHz, to obtain a sulfur-containing hydrogenation active protected catalyst.

[0023] Embodiment 1:

[0024] 4 grams of ammonium dithiocarbamate, 2 grams of basic nickel carbonate, 3 grams of ethylenediaminetetramethylenephosphonic acid and 40 grams of deionized water were mixed, heated and stirred at 90°C, and then 10 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 in 100 grams of modified alumina carrier (containing 2wt% of phosphorus pentoxide and 3wt% of magnesium oxide) containing 1wt% activated carbon and 1wt% carbon fiber sensitizer at 90°C, firstly treated with ultrasound at a frequency of 20KHz for 3 minutes, then treated with ultrasound at a frequency of 50KHz for 2 minutes, and then under nitrogen protection, first dried with microwaves with a radiation frequency of 840MHz, a microwave drying temperature of 120°C, and a drying time of 10 minutes, and then dried with microwaves with a radiation frequency of 2450MHz, a microwave drying temperature of 120°C, and a drying time of 20 minutes to obtain a sulfur-containing hydrogenation active protected catalyst 1.

[0025] Embodiment 2:

[0026] 1 gram of ammonium dithiocarbamate, 2 grams of nickel nitrate, 1 gram of nickel acetate, 1 gram of ethylenediaminetetramethylenephosphonic acid and 40 grams of deionized water were mixed, heated and stirred at 80°C, and then 10 grams of ammonium tetrathiotungstate were added. The obtained sulfur-containing composite active metal precursor impregnation solution was made up to volume with deionized water, and an equal volume of a modified alumina carrier (containing 10wt% of silicon dioxide and 10wt% of boron oxide) containing 2wt% of Fenton's reagent was impregnated at 80°C, firstly treated with ultrasound at a frequency of 20KHz for 5 minutes, and then treated with ultrasound at a frequency of 50KHz for 5 minutes, and then under nitrogen protection, first dried with microwaves at a radiation frequency of 840MHz, the microwave drying temperature was 100°C, and the drying time was 60 minutes, and then dried with microwaves at a radiation frequency of 2450MHz, the microwave drying temperature was 100°C, and the drying time was 60 minutes, to obtain a sulfur-containing hydrogenation active protected catalyst 2.

[0027] Embodiment 3:

[0028] 1.5 g of ammonium dithiocarbamate, 1.5 g of nickel nitrate, 1.3 g of nickel acetate, 2 g of ethylenediaminetetramethylenephosphonic acid and 40 g of deionized water were mixed, heated and stirred at 70°C, then 7 g of ammonium tetrathiomolybdate and 3 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 of a modified alumina carrier containing 3 wt% graphite (containing 0.5 wt% zirconium dioxide and 0.5 wt% zinc oxide) was impregnated at 70°C, firstly treated with ultrasound at a frequency of 20 KHz for 10 minutes, then treated with ultrasound at a frequency of 50 KHz for 8 minutes, and then, under nitrogen protection, first dried with microwaves at a radiation frequency of 840 MHz, a microwave drying temperature of 110°C, and a drying time of 30 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 sulfur-containing hydrogenation active protected catalyst 3.

[0029] Embodiment 4:

[0030] 1.5 g of ammonium dithiocarbamate, 2.8 g of nickel acetate, 1 g of ethylenediaminetetramethylenephosphonic acid and 40 g of deionized water were mixed, heated and stirred at 60°C, then 3 g of ammonium tetrathiomolybdate and 7 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 of a modified alumina carrier (containing 8 wt % of titanium dioxide and 5 wt % of potassium oxide) containing 5 wt % of semi-conductive carbon black was impregnated at 60°C, firstly treated with ultrasound at a frequency of 20 KHz for 15 minutes, then treated with ultrasound at a frequency of 50 KHz for 15 minutes, and then, under nitrogen protection, first dried with microwaves at a radiation frequency of 840 MHz, a microwave drying temperature of 120°C, and a drying time of 20 minutes, and then dried with microwaves at a radiation frequency of 2450 MHz, a microwave drying temperature of 120°C, and a drying time of 20 minutes, to obtain a sulfur-containing hydrogenation active protected catalyst 4.

[0031] Embodiment 5:

[0032] 2 grams of ammonium dithiocarbamate, 2 grams of nickel nitrate, 1 gram of cobalt nitrate, 1.5 grams of ethylenediaminetetramethylenephosphonic acid and 40 grams of deionized water were mixed, heated and stirred at 50°C, and then 10 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 of a modified alumina carrier (containing 5wt% of silicon dioxide, 3wt% of potassium oxide and 2wt% of titanium dioxide) containing 2wt% of conductive carbon black was impregnated at 50°C, firstly treated with ultrasound at a frequency of 20KHz for 20 minutes, and then treated with ultrasound at a frequency of 50KHz for 10 minutes, and then under nitrogen protection, first dried with microwaves at a radiation frequency of 840MHz, a microwave drying temperature of 110°C, and a drying time of 30 minutes, and then microwave radiation frequency of 2450MHz, a microwave drying temperature of 110°C, and a drying time of 25 minutes to obtain a sulfur-containing hydrogenation active protected catalyst 5.

[0033] Comparative Example 1:

[0034] Mix 2 grams of nickel nitrate, 1 gram of cobalt nitrate, 1 gram of citric acid and 40 grams of deionized water, stir at 30°C for 1 hour, then add 10 grams of ammonium tetrathiomolybdate, and use the obtained sulfur-containing composite active metal precursor impregnation solution to impregnate 100 grams of alumina carrier in equal volume at 30°C, let it stand for 6 hours, and then dry it at 120°C for 5 hours under nitrogen protection to obtain hydrogenation active protected catalyst A.

[0035] The physicochemical properties of the sulfur-containing hydrogenation active protection catalysts 1, 2, 3, 4 and 5 prepared by the present invention and the comparative example hydrogenation protection catalyst A are shown in Table 1.

[0036] Table 1 Physicochemical properties of hydrogenation protected catalysts

[0037] Catalyst No. 1 2 3 4 5 A <![CDATA[Specific surface area, m 2 / g]]> 212 225 236 227 232 167 Pore ​​volume, mL / g 0.52 0.48 0.53 0.55 0.49 0.31 Crushing strength, N / cm 192 183 185 186 193 137

[0038] The sulfur-containing hydrogenation active protection catalysts 1, 2, 3, 4 and 5 prepared by the present invention and the comparative hydrogenation protection catalyst A were respectively loaded into a fixed bed hydrogenation reactor, and the treated raw materials (see Table 2) were subjected to the following test conditions: reaction pressure of 12 MPa, hydrogen-to-oil volume ratio of 1200:1, volume space velocity of 1.5 h -1 , the reaction temperature is 380℃, the continuous operation is 5000 hours, and the impurity removal properties are shown in Table 3.

[0039] Table 2 Main properties of crude oil

[0040] project data <![CDATA[Density (20 °C), g / cm 3 > 0.953 Ni, μg / g 28.5 V, μg / g 79.6 Fe, μg / g 6.5 Ca, μg / g 7.8

[0041] Table 3 Evaluation results of catalysts

[0042] Catalyst No. 1 2 3 4 5 A Remove Ni+V, wt% 60.2 61.3 58.5 57.8 61.8 30.5 Fe removal, wt% 80.6 82.6 79.3 77.9 84.2 47.8 Ca removal, wt% 71.5 73.8 70.2 69.7 77.3 38.9

[0043] It can be seen from the results in Table 3 that the sulfur-containing hydrogenation active protection catalyst prepared by the method of the present invention has better Ni, V, Fe, Ca removal rates and good stability.

Claims

1. A method for preparing a sulfur-containing hydrogenation active protected catalyst, characterized in that: The preparation method comprises: firstly mixing ammonium dithiocarbamate, nickel salt and / or cobalt salt, ethylenediaminetetramethylenephosphonic acid and a certain amount of deionized water, heating and stirring, then adding ammonium tetrathiomolybdate and / or ammonium tetrathiotungstate, and impregnating the obtained sulfur-containing composite active metal precursor impregnation liquid on a modified alumina carrier containing a microwave sensitizer at a temperature of 50° C. to 90° C. in equal volumes, firstly performing ultrasonic treatment with a frequency of 20 KHz, and then performing ultrasonic treatment with a frequency of 50 KHz, and then, under nitrogen protection, first performing microwave treatment with a radiation frequency of 840 MHz. The method comprises drying the catalyst and then drying it with a microwave having a radiation frequency of 2450 MHz to obtain a sulfur-containing hydrogenation active protected 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 modified alumina carrier contains at least two or more compounds of phosphorus pentoxide, silicon dioxide, zirconium dioxide, magnesium oxide, zinc oxide, potassium oxide, boron oxide and titanium dioxide, and the content is 1wt% to 20wt% of the weight of the carrier component.

2. The method for preparing a sulfur-containing hydrogenation active protected 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 sulfur-containing hydrogenation active protected 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 sulfur-containing hydrogenation active protected 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 sulfur-containing hydrogenation active protected catalyst according to claim 1, characterized in that: The ultrasonic time is 5 to 30 minutes.

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

7. The method for preparing a sulfur-containing hydrogenation active protected catalyst according to claim 1, characterized in that: The sulfur-containing hydrogenation active protection catalyst has a total nickel and / or cobalt content of 0.5wt% to 5wt% and a total molybdenum and / or tungsten content of 1wt% to 15wt% based on the weight of the final catalyst.

8. A sulfur hydrogenation active protected catalyst prepared by the preparation method according to any one of claims 1 to 7.

9. Use of the sulfur hydrogenation activity protected catalyst according to claim 8 in an oil product hydrotreating process.