CN116809123A - Natural gas hydrodesulfurization catalyst and preparation method thereof - Google Patents
Natural gas hydrodesulfurization catalyst and preparation method thereof Download PDFInfo
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
A natural gas hydrodesulfurization catalyst and a preparation method thereof belong to the field of hydrodesulfurization, a carrier is a metal organic framework material MIL-101 (Cr), an active component is a mixture of molybdenum and cobalt, a promoter component c is a mixture of two of B, F, P, si, mn, ca, zn, and the active component cobalt, the active component molybdenum and the promoter component c have an element mole ratio n Co ：n Mo ：n c = (2 to 5): 10: (1-5). The invention can still maintain higher conversion rate of organic sulfur in natural gas at higher airspeed, thereby greatly improving the processing capacity of the hydrodesulfurization flow of the natural gas in unit time, effectively improving the quality of the natural gas, strengthening the protection of the environment and helping enterprises to reduce the productionThe production cost is increased, and the production efficiency is improved.
Description
Technical Field
The invention relates to a catalyst used in the field of hydrodesulfurization, in particular to a natural gas hydrodesulfurization catalyst and a preparation method thereof.
Background
In recent years, petroleum resources are increasingly scarce, coal chemical industry is limited by environmental problems, safety problems and energy consumption problems, and the proportion of natural gas in chemical production and energy structures is increasingly large along with the increasing demand of clean energy. The main component of natural gas is mainly methane, and natural gas from underground reservoirs usually contains H to varying degrees 2 S, CO2 and organosulfides (RSH, COS, RSSR, R' SR and C) 4 H 4 S) and the like. When natural gas is used as a chemical raw material, the acidic components can also cause catalyst poisoning, equipment and pipelines can be corroded during exploitation, gathering and processing, and thus, the desulfurization of the natural gas is of great significance.
Inorganic sulfur in natural gas as H 2 S is mainly removed by a zinc oxide desulfurizing agent, but organic sulfur (carbonyl sulfide, mercaptan, thioether and the like) is usually converted into H by adopting a hydrogenation catalysis mode 2 S, removing with desulfurizing agent such as zinc oxide. GB 17820-2018 Natural gas issued and implemented in 2018 has stricter requirements on total sulfur content in commodity gas of natural gas purification plant, and the long-term goal in China is to control total sulfur to 8mg/m 3 The standard is exported to bring great opportunity and challenges for upgrading the desulfurization technology of natural gas purification plants.
The active components of the traditional natural gas hydrodesulfurization catalyst are Co-Mo, ni-Mo and Ni-W, and the prepared oxidation state catalyst needs to be vulcanized before HDS reaction. The carrier is generally porous inorganic oxide, and is usually one or more of alumina, silica, zirconium dioxide and aluminosilicate. The carrier has two main functions in the hydrodesulfurization reaction, namely, the carrier is used for loading active metal, and the reaction space is provided for enabling the active metal to fully contact and react with impurities to be removed, so that the functions of deep desulfurization and denitrification are achieved. This requires a relatively large specific surface area, pore volume and mechanical strength of the support, which allows the impurity molecules to react sufficiently with the active metal through the support pores in a long-term production reaction. If the pore diameter of the carrier is too small, larger resistance is generated in the transfer process, which is unfavorable for the effective progress of the reaction and reduces the activity of the catalyst. However, the carrier has not only the function of supporting the active component, but also the interaction with the active component, sometimes even strong interaction, and under the influence of such action, the performance of the active component is greatly changed, thereby affecting the catalytic activity of the catalyst.
The conventional organic sulfur hydrogenation catalyst has low space velocity and low organic sulfur conversion rate, and cannot realize efficient utilization of the catalyst and miniaturization of device equipment. Therefore, the specific surface area of the hydrogenation catalyst needs to be increased, and the contact area of organic sulfur and catalyst active components is increased, so that the purposes of increasing the space velocity of the hydrodesulfurization reaction and increasing the equipment production capacity on the premise of ensuring the utilization rate of the catalyst are achieved.
The metal organic framework material MOFs is a novel porous crystal material with a regular pore structure, which is formed by mutually connecting organic functional groups in a multidentate organic ligand of an inorganic metal center and an aromatic acid or alkali through covalent bonds or ionic bonds and is also called as a porous coordination polymer. MOFs can be designed to synthesize organic ligands with suitable structures and molecular shapes by adjusting the organic ligands to control the porosity of the material, thereby allowing MOFs to perform optimally in applications such as various separation processes and shape selective catalysis. Compared with active carbon and molecular sieve, the metal organic framework material has the advantages of large specific surface area, large porosity, adjustable pore size and the like, and the adjustable pore size and high porosity can be used as an ideal carrier of the catalyst.
As is well known, the catalytic performance of the catalyst is affected by the active ingredient and the auxiliary agent in addition to the influence of the carrier, and at present, the active ingredient and the auxiliary agent used in the field of desulfurization catalysts are various, and how to select the carrier, the active ingredient and the auxiliary agent which are adapted to play a better catalytic effect is the direction of continuous research of the person skilled in the art.
Disclosure of Invention
The invention aims to provide a natural gas hydrodesulfurization catalyst and a preparation method thereof, and the types and proportions of a carrier, an active component and a cocatalyst component are optimized, so that a better catalytic effect is realized, and the service life of the catalyst is effectively prolonged.
The technical scheme adopted by the invention for realizing the technical purposes is as follows: the natural gas hydrodesulfurization catalyst consists of a carrier a, an active component b and a cocatalyst component c, wherein the carrier a is a metal organic framework material MIL-101 (Cr), the mass content of the carrier a accounts for 20-40% of the total catalyst amount, the active component b is a mixture of molybdenum and cobalt, the mass content of the active component b accounts for 50-70% of the total catalyst amount, the cocatalyst component c is any two of B, F, P, si, mn, ca, zn, the mass content of the cocatalyst component c accounts for 1-10% of the total catalyst amount, and the molar ratio n of elements of the active component cobalt, the active component molybdenum and the cocatalyst component c Co ：n Mo ：n c ＝(2～5)：10：(1～5)。
As an optimization scheme of the natural gas hydrodesulfurization catalyst, the cocatalyst component c is a mixture of two of B, F, P, si, mn, ca, zn, preferably a mixture of Zn and Mn, a mixture of B and Ca, a mixture of F and P, and a mixture of B and Si.
As another optimization scheme of the natural gas hydrodesulfurization catalyst, the mass content of the carrier a accounts for 25-35% of the total catalyst, the mass content of the active component b accounts for 55-65% of the total catalyst, and the mass content of the cocatalyst component c accounts for 5-8% of the total catalyst.
As another optimization scheme of the natural gas hydrodesulfurization catalyst, the active component cobalt, the active component molybdenum and the promoter component c have the element mol ratio n Co ：n Mo ：n c ＝(3～4)：10：(3～4)。
As another optimization scheme of the natural gas hydrodesulfurization catalyst, the preparation method of the metal organic framework material MIL-101 (Cr) comprises the following steps:
(1) uniformly mixing chromium nitrate nonahydrate, terephthalic acid and deionized water according to the molar ratio of 1:1 (4.64-4.93) to prepare a buffer solution of MIL-101 (Cr) metal organic framework material;
(2) adding hydrofluoric acid into the buffer solution, uniformly stirring, reacting for 1-24 h at 100-200 ℃, and cooling to room temperature after the reaction is finished;
(3) sequentially centrifugally washing with N, N-dimethylformamide and absolute ethyl alcohol to remove unreacted terephthalic acid and N, N-dimethylformamide in a buffer solution;
(4) and (3) drying in vacuum to remove absolute ethyl alcohol and crystal water, so as to obtain the activated metal-organic framework material MIL-101 (Cr).
As another optimization scheme of the natural gas hydrodesulfurization catalyst, in the step (2), hydrofluoric acid is added into a buffer solution and then reacted for 5-9 hours at 150-180 ℃.
As another optimization scheme of the natural gas hydrodesulfurization catalyst, in the step (4), the vacuum drying temperature is 80-150 ℃, preferably 90-120 ℃, and the drying time is 1-50 h, preferably 5-20 h.
As another optimization scheme of the natural gas hydrodesulfurization catalyst, the specific surface area of the metal organic framework material MIL-101 (Cr) is 100-6000 m 2 Preferably 1000 to 4500m per gram 2 The pore volume per gram is 0.01-5 mL/g, preferably 0.1-2 mL/g.
The preparation method of the natural gas hydrodesulfurization catalyst comprises the steps of respectively soaking the active component b and the cocatalyst component c on the carrier a, drying and roasting to obtain a product.
An optimization scheme of the preparation method of the natural gas hydrodesulfurization catalyst is that the drying temperature is 50-500 ℃, preferably 50-300 ℃, and the roasting temperature is 100-850 ℃, preferably 200-300 ℃.
In the invention, the active components cobalt and molybdenum are generally selected from soluble salts, such as cobalt nitrate and molybdenum nitrate, which are combined with a carrier by adopting an impregnation method, and can be impregnated once or in a mode of repeated impregnation; the promoter component can be added by adopting a form of soluble salt to be impregnated with the active component on the composite carrier, or can be adopted to be impregnated with the active component on the carrier separately.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, a metal organic framework material MIL-101 (Cr) with high specific surface area and pore volume is adopted as a carrier, so that more dispersing sites are provided for the supported catalyst active components, the number of catalyst active centers is increased, and metal center ions in the metal organic framework material structure are provided with coordination unsaturated sites, and can accept a pair of electrons to serve as Lewis acid, thereby promoting adsorption and removal of macromolecular sulfides such as alkaline thiophene through the acidic sites, and enhancing the contact probability of organic sulfur molecules and the catalyst active components; meanwhile, cobalt and molybdenum are selected as mixed active components, any two of B, F, P, si, mn, ca, zn are adopted as auxiliary agents, and the molar ratio of the cobalt to the molybdenum to the auxiliary agents is limited to be kept in a specific range, so that the prepared catalyst can still keep higher conversion rate on organic sulfur in natural gas even at higher airspeed, the processing capacity of a unit-time natural gas hydrodesulfurization process is greatly improved, the quality of the natural gas can be effectively improved, the environmental protection is enhanced, and enterprises can reduce the production cost and improve the production efficiency.
Drawings
FIG. 1 is a schematic structural diagram of a MIL-101 (Cr) carrier as a metal-organic framework material prepared in example 1;
FIG. 2 is a microscopic morphology of the MIL-101 (Cr) carrier of the metal-organic framework material prepared in example 1 under a scanning electron microscope;
FIG. 3 is an isothermal adsorption-desorption curve of nitrogen of the metal organic framework material MIL-101 (Cr) carrier prepared in example 1;
FIG. 4 is a XRD characterization spectrum of an MIL-101 (Cr) activated sample prepared in example 1 after adsorption of three sulfides;
FIG. 5 is a table showing the desulfurization rate data of each catalyst in the comparative experiment (120 h of operation);
FIG. 6 is a table showing the variation of desulfurization rate in each catalyst long-period experiment in comparison experiment.
Detailed Description
The technical solutions of the present invention will be further described in detail with reference to specific examples, and the parts of the present invention not described in the following examples should be understood as techniques known or understood by those skilled in the art, such as the method of selecting soluble salts of cobalt and molybdenum, introducing auxiliary agents such as B, F, P, si, mn, ca, zn, and the method of impregnating and preparing the catalyst.
Example 1
The natural gas hydrodesulfurization catalyst consists of a carrier a, an active component b and a cocatalyst component c, wherein the carrier a is a metal organic framework material MIL-101 (Cr) and accounts for 30% of the total catalyst weight, the active component b is a mixture of molybdenum and cobalt and accounts for 65% of the total catalyst weight, the cocatalyst component c is a mixture of Mn and Zn and accounts for 5% of the total catalyst weight, and the molar ratio n of elements of the active component cobalt, the active component molybdenum and the cocatalyst component c is as follows Co ：n Mo ：n c ＝3.5：10：3。
The preparation method of the catalyst comprises the following steps:
1) Preparing a metal organic framework material MIL-101 (Cr);
(1) uniformly mixing chromium nitrate nonahydrate, terephthalic acid and deionized water in a molar ratio of 1:1:4.64 to prepare a buffer solution of MIL-101 (Cr) metal organic framework material;
(2) adding hydrofluoric acid into the buffer solution, uniformly stirring, reacting for 24 hours at 100 ℃, and cooling to room temperature after the reaction is finished;
(3) sequentially centrifugally washing with N, N-dimethylformamide and absolute ethyl alcohol to remove unreacted terephthalic acid and N, N-dimethylformamide in a buffer solution;
(4) vacuum drying to remove absolute ethyl alcohol and crystal water to obtain an activated metal organic framework material MIL-101 (Cr);
the temperature of vacuum drying is 80 ℃ and the drying time is 50 hours; the specific surface area of the prepared metal organic framework material MIL-101 (Cr) is about 1500m 2 Per g, pore volume was 1.39mL/g.
2) Impregnating the active component b and the cocatalyst component c onto the carrier a according to the above proportion; the specific operation is as follows:
respectively weighing manganese nitrate and zinc nitrate as promoter components c, and dispersing the manganese nitrate and the zinc nitrate into deionized water to prepare a mixed solution of the promoter components;
uniformly mixing the auxiliary component mixed solution with the activated metal organic framework material MIL-101 (Cr) prepared in the step (4), then carrying out ultrasonic impregnation for 2 hours, drying at 50 ℃ for 24 hours, and roasting at 850 ℃ for 24 hours to obtain semi-finished catalyst powder;
and respectively taking cobalt nitrate hexahydrate and molybdenum nitrate pentahydrate as active components b, uniformly dispersing the active components b into deionized water to prepare an active component mixed solution, uniformly mixing the obtained semi-finished catalyst powder with the active component solution, soaking the semi-finished catalyst powder in ultrasonic waves for 2 hours, drying the semi-finished catalyst powder at 50 ℃ for 24 hours, and roasting the semi-finished catalyst powder at 100 ℃ for 24 hours to obtain the product which is named CAT1.
FIG. 1 is a schematic structural diagram of MIL-101 (Cr) carrier as a metal-organic framework material prepared in example 1. MIL-101 (Cr) is a metal oxide derived from terephthalic acid ligand and trimeric chromium [ Cr ] 3 O(CO 2 ) 6 ]The octahedral cluster is constructed to comprise two types of quasi-spherical cages with diameters ofAnd->
FIG. 2 shows the microscopic morphology of MIL-101 (Cr) carrier as one kind of metal-organic skeleton material under scanning electron microscope, and the synthesized MIL-101 (Cr) crystal has homogeneous size, high dispersivity and grain size of about 100 nm.
FIG. 3 is an isothermal adsorption-desorption curve of nitrogen for a metal organic framework material MIL-101 (Cr) carrier. As can be seen in fig. 3, the sample shows a sharp increase in adsorption in the region of lower relative pressure, indicating the presence of a large number of micropores in the material. With the increase of the relative pressure, the adsorption quantity of the material is slowly increased, but no hysteresis loop appears, and the adsorption quantity of the material is almost unchanged under a certain relative pressure, which indicates that the pore size distribution of the material is more concentrated and mesoporous is almost not present.
FIG. 4 is a chart showing XRD characterization of an MIL-101 (Cr) activated sample prepared in example 1 after adsorption of three sulfides, and it can be seen from FIG. 4 that the XRD spectrum after sulfidation has substantially no change in shape, position, characteristics, etc. of peaks, but the intensity of peaks is reduced, wherein the peak intensity of hydrogen sulfide varies the most, compared with those before sulfidation; it can be said that the adsorption of three sulfides only affects the structure of the MIL-101 (Cr) skeleton to a small extent, and does not destroy the main structure of the MIL-101 (Cr), and the structure of the MIL-101 (Cr) is affected more than the structure of the MIL-101 (Cr) when the MIL-101 (Cr) adsorbs hydrogen sulfide. This phenomenon may be due on the one hand to the fact that the amount of participating reactions is small and insufficient to cause destruction of the whole structure. On the other hand, the MIL-101 (Cr) structure is very stable.
Example 2
The natural gas hydrodesulfurization catalyst consists of a carrier a, an active component B and a cocatalyst component c, wherein the carrier a is a metal organic framework material MIL-101 (Cr) and accounts for 40% of the total catalyst weight, the active component B is a mixture of molybdenum and cobalt and accounts for 50% of the total catalyst weight, the cocatalyst component c is a mixture of B and Ca and accounts for 10% of the total catalyst weight, and the molar ratio n of elements of the active component cobalt, the active component molybdenum and the cocatalyst component c Co ：n Mo ：n c ＝5：10：5。
The preparation method of the catalyst comprises the following steps:
1) Preparing a metal organic framework material MIL-101 (Cr);
(1) uniformly mixing chromium nitrate nonahydrate, terephthalic acid and deionized water in a molar ratio of 1:1:4.93 to prepare a buffer solution of MIL-101 (Cr) metal organic framework material;
(2) adding hydrofluoric acid into the buffer solution, uniformly stirring, reacting for 1h at 200 ℃, and cooling to room temperature after the reaction is finished;
(3) sequentially centrifugally washing with N, N-dimethylformamide and absolute ethyl alcohol to remove unreacted terephthalic acid and N, N-dimethylformamide in a buffer solution;
(4) vacuum drying to remove absolute ethyl alcohol and crystal water to obtain an activated metal organic framework material MIL-101 (Cr);
the temperature of vacuum drying is 150 ℃ and the drying time is 1h; the specific surface area of the prepared metal organic framework material MIL-101 (Cr) is about 1900m 2 Per g, pore volume is 3.26mL/g.
2) Impregnating the active component b and the cocatalyst component c onto the carrier a according to the above proportion; the specific operation is as follows:
boric acid and calcium nitrate are respectively weighed as a promoter component c and dispersed into deionized water to prepare a promoter component mixed solution;
uniformly mixing the auxiliary component mixed solution with the activated metal organic framework material MIL-101 (Cr) prepared in the step (4), then carrying out ultrasonic impregnation for 2 hours, drying at 500 ℃ for 24 hours, and roasting at 100 ℃ for 24 hours to obtain semi-finished catalyst powder;
and respectively taking cobalt nitrate hexahydrate and molybdenum nitrate pentahydrate as active components b, uniformly dispersing the active components b into deionized water to prepare an active component mixed solution, uniformly mixing the obtained semi-finished catalyst powder with the active component solution, soaking the semi-finished catalyst powder in ultrasonic waves for 2 hours, drying the semi-finished catalyst powder at 500 ℃ for 24 hours, and roasting the semi-finished catalyst powder at 850 ℃ for 24 hours to obtain the product which is named CAT2.
Example 3
The natural gas hydrodesulfurization catalyst consists of a carrier a, an active component b and a cocatalyst component c, wherein the carrierThe body a is metal organic framework material MIL-101 (Cr) with the mass content accounting for 20 percent of the total catalyst, the active component b is a mixture of molybdenum and cobalt with the mass content accounting for 70 percent of the total catalyst, the promoter component c is a mixture of F and P with the mass content accounting for 10 percent of the total catalyst, and the active component cobalt, the active component molybdenum and the promoter component c have the element mole ratio n Co ：n Mo ：n c ＝2：10：1。
The preparation method of the catalyst comprises the following steps:
1) Preparing a metal organic framework material MIL-101 (Cr);
(1) uniformly mixing chromium nitrate nonahydrate, terephthalic acid and deionized water in a molar ratio of 1:1:4.93 to prepare a buffer solution of MIL-101 (Cr) metal organic framework material;
(2) adding hydrofluoric acid into the buffer solution, uniformly stirring, reacting for 12 hours at 150 ℃, and cooling to room temperature after the reaction is finished;
(3) sequentially centrifugally washing with N, N-dimethylformamide and absolute ethyl alcohol to remove unreacted terephthalic acid and N, N-dimethylformamide in a buffer solution;
(4) vacuum drying to remove absolute ethyl alcohol and crystal water to obtain an activated metal organic framework material MIL-101 (Cr);
the temperature of vacuum drying is 90 ℃ and the drying time is 25 hours; the specific surface area of the prepared metal organic framework material MIL-101 (Cr) is about 2200m 2 Per g, pore volume was 2.24mL/g.
2) Impregnating the active component b and the cocatalyst component c onto the carrier a according to the above proportion; the specific operation is as follows:
respectively weighing hydrofluoric acid and phosphoric acid as promoter components c, and dispersing the promoter components c into deionized water to prepare a mixed solution of the promoter components;
uniformly mixing the auxiliary component mixed solution with the activated metal organic framework material MIL-101 (Cr) prepared in the step (4), then carrying out ultrasonic impregnation for 2h, drying at 300 ℃ for 24h, and roasting at 500 ℃ for 24h to obtain semi-finished catalyst powder;
and respectively taking cobalt nitrate hexahydrate and molybdenum nitrate pentahydrate as active components b, uniformly dispersing the active components b into deionized water to prepare an active component mixed solution, uniformly mixing the obtained semi-finished catalyst powder with the active component solution, soaking the semi-finished catalyst powder in ultrasonic waves for 2 hours, drying the semi-finished catalyst powder at 300 ℃ for 24 hours, and roasting the semi-finished catalyst powder at 500 ℃ for 24 hours to obtain the product which is named CAT3.
Example 4
The natural gas hydrodesulfurization catalyst consists of a carrier a, an active component B and a cocatalyst component c, wherein the carrier a is a metal organic framework material MIL-101 (Cr) and accounts for 35% of the total catalyst weight, the active component B is a mixture of molybdenum and cobalt and accounts for 57% of the total catalyst weight, the cocatalyst component c is a mixture of B and Si and accounts for 8% of the total catalyst weight, and the molar ratio n of elements of the active component cobalt, the active component molybdenum and the cocatalyst component c Co ：n Mo ：n c ＝3：10：2。
The preparation method of the catalyst comprises the following steps:
1) Preparing a metal organic framework material MIL-101 (Cr);
(1) uniformly mixing chromium nitrate nonahydrate, terephthalic acid and deionized water in a molar ratio of 1:1:4.93 to prepare a buffer solution of MIL-101 (Cr) metal organic framework material;
(2) adding hydrofluoric acid into the buffer solution, uniformly stirring, reacting for 5 hours at 180 ℃, and cooling to room temperature after the reaction is finished;
(3) sequentially centrifugally washing with N, N-dimethylformamide and absolute ethyl alcohol to remove unreacted terephthalic acid and N, N-dimethylformamide in a buffer solution;
(4) vacuum drying to remove absolute ethyl alcohol and crystal water to obtain an activated metal organic framework material MIL-101 (Cr);
the temperature of vacuum drying is 120 ℃, and the drying time is 20 hours; the specific surface area of the prepared metal organic framework material MIL-101 (Cr) is about 2700m 2 Per g, pore volume is 1.90mL/g.
2) Impregnating the active component b and the cocatalyst component c onto the carrier a according to the above proportion; the specific operation is as follows:
boric acid and silica sol are respectively weighed as a promoter component c and dispersed into deionized water to prepare a mixed solution of the promoter components;
uniformly mixing the auxiliary component mixed solution with the activated metal organic framework material MIL-101 (Cr) prepared in the step (4), then carrying out ultrasonic impregnation for 2h, drying at 300 ℃ for 24h, and roasting at 300 ℃ for 24h to obtain semi-finished catalyst powder;
and respectively taking cobalt nitrate hexahydrate and molybdenum nitrate pentahydrate as active components b, uniformly dispersing the active components b into deionized water to prepare an active component mixed solution, uniformly mixing the obtained semi-finished catalyst powder with the active component solution, soaking the semi-finished catalyst powder in ultrasonic waves for 2 hours, drying the semi-finished catalyst powder at 300 ℃ for 24 hours, and roasting the semi-finished catalyst powder at 300 ℃ for 24 hours to obtain the product which is named CAT4.
Example 5
The natural gas hydrodesulfurization catalyst consists of a carrier a, an active component b and a cocatalyst component c, wherein the carrier a is a metal organic framework material MIL-101 (Cr) and accounts for 25% of the total catalyst weight, the active component b is a mixture of molybdenum and cobalt and accounts for 70% of the total catalyst weight, the cocatalyst component c is a mixture of Ca and Zn and accounts for 5% of the total catalyst weight, and the molar ratio n of elements of the active component cobalt, the active component molybdenum and the cocatalyst component c is as follows Co ：n Mo ：n c ＝4：10：3。
The preparation method of the catalyst comprises the following steps:
1) Preparing a metal organic framework material MIL-101 (Cr);
(1) uniformly mixing chromium nitrate nonahydrate, terephthalic acid and deionized water in a molar ratio of 1:1:4.93 to prepare a buffer solution of MIL-101 (Cr) metal organic framework material;
(2) adding hydrofluoric acid into the buffer solution, uniformly stirring, reacting for 9 hours at 180 ℃, and cooling to room temperature after the reaction is finished;
(3) sequentially centrifugally washing with N, N-dimethylformamide and absolute ethyl alcohol to remove unreacted terephthalic acid and N, N-dimethylformamide in a buffer solution;
(4) vacuum drying to remove absolute ethyl alcohol and crystal water to obtain an activated metal organic framework material MIL-101 (Cr);
the temperature of vacuum drying is 110 ℃, and the drying time is 10 hours; the specific surface area of the prepared metal organic framework material MIL-101 (Cr) is about 3500m 2 Per g, pore volume was 1.71mL/g.
2) Impregnating the active component b and the cocatalyst component c onto the carrier a according to the above proportion; the specific operation is as follows:
respectively weighing calcium nitrate and zinc nitrate as promoter components c, and dispersing the calcium nitrate and the zinc nitrate into deionized water to prepare a mixed solution of the promoter components;
uniformly mixing the auxiliary component mixed solution with the activated metal organic framework material MIL-101 (Cr) prepared in the step (4), then carrying out ultrasonic impregnation for 2h, drying at 300 ℃ for 24h, and roasting at 300 ℃ for 24h to obtain semi-finished catalyst powder;
and respectively taking cobalt nitrate hexahydrate and molybdenum nitrate pentahydrate as active components b, uniformly dispersing the active components b into deionized water to prepare an active component mixed solution, uniformly mixing the obtained semi-finished catalyst powder with the active component solution, soaking the semi-finished catalyst powder in ultrasonic waves for 2 hours, drying the semi-finished catalyst powder at 300 ℃ for 24 hours, and roasting the semi-finished catalyst powder at 300 ℃ for 24 hours to obtain the product which is named CAT5.
Example 6
The natural gas hydrodesulfurization catalyst consists of a carrier a, an active component b and a cocatalyst component c, wherein the carrier a is a metal organic framework material MIL-101 (Cr) and accounts for 35% of the total catalyst weight, the active component b is a mixture of molybdenum and cobalt and accounts for 55% of the total catalyst weight, the cocatalyst component c is a mixture of F and Ca and accounts for 10% of the total catalyst weight, and the molar ratio n of elements of the active component cobalt, the active component molybdenum and the cocatalyst component c Co ：n Mo ：n c ＝2.5：10：1。
The preparation method of the catalyst comprises the following steps:
1) Preparing a metal organic framework material MIL-101 (Cr);
(1) uniformly mixing chromium nitrate nonahydrate, terephthalic acid and deionized water in a molar ratio of 1:1:4.82 to prepare a buffer solution of MIL-101 (Cr) metal organic framework material;
(2) adding hydrofluoric acid into the buffer solution, uniformly stirring, reacting for 5 hours at 150 ℃, and cooling to room temperature after the reaction is finished;
(3) sequentially centrifugally washing with N, N-dimethylformamide and absolute ethyl alcohol to remove unreacted terephthalic acid and N, N-dimethylformamide in a buffer solution;
(4) vacuum drying to remove absolute ethyl alcohol and crystal water to obtain an activated metal organic framework material MIL-101 (Cr);
the temperature of vacuum drying is 120 ℃, and the drying time is 36h; the specific surface area of the prepared metal organic framework material MIL-101 (Cr) is about 3900m 2 Per g, pore volume is 1.85mL/g.
2) Impregnating the active component b and the cocatalyst component c onto the carrier a according to the above proportion; the specific operation is as follows:
respectively weighing hydrofluoric acid and calcium nitrate as promoter components c, and dispersing the promoter components c into deionized water to prepare a mixed solution of the promoter components;
uniformly mixing the auxiliary component mixed solution with the activated metal organic framework material MIL-101 (Cr) prepared in the step (4), then carrying out ultrasonic impregnation for 2h, drying at 300 ℃ for 24h, and roasting at 300 ℃ for 24h to obtain semi-finished catalyst powder;
and respectively taking cobalt nitrate hexahydrate and molybdenum nitrate pentahydrate as active components b, uniformly dispersing the active components b into deionized water to prepare an active component mixed solution, uniformly mixing the obtained semi-finished catalyst powder with the active component solution, soaking the semi-finished catalyst powder in ultrasonic waves for 2 hours, drying the semi-finished catalyst powder at 300 ℃ for 24 hours, and roasting the semi-finished catalyst powder at 300 ℃ for 24 hours to obtain the product which is named CAT6.
Example 7
The natural gas hydrodesulfurization catalyst consists of a carrier a, an active component b and a cocatalyst component c, wherein the carrier a is a metal organic framework material MIL-101 (Cr) and comprises the following components in percentage by mass25% of the total catalyst, wherein the active component B is a mixture of molybdenum and cobalt, the mass content of the active component B is 65% of the total catalyst, the promoter component c is a mixture of B and P, the mass content of the promoter component c is 10% of the total catalyst, and the molar ratio n of the elements of the active component cobalt, the active component molybdenum and the promoter component c Co ：n Mo ：n c ＝4.5：10：4。
The preparation method of the catalyst comprises the following steps:
1) Preparing a metal organic framework material MIL-101 (Cr);
(1) uniformly mixing chromium nitrate nonahydrate, terephthalic acid and deionized water in a molar ratio of 1:1:4.76 to prepare a buffer solution of MIL-101 (Cr) metal organic framework material;
(2) adding hydrofluoric acid into the buffer solution, uniformly stirring, reacting for 5 hours at 180 ℃, and cooling to room temperature after the reaction is finished;
(3) sequentially centrifugally washing with N, N-dimethylformamide and absolute ethyl alcohol to remove unreacted terephthalic acid and N, N-dimethylformamide in a buffer solution;
(4) vacuum drying to remove absolute ethyl alcohol and crystal water to obtain an activated metal organic framework material MIL-101 (Cr);
the temperature of vacuum drying is 150 ℃ and the drying time is 20h; the specific surface area of the prepared metal organic framework material MIL-101 (Cr) is about 3700m 2 Per g, pore volume was 1.82mL/g.
2) Impregnating the active component b and the cocatalyst component c onto the carrier a according to the above proportion; the specific operation is as follows:
respectively weighing phosphoric acid and boric acid as a promoter component c, and dispersing the promoter component c into deionized water to prepare a mixed solution of the promoter components;
uniformly mixing the auxiliary component mixed solution with the activated metal organic framework material MIL-101 (Cr) prepared in the step (4), then carrying out ultrasonic impregnation for 2h, drying at 300 ℃ for 24h, and roasting at 300 ℃ for 24h to obtain semi-finished catalyst powder;
and respectively taking cobalt nitrate hexahydrate and molybdenum nitrate pentahydrate as active components b, uniformly dispersing the active components b into deionized water to prepare an active component mixed solution, uniformly mixing the obtained semi-finished catalyst powder with the active component solution, soaking the semi-finished catalyst powder in ultrasonic waves for 2 hours, drying the semi-finished catalyst powder at 300 ℃ for 24 hours, and roasting the semi-finished catalyst powder at 300 ℃ for 24 hours to obtain the product named CAT7.
Example 8
The natural gas hydrodesulfurization catalyst consists of a carrier a, an active component b and a cocatalyst component c, wherein the carrier a is a metal organic framework material MIL-101 (Cr) and accounts for 29% of the total catalyst, the active component b is a mixture of molybdenum and cobalt and accounts for 70% of the total catalyst, the cocatalyst component c is a mixture of Si and Mn and accounts for 1% of the total catalyst, and the molar ratio n of elements of the active component cobalt, the active component molybdenum and the cocatalyst component c is as follows Co ：n Mo ：n c ＝3：10：4.5。
The preparation method of the catalyst comprises the following steps:
1) Preparing a metal organic framework material MIL-101 (Cr);
(1) uniformly mixing chromium nitrate nonahydrate, terephthalic acid and deionized water in a molar ratio of 1:1:4.93 to prepare a buffer solution of MIL-101 (Cr) metal organic framework material;
(2) adding hydrofluoric acid into the buffer solution, uniformly stirring, reacting for 7 hours at 180 ℃, and cooling to room temperature after the reaction is finished;
(3) sequentially centrifugally washing with N, N-dimethylformamide and absolute ethyl alcohol to remove unreacted terephthalic acid and N, N-dimethylformamide in a buffer solution;
(4) vacuum drying to remove absolute ethyl alcohol and crystal water to obtain an activated metal organic framework material MIL-101 (Cr);
the temperature of vacuum drying is 120 ℃, and the drying time is 20 hours; the specific surface area of the prepared metal organic framework material MIL-101 (Cr) is about 3400m 2 Per g, pore volume was 1.83mL/g.
2) Impregnating the active component b and the cocatalyst component c onto the carrier a according to the above proportion; the specific operation is as follows:
respectively weighing manganese nitrate and silica sol as promoter components c, and dispersing the manganese nitrate and the silica sol into deionized water to prepare a mixed solution of the promoter components;
uniformly mixing the auxiliary component mixed solution with the activated metal organic framework material MIL-101 (Cr) prepared in the step (4), then carrying out ultrasonic impregnation for 2h, drying at 300 ℃ for 24h, and roasting at 300 ℃ for 24h to obtain semi-finished catalyst powder;
and respectively taking cobalt nitrate hexahydrate and molybdenum nitrate pentahydrate as active components b, uniformly dispersing the active components b into deionized water to prepare an active component mixed solution, uniformly mixing the obtained semi-finished catalyst powder with the active component solution, soaking the semi-finished catalyst powder in ultrasonic waves for 2 hours, drying the semi-finished catalyst powder at 300 ℃ for 24 hours, and roasting the semi-finished catalyst powder at 300 ℃ for 24 hours to obtain the product which is named CAT8.
In order to verify the desulfurization effect of the catalyst of the present invention, the following comparative experiments were performed:
comparative example 1
Consists of a carrier a, an active component b and a cocatalyst component c, wherein the carrier a is gamma-A1 2 O 3 The mass content of the carrier is 30% of the total catalyst, the mass content of the active component b is a mixture of molybdenum and cobalt, the mass content of the active component b is 65% of the total catalyst, the mass content of the cocatalyst component c is a mixture of Mn and Zn, the mass content of the cocatalyst component c is 5% of the total catalyst, and the element mole ratio n of the active component cobalt, the active component molybdenum and the cocatalyst component c Co ：n Mo ：n c ＝3.5：10：3。
The preparation method of the catalyst comprises the following steps:
1) Calcining pseudo-boehmite at 500 ℃ for 4 hours to obtain gamma-A1 2 O 3 A carrier;
2) Impregnating the active component b and the cocatalyst component c onto the carrier a according to the above proportion; the specific operation is as follows:
respectively weighing manganese nitrate and zinc nitrate as promoter components c, and dispersing the manganese nitrate and the zinc nitrate into deionized water to prepare a mixed solution of the promoter components;
uniformly mixing the auxiliary component mixed solution with the activated metal organic framework material MIL-101 (Cr) prepared in the step (4), then carrying out ultrasonic impregnation for 2 hours, drying at 50 ℃ for 24 hours, and roasting at 850 ℃ for 24 hours to obtain semi-finished catalyst powder;
and respectively taking cobalt nitrate hexahydrate and molybdenum nitrate pentahydrate as active components b, uniformly dispersing the active components b into deionized water to prepare an active component mixed solution, uniformly mixing the obtained semi-finished catalyst powder with the active component solution, soaking the semi-finished catalyst powder in ultrasonic waves for 2 hours, drying the semi-finished catalyst powder at 50 ℃ for 24 hours, and roasting the semi-finished catalyst powder at 100 ℃ for 24 hours to obtain the product which is named CAT1.
Comparative example 2
Consists of a carrier a, an active component b and a promoter component c, wherein the carrier a is MIL-101 (Fe) and accounts for 30% of the total catalyst, the active component b is a mixture of molybdenum and cobalt and accounts for 65% of the total catalyst, the promoter component c is a mixture of Mn and Zn and accounts for 5% of the total catalyst, and the molar ratio n of elements of the active component cobalt, the active component molybdenum and the promoter component c Co ：n Mo ：n c ＝3.5：10：3。
The preparation method is the same as in example 1.
Comparative example 3
Consists of a carrier a, an active component b and a cocatalyst component c, wherein the carrier a is a metal organic framework material MIL-101 (Cr), the mass content of the carrier a accounts for 30 percent of the total catalyst, the active component b is a mixture of molybdenum and cobalt, the mass content of the active component b accounts for 65 percent of the total catalyst, the cocatalyst component c is a mixture of K and Mg, the mass content of the cocatalyst component c accounts for 5 percent of the total catalyst, and the molar ratio n of elements of the active component cobalt, the active component molybdenum and the cocatalyst component c Co ：n Mo ：n c ＝3.5：10：3。
The preparation method is the same as in example 1.
Comparative example 4
Consists of a carrier a, an active component b and a cocatalyst component c, wherein the carrier a is a metal organic framework material MIL-101 (Cr) with the mass content accounting for 30 percent of the total catalyst, and the active component b is a mixture of molybdenum and cobalt with the mass content65% of the total catalyst, the promoter component c is a mixture of Mn and Zn, the mass content of the promoter component c is 5% of the total catalyst, and the element mole ratio n of the active component cobalt, the active component molybdenum and the promoter component c Co ：n Mo ：n c ＝7：10：6。
The preparation method is the same as in example 1.
Comparative example 5
Consists of a carrier a, an active component b and a promoter component c, wherein the carrier a is a metal organic framework material MIL-101 (Cr), the mass content of the carrier a accounts for 30 percent of the total catalyst, the active component b is a mixture of molybdenum and cobalt, the mass content of the active component b accounts for 65 percent of the total catalyst, the promoter component c is a mixture of Mn and Zn, the mass content of the promoter component c accounts for 5 percent of the total catalyst, and the molar ratio n of elements of the active component cobalt, the active component molybdenum and the promoter component c Co ：n Mo ：n c ＝1：10：0.5。
The preparation method is the same as in example 1.
Comparative example 6
Consists of a carrier a, an active component b and a promoter component c, wherein the carrier a is a metal organic framework material MIL-101 (Cr), the mass content of the carrier a accounts for 30 percent of the total catalyst, the active component b is a mixture of molybdenum and cobalt, the mass content of the active component b accounts for 65 percent of the total catalyst, the promoter component c is a mixture of Mn and Zn, the mass content of the promoter component c accounts for 5 percent of the total catalyst, and the molar ratio n of elements of the active component cobalt, the active component molybdenum and the promoter component c Co ：n Mo ：n c ＝1：10：7。
The preparation method is the same as in example 1.
Experimental details
The products CAT1-8 of examples 1-8 and the products of comparative examples 1-6 were used for the same hydrodesulfurization of natural gas under the following reaction conditions: the hydrogen content in the feed gas is 12% and the sulfur content is 350ppm; the reaction temperature is 350 ℃, and the reaction pressure is 2.5MPa; the space velocity of the raw material gas is 20000h -1 。
The catalysts were tested for their reactivity and long cycle test, respectively, the results of which are shown in fig. 5 and 6.
As can be seen from the table data of FIG. 5, the desulfurization rate of the embodiment of the present invention was substantially stabilized at 99% or more at 120 hours of operation, while using gamma-A1 2 O 3 Comparative example 1, which is a carrier, has the same active ingredient and cocatalyst as the present invention, but has a desulfurization rate of only about 68.17%; in comparative example 2 in which MIL101 (Fe) was used as a carrier, the desulfurization rate was also kept at 93.52%, while MIL-101 (Cr) was used as a carrier, but the desulfurization efficiency was lower than that of the present invention in the case of different promoter components and different ratios. This shows that the catalyst promoter and the active component of specific components are matched with MIL-101 (Cr), and the desulfurization effect can be well achieved under the specific proportion.
As can be seen from the tabular data of FIG. 6, at the same reaction temperature, pressure and space velocity (20000 h -1 ) The catalyst CAT1-8 and the comparative examples 1-6 are subjected to long-period natural gas hydrodesulfurization operation experiments, and the catalyst CAT1-8 is found to have higher and more stable catalytic activity after long-time reaction, and the desulfurization efficiency is basically stabilized to be more than 99.9%; whereas the desulfurization rate of comparative example 1 began to gradually decrease after the hydrodesulfurization reaction was carried out for 192 hours, and the desulfurization rate of comparative examples 2 to 6 began to gradually decrease after the hydrodesulfurization reaction was carried out for 240 hours; the decrease in desulfurization rate indicates a gradual decrease in catalytic activity. The experimental result shows that the catalyst has longer catalyst life, high and stable catalytic activity and greatly reduces the use cost of the natural gas hydrodesulfurization catalyst by selecting the cocatalyst and the active component of specific components to match with MIL-101 (Cr).
Claims (10)
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