CN114643044A - Modified metal organic framework material and preparation method and application thereof - Google Patents

Modified metal organic framework material and preparation method and application thereof Download PDF

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CN114643044A
CN114643044A CN202011506839.4A CN202011506839A CN114643044A CN 114643044 A CN114643044 A CN 114643044A CN 202011506839 A CN202011506839 A CN 202011506839A CN 114643044 A CN114643044 A CN 114643044A
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organic framework
framework material
metal organic
modified metal
copper
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CN114643044B (en
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韩笑
高晓晨
柏诗哲
高焕新
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • C10L3/103—Sulfur containing contaminants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds

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Abstract

The invention relates to a modified metal organic framework material, a preparation method and application thereof. The modified metal organic framework material can furthest preserve the original structure of the metal organic framework material, improves the desulfurization performance of the material, and can be used for removing sulfur impurities in natural gas, synthesis gas and light gas-liquid hydrocarbons at normal temperature.

Description

Modified metal organic framework material and preparation method and application thereof
Technical Field
The invention relates to the field of adsorption desulfurization, in particular to a modified metal organic framework material, a preparation method thereof and application of the material in adsorption desulfurization.
Background
The average sulfur content of crude oil is around 1.2% from the global perspective, and the sulfur content of the oil to be recovered is at a higher level for a long period of time in the future. Therefore, under the condition that petroleum cannot be widely replaced by other non-fossil green new energy sources, refining crude oil with high sulfur content is necessarily the main way of energy supply in the future, so that the reduction of the sulfur content in oil products is still an urgent problem to be solved.
The sulfides in Liquefied Petroleum Gas (LPG) are mainly hydrogen sulfide, mercaptans, carbonyl sulfide, sulfides, disulfides, and the like. Because of the existence of a certain amount of mercaptan, light oil products such as gasoline have foul smell, and meanwhile, the mercaptan can promote oxidation of unstable components in the oil products to deteriorate the stability of the oil products. The traditional sweetening method is alkali washing, but alkali washing desulphurization is not ideal due to the problems of alkali liquor pollution and corrosiveness. Other methods for removing mercaptans are mainly catalytic oxidation methods, but expensive materials are needed as catalysts, oxygen or air is needed as an oxidant, the cost is high, and the process is complex.
In recent years, selective adsorption desulfurization has been considered as a promising new technology for fine desulfurization and deep desulfurization due to its advantages of mild and simple operation conditions, low equipment requirements, easy regeneration, and the like. The Metal Organic Frameworks (MOFs) material shows wide application prospect in the field of selective adsorption desulfurization of hydrocarbon mixtures by virtue of the extremely large specific surface area, the flexible and adjustable framework and pore channel structures.
CN106984279A relates to a preparation method of a modified metal organic framework material capable of efficiently removing inactive sulfur and a prepared material. The modified metal organic framework material PTA @ PCN-10 is obtained by mixing and reacting a metal ion precursor, a solvent, phosphotungstic acid (PTA) and an organic ligand and carrying out hydrothermal crystallization treatment. The preparation and forming process has low yield and long time consumption. And because the forming of the MOFs material is not involved, the powdered MOFs material has smaller density, and the particles are finer, so that the powdered MOFs material is not suitable for industrial production.
Disclosure of Invention
The invention provides a modified metal organic framework material and a preparation method and application thereof, aiming at solving the problems of low sulfur capacity, long synthesis-forming time consumption, complex preparation process and the like in the existing adsorption material. The modified metal organic framework material can furthest preserve the original structure of the metal organic framework material, improves the desulfurization performance of the material, and can be used for removing sulfur impurities in natural gas, synthesis gas and light gas-liquid hydrocarbons at normal temperature.
The invention provides a modified metal organic framework material, wherein the metal in the modified metal organic framework material is Cu, the crystal of the material is in a regular octahedron or octahedron-like structure, and hemispherical bulges are distributed on the surface of the crystal.
In the technical scheme, the edge length of the regular octahedral crystal of the modified metal organic framework material is 5-15 mu m.
In the technical scheme, the diameter of the convex hemisphere on the surface of the modified metal organic framework material is 0.2-0.5 μm.
In the technical scheme, the mass content of Cu in the modified metal organic framework material is 15-40%.
In the above technical scheme, Cu in the modified metal organic framework material+And Cu2+Is 0.01 to 1.0, preferably 0.1 to 1.0.
In the technical scheme, the modified metal organic framework material comprises but is not limited to one of Cu-BDC, Cu-IM and HKUST-1, wherein HKUST-1 is preferred.
The second aspect of the invention provides a preparation method of a modified metal organic framework material, which comprises the following steps:
s1: dissolving copper salt, ligand and alkaline substance in a solvent to form a copper-based MOF mother solution A, and dissolving glucose in deionized water to prepare a solution B;
s2: mixing the solution A and the solution B in the S1 and carrying out reaction;
s3: and (4) adding a gelling agent and a solvent into a colloidal substance obtained by separating the mixture after the reaction in the S2, continuing the reaction, and drying to obtain the modified metal organic framework material.
In the above technical solution, the copper salt in step S1 includes one or more of copper nitrate, copper sulfate, and copper acetate.
In the above technical solution, the ligand in step S1 is selected from one or more of trimesic acid, terephthalic acid, 4-bipyridine and 3, 4', 5-biphenyltricarboxylic acid.
In the above technical solution, the basic substance in step S1 includes one or more of ammonia, methylamine, ethylamine, propylamine, dimethylamine, trimethylamine, ethylenediamine, diethylamine, triethylamine, aniline, acetamide, and urea, preferably triethylamine.
In the above technical solution, in step S1, the volume ratio of the alkaline substance to the solvent is 1:50-500, preferably 1: 80-360; the molar ratio of the copper salt to the ligand is 1 (0.2-5); the dosage ratio of the solvent to the copper salt is 5-100mL of solvent per 1.0g of copper salt; the molar ratio of the glucose to the copper ions in the copper salt is 1 (0.1-10), preferably 1: 0.5-6.
In the above technical solution, the reactor of the reaction in step S2 is preferably made of a high temperature resistant material, and the high temperature resistant material is preferably polytetrafluoroethylene; the high-temperature resistant material is rod-shaped, strip-shaped or plate-shaped.
In the above technical scheme, the reaction conditions of step S2 include a reaction temperature of 30-150 ℃, preferably 70-90 ℃, and a reaction time of 3-24h, preferably 12-16 h.
In the above technical solution, in step S3, the gelling agent is selected from one or more of carboxymethyl cellulose, propylene glycol alginate, methyl cellulose, sodium starch phosphate, sodium carboxymethyl cellulose, sodium alginate, casein, sodium polyacrylate, polyoxyethylene, polyvinylpyrrolidone, starch, and polysaccharide derivatives.
In the above technical solution, the solvents in steps S1 and S3 are each independently selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, methanol, ethanol, and deionized water.
In the above technical solution, the solvent in step S3 is preferably a mixture of ethanol and deionized water.
In the above technical solution, the dosage ratio of the gelling agent in step S3 to the solvent in S3 is 1.0g gelling agent/50-800 mL solvent, preferably 1.0g gelling agent/300-400 mL solvent.
In the above technical solution, in the step S3, the reaction temperature is 30-150 ℃, preferably 60-70 ℃, the reaction time is 3-24h, preferably 5-6h, the drying is performed in two stages, preferably, the first stage is at 70-100 ℃ for 1-24h, and the second stage is at 120-200 ℃ for 1-24 h.
In the above technical solution, in step S3, the obtained metal organic framework material is ground and screened to obtain a 20-80 mesh finished product, preferably 20-40 mesh.
In a third aspect, the invention provides a method for removing sulfides, which comprises contacting the modified metal organic framework material as an adsorbent or the modified metal organic framework material obtained by the preparation method as an adsorbent with a material containing mercaptan and/or hydrogen sulfide.
In the technical scheme, the concentration of mercaptan in the mercaptan-containing material is 50-3000ppm, and the space velocity is 0.01-5h-1。
In the technical scheme, the mole fraction of the hydrogen sulfide in the material containing the hydrogen sulfide is 1-10%, and the airspeed is 1-10min-1。
The modified metal organic framework material provided by the invention is a copper-based metal organic framework material with a crystal shape presenting a regular octahedral structure. After the metal organic framework material is modified, the copper-based metal organic framework material contains a proper proportion of monovalent copper/divalent copper, so that the sulfur capacity is improved to a great extent. The modified material has special appearance, hemispherical bulges are distributed on the surface, and the specific surface area and special defect positions are increased, so that the desulfurization performance of the material is improved.
According to the preparation method of the modified metal organic framework material, the metal organic framework material is exposed to a weak alkaline environment in the forming process, glucose is modified, so that part of bivalent copper in the material is reduced into monovalent copper, the monovalent copper/bivalent copper with a proper proportion is obtained, a special crystal morphology is obtained, and the desulfurization performance is improved.
Drawings
FIG. 1 is an SEM photograph of the metal-organic framework material obtained in example 1;
FIG. 2 is an SEM photograph of the metal organic framework material obtained in example 2;
FIG. 3 is an SEM photograph of the metal-organic framework material obtained in example 4;
FIG. 4 is an SEM photograph of the metal-organic framework material obtained in comparative example 1;
FIG. 5 is an SEM photograph of the metal-organic framework material obtained in comparative example 3;
FIG. 6 is an SEM photograph of the metal-organic framework material obtained in comparative example 4;
FIG. 7 is an SEM photograph of the metal-organic framework material obtained in comparative example 6;
FIG. 8 is an XRD pattern of the metal organic framework materials obtained in examples and comparative examples;
FIG. 9 shows Cu 2p of a modified metal organic framework material obtained in example 13/2An X-ray photoelectron energy spectrum;
FIG. 10 shows Cu 2p of a modified metal organic framework material obtained in example 23/2An X-ray photoelectron energy spectrum;
FIG. 11 is Cu 2p of the modified metal organic framework material obtained in comparative example 13/2An X-ray photoelectron energy spectrum;
FIG. 12 is Cu 2p of the modified metal organic framework material obtained in comparative example 33/2X-ray photoelectron spectroscopy.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples, but the scope of the present invention is not limited by the examples. In the present invention, wt% is a mass fraction.
Scanning Electron Microscope (SEM) photographs of the samples were taken on a scanning electron microscope, type S-4800II, Hitachi.
Test conditions of XRD: the crystal phase analysis of the molecular sieve was carried out by using an X-ray diffractometer of Rigaku-Ultima type in Japan. CuK α radiation, wavelength λ 0.15432 nm. The scanning range 2 theta of the X-ray diffraction pattern is 5-75 degrees, the scanning speed is 5 degrees/min, and the step length is 0.02 degree.
The X-ray photoelectron spectroscopy is carried out by using an ESCALB 250Xi system of American Saimer Feishell science and technology, and the instrument test conditions are as follows: al target, 14kV and 250W power.
Example 1
4.5g of trimesic acid was weighed and added to a mixture of 80mL of anhydrous ethanol and 40mL of N, N-dimethylformamide, and sufficiently stirred for 20 min. 7.2g of copper nitrate trihydrate (30mmol) were weighed out and dissolved in 60mL of deionized water, after which the two solutions were mixed and stirred for 20 min. And dropwise adding 2mL of triethylamine, and fully stirring for 20min to obtain copper-based MOF mother liquor A. 2.7g (15mmol) of glucose is weighed and dissolved in 20mL of deionized water to prepare a solution B, and then the solution B is added into the copper-based MOF mother liquor A and is continuously stirred for 30 min. Ultrasonic treating at room temperature for 15min, transferring into stainless steel high-pressure reactor with polytetrafluoroethylene lining and spacer, and oven-reacting at 85 deg.C for 16 h. Standing and naturally cooling to room temperature. The mother liquor was centrifuged off and washed several times with ethanol.
Adding the obtained product into 150mL of ethanol-water mixed solution, wherein the volume ratio of ethanol to deionized water is 1:1, and fully and uniformly mixing. 0.6g of sodium carboxymethylcellulose is mixed with 50mL of deionized water to prepare a pasty glue solution. And then slowly adding the prepared mixed solution into the pasty glue solution, stirring while adding, and fully stirring for 30min to obtain copper-based MOF mother liquor C. Then transferring the mixture into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, and carrying out oven reaction for 5 hours at 65 ℃. Standing and naturally cooling to room temperature. The mother liquor was centrifuged off and washed several times with ethanol. Drying, grinding, and sieving with a screen to obtain 20-40 mesh product, which is named as Glc (0.5)/HKUST-1/TEA (1).
As can be seen from the SEM photograph of FIG. 1, the modified metal organic framework material crystal prepared in this example is in a regular octahedral structure, and has a large number of white spherical small protrusions on the surface, the edge length of the regular octahedral crystal is 8-10 μm, and the diameter of the hemisphere is 0.4-0.5 μm.
As can be seen from the XRD pattern of FIG. 8, several characteristic peaks of Glc (0.5)/HKUST-1/TEA (1) prepared in example 1 at 2 θ ═ 5.4 °, 9.4 °, 11.62 °, 17.4 °, 19 °, 29.3 ° are also consistent with the characteristic peak reports of HKUST-1 in the literature, indicating that the crystal structure of the sample Glc (0.5)/HKUST-1/TEA (1) is complete.
As can be seen from the X-ray photoelectron spectrum of FIG. 9, the modified metal-organic framework material prepared in example 1 contains both monovalent and divalent Cu, and Cu is obtained by XPS Peak41 Peak separation software and Peak area integral calculation+And Cu2+The molar ratio of (A) is shown in Table 1.
The desulfurization performance was evaluated by fixed bed propanol and hydrogen sulfide adsorption units, and the sulfur capacities obtained are shown in table 1. Wherein the concentration of the propyl mercaptan in the raw material is 2300ppm, and the airspeed is set to be 0.2h-1(ii) a The initial mole fraction of hydrogen sulfide of the feed was 5% and the space velocity was set to 4.5min-1。
Example 2
4.5g of trimesic acid is weighed and added into a mixture of 80mL of absolute ethyl alcohol and 40mL of N, N-dimethylformamide, and the mixture is fully stirred for 20 min. 7.2g of copper nitrate trihydrate (30mmol) were weighed out and dissolved in 60mL of deionized water, after which the two solutions were mixed and stirred for 20 min. Dropwise adding 2mL of triethylamine, and fully stirring for 20min to obtain the copper-based MOF mother liquor A. Weighing 5.4g (30mmol) of glucose, dissolving in 20mL of deionized water to prepare a solution B, and adding the prepared solution B into the copper-based MOF mother liquor A to continue stirring for 30 min. Ultrasonic treating at room temperature for 15min, transferring into stainless steel high-pressure reactor with polytetrafluoroethylene lining and spacer, and oven-reacting at 85 deg.C for 16 h. Standing and naturally cooling to room temperature. The mother liquor was centrifuged off and washed several times with ethanol.
Adding the obtained product into 150mL of ethanol-water mixed solution, wherein the volume ratio of ethanol to deionized water is 1:1, and fully and uniformly mixing. 0.6g of sodium carboxymethylcellulose is mixed with 50mL of deionized water to prepare a pasty glue solution. And then slowly adding the prepared mixed solution into the pasty glue solution, stirring while adding, and fully stirring for 30min to obtain copper-based MOF mother liquor C. Then transferring the mixture into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, and carrying out oven reaction for 5 hours at 65 ℃. Standing and naturally cooling to room temperature. The mother liquor was centrifuged off and washed several times with ethanol. Drying, grinding, and sieving with a screen to obtain 20-40 mesh product, which is named as Glc (1.0)/HKUST-1/TEA (1).
As can be seen from the SEM photograph of FIG. 2, the modified metal organic framework material crystal prepared in this example is in a regular octahedral structure, and has a large number of white spherical small protrusions on the surface, the edge length of the regular octahedral crystal is 8-10 μm, and the diameter of the hemisphere is 0.4-0.5 μm.
As can be seen from the XRD pattern of fig. 8, several characteristic peaks of Glc (1.0)/HKUST-1/TEA (1) prepared in example 2 at 2 θ of 5.4 °, 9.4 °, 11.62 °, 17.4 °, 19 °, 29.3 ° are also consistent with literature reports, indicating that the crystal structure of the sample Glc (1.0)/HKUST-1/TEA (1) is complete.
As can be seen from the X-ray photoelectron spectrum of FIG. 10, the modified metal-organic framework material prepared in example 2 contains both monovalent and divalent Cu, and Cu is obtained by XPS Peak41 Peak separation software and Peak area integral calculation+And Cu2+The molar ratio of (A) is shown in Table 1.
The desulfurization performance was evaluated by fixed bed propanol and hydrogen sulfide adsorption units, and the sulfur capacities obtained are shown in table 1. Wherein the concentration of the propyl mercaptan in the raw material is 2300ppm, and the airspeed is set to be 0.2h-1(ii) a The initial mole fraction of hydrogen sulfide of the feed was 5% and the space velocity was set to 4.5min-1。
Example 3
4.5g of trimesic acid is weighed and added into a mixture of 80mL of absolute ethyl alcohol and 40mL of N, N-dimethylformamide, and the mixture is fully stirred for 20 min. 7.2g of copper nitrate trihydrate (30mmol) were weighed out and dissolved in 60mL of deionized water, after which the two solutions were mixed and stirred for 20 min. And dropwise adding 2mL of triethylamine, and fully stirring for 20min to obtain copper-based MOF mother liquor A. 0.9g (5mmol) of glucose is weighed and dissolved in 20mL of deionized water to prepare a solution B, and then the prepared solution B is added into the copper-based MOF mother liquor 1 and is continuously stirred for 30 min. Ultrasonic treating at room temperature for 15min, transferring into stainless steel high-pressure reactor with polytetrafluoroethylene lining and spacer, and oven-reacting at 85 deg.C for 16 h. Standing and naturally cooling to room temperature. The mother liquor was centrifuged off and washed several times with ethanol.
Adding the obtained product into 150mL of ethanol-water mixed solution, wherein the volume ratio of ethanol to deionized water is 1:1, and fully and uniformly mixing. 0.6g of sodium carboxymethylcellulose is mixed with 50mL of deionized water to prepare pasty glue solution. And then slowly adding the prepared mixed solution into the pasty glue solution, stirring while adding, and fully stirring for 30min to obtain copper-based MOF mother liquor C. Then transferring the mixture into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, and carrying out oven reaction for 5 hours at 65 ℃.
Standing and naturally cooling to room temperature. The mother liquor was centrifuged off and washed several times with ethanol. Drying, grinding, and sieving to obtain 20-40 mesh product named as Glc (0.17)/HKUST-1/TEA (1). The morphology of the modified metal organic framework material prepared in the embodiment is similar to that of the modified metal organic framework material prepared in the embodiment 1, the crystal is in an octahedral structure, more white spherical small bulges appear on the surface, the edge length of the octahedral crystal is 8-10 mu m, and the diameter of a hemisphere is 0.4-0.5 mu m.
The XRD pattern of the modified metal organic framework material prepared in this example 3 is similar to that of example 1.
The X-ray photoelectron spectrum of the modified metal-organic framework material prepared in this example 3 is similar to that of example 1. The modified metal organic framework material prepared in example 3 contains both monovalent and divalent Cu, and Cu is obtained by XPS Peak41 Peak separation software and Peak area integral calculation+And Cu2+The molar ratio of (A) to (B) is shown in Table 1.
The desulfurization performance was evaluated by fixed bed propanol and hydrogen sulfide adsorption units, and the sulfur capacities obtained are shown in table 1. Wherein the concentration of the propyl mercaptan in the raw material is 2300ppm, and the airspeed is set to be 0.2h-1(ii) a The initial mole fraction of hydrogen sulfide of the feed was 5% and the space velocity was set at 4.5min-1。
Example 4
4.5g of trimesic acid is weighed and added into a mixture of 80mL of absolute ethyl alcohol and 40mL of N, N-dimethylformamide, and the mixture is fully stirred for 20 min. 7.2g of copper nitrate trihydrate (30mmol) were weighed out and dissolved in 60mL of deionized water, after which the two solutions were mixed and stirred for 20 min. 0.5mL of triethylamine is added dropwise, and the mixture is fully stirred for 20min to obtain copper-based MOF mother liquor A. 2.7g (15mmol) of glucose is weighed and dissolved in 20mL of deionized water to prepare a solution B, and then the prepared solution B is added into the copper-based MOF mother liquor 1 and is continuously stirred for 30 min. Ultrasonic treating at room temperature for 15min, transferring into stainless steel high-pressure reactor with polytetrafluoroethylene lining and spacer, and oven-reacting at 85 deg.C for 16 h. Standing and naturally cooling to room temperature. The mother liquor was centrifuged off and washed several times with ethanol.
Adding the obtained product into 150mL of ethanol-water mixed solution, wherein the volume ratio of ethanol to deionized water is 1:1, and fully and uniformly mixing. 0.6g of sodium carboxymethylcellulose is mixed with 50mL of deionized water to prepare a pasty glue solution. And then slowly adding the prepared mixed solution into the pasty glue solution, stirring while adding, and fully stirring for 30min to obtain copper-based MOF mother liquor C. Then transferring the mixture into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, and carrying out oven reaction for 5 hours at 65 ℃. Standing and naturally cooling to room temperature. The mother liquor was centrifuged off and washed several times with ethanol. Drying, grinding, and sieving to obtain 20-40 mesh product named as Glc (0.5)/HKUST-1/TEA (0.5).
The morphology of the modified metal organic framework material prepared in the embodiment is shown in figure 3, the crystal is in an octahedral structure, more white spherical small bulges appear on the surface, the edge length of the octahedral crystal is 8-10 mu m, and the diameter of a hemisphere is 0.4-0.5 mu m.
The XRD pattern of the modified metal organic framework material prepared in this example 4 is similar to that of example 1.
The X-ray photoelectron spectrum of the modified metal-organic framework material prepared in this example 4 is similar to that of example 1. The modified metal organic framework material prepared in example 4 contains both the monovalent and divalent Cu, and the Cu is obtained by XPS Peak41 Peak separation software and Peak area integral calculation+And Cu2+The molar ratio of (A) to (B) is shown in Table 1.
The desulfurization performance was evaluated by fixed bed propanol and hydrogen sulfide adsorption units, and the sulfur capacities obtained are shown in table 1. Wherein the concentration of the propyl mercaptan in the raw material is 2300ppm, and the airspeed is set to be 0.2h-1(ii) a The initial mole fraction of hydrogen sulfide of the feed was 5% and the space velocity was set to 4.5min-1。
Comparative example 1
4.5g of trimesic acid is weighed and added into a mixture of 80mL of absolute ethyl alcohol and 40mL of N, N-dimethylformamide, and the mixture is fully stirred for 20 min. 7.2g of copper nitrate trihydrate (30mmol) is weighed and dissolved in 60mL of deionized water, and then the two solutions are mixed and stirred for 20min to obtain copper-based MOF mother liquor A. Weighing 2.7g (15mmol) of glucose, dissolving in 20mL of deionized water to prepare a solution B, and adding the prepared solution B into the copper-based MOF mother liquor A to continue stirring for 30 min. Ultrasonic treating at room temperature for 15min, transferring into stainless steel high-pressure reactor with polytetrafluoroethylene lining and spacer, and oven-reacting at 85 deg.C for 16 h. Standing and naturally cooling to room temperature. The mother liquor was centrifuged off and washed several times with ethanol.
Adding the obtained product into 150mL of ethanol-water mixed solution, wherein the volume ratio of ethanol to deionized water is 1:1, and fully and uniformly mixing. 0.6g of sodium carboxymethylcellulose is mixed with 50mL of deionized water to prepare a pasty glue solution. And then slowly adding the prepared mixed solution into the pasty glue solution, stirring while adding, and fully stirring for 30min to obtain copper-based MOF mother liquor C. Then transferring the mixture into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, and carrying out oven reaction for 5 hours at 65 ℃. Standing and naturally cooling to room temperature. The mother liquor was centrifuged off and washed several times with ethanol. Drying, grinding, and sieving with a screen to obtain 20-40 mesh product named as Glc (0.5)/HKUST-1.
SEM figure 4 of this material shows that only the glucose modified crystal surface had only slight projections without addition of alkali. The edge length of the octahedral crystal is 8-10 μm.
As can be seen from the XRD pattern of FIG. 8, several characteristic peaks of Glc (0.5)/HKUST-1 prepared in comparative example 1 at 2 θ ═ 5.4 °, 9.4 °, 11.62 °, 17.4 °, 19 °, 29.3 ° were also consistent with those reported in HKUST-1 in the literature.
As can be seen from the X-ray photoelectron spectrum of FIG. 11, the metal-organic framework material prepared in comparative example 1 contains both the monovalent and divalent Cu, and the Cu is obtained by XPS Peak41 Peak separation software and Peak area integral calculation+And Cu2+The molar ratio of (A) is shown in Table 1.
Are respectively fixed byThe desulfurization performance of the fixed bed propanol and hydrogen sulfide adsorption device was evaluated, and the sulfur capacities obtained are shown in table 1. Wherein the concentration of the propyl mercaptan in the raw material is 2300ppm, and the airspeed is set to be 0.2h-1(ii) a The initial mole fraction of hydrogen sulfide of the feed was 5% and the space velocity was set to 4.5min-1。
Comparative example 2
Trimesic acid 4.5g was weighed into a mixture of 80mL absolute ethanol and 40mL N, N-dimethylformamide and stirred well for 20 min. 7.2g of copper nitrate trihydrate (30mmol) were weighed out and dissolved in 60mL of deionized water, after which the two solutions were mixed and stirred for 20 min. And dropwise adding 2mL of triethylamine, and fully stirring for 20min to obtain copper-based MOF mother liquor A. Ultrasonic treating at room temperature for 15min, transferring into stainless steel high-pressure reactor with polytetrafluoroethylene lining and spacer, and oven-reacting at 85 deg.C for 16 h. Standing and naturally cooling to room temperature. The mother liquor was centrifuged off and washed several times with ethanol.
Adding the obtained product into 150mL of ethanol-water mixed solution, wherein the volume ratio of ethanol to deionized water is 1:1, and fully and uniformly mixing. 0.6g of sodium carboxymethylcellulose is mixed with 50mL of deionized water to prepare a pasty glue solution. And then slowly adding the prepared mixed solution into the pasty glue solution, stirring while adding, and fully stirring for 30min to obtain copper-based MOF mother liquor C. Then transferring the mixture into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, and carrying out oven reaction for 5 hours at 65 ℃. Standing and naturally cooling to room temperature. The mother liquor was centrifuged off and washed several times with ethanol. Drying, grinding, and sieving with a screen to obtain 20-40 mesh product named HKUST-1/TEA (1).
The morphology of comparative example 2 is similar to that of comparative example 3, and is octahedral, the surface is smooth, no small protrusions are formed on the surface, and the edge length of octahedral crystals is 8-10 μm. The characteristic diffraction peak of comparative example 2 is similar to that of comparative example 3, and the peak intensity is weaker. The XPS chart of comparative example 2 does not have a characteristic peak for monovalent copper.
The desulfurization performance was evaluated by fixed bed propanol and hydrogen sulfide adsorption units, and the sulfur capacities obtained are shown in table 1. Wherein the concentration of the propyl mercaptan in the raw material is 2300ppm, and the airspeed is set to be 0.2h-1(ii) a Initial mole fraction of hydrogen sulfide of the feed is 5%, space velocitySet for 4.5min-1。
Comparative example 3
4.5g of trimesic acid is weighed and added into a mixture of 80mL of absolute ethyl alcohol and 40mL of N, N-dimethylformamide, and the mixture is fully stirred for 20 min. 7.2g of copper nitrate trihydrate (30mmol) was weighed and dissolved in 60mL of deionized water, after which the two solutions were mixed and stirred for 20min to obtain copper-based MOF mother liquor A. Ultrasonic treating at room temperature for 15min, transferring into stainless steel high-pressure reactor with polytetrafluoroethylene lining, and oven reacting at 85 deg.C for 16 h. Standing and naturally cooling to room temperature. The mother liquor was centrifuged off and washed several times with ethanol.
Adding the obtained product into 150mL of ethanol-water mixed solution, wherein the volume ratio of ethanol to deionized water is 1:1, and fully and uniformly mixing. 0.6g of sodium carboxymethylcellulose is mixed with 50mL of deionized water to prepare pasty glue solution. And then slowly adding the prepared mixed solution into the pasty glue solution, stirring while adding, and fully stirring for 30min to obtain copper-based MOF mother liquor C. Then transferring the mixture into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, and carrying out oven reaction for 5 hours at 65 ℃. Standing and naturally cooling to room temperature. The mother liquor was centrifuged off and washed several times with ethanol. Drying, grinding, and sieving with a screen to obtain 20-40 mesh product named as HKUST-1.
As can be seen from FIG. 5, the HKUST-1 sample which is not modified by glucose and alkali is octahedral, the surface is smooth, no small protrusions are formed on the surface, and the edge length of the octahedral crystal is 8-10 μm.
As can be seen from FIG. 12, the Cu in the unmodified HKUST-1 structure exists in the form of Cu (II) through XPS test. The sample modified by glucose and alkaline solution glucose has a new characteristic peak at 933.0-933.2eV, corresponding to Cu 2p of Cu (I)3/2Binding energy. The result shows that after the HKUST-1 is modified, part of Cu (II) in the framework is reduced to Cu (I), and under the action of an alkaline solution, the content of Cu (I) in the HKUST-1 after the reduction modification is higher than that of Cu (I) modified by glucose alone.
As can be seen from fig. 8, the characteristic peak intensities of comparative example 3 and example 1 are relatively consistent. It is shown that example 1 has a higher crystal purity, a product with a single HKUST-1 crystal phase.
The desulfurization performance was evaluated by fixed bed propanol and hydrogen sulfide adsorption units, and the sulfur capacities obtained are shown in table 1. Wherein the concentration of the propyl mercaptan in the raw material is 2300ppm, and the airspeed is set to be 0.2h-1(ii) a The initial mole fraction of hydrogen sulfide of the feed was 5% and the space velocity was set at 4.5min-1。
Comparative example 4
Trimesic acid 4.5g was weighed into a mixture of 80mL absolute ethanol and 40mL N, N-dimethylformamide and stirred well for 20 min. Weighing 7.2g of copper nitrate trihydrate (30mmol) and dissolving in 60mL of deionized water, mixing and stirring the two solutions for 20min, dropwise adding 2mL of triethylamine, and fully stirring for 20min to obtain copper-based MOF mother liquor A. Obtaining copper-based MOF mother liquor A. Weighing 2.7g (15mmol) of glucose, dissolving in 20mL of deionized water to prepare a solution B, and adding the prepared solution B into the copper-based MOF mother liquor A to continue stirring for 30 min. Ultrasonic treating at room temperature for 15min, transferring into stainless steel high-pressure reactor with polytetrafluoroethylene lining and spacer, and oven-reacting at 85 deg.C for 16 h. Standing and naturally cooling to room temperature. The mother liquor was centrifuged off and washed several times with ethanol. Dried, ground and tabletted, named Glc (0.5)/HKUST-1/TEA (1) -2.
As can be seen from SEM figure 6, the tablet formation greatly destroyed the crystal structure of the material.
As can be seen from FIG. 8, in comparative example 4, since the molding method using a tablet was employed, the destruction of the metal-organic framework structure was large, and the characteristic peak of HKUST-1 was not evident, it can be presumed that most of the secondary structural units coordinated with copper tetracarboxylic acid were destroyed.
The desulfurization performance was evaluated by fixed bed propanol and hydrogen sulfide adsorption units, and the sulfur capacities obtained are shown in table 1. Wherein the concentration of the propyl mercaptan in the raw material is 2300ppm, and the airspeed is set to be 0.2h-1(ii) a The initial mole fraction of hydrogen sulfide of the feed was 5% and the space velocity was set to 4.5min-1。
Comparative example 5
4.5g of trimesic acid is weighed and added into a mixture of 80mL of absolute ethyl alcohol and 40mL of N, N-dimethylformamide, and the mixture is fully stirred for 20 min. 7.2g of copper nitrate trihydrate (30mmol) were weighed out and dissolved in 60mL of deionized water, after which the two solutions were mixed and stirred for 20 min. 10mL of triethylamine is added dropwise, and the mixture is fully stirred for 20min to obtain a copper-based MOF mother liquor A. 2.7g (15mmol) of glucose is weighed and dissolved in 20mL of deionized water to prepare a solution B, and then the prepared solution B is added into the copper-based MOF mother liquor 1 and is continuously stirred for 30 min. Ultrasonic treating at room temperature for 15min, transferring into stainless steel high-pressure reactor with polytetrafluoroethylene lining and spacer, and oven-reacting at 85 deg.C for 16 h. Standing and naturally cooling to room temperature. The mother liquor was centrifuged off and washed several times with ethanol.
Adding the obtained product into 150mL of ethanol-water mixed solution, wherein the volume ratio of ethanol to deionized water is 1:1, and fully and uniformly mixing. 0.6g of sodium carboxymethylcellulose is mixed with 50mL of deionized water to prepare a pasty glue solution. And then slowly adding the prepared mixed solution into the pasty glue solution, stirring while adding, and fully stirring for 30min to obtain copper-based MOF mother liquor C. Then transferring the mixture into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, and carrying out oven reaction for 5 hours at 65 ℃. Standing and naturally cooling to room temperature. The mother liquor was centrifuged off and washed several times with ethanol. Drying, grinding, and sieving to obtain 20-40 mesh product named as Glc (0.5)/HKUST-1/TEA (5).
The morphology of the metal organic framework material prepared by the comparative example is similar to that of the metal organic framework material prepared by the example 1 shown in figure 1, the crystal is in a regular octahedral structure, more white spherical small bulges appear on the surface, the edge length of the regular octahedral crystal is 8-10 mu m, and the diameter of a hemisphere is 0.4-0.5 mu m.
As can be seen from FIG. 8, the comparative example 5 has a certain difference from example 1 in the intensity of the characteristic peak, and has a larger difference from example 1 in the intensity of the characteristic peak, which indicates that excessive alkali can adversely affect the crystal formation, so that the crystal purity of HKUST-1 is greatly reduced, and the crystal structure is damaged to form defects.
The X-ray photoelectron spectrum of the modified metal-organic framework material prepared in comparative example 5 is similar to that of example 1. The metal organic framework material prepared in comparative example 5 contains both the monovalent and divalent Cu, and the Cu is obtained by XPS Peak41 Peak separation software and Peak area integral calculation+And Cu2+The molar ratio of (A) to (B) is shown in Table 1.
The desulfurization performance was evaluated by fixed bed propanol and hydrogen sulfide adsorption units, and the sulfur capacities obtained are shown in table 1. Wherein the concentration of the propyl mercaptan in the raw material is 2300ppm, and the airspeed is set to be 0.2h-1(ii) a The initial mole fraction of hydrogen sulfide of the feed was 5% and the space velocity was set to 4.5min-1。
Comparative example 6
4.5g of trimesic acid is weighed and added into a mixture of 80mL of absolute ethyl alcohol and 40mL of N, N-dimethylformamide, and the mixture is fully stirred for 20 min. 7.2g of copper nitrate trihydrate (30mmol) were weighed out and dissolved in 60mL of deionized water, after which the two solutions were mixed and stirred for 20 min. And dropwise adding 2mL of triethylamine, and fully stirring for 20min to obtain copper-based MOF mother liquor A. Weighing 2.7g (15mmol) of glucose, dissolving in 20mL of deionized water to prepare a solution B, and adding the prepared solution B into the copper-based MOF mother liquor A to continue stirring for 30 min. Ultrasonic treating at room temperature for 15min, transferring into stainless steel high-pressure reactor with polytetrafluoroethylene lining and partition board, and oven-reacting at 200 deg.C for 16 h. Standing and naturally cooling to room temperature. The mother liquor was centrifuged off and washed several times with ethanol.
Adding the obtained product into 150mL of ethanol-water mixed solution, wherein the volume ratio of ethanol to deionized water is 1:1, and fully and uniformly mixing. 0.6g of sodium carboxymethylcellulose is mixed with 50mL of deionized water to prepare a pasty glue solution. And then slowly adding the prepared mixed solution into the pasty glue solution while stirring, and fully stirring for 30min to obtain the copper-based MOF mother liquor C. Then transferring the mixture into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, and carrying out oven reaction for 5 hours at 65 ℃. Standing and naturally cooling to room temperature. The mother liquor was centrifuged off and washed several times with ethanol. The finished product of 20-40 meshes is obtained by drying, grinding and sieving by a screen and is named as Glc (0.5)/HKUST-1/TEA (1) -1.
As can be seen from the SEM photograph of fig. 7, the crystal structure of the material is still octahedral shape, and more small protrusions appear on the surface, but slight cracks appear on the surface. The length of the octahedral crystal edge is 8-10 μm, and the diameter of the hemisphere is 0.4-0.5 μm.
As can be seen from the XRD pattern of FIG. 8, the difference between the characteristic peak intensities of comparative example 6 and example 1 is large, which indicates that an excessively high reaction temperature has a certain influence on the crystal formation, so that the purity of HKUST-1 crystals is reduced to a certain extent and the crystal structure is damaged.
The X-ray photoelectron spectrum of the metal-organic framework material prepared in comparative example 6 is similar to that of example 1. The metal organic framework material prepared in comparative example 6 contains Cu of both the first valence state and the second valence state, and the Cu is obtained by XPS Peak41 Peak separation software and Peak area integral calculation+And Cu2+The molar ratio of (A) to (B) is shown in Table 1.
The desulfurization performance was evaluated by fixed bed propanol and hydrogen sulfide adsorption units, and the sulfur capacities obtained are shown in table 1. Wherein the concentration of the propyl mercaptan in the raw material is 2300ppm, and the airspeed is set to be 0.2h-1(ii) a The initial mole fraction of hydrogen sulfide of the feed was 5% and the space velocity was set to 4.5min-1。
TABLE 1 Properties and desulfurization Properties of each example and comparative example
Figure BDA0002845167470000121

Claims (14)

1. A modified metal organic framework material is characterized in that the metal in the modified metal organic framework material is Cu, the crystal of the material is in a regular octahedral or octahedral structure, and hemispherical bulges are distributed on the surface of the crystal.
2. The modified metal-organic framework material of claim 1, wherein the modified metal-organic framework material has a length of octahedral crystals ranging from 5 to 15 μm.
3. The modified metal organic framework material of claim 1, wherein the diameter of the hemispheres protruding from the surface of the modified metal organic framework material is in the range of 0.2 to 0.5 μm.
4. The modified metal organic framework material of claim 1, wherein the modified metal organic framework material comprises 15-40% by mass of Cu.
5. The modified metal organic framework material of claim 1, wherein the modified metal organic framework material comprises Cu+And Cu2+Is 0.01 to 1.0, preferably 0.1 to 1.0.
6. A preparation method of a modified metal organic framework material comprises the following steps:
s1: dissolving copper salt, ligand and alkaline substance in a solvent to form a copper-based MOF mother solution A, and dissolving glucose in deionized water to prepare a solution B;
s2: mixing the solution A and the solution B in the S1 and carrying out reaction;
s3: and (4) adding a gelling agent and a solvent into a colloidal substance obtained by separating the mixture after the reaction in the S2, continuing the reaction, and drying to obtain the modified metal organic framework material.
7. The method according to claim 6, wherein the copper salt in step S1 comprises one or more of copper nitrate, copper sulfate and copper acetate; in the step S1, the ligand is selected from one or more of trimesic acid, terephthalic acid, 4-bipyridyl and 3, 4', 5-biphenyl tricarboxylic acid; in step S1, the basic substance includes one or more of ammonia, methylamine, ethylamine, propylamine, dimethylamine, trimethylamine, ethylenediamine, diethylamine, triethylamine, aniline, acetamide, and urea, preferably triethylamine.
8. The method according to claim 6, wherein in step S1, the volume ratio of the alkaline substance to the solvent is 1:50-500, preferably 1: 80-360; the molar ratio of the copper salt to the ligand is 1 (0.2-5); the dosage ratio of the solvent to the copper salt is 5-100mL of solvent per 1.0g of copper salt; the molar ratio of the glucose to the copper ions in the copper salt is 1 (0.1-10), preferably 1: 0.5-6.
9. The process according to claim 6, wherein the reaction conditions of step S2 include a reaction temperature of 30-150 ℃, preferably 70-90 ℃, and a reaction time of 3-24h, preferably 12-16 h.
10. The method of claim 6, wherein the gelling agent in step S3 is selected from one or more of carboxymethyl cellulose, propylene glycol alginate, methyl cellulose, sodium starch phosphate, sodium carboxymethyl cellulose, sodium alginate, casein, sodium polyacrylate, polyoxyethylene, polyvinylpyrrolidone, starch, and polysaccharide derivatives.
11. The method as claimed in claim 6, wherein the ratio of the amount of the gelling agent to the solvent in S3 in step S3 is 1.0g gelling agent/50-800 mL solvent, preferably 1.0g gelling agent/300-400 mL solvent.
12. The method according to claim 6, wherein in step S3, the reaction temperature is 30-150 ℃, preferably 60-70 ℃, the reaction time is 3-24h, preferably 5-6h, and the drying is carried out in two stages, preferably the first stage temperature is 70-100 ℃, the time is 1-24h, and the second stage drying temperature is 120-200 ℃, and the time is 1-24 h.
13. A method for removing sulfides, comprising contacting a material containing mercaptans and/or hydrogen sulfide with the modified metal organic framework material according to any one of claims 1 to 5 or the modified metal organic framework material obtained by the production method according to any one of claims 6 to 12 as an adsorbent.
14. The method of claim 13, wherein the concentration of mercaptans in the mercaptan-containing feed is 50 to 3000ppm and the space velocity is 0.01 to 5h-1(ii) a The molar fraction of the hydrogen sulfide in the material containing the hydrogen sulfide is 1-10 percent, and the airspeed is 1-10min-1。
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