Solid amine supported molecular sieve material, preparation method and application thereof, and hydrogen sulfide adsorption method

Abstract

The invention provides a solid amine supported molecular sieve material, a preparation method and application thereof, and a hydrogen sulfide adsorption method, and belongs to the technical field of adsorbents. The method comprises the following steps: sequentially roasting and carrying out surface hydrophilic treatment on a molecular sieve to obtain a pretreated molecular sieve; the surface hydrophilic treatment is carried out in an alkaline solution; mixing the pretreated molecular sieve, an alcohol amine organic amine solution and an organic solvent, and carrying out solid amine loading to obtain a loaded molecular sieve; and carrying out load consolidation on the supported molecular sieve to obtain the solid amine supported molecular sieve material. According to the method, impurities on the surface of the molecular sieve can be removed through roasting, influence on loading of the alcamines organic amine is avoided, the loading capacity of the alcamines organic amine can be improved through surface hydrophilic treatment in an alkaline solution, then loaded substances are consolidated, loss of the alcamines organic amine is avoided, adsorption of acid gas is improved, and the service life of the molecular sieve is prolonged. The high-capacity adsorption on H2S is realized.

Description

Technical Field

[0001] The invention relates to the technical field of adsorbents, and in particular to a solid amine-loaded molecular sieve material, a preparation method and application thereof, and a method for adsorbing hydrogen sulfide. Background Art

[0002] Hydrogen sulfide (H2S) is a toxic and harmful colorless acidic gas with a certain degree of corrosiveness. In the presence of extremely small amounts of H2S, a distinct smell of rotten eggs can be smelled, which is one of the main sources of odor pollution. H2S is also a strong neurotoxin, which is highly toxic along with cyanide and has a strong irritating effect on human mucous membranes. In the presence of a certain concentration of H2S, it can cause damage to the central nervous system and respiratory system, endangering human health. When the concentration of H2S is greater than 1000ppm, it can cause respiratory arrest and suffocation and death. At the same time, as one of the main gaseous pollutants, H2S is easily oxidized to SO2 in the air, which promotes the formation of acid rain and damages the environment. In industrial production, the presence of H2S can cause catalyst poisoning, acid corrosion of metal instruments and pipelines, and hydrogen embrittlement of steel materials; in severe cases, it can cause corrosion, cracking, and leakage of equipment, instruments, and gas pipelines, causing safety accidents and endangering human health. Therefore, developing a new and efficient desulfurization method for removing H2S from industrial production and various gases is of great significance to the development of the global economy and environmental protection. In order to reduce the negative impact of H2S in industrial production and protect the environment, separation and desulfurization have become a hot research topic, and scholars at home and abroad have developed many desulfurization methods.

[0003] Many H2S treatment technologies are being developed in related technologies. They can be mainly divided into: wet desulfurization, dry desulfurization and other technical desulfurization. In dry desulfurization, the adsorption method can be widely used for hydrogen sulfide removal due to its advantages such as good adsorption effect, simple equipment and low cost. The adsorption method uses the physical adsorption properties of adsorbents (common ones such as activated carbon, zeolite molecular sieves, activated alumina, silica gel, etc.) as porous materials, and their possible chemical adsorption reactions with pollutants to achieve the adsorption and removal of gaseous pollutants. However, the adsorption capacity of current dry desulfurization materials is low. Summary of the invention

[0004] In view of this, the object of the present invention is to provide a solid amine-supported molecular sieve material and a preparation method and application thereof, and a method for adsorbing hydrogen sulfide. The solid amine-supported molecular sieve material of the present invention has a high adsorption capacity for H2S.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a method for preparing a solid amine-supported molecular sieve material, comprising the following steps:

[0007] The molecular sieve is sequentially calcined and subjected to surface hydrophilic treatment to obtain a pretreated molecular sieve; the surface hydrophilic treatment is performed in an alkaline solution;

[0008] The pretreated molecular sieve, a solution of an alcoholamine organic amine and an organic solvent are mixed to carry out solid amine loading to obtain a loaded molecular sieve;

[0009] The loaded molecular sieve is subjected to loading consolidation to obtain the solid amine-loaded molecular sieve material.

[0010] Preferably, the calcination temperature is 300-450° C. and the calcination time is 1-5 hours.

[0011] Preferably, the alkaline substance in the alkaline solution includes fatty amine substances and / or ammonia water.

[0012] Preferably, the aliphatic amine substance includes one or more of dimethylamine, triethylamine and diethylamine.

[0013] Preferably, the loading amount of the alcoholamine organic amine in the loaded molecular sieve is 10-40 wt %.

[0014] Preferably, the alcoholamine organic amine includes triethanolamine.

[0015] The present invention also provides a solid amine-loaded molecular sieve material prepared by the preparation method described in the above technical solution.

[0016] The present invention also provides the use of the solid amine-loaded molecular sieve material described in the above technical solution as an adsorbent in the field of acid gas adsorption.

[0017] The present invention also provides a method for adsorbing hydrogen sulfide, comprising the following steps:

[0018] A fixed bed reactor is used for continuous operation, and the solid amine-loaded molecular sieve material described in the above technical solution is used to adsorb hydrogen sulfide.

[0019] Preferably, the flow rate of hydrogen sulfide is 10 mL / min, the adsorption temperature is 25-60°C; the space velocity of the fixed bed reactor is 6000-12000 mL·h -1 ·g -1 .

[0020] The invention provides a preparation method of a solid amine-loaded molecular sieve material, comprising the following steps: calcining and surface hydrophilic treatment of a molecular sieve in sequence to obtain a pretreated molecular sieve; the surface hydrophilic treatment is performed in an alkaline solution; the pretreated molecular sieve, a solution of an alcohol amine organic amine and an organic solvent are mixed to carry out solid amine loading to obtain a loaded molecular sieve; and the loaded molecular sieve is loaded with a load to obtain the solid amine-loaded molecular sieve material.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] The present invention helps to remove impurities on the surface of the molecular sieve by roasting, avoids affecting the loading of alcohol amine organic amines, performs surface hydrophilic treatment in an alkaline solution, can increase the loading amount of alcohol amine organic amines, and then consolidates the loading material to avoid the loss of alcohol amine organic amines, thereby improving the adsorption of acidic gases and achieving high-capacity adsorption of H2S. The solid amine-loaded molecular sieve material of the present invention has high adsorption capacity, good stability, strong operability of the preparation process, is conducive to large-scale production, and can meet the actual industrial application needs.

[0023] The present invention also provides a solid amine-loaded molecular sieve material prepared by the preparation method described in the above technical solution. The solid amine-loaded molecular sieve material of the present invention is a hydrophilic adsorbent with excellent adsorption effect on acidic gases. DETAILED DESCRIPTION

[0024] The present invention provides a method for preparing a solid amine-supported molecular sieve material, comprising the following steps:

[0025] The molecular sieve is sequentially calcined and subjected to surface hydrophilic treatment to obtain a pretreated molecular sieve; the surface hydrophilic treatment is performed in an alkaline solution;

[0026] The pretreated molecular sieve, a solution of an alcoholamine organic amine and an organic solvent are mixed to carry out solid amine loading to obtain a loaded molecular sieve;

[0027] The loaded molecular sieve is subjected to loading consolidation to obtain the solid amine-loaded molecular sieve material.

[0028] In the present invention, unless otherwise specified, the raw materials used are all commercially available products in the art.

[0029] The present invention sequentially performs calcination and surface hydrophilic treatment on a molecular sieve to obtain a pretreated molecular sieve; the surface hydrophilic treatment is performed in an alkaline solution.

[0030] In the present invention, the molecular sieve is preferably a ZSM-5 mesoporous molecular sieve or an all-silicon molecular sieve, more preferably a ZSM-5 mesoporous molecular sieve. The ZSM-5 mesoporous molecular sieve is cheap and has low cost. The present invention uses the molecular sieve as a carrier, and the obtained solid amine-loaded molecular sieve material has good stability.

[0031] In the present invention, the calcination temperature is preferably 300-450°C, specifically 300, 350, 400 or 450°C, and the time is preferably 1-5h, specifically 1, 2, 3, 4 or 5h; the calcination is preferably carried out in an air atmosphere, which helps to remove impurities on the surface of the molecular sieve and avoid affecting the organic amine loading.

[0032] In the present invention, the molecular sieve is preferably washed and dried in sequence before calcination, and the washing detergent is preferably deionized water. The present invention has no particular limitation on the specific methods of washing and drying.

[0033] In the present invention, the alkaline substance in the alkaline solution preferably includes fatty amine substances and / or ammonia water, and more preferably fatty amine substances. Compared with ammonia water, the fatty amine substances have weaker alkalinity and are more conducive to the loading of alcoholamine organic amines.

[0034] In the present invention, the aliphatic amine substance preferably includes one or more of dimethylamine (DMA), triethylamine (TEA) and diethylamine (DEA).

[0035] In the present invention, the surface hydrophilic treatment is preferably performed by immersing the calcined material obtained by calcination in an alkaline solution.

[0036] In the present invention, the immersion time is preferably 5 to 30 minutes, specifically 5, 10, 15, 20, 25 or 30 minutes.

[0037] After the impregnation is completed, the present invention preferably washes with ethanol and deionized water in sequence, and then dries to obtain the pretreated molecular sieve.

[0038] In the present invention, the drying temperature is preferably 80° C. The present invention has no particular limitation on the drying time as long as the moisture can be completely removed.

[0039] After the pretreated molecular sieve is obtained, the present invention mixes the pretreated molecular sieve, a solution of an alcoholamine organic amine and an organic solvent to carry out solid amine loading to obtain a loaded molecular sieve.

[0040] In the present invention, the loading amount of the alcoholamine organic amine in the loaded molecular sieve is preferably 10-40wt%, specifically 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt% or 40wt%.

[0041] In the present invention, the alcoholamine organic amine preferably includes triethanolamine (TEOA), which is helpful for loading and has good hydrophilicity.

[0042] In the present invention, the solvent of the solution of the alcoholamine organic amine is preferably ethanol.

[0043] In the present invention, the organic solvent is preferably acetone.

[0044] In a specific embodiment of the present invention, an ethanol solution of an alcoholamine organic amine is preferably prepared, and acetone is added to obtain a mixed solution. A glass container containing a pretreated molecular sieve is evacuated, and the mixed solution is added dropwise after evacuation. After the addition is completed, the pretreated molecular sieve is immersed in the mixed solution. After immersion for 30 minutes, the vacuum is removed, and the mixture is placed in an oven and dried at 80°C to obtain the loaded molecular sieve.

[0045] In the present invention, the concentration of the alcohol amine organic amine in the mixed solution is preferably 30wt%

[0046] After obtaining the loaded molecular sieve, the present invention solidifies the loaded molecular sieve with a loaded substance to obtain the solid amine-loaded molecular sieve material.

[0047] In the present invention, the load consolidation is preferably carried out in a vacuum oven, the temperature of the vacuum oven is preferably 40 to 70°C, specifically 40, 50, 60 or 70°C, to avoid excessive temperature leading to the loss of organic amines, the time is preferably 3 to 4 hours, and the vacuum degree is preferably -100 to -50 kPa.

[0048] The present invention also provides a solid amine-loaded molecular sieve material prepared by the preparation method described in the above technical solution. The solid amine-loaded molecular sieve material is obtained by using a molecular sieve as a carrier, performing surface hydrophilic treatment with an alkaline substance, and then loading an alcoholamine organic amine.

[0049] The present invention also provides the use of the solid amine-loaded molecular sieve material described in the above technical solution as an adsorbent in the field of acid gas adsorption.

[0050] In the present invention, the acid gas preferably includes sulfur-containing compounds, and the sulfur-containing compounds preferably include hydrogen sulfide, sulfur dioxide and carbonyl sulfide.

[0051] The present invention also provides a method for adsorbing hydrogen sulfide, comprising the following steps:

[0052] A fixed bed reactor is used for continuous operation, and the solid amine-loaded molecular sieve material described in the above technical solution is used to adsorb hydrogen sulfide.

[0053] In the present invention, the flow rate of hydrogen sulfide is preferably 10 mL / min, the adsorption temperature is preferably 25-60°C, specifically 25, 40 or 60°C; the space velocity of the fixed bed reactor is preferably 6000-12000 mL·h -1 ·g -1 , specifically 6000, 10000 or 12000 mL·h -1 ·g-1 .

[0054] The technical solutions in the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0055] The ZSM-5 mesoporous molecular sieve used in the examples and comparative examples of the present invention was purchased from Shanghai Fuyu New Materials Technology Co., Ltd.

[0056] Example 1

[0057] The preparation of solid amine-supported molecular sieve material comprises the following steps:

[0058] Surface hydrophilic treatment: The ZSM-5 mesoporous molecular sieve washed with deionized water and then dried was calcined at 400°C for 2h. The calcined ZSM-5 beads were immersed in triethylamine for 15min and then taken out. They were washed with ethanol solution and deionized water in turn, and then dried at 80°C. The obtained sample was marked as S1.

[0059] Solid amine loading: Prepare an ethanol solution of triethanolamine, add acetone, and obtain a mixed solution. The concentration of triethanolamine in the mixed solution is 30wt%. Vacuum the glass container containing S1, and then add the mixed solution dropwise after vacuuming. After the addition is completed, the mixed solution just immerses S1. After immersion for 30 minutes, remove the vacuum, put it in an oven and dry it at 80°C. The sample is marked as S2, and the loading amount of triethanolamine organic amine in S2 is 30wt%.

[0060] Load consolidation: Take out S2 and put it into a vacuum oven to continue drying, evacuate to a vacuum degree of -100 kPa, and dry at 40°C for 4 hours to obtain a solid amine-loaded molecular sieve material.

[0061] Example 2

[0062] The preparation of solid amine-supported molecular sieve material comprises the following steps:

[0063] Surface hydrophilic treatment: The ZSM-5 mesoporous molecular sieve washed with deionized water and then dried was calcined at 400°C for 2h. The calcined ZSM-5 pellets were immersed in ammonia water for 15min and then taken out. They were washed with ethanol solution and deionized water in turn, and then dried at 80°C. The obtained sample was marked as S1.

[0064] Solid amine loading: Prepare an ethanol solution of triethanolamine, add acetone, and obtain a mixed solution. The concentration of triethanolamine in the mixed solution is 30wt%. Vacuum the glass container containing S1, and then add the mixed solution dropwise after vacuuming. After the addition is completed, the mixed solution just immerses S1. After immersion for 30 minutes, remove the vacuum, put it in an oven and dry it at 80°C. The sample is marked as S2, and the loading amount of triethanolamine organic amine in S2 is 30wt%.

[0065] Load consolidation: Take out S2 and put it into a vacuum oven to continue drying, evacuate to a vacuum degree of -100 kPa, and dry at 40°C for 4 hours to obtain a solid amine-loaded molecular sieve material.

[0066] Comparative Example 1

[0067] The same as Example 1, the only difference is that triethanolamine is replaced by triethylenetetramine.

[0068] Comparative Example 2

[0069] The same as Example 1, the only difference is that triethanolamine is replaced by hexamethylenediamine.

[0070] Comparative Example 3

[0071] The adsorbent Ag / AC was prepared by using AC to impregnate at room temperature, which specifically includes the following steps: preparing a 0.5M silver nitrate solution with a liquid-to-solid ratio of 20 mL·g -1 , stirred at room temperature for 3 h, then subjected to rotary evaporation to remove moisture, dried at 80°C for 12 h, and finally reduced in a 10 vol% hydrogen-helium atmosphere at 350°C for 2 h.

[0072] Comparative Example 4

[0073] Adsorbent Ag / NaY.

[0074] Ag / NaY was prepared based on commercial NaY zeolite by conventional ion exchange in 0.5 M corresponding silver nitrate with a liquid-to-solid ratio of 50 mL g -1 , after stirring at 80°C for 3 h, it was washed and filtered, and then dried at 80°C for 12 h. The ion exchange process was repeated twice.

[0075] Comparative Example 5

[0076] Adsorbent AgY.

[0077] Comparative Example 6

[0078] Adsorbent CaX.

[0079] Comparative Example 7

[0080] Adsorbent BaX.

[0081] Comparative Example 8

[0082] Adsorbent AgX.

[0083] AgX, AgY, CaX, and BaX were prepared by conventional ion exchange on the basis of commercial NaX zeolite, which has a Si / Al ratio of 1.2 and a BET surface area of ​​770 m 2 ·g -1 The ion exchange was carried out in a 0.5 M solution of the corresponding nitrate (including silver nitrate, calcium nitrate, and barium nitrate) with a liquid-to-solid ratio of 50 mL g -1 , after stirring at 80°C for 3 h, it was washed and filtered, and then dried at 80°C for 12 h. The ion exchange process was repeated twice.

[0084] Application Examples

[0085] The fixed bed reactor was continuously operated, and hydrogen sulfide was adsorbed by the adsorbents of the embodiments and comparative examples. The flow rate of hydrogen sulfide was 10 mL / min, and the adsorption capacity was as shown in Table 1. It can be seen that the present invention helps to remove impurities on the surface of the molecular sieve through calcination to avoid affecting the loading of the alcoholamine organic amine. The surface hydrophilic treatment in an alkaline solution can increase the loading amount of the alcoholamine organic amine, and then the loading material is consolidated to avoid the loss of the alcoholamine organic amine, thereby improving the adsorption of acidic gases and achieving high-capacity adsorption of H2S.

[0086] Table 1 Adsorption capacity of adsorbents of Examples and Comparative Examples

[0087] Adsorption temperature (℃) <![CDATA[Air velocity (mL·h -1 ·g -1 )]]> Adsorption capacity (mg / g) Example 2 40 12000 164.1 Example 1 25 12000 174.1 Example 1 40 12000 250.7 Example 1 60 12000 163.7 Example 1 40 6000 284.7 Comparative Example 1 40 12000 0 Comparative Example 2 40 12000 0 Comparative Example 3 40 12000 0.81 Comparative Example 4 25 12000 7.1 Comparative Example 4 40 12000 8.6 Comparative Example 4 60 12000 9.1 Comparative Example 5 40 24000 36.4 Comparative Example 6 40 12000 0 Comparative Example 7 40 12000 0 Comparative Example 8 40 36000 43.3

[0088] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims

1. A method for preparing a solid amine-supported molecular sieve material, characterized in that: The following steps are involved: The molecular sieve is sequentially calcined and subjected to surface hydrophilic treatment to obtain a pretreated molecular sieve; the surface hydrophilic treatment is performed in an alkaline solution; The pretreated molecular sieve, a solution of an alcoholamine organic amine and an organic solvent are mixed to carry out solid amine loading to obtain a loaded molecular sieve; The loaded molecular sieve is subjected to loading consolidation to obtain the solid amine-loaded molecular sieve material.

2. The preparation method according to claim 1, characterized in that: The calcination temperature is 300-450° C. and the calcination time is 1-5 hours.

3. The preparation method according to claim 1, characterized in that: The alkaline substance in the alkaline solution includes aliphatic amine substances and / or ammonia water.

4. The preparation method according to claim 3, characterized in that: The aliphatic amine substances include one or more of dimethylamine, triethylamine and diethylamine.

5. The preparation method according to claim 1, characterized in that: The loading amount of the alcoholamine organic amine in the loaded molecular sieve is 10-40 wt %.

6. The preparation method according to claim 1 or 5, characterized in that: The alcoholamine organic amine includes triethanolamine.

7. The solid amine-supported molecular sieve material obtained by the preparation method according to any one of claims 1 to 6.

8. Use of the solid amine-supported molecular sieve material according to claim 7 as an adsorbent in the field of acid gas adsorption.

9. A method for adsorbing hydrogen sulfide, characterized in that: The following steps are involved: A fixed bed reactor is used for continuous operation, and the solid amine-supported molecular sieve material according to claim 7 is used to adsorb hydrogen sulfide.

10. The adsorption method according to claim 9, characterized in that The flow rate of hydrogen sulfide is 10 mL / min, and the adsorption temperature is 25-60°C; the space velocity of the fixed bed reactor is 6000-12000 mL·h -1 ·g -1 .