Process treatment method for separating out resin-based spherical activated carbon impregnation components

Abstract

The invention relates to activated carbon for adsorbing hydrogen sulfide gas, in particular to a process treatment method for separating out resin-based spherical activated carbon impregnation components. The method comprises the following steps: S1, selecting styrene skeleton macroporous strong acid cation exchange resin balls, and drying the resin at 120 DEG C until the moisture is less than or equal to 3%; s2, carbonizing and activating the resin dried in the step S1 in a tubular furnace; s3, carrying out modification treatment on the activated product; and S4, impregnating a metal component with the modified resin spherical carbon to prepare the impregnated carbon. The treatment method of the impregnation component analysis method provided by the invention is simple and easy to operate and can be used for industrial production. The loading capacity of active metal components of the prepared spherical impregnated carbon can reach 40% or above, the appearance of the impregnated spherical carbon keeps the form of original spherical carbon, and no other impurities exist. And the protection time of the hydrogen sulfide of the impregnated ball carbon is improved by more than 100% compared with that of the active component.

Description

Technical Field

[0001] The present invention relates to activated carbon for adsorbing hydrogen sulfide gas, and particularly to a process treatment method for the precipitation of impregnated components of resin-based spherical activated carbon. Background Art

[0002] During deep-sea operations, high-concentration hydrogen sulfide gas is generated in the toilet cabin, which seriously endangers human health. Therefore, strict control is imposed on the concentration standard of hydrogen sulfide inside the toilet cabin.

[0003] Activated carbon has rich surface chemical activity and developed pore structure, and is a good adsorbent for removing hydrogen sulfide gas. However, relying solely on the physical adsorption of activated carbon itself far fails to meet the actual desulfurization requirements. The impregnation of activated carbon with metal active components combines the principles of physical and chemical adsorption and catalytic reaction, which can greatly improve the desulfurization efficiency. According to the test method WJ20453.2, the protection time against hydrogen sulfide is required to be ≥150 min. Under this protection time, a high proportion of metal active components needs to be impregnated to achieve this. The disadvantages of the current technology are as follows:

[0004] 1. The resin-based spherical activated carbon after direct carbon activation has poor adsorption effect on impregnated metal active components, and a large amount of active components directly crystallize on the outer surface of the spherical carbon after impregnation and drying.

[0005] 2. During the impregnation process, there will be competitive adsorption among various metal impregnated components. The impregnated components with stronger interaction with activated carbon will be preferentially impregnated onto the activated carbon carrier, and then combined with another impregnated component, thus affecting the dispersion degree of the latter impregnated component and the reaction activity. Summary of the Invention

[0006] In order to solve the technical problem of the precipitation of impregnated components of resin-based spherical activated carbon and further improve the protection performance of resin-based spherical activated carbon against hydrogen sulfide, the present invention provides a process treatment method for the precipitation of impregnated components of resin-based spherical activated carbon.

[0007] In order to solve the above technical problems, the technical solution adopted by the present invention is as follows: A process treatment method for the precipitation of impregnated components of resin-based spherical activated carbon, comprising the following steps:

[0008] S1. Select a styrene-based macroporous strong acid cation exchange resin ball, and dry the resin at 120°C until the moisture content ≤ 3%;

[0009] S2. Carbonize and activate the resin dried in step S1 in a tube furnace;

[0010] S3. Modify the activated product;

[0011] S4. Impregnate the modified resin spherical carbon with metal components to prepare impregnated carbon.

[0012] As a further limitation of the technical solution of the present invention, the crosslinking degree of the macroporous strong acid cation exchange resin beads in step S1 is ≥16.

[0013] As a further limitation of the technical solution of the present invention, in step S2, the carbonization temperature is 550 - 620 °C, the carbonization time is 60 min; the activation temperature is 850 - 900 °C, the activation time is 60 min; the heating rate is 3 °C / min for both.

[0014] As a further limitation of the technical solution of the present invention, in step S3, the modification treatment is as follows: using nitrogen as the carrier gas, under different oxygen-containing gas conditions, the modification temperature is 400 - 500 °C.

[0015] As a further limitation of the technical solution of the present invention, in step S4, one or more metal salts are impregnated by the equal-volume impregnation method, and the impregnation of multiple components adopts the step-by-step impregnation method.

[0016] As a further limitation of the technical solution of the present invention, the metal salt in step S4 is Cu 2+ salt, Zn 2+ salt, Fe 3+ salt, etc.

[0017] As a further limitation of the technical solution of the present invention, in step S4, the temperature of the impregnation solution is 60 - 80 °C, the aging time of the spherical impregnated carbon is 2 - 4 h, the drying temperature is 140 °C, and the water content of the obtained spherical impregnated carbon is ≤5%.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] 1. The metal salt precursor with an impregnation ratio ≥35% can be fully impregnated and adsorbed into the prepared resin spherical activated carbon. After drying, the impregnated spherical carbon will maintain the original morphology of the spherical base carbon, and there will be no precipitation of the impregnated components.

[0020] 2. Improve the dispersion degree of multi-component active metals in the resin spherical activated carbon, change the catalytic activity of the impregnated spherical carbon, and thus improve the protection time against hydrogen sulfide.

[0021] 3. The process treatment method for the precipitation of the impregnated components provided by the present invention is simple and easy to operate, and can be used for industrial production.

[0022] 4. The loading amount of the active metal components of the spherical impregnated carbon prepared by the present invention can reach more than 40%, and the appearance of the impregnated spherical carbon maintains the shape of the original spherical carbon without any other impurities. The protection time against hydrogen sulfide of the impregnated spherical carbon with the precipitation of the specific active components is increased by more than 100%. Description of the Drawings

[0023] Figure 1This is the effect diagram of the precipitation and non - precipitation of the surface components of the spherical impregnated carbon of the present invention. In the left figure, the surface components are precipitated, and in the right figure, the surface components are not precipitated. Detailed implementation mode

[0024] The present invention will be further described below in conjunction with specific embodiments.

[0025] Example 1

[0026] A process treatment method for the precipitation of impregnated components of resin - based spherical activated carbon includes the following steps:

[0027] (1) Dry the resin ball raw materials with a particle size of 1.0 - 2.0 mm until the moisture content is less than 3%.

[0028] (2) Feed the raw materials into a tubular furnace, with a carbonization temperature of 600 °C and a carbonization time of 60 min. Heat up for activation, with an activation temperature of 880 °C and an activation time of 60 min.

[0029] (3) Immerse the activated material in a single - metal active component, with an immersion temperature of 80 °C, an immersion time of 2 h, a drying temperature of 120 °C, and a drying time of 2 h.

[0030] Example 2

[0031] A process treatment method for the precipitation of impregnated components of resin - based spherical activated carbon includes the following steps:

[0032] (1) Dry the resin ball raw materials with a particle size of 1.0 - 2.0 mm until the moisture content is less than 3%.

[0033] (2) Feed the raw materials into a tubular furnace, with a carbonization temperature of 600 °C and a carbonization time of 60 min. Heat up for activation, with an activation temperature of 880 °C and an activation time of 60 min.

[0034] (3) Modify the activated material in air, with a modification temperature of 400 °C and a modification time of 4 h.

[0035] (4) Immerse the activated material in a single - metal active component, with an immersion temperature of 80 °C, an immersion time of 2 h, a drying temperature of 120 °C, and a drying time of 2 h.

[0036] Example 3

[0037] A process treatment method for the precipitation of impregnated components of resin - based spherical activated carbon includes the following steps:

[0038] (1) Dry the resin ball raw materials with a particle size of 1.0 - 2.0 mm until the moisture content is less than 3%.

[0039] (2) Feed the raw materials into a tubular furnace, carbonize at 600 °C for 60 min. Raise the temperature for activation, with the activation temperature being 880 °C and the activation time being 60 min.

[0040] (3) Carry out air modification on the activated material at a modification temperature of 400 °C for 4 h.

[0041] (4) Immerse the activated material with bimetallic active components by co - impregnation method. The impregnation temperature is 80 °C, the impregnation time is 2 h, the drying temperature is 120 °C, and the drying time is 2 h.

[0042] Example 4

[0043] A process treatment method for the precipitation of the impregnation components of resin - based spherical activated carbon includes the following steps:

[0044] (1) Dry the resin ball raw materials with a particle size of 1.0 - 2.0 mm until the moisture content is less than 3%.

[0045] (2) Feed the raw materials into a tubular furnace, carbonize at 600 °C for 60 min. Raise the temperature for activation, with the activation temperature being 880 °C and the activation time being 60 min.

[0046] (3) Carry out air modification on the activated material at a modification temperature of 400 °C for 4 h.

[0047] (4) Immerse the activated material with bimetallic active components by distributed impregnation method. After the first metal impregnation and drying, then impregnate the second component. The impregnation temperature is 80 °C, the impregnation time is 2 h, the drying temperature is 120 °C, and the drying time is 2 h.

[0048] Conduct a protection performance test on the impregnated spherical carbon prepared in Examples 1 - 4

[0049] The test gas flow temperature is 20 °C, the test gas flow humidity is 50%, the test gas flow rate is 1.5 L / min, and the H 2 S test concentration is (4.6 ± 0.46) mg / L. Place the sample in an electro - thermal drying oven at 110 °C, take it out after drying for 3 h and put it in a desiccator to cool for standby. Pack the treated sample into a measuring tube according to the provisions of 9.7 in GB / T7702.10 - 2008, and the packing height is 5.0 cm. Conduct a measurement of the H 2 S concentration before the test, and connect the measuring tube to the prepared H 2 S protection performance measurement test device. The test time is the protection time of the impregnated activated carbon against H 2 S.

[0050] H 2 The H

[0051]

[0052] ρ 0 — The numerical value of the hydrogen sulfide test concentration, unit: milligram per liter (mg / L);

[0053] c 1 — The numerical value of the concentration of the iodine standard solution, unit: mole per liter (mol / L);

[0054] V 1 — The numerical value of the volume of the iodine standard solution, unit: milliliter (mL);

[0055] c 2 — The numerical value of the concentration of the sodium thiosulfate standard solution, unit: mole per liter (mol / L);

[0056] V 2 — The numerical value of the volume of the sodium thiosulfate standard solution, unit: milliliter (mL);

[0057] 17— The numerical value of the molar mass with 1 / 2H 2 S as the basic unit, unit: gram per mole (g / mol);

[0058] V — The numerical value of the air volume passing through the Mariotte bottle, unit: (L).

[0059] The results are shown in Table 1 below.

[0060] Table 1 Protection performance

[0061]

[0062] The process method for precipitation of the impregnation group provided by the present invention is simple and easy to operate, and can be used for industrial production. The loading amount of the active metal component of the spherical impregnated carbon prepared by the present invention can reach more than 40%, and the appearance of the impregnated spherical carbon maintains the form of the original spherical carbon without any other impurities. The protection time of hydrogen sulfide of the impregnated spherical carbon with precipitated specific active components is increased by more than 100%.

Claims

1. A process for treating resin-based spherical activated carbon impregnation group analysis, characterized in that: The following steps are involved: S1. Select styrene skeleton macroporous strong acid cation exchange resin balls and dry the resin at 120°C until the moisture content is ≤3%; S2, carbonizing and activating the resin dried in step S1 in a tube furnace; S3, modifying the activated product; S4. Impregnating the modified resin spherical carbon with metal components to prepare impregnated carbon.

2. A process for treating the resin-based spherical activated carbon impregnation group according to claim 1, characterized in that: The styrene crosslinking degree of the macroporous strong acid cation exchange resin beads in step S1 is ≥16.

3. A process for treating the resin-based spherical activated carbon impregnation group according to claim 1, characterized in that: In step S2, the carbonization temperature is 550-620° C., and the carbonization time is 60 min; the activation temperature is 850-900° C., and the activation time is 60 min; and the heating rate is 3° C. / min.

4. A process for treating the resin-based spherical activated carbon impregnation group analysis according to claim 1, characterized in that: The modification treatment in step S3 is: using nitrogen as carrier gas, under different oxygen-containing gas conditions, and the modification temperature is 400-500°C.

5. The process for treating the resin-based spherical activated carbon impregnation group according to claim 1 is characterized in that: In step S4, one or more metal salts are impregnated by an equal volume impregnation method, and the impregnation of multiple components is carried out by a step-by-step impregnation method.

6. A process for treating the resin-based spherical activated carbon impregnation group analysis according to claim 5, characterized in that: In step S4, the metal salt is Cu 2+ Salt, Zn 2+ Salt, Fe 3+ Salt.

7. A process for treating the resin-based spherical activated carbon impregnation group analysis according to claim 5, characterized in that: In step S4, the temperature of the impregnation solution is 60-80° C., the aging time of the spherical impregnated carbon is 2-4 hours, the drying temperature is 140° C., and the moisture content of the spherical impregnated carbon is ≤5%.

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