Regeneration method of ruthenium-based benzene refined desulfurization adsorbent

Abstract

The invention discloses a regeneration method of a ruthenium-based benzene refined desulfurization adsorbent, and belongs to the technical field of regeneration of noble metal adsorbents. According to the method, the inactivated ruthenium-based benzene refined desulfurization adsorbent is sequentially subjected to the steps of cleaning, passivation, roasting and reduction, and the activity of the ruthenium-based benzene refined desulfurization adsorbent which loses activity due to poisoning caused by adsorbing thiophene in benzene can be recovered to 70-75% of that of a new agent at most.

Description

Technical Field

[0001] The invention belongs to the technical field of precious metal adsorbent regeneration, and in particular relates to a regeneration method for a ruthenium-based benzene refined desulfurization adsorbent. Background Art

[0002] Benzene is an important petrochemical raw material and a commonly used organic solvent. It is widely used in the pharmaceutical, petrochemical, fine chemicals, rubber and plastic industries. It is also an intermediate for synthesizing other important chemicals such as benzoic acid, phenol, styrene and phenylacetone, and its quality requirements are becoming increasingly stringent. At present, desulfurization adsorbents are the absolute mainstream method for removing trace organic sulfur (mainly thiophene) in the world's benzene refining process, with a market capacity of billions.

[0003] Chinese invention patents CN102806062B, Chinese invention patent applications CN103041766A and CN103480325A have successively reported patents for palladium-based adsorbents for benzene refining desulfurization. Compared with metallic palladium, the market price of metallic ruthenium is about one-tenth of that of metallic palladium, but its activity is comparable and its cost advantage is huge. Therefore, researchers have explored ruthenium-based adsorbents, such as: Chinese invention patent applications CN104941570A, CN104307464A, CN104841357A and Chinese invention patents CN107008223B have successively reported patents for ruthenium-based adsorbents for benzene refining desulfurization. The present invention has found that palladium and platinum-based adsorbents have better anti-interference properties, but the deactivation of adsorbents such as palladium and platinum is permanent deactivation. Although ruthenium-based adsorbents have poor anti-interference properties, which affects their promotion and use, the inventors have found that ruthenium-based catalysts can be regenerated. Therefore, the present invention has innovatively invented a regeneration method for ruthenium-based adsorbents, which extends the service life of ruthenium-based adsorbents to more than five years, greatly improving their economy and practicality. Summary of the invention

[0004] In view of the above technical problems to be solved, the present invention provides a method for regenerating a ruthenium-based benzene refining desulfurization adsorbent.

[0005] To achieve the above object, the technical solution adopted by the present invention is:

[0006] A regeneration method for a ruthenium-based benzene refined desulfurization adsorbent is only applicable to the active regeneration of the ruthenium-based benzene refined desulfurization adsorbent; the method must include the steps of cleaning, passivation, roasting and reduction.

[0007] A method for regenerating a ruthenium-based benzene refining desulfurization adsorbent comprises the following steps:

[0008] (1) placing the deactivated ruthenium-based benzene refining desulfurization adsorbent in a mixed solvent of ethanol and water for heating and cleaning, and then performing solid-liquid separation;

[0009] (2) passing nitrogen gas through the cleaned adsorbent at room temperature for passivation;

[0010] (3) Then, calcination is performed under nitrogen atmosphere.

[0011] (4) Finally, heating reduction is carried out in a hydrogen environment.

[0012] As a preferred embodiment of the present invention, the ruthenium-based benzene refining desulfurization adsorbent comprises an active component Ru and an alumina carrier loaded with Ru.

[0013] The deactivated ruthenium-based benzene refining desulfurization adsorbent refers to a ruthenium-based adsorbent that has been used for a long time and has adsorbed organic sulfur such as thiophene (mainly chemical adsorption) and is unable to adsorb thiophene (surface active sites are fully occupied).

[0014] Organic sulfur, benzene compounds and trace amounts of other organic impurities are adsorbed on the surface and pores of the deactivated ruthenium-based benzene refining desulfurization adsorbent; the organic sulfur includes thiophenes.

[0015] As a preferred embodiment of the present invention, the volume ratio of ethanol to water is (1.5-2.4): 1. The present invention finds that the use of pure water, ethanol or other organic solvents cannot clean the adsorbed benzene compounds and other organic impurities on the completely deactivated ruthenium-based benzene refining desulfurization adsorbent, resulting in the regeneration effect of the ruthenium-based benzene refining desulfurization adsorbent not meeting expectations, and cleaning the surface of the deactivated adsorbent can also prevent safety accidents or side reactions from occurring in the subsequent reduction step.

[0016] As a preferred embodiment of the present invention, the temperature of the heating cleaning is 60-70°C.

[0017] As a preferred embodiment of the present invention, in the step (2), the flow rate of nitrogen is 0.1-10 L / min.

[0018] As a preferred embodiment of the present invention, in the step (3), the flow rate of nitrogen is 0.05-2L / min; the calcination temperature is 80-100° C. The present invention calcines under inert gas to completely remove alcohol and water in the adsorbent, and the temperature cannot be higher than 100° C., otherwise it will cause the ruthenium grains in the ruthenium-based benzene refined desulfurization adsorbent to grow, affecting the regeneration effect.

[0019] As a preferred embodiment of the present invention, the flow rate of the hydrogen is 0.1-5 L / min, and the temperature of the heating reduction is 120-140° C. The present invention finds that 120-140° C. is a suitable reduction temperature, and maintaining this temperature range can achieve effective regeneration of the ruthenium-based benzene refining desulfurization adsorbent, and the activity after regeneration is restored to more than 70% of the new agent.

[0020] Ruthenium-based precious metal adsorbent is a new thing, and there is no prior art for its regeneration. The beneficial effects of the present invention are: the present invention sequentially restores the activity of the deactivated ruthenium-based benzene refining desulfurization adsorbent to 70-75% of the new agent through the steps of cleaning, passivation, calcination and reduction, and the regeneration method of the ruthenium-based benzene refining desulfurization adsorbent can achieve multiple regeneration of the ruthenium-based adsorbent. DETAILED DESCRIPTION

[0021] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0022] The ruthenium-based benzene refining desulfurization adsorbent, palladium-based benzene refining desulfurization adsorbent, and platinum-based benzene refining desulfurization adsorbent used in Example 1 and Comparative Examples 1-6 of the present invention are all commercially available products.

[0023] The deactivated ruthenium-based benzene refining desulfurization adsorbent used in Example 1 and Comparative Examples 1-4 of the present invention is a ruthenium-based benzene refining desulfurization adsorbent deactivated by removing thiophene from benzene.

[0024] The deactivated palladium-based benzene refining desulfurization adsorbent used in Comparative Example 5 is a palladium-based benzene refining desulfurization adsorbent that has been deactivated by removing thiophene from benzene.

[0025] The new palladium-based benzene refining desulfurization adsorbent comprises an active component of palladium and an alumina carrier loaded with palladium.

[0026] The deactivated platinum-based benzene refining desulfurization adsorbent used in Comparative Example 6 is a platinum-based benzene refining desulfurization adsorbent that has been deactivated by removing thiophene from benzene.

[0027] The new platinum-based benzene refining desulfurization adsorption agent comprises an active component of platinum and an alumina carrier loaded with platinum.

[0028] Example 1

[0029] A method for regenerating a ruthenium-based benzene refining desulfurization adsorbent comprises the following steps:

[0030] (1) Place 500 g of deactivated ruthenium-based benzene refining desulfurization adsorbent in a 2000 ml beaker, mix 600 ml of ethanol and 400 ml of water, add to the beaker to cover the adsorbent, cover the beaker with a watch glass, move to a low-temperature electric furnace, heat to 60°C, pay attention to prevent boiling, keep for 30 minutes, then filter, and repeat 5 times.

[0031] (2) After the cleaned adsorbent is added to the reaction tube, high-purity nitrogen is introduced, and the outlet gas flow rate is maintained at 0.1 L / min for 0.5 h.

[0032] (3) While maintaining a nitrogen inert atmosphere (outlet gas flow rate 0.05 L / min), heat to 95°C and maintain for 4 h.

[0033] (4) The calcined adsorbent was introduced with industrial hydrogen (export gas flow rate 0.1 L / min), heated to 140° C. for reduction, and the reduction was performed for 4 h to obtain regenerated agent 1.

[0034] Example 2

[0035] A method for regenerating a ruthenium-based benzene refining desulfurization adsorbent comprises the following steps:

[0036] (1) Place 10 tons of deactivated ruthenium-based benzene refined desulfurization adsorbent into the adsorption device, take about 10 cubic meters of ethanol and water (the volume ratio of ethanol to water is 6:4), add it to the adsorption device to cover the adsorbent, heat to 70°C, pay attention to prevent boiling, keep it for 30 minutes, then filter, and repeat 5 times.

[0037] (2) After the cleaned adsorbent is placed in an adsorption device, it is sealed and high-purity nitrogen is introduced, maintaining an outlet gas flow rate of 10 L / min for 2 h.

[0038] (3) While maintaining a nitrogen inert atmosphere (outlet gas flow rate 2 L / min), heat to 95°C and maintain for 2 h.

[0039] (4) The calcined adsorbent was introduced with industrial hydrogen (export gas flow rate 5 L / min), heated to 120° C. for reduction, and the reduction was performed for 5 h to obtain regenerated agent 2.

[0040] Comparative Example 1

[0041] A method for regenerating a ruthenium-based benzene refining desulfurization adsorbent comprises the following steps:

[0042] (1) Place 500 g of deactivated ruthenium-based benzene refining desulfurization adsorbent into a 2000 ml beaker, add 1000 ml of water to the beaker to cover the adsorbent, keep for 30 minutes, then filter, and repeat 5 times.

[0043] (2) After the cleaned adsorbent is added to the reaction tube, high-purity nitrogen is introduced, and the outlet gas flow rate is maintained at 0.1 L / min for 0.5 h.

[0044] (3) While maintaining a nitrogen inert atmosphere (outlet gas flow rate 0.05 L / min), heat to 95°C and maintain for 4 h.

[0045] (4) The calcined adsorbent was introduced with industrial hydrogen (export gas flow rate 0.1 / min), heated to 140° C. for reduction, and the reduction was performed for 4 hours to obtain contrast agent 1.

[0046] Comparative Example 2

[0047] A method for regenerating a ruthenium-based benzene refining desulfurization adsorbent comprises the following steps:

[0048] (1) Place 500 g of deactivated ruthenium-based benzene refining desulfurization adsorbent into a 2000 ml beaker, add 1000 ml of ethanol to the beaker until it covers the adsorbent, keep it for 30 minutes, then filter, and repeat 5 times.

[0049] (2) After the cleaned adsorbent is added to the reaction tube, high-purity nitrogen is introduced, and the outlet gas flow rate is maintained at 0.1 L / min for 0.5 h.

[0050] (3) While maintaining a nitrogen inert atmosphere (outlet gas flow rate 0.05 L / min), heat to 95°C and maintain for 4 h.

[0051] (4) The calcined adsorbent was introduced with industrial hydrogen (export gas flow rate 0.1 / min), heated to 140° C. for reduction, and the reduction was performed for 4 hours to obtain contrast agent 2.

[0052] Comparative Example 3

[0053] A method for regenerating a ruthenium-based benzene refining desulfurization adsorbent comprises the following steps:

[0054] (1) Place 500 g of deactivated ruthenium-based benzene refining desulfurization adsorbent in a 2000 ml beaker, mix 600 ml of ethanol and 400 ml of water, add to the beaker to cover the adsorbent, cover the beaker with a watch glass, move to a low-temperature electric furnace, heat to 60°C, pay attention to prevent boiling, keep for 30 minutes, then filter, and repeat 5 times.

[0055] (2) The cleaned adsorbent was introduced with industrial hydrogen (export gas flow rate 0.1 / min), heated to 140° C. for reduction, and the reduction was performed for 4 hours to obtain contrast agent 3.

[0056] Comparative Example 4

[0057] A method for regenerating a ruthenium-based benzene refining desulfurization adsorbent comprises the following steps:

[0058] (1) Place 500 g of deactivated ruthenium-based benzene refining desulfurization adsorbent in a 2000 ml beaker, mix 600 ml of ethanol and 400 ml of water, add to the beaker to cover the adsorbent, cover the beaker with a watch glass, move to a low-temperature electric furnace, heat to 60°C, pay attention to prevent boiling, keep for 30 minutes, then filter, and repeat 5 times.

[0059] (2) After the cleaned adsorbent is added to the reaction tube, high-purity nitrogen is introduced, and the outlet gas flow rate is maintained at 0.1 L / min for 0.5 h.

[0060] (3) While maintaining a nitrogen inert atmosphere (outlet gas flow rate 0.05 L / min), heat to 95°C and maintain for 4 h.

[0061] (4) The calcined adsorbent was introduced with industrial hydrogen (outlet gas flow rate 0.1 / min), heated to 180° C. for reduction, and the reduction was performed for 4 h to obtain contrast agent 4.

[0062] Comparative Example 5

[0063] A method for regenerating a palladium-based benzene refining desulfurization adsorbent comprises the following steps:

[0064] (1) Place 500 g of deactivated palladium-based benzene refining desulfurization adsorbent in a 2000 ml beaker, mix 600 ml of ethanol and 400 ml of water, add to the beaker to cover the adsorbent, cover the beaker with a watch glass, move to a low-temperature electric furnace, heat to 60°C, pay attention to prevent boiling, keep for 30 minutes, then filter, and repeat 5 times.

[0065] (2) After the cleaned adsorbent is added to the reaction tube, high-purity nitrogen is introduced, and the outlet gas flow rate is maintained at 0.1 L / min for 0.5 h.

[0066] (3) While maintaining a nitrogen inert atmosphere (outlet gas flow rate 0.05 L / min), heat to 95°C and maintain for 4 h.

[0067] (4) The calcined adsorbent was introduced with industrial hydrogen (export gas flow rate 0.1 / min), heated to 140° C. for reduction, and the reduction was performed for 4 hours to obtain a palladium contrast agent.

[0068] Comparative Example 6

[0069] A method for regenerating a platinum-based benzene refining desulfurization adsorbent comprises the following steps:

[0070] (1) Place 500 g of deactivated platinum-based benzene refined desulfurization adsorbent in a 2000 ml beaker, mix 600 ml of ethanol and 400 ml of water, add to the beaker to cover the adsorbent, cover the beaker with a watch glass, move to a low-temperature electric furnace, heat to 60°C, pay attention to prevent boiling, keep for 30 minutes, then filter, and repeat 5 times.

[0071] (2) After the cleaned adsorbent is added to the reaction tube, high-purity nitrogen is introduced, and the outlet gas flow rate is maintained at 0.1 L / min for 0.5 h.

[0072] (3) While maintaining a nitrogen inert atmosphere (outlet gas flow rate 0.05 L / min), heat to 95°C and maintain for 4 h.

[0073] (4) The calcined adsorbent was introduced with industrial hydrogen (export gas flow rate 0.1 / min), heated to 140° C. for reduction, and the reduction was performed for 4 hours to obtain a platinum contrast agent.

[0074] Effect example

[0075] The adsorption activity of the adsorbent was evaluated using a fixed bed reactor. The evaluation method is as follows:

[0076] The test method for removing thiophene from benzene was carried out in accordance with Appendix B of YS / T 1661-2023. The reaction temperature was 150°C, the pressure was 1.0 Mp, the mass space velocity was 4 ml / min, the adsorbents of Examples 1-2 and Comparative Examples 1-6 were 70 g respectively, the reaction time was 12 h, and the evaluation results are shown in Table 1.

[0077] Table 1

[0078]

[0079] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A method for regenerating a ruthenium-based benzene refining desulfurization adsorbent, characterized in that: Only applicable to the active regeneration of ruthenium-based benzene refining desulfurization adsorbent; must include cleaning, passivation, calcination and reduction steps.

2. The regeneration method of the ruthenium-based benzene refining desulfurization adsorbent as claimed in claim 1, characterized in that: The specific steps include: (1) washing the deactivated ruthenium-based benzene refining desulfurization adsorbent in a mixed solvent of ethanol and water, and then performing solid-liquid separation; (2) passing nitrogen gas through the cleaned adsorbent at room temperature for passivation; (3) The product is then calcined in a nitrogen atmosphere and finally reduced in a hydrogen atmosphere.

3. The regeneration method of the ruthenium-based benzene refining desulfurization adsorbent according to claim 2, characterized in that: The volume ratio of the ethanol to water is (1.5-2.4):

1.

4. The regeneration method of the ruthenium-based benzene refining desulfurization adsorbent according to claim 1 or 2, characterized in that: The cleaning temperature is 60-70°C.

5. The regeneration method of the ruthenium-based benzene refining desulfurization adsorbent according to claim 1 or 2, characterized in that: The calcination temperature is 80-100°C.

6. The regeneration method of the ruthenium-based benzene refining desulfurization adsorbent according to claim 1 or 2, characterized in that: The reduction temperature is 120-140°C.

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