阅读说明：本技术 一种回收脱氯剂及其制备方法与应用 (Recovered dechlorinating agent and preparation method and application thereof ) 是由 王继元 王彩杰 堵文斌 孟海 王亚明 杨爱武 朱庆奋 柏基业 刘建新 于 2018-09-07 设计创作，主要内容包括：本发明公开了一种回收脱氯剂,由含氯重整生成油液相脱氯产生的废脱氯剂制成。将含氯重整生成油液相脱氯产生的废脱氯剂进行超声处理剥离掉其表层后干燥,既得回收脱氯剂。将所述回收脱氯剂用于含氯重整生成油的液相脱氯,仍具有较高的反应活性,其脱氯效果与新鲜脱氯剂相当。本发明实现了废脱氯剂的回收利用,减少了废脱氯剂处置不当造成的环境污染,且降低了现有脱氯剂的使用成本。(The invention discloses a recovered dechlorinating agent, which is prepared from a waste dechlorinating agent generated by dechlorinating a chlorine-containing reforming oil liquid phase. Carrying out ultrasonic treatment on a waste dechlorinating agent generated by dechlorinating the chlorine reforming oil liquid phase to strip the surface layer of the waste dechlorinating agent, and drying to obtain a recovered dechlorinating agent. The recovered dechlorinating agent is used for liquid phase dechlorination of the chlorine-containing reformate, still has higher reaction activity, and has dechlorination effect equivalent to that of a fresh dechlorinating agent. The invention realizes the recycling of the waste dechlorinating agent, reduces the environmental pollution caused by improper disposal of the waste dechlorinating agent and reduces the use cost of the prior dechlorinating agent.)

1. The recovered dechlorinating agent is characterized by being prepared from a waste dechlorinating agent generated by dechlorinating a chlorine reforming oil liquid phase.

2. The recycling dechlorination agent according to claim 1, wherein the waste dechlorination agent generated by dechlorinating the chlorine reforming oil liquid phase is subjected to ultrasonic treatment to strip the surface layer of the waste dechlorination agent and then dried to obtain the recycling dechlorination agent.

3. The recovery dechlorination agent of claim 1, wherein the sonication is performed in water or an alcoholic solvent.

4. The recovery dechlorinating agent according to claim 2, wherein the alcohol solvent is one or more than two of alcohol solvents containing 1 to 5 carbon atoms.

5. The recovery dechlorination agent according to claim 1, wherein the ultrasonic frequency of the ultrasonic treatment is 20 KHZ-30 MHZ, and the ultrasonic treatment time is 0.1-10 h.

6. The recovery dechlorination agent according to claim 1, wherein the particle diameter of the waste dechlorination agent is 3 to 5mm, and the waste dechlorination agent is composed of an egg shell layer and a bulk phase layer, wherein the thickness of the egg shell layer is 50 to 100 μm.

7. The recovery dechlorination agent according to claim 6, wherein the mass concentration of chlorine in the egg shell layer is 10-25% and the mass concentration of chlorine in the bulk phase layer is 1-5%.

8. The use of the recovered dechlorinating agent according to any one of claims 1 to 7, wherein the recovered dechlorinating agent is used for liquid phase dechlorination of the chlorine-containing reformate.

9. The use of the recovered dechlorination agent according to claim 8, wherein: the chlorine content of the chlorine-containing reformate is 10-100 ppm.

10. The method of claim 8 wherein the dechlorination agent is applied by: the process conditions of the dechlorination reaction are as follows: the reaction temperature is 20-120 ℃; the liquid hourly space velocity is 0.5-10 h^-1(ii) a The reaction pressure is 0.1-1 MPa.

Technical Field

The invention relates to the technical field of petrochemical industry, in particular to a recovered dechlorinating agent prepared from a waste dechlorinating agent generated by dechlorinating a reformed oil liquid phase and application thereof.

Background

Catalytic reforming is a process of rearranging the molecular structure of hydrocarbons in gasoline fraction into a new molecular structure under the action of a catalyst, and is one of petroleum refining processes. In order to ensure the catalytic performance of the catalytic reforming catalyst, the reformed raw oil needs to be subjected to hydrogenation pre-refining, but as various chloralkane auxiliaries are added in the process of extracting the raw oil, organic chloride can be converted into HCl in the process of hydrogenation pre-refining of the raw oil, so that the HCl becomes a main source of HCl in the reforming process. In addition to this, the catalyst is gradually reduced in activity during use, and thus in order to maintain the activity of the catalyst, it is necessary to continuously supplement chlorine, thereby allowing the gas produced by the reforming process to contain a certain amount of HCl. In order to eliminate the influence of hydrogen chloride, the method for removing hydrogen chloride in the generated oil by using a dechlorinating agent is a common method at present.

In recent years, a solid dechlorinating agent is generally adopted in industrial devices to remove hydrogen chloride in reformed oil, and the dechlorinating mechanism is that active components in the dechlorinating agent and HCL are sent to carry out acid-base neutralization reaction to generate stable metal chloride to be fixed, so that the aim of removing HCL is fulfilled. The active component is usually selected from alkali metal or alkaline earth metal oxide capable of reacting with HCL, and then the active component and the binder are prepared into the dechlorinating agent by a kneading method, or the active component is loaded on the carrier by an impregnation method. A high-precision liquid-phase dechlorinating agent for liquid-phase dechlorination of reformate as disclosed in chinese patent CN 105542836A; chinese patent CN104437342A discloses a high-chlorine capacity liquid phase dechlorinating agent and a preparation method and application thereof; chinese patent CN 105478000 a discloses a dechlorinating agent for purifying reformed regeneration gas and a preparation method thereof.

In the existing petrochemical enterprises, dechlorination agents used in the dechlorination reaction are generally used as industrial garbage for landfill treatment after being used once, and a small amount of dechlorination agents are ground and used as road building fillers for waste utilization. However, chlorine is known to be a poison for catalysts and adsorbents which are common in industry, and is also a great pollution to the environment. It can be seen that the above two methods are not ideal treatment methods. The oil liquid phase generated by reforming is dechlorinated by a fixed bed process generally, and the particles of the dechlorinating agent are large (3-5 mm). Research shows that dechlorination reaction of the dechlorinating agent mainly occurs on the surface layer (egg shell layer) of the dechlorinating agent in the dechlorinating process, and the body phase layer inside the surface layer has less chance of reacting, so that the active center of the dechlorinating agent is seriously wasted. The inventors have also conducted long-term research work on this, and have conducted a number of characterization tests on dechlorinating agents and waste dechlorinating agents for chlorine-containing reformate, see fig. 1, fig. 2, fig. 3, fig. 4, and fig. 5. Fig. 1 is a macro-morphology of a fresh dechlorination agent, fig. 2 is a micro-morphology of a fresh dechlorination agent, fig. 3 is a macro-morphology of a spent dechlorination agent, fig. 4 is a micro-morphology of a spent dechlorination agent, and fig. 5 is a chlorine distribution of a profile of a spent dechlorination agent. As can be seen from the figure, the fresh dechlorinating agent is dense on the surface, and only a small amount of macropores and extra-macropores are present. The surface of the waste dechlorinating agent has an egg shell layer, the gaps are rich, and the dechlorinating agent has the characteristics of obvious macropores and extra macropores. And chlorine elements of the waste dechlorinating agent are mainly distributed on an eggshell layer on the surface of the dechlorinating agent in a concentrated mode, and the concentration of the chlorine elements in other body phase layers is low.

It is assumed that when the egg shell layer on the surface of the waste dechlorinating agent is peeled off and the bulk layer is exposed, the active ingredients in the bulk layer can still undergo dechlorination. If the waste dechlorinating agent can be recycled, the pollution problem of the waste dechlorinating agent is solved, and the use cost of the dechlorinating agent is reduced. However, there is no report in the prior art that the waste dechlorinating agent is processed and reused for production.

Disclosure of Invention

In order to solve the problem of recycling of the waste dechlorinating agent in the prior art, the invention provides a method for recycling the waste dechlorinating agent.

The technical scheme adopted by the invention is as follows: a recovered dechlorinating agent is prepared from a waste dechlorinating agent generated by dechlorinating an oil liquid phase generated by reforming chlorine.

Further, carrying out ultrasonic treatment on a waste dechlorinating agent generated by dechlorinating the chlorine reforming oil liquid phase to strip the surface layer of the waste dechlorinating agent, and drying to obtain a recovered dechlorinating agent.

According to the invention, the high-frequency ultrasonic wave is adopted to treat the waste dechlorinating agent generated by dechlorinating the oil phase generated by reforming chlorine-containing gas, and the high-frequency oscillation effect of the high-frequency ultrasonic wave is utilized to strip the egg shell layer of the waste dechlorinating agent so as to expose the phase layer of the waste dechlorinating agent, thereby obtaining the recovered dechlorinating agent. The preparation method is simple and easy to implement and has no environmental pollution.

Further, the ultrasonic treatment is carried out in water or an alcohol solvent, and the water or the alcohol solvent is used as a medium to drive the water or the alcohol solvent to vibrate to strip the surface layer of the waste dechlorinating agent.

In order to improve the dechlorination effect of the recovered dechlorinating agent, the alcohol solvent is preferably one or more than two of alcohol solvents containing 1-5 carbon atoms.

In order to improve the dechlorination effect of the recovered dechlorinating agent, the ultrasonic frequency of the ultrasonic treatment is preferably 20 KHZ-30 MHZ, and the ultrasonic treatment time is preferably 0.1-10 h.

In order to improve the dechlorination effect of the recovered dechlorination agent, the particle diameter of the waste dechlorination agent is preferably 3-5 mm, and the waste dechlorination agent is composed of an egg shell layer and a bulk phase layer, wherein the thickness of the egg shell layer is 50-100 mu m.

In order to further improve the dechlorination effect of the recovered dechlorinating agent, the mass concentration of chlorine in the egg shell layer is more preferably 10-25%, and the mass concentration of chlorine in the bulk phase layer is more preferably 1-5%.

The application method of the recovered dechlorinating agent is used for liquid-phase dechlorination of the chlorine-containing reformate.

In order to improve the dechlorination effect of the recovered dechlorinating agent, the chlorine content of the chlorine-containing reformate is preferably 10 to 100 ppm.

In order to improve the dechlorination effect of the obtained recovered dechlorinating agent,preferably, the process conditions of the dechlorination reaction are as follows: the reaction temperature is 20-120 ℃; the liquid hourly space velocity is 0.5-10 h^-1(ii) a The reaction pressure is 0.1-1 MPa.

Compared with the prior art, the invention has the beneficial effects that:

firstly, the invention adopts high-frequency ultrasonic waves to treat the waste dechlorinating agent generated by dechlorinating the chlorine-containing reforming oil liquid phase to obtain the recycled dechlorinating agent with high reaction activity, thereby realizing recycling of the waste dechlorinating agent and reducing the environmental pollution caused by improper disposal of the waste dechlorinating agent.

Secondly, when the recovered dechlorinating agent obtained by the invention is used for the dechlorinating reaction of the reformed oil, the recovered dechlorinating agent still has higher reaction activity, the dechlorinating effect is equivalent to that of a fresh dechlorinating agent, and the use cost of the dechlorinating agent is greatly reduced.

And thirdly, the ultrasonic treatment method is simple and easy to implement, has no environmental pollution and is easy to realize industrial production.

Drawings

FIG. 1 is a macro-topographic map of fresh dechlorination agent.

FIG. 2 is a microscopic topography of fresh dechlorination agent.

FIG. 3 is a macro-topographic map of the spent dechlorination agent.

FIG. 4 is a microscopic topography of the spent dechlorination agent.

FIG. 5 is a chlorine profile of a spent dechlorination agent.

Fig. 6 is a schematic view showing a state in the ultrasonic peeling process of the waste dechlorinating agent of the present invention.

Detailed Description

The technical features of the present invention will be further described below with reference to the accompanying drawings and examples, but the scope of the present invention is not limited to the examples.

The fresh dechlorinating agent used in the following comparative examples was derived from NC-L dechlorinating agent from south kyo huahuahua chemical limited.

The following examples are examples in which the waste dechlorinating agent is derived from petrochemical Yangzi oil chemical Co., Ltd, China.

The chemicals used in the following examples are all commercially available.

The method for measuring the chlorine content of the reformate refers to the GB/T18612-2011 standard.

Determination of the chlorine content of antichlors is described in reference to the SH/T0343-1992 Standard