阅读说明：本技术 一种脱砷剂及制备方法 (Dearsenic agent and preparation method thereof ) 是由 周张锋 陶凌云 薛铮 石旭 高杰杭 艾关林 孙睿雷 张洁 于 2019-10-24 设计创作，主要内容包括：本发明涉及一种脱砷剂及制备方法,所述脱砷剂包括：活性组分、分散助剂组分及负载体；其中,所述活性组分占所述脱砷剂的质量百分比为20％～80％,所述负载体组分占所述脱砷剂的质量百分比为15％～70％,所述分散助剂占所述脱砷剂的质量百分比为1％～10％。与现有技术相比,本发明的有益效果在于：用大孔拟薄水铝石作为载体具有大的孔道和比表面积,有利于反应物在脱砷剂中的扩散,提高出口精度；采用分步沉淀方法增加各组分之间的协同作用,采用分散助剂进一步提高活性组分的分散性。(The invention relates to a dearsenic agent and a preparation method thereof, wherein the dearsenic agent comprises the following components: an active component, a dispersing aid component and a loading body; the active component accounts for 20-80% of the dearsenic agent by mass, the loading component accounts for 15-70% of the dearsenic agent by mass, and the dispersing auxiliary agent accounts for 1-10% of the dearsenic agent by mass. Compared with the prior art, the invention has the beneficial effects that: the macroporous pseudo-boehmite is used as a carrier, has large pore channels and large specific surface area, is favorable for the diffusion of reactants in the dearsenifying agent, and improves the outlet precision; the synergistic effect among the components is increased by adopting a fractional precipitation method, and the dispersibility of the active components is further improved by adopting a dispersing auxiliary agent.)

1. A dearsenicating agent, comprising: an active component, a dispersing aid component and a loading body;

the active components comprise zinc oxide and copper oxide, and the dispersing auxiliary agent is manganese oxide;

the active component accounts for 20-80% of the dearsenic agent by mass, the loading component accounts for 15-70% of the dearsenic agent by mass, and the dispersing auxiliary agent accounts for 1-10% of the dearsenic agent by mass.

2. The dearsenicating agent as claimed in claim 1, wherein the carrier is macroporous pseudoboehmite.

3. The dearsenic agent as claimed in claim 1, wherein said dearsenic agent is prepared by the steps of:

step S1, adding the load, a precipitator and a solvent into a reaction container, and uniformly mixing to obtain a first suspension, wherein the precipitator is soluble carbonate or bicarbonate;

step S2: adding soluble zinc salt into the reaction standby liquid for reaction, and precipitating the zinc salt on the load to obtain a second suspension;

step S3: adding soluble copper salt and soluble manganese salt into the first suspension for reaction to generate precipitate, and washing, filtering and drying the precipitate in sequence to obtain a dearsenic agent precursor;

step S4: and roasting the dearsenic agent precursor, crushing, and tabletting to obtain the dearsenic agent.

4. The dearsenic agent as claimed in claim 1, wherein the dearsenic agent comprises the following components in percentage by mass:

zinc oxide: 5% -25%, copper oxide: 10% -65%, manganese oxide: 1% -10% and a carrier: 15 to 70 percent.

5. The method of any one of claims 1 to 4, wherein the dearsenic agent is prepared by the steps of:

step S1, adding the load, a precipitator and water into a reaction container, and uniformly stirring to obtain a first suspension, wherein the precipitator is soluble carbonate or bicarbonate;

step S2: adding soluble zinc salt into the first suspension liquid in the step S1, and precipitating the zinc salt on the load to obtain a second suspension liquid;

step S3: adding soluble copper salt and soluble manganese salt into the second suspension for reaction to generate precipitate, and filtering, washing and drying the precipitate in sequence to obtain a dearsenic agent precursor;

step S4: and roasting the dearsenic agent precursor, crushing, and tabletting to obtain the dearsenic agent.

6. The method for preparing the dearsenifying agent according to claim 5, wherein in the step S1, the load and water are added into a reaction kettle, stirred and pulped, heated to 50-70 ℃, and after the temperature is constant, the precipitant is added into the kettle, stirred for 20-40 min and uniformly mixed to obtain the first suspension.

7. The method for preparing the dearsenicating agent as claimed in claim 5, wherein the step S2 is to drop the soluble zinc salt solution into the reaction kettle for 10min to 30min and stir at a constant temperature of 55 ℃ to 70 ℃ for 10min to 30min to obtain the second suspension.

8. The method of claim 5, wherein in step S3, the soluble copper salt solution and the soluble manganese salt solution are added dropwise to the second suspension within 30-60 min, and K is used₂CO₃And/or Na₂CO₃Adjusting the pH value of the solution to 8-9, continuously stirring at 55-70 ℃, aging for 3-5 h, filtering, washing, and drying at 120-130 ℃ for 2-3 h to ensure that the water content in the precipitate is less than 5% to obtain the dearsenic agent precursor.

9. The method for preparing the dearsenifying agent according to claim 5, wherein in the step S4, the dearsenifying agent precursor is roasted for 1 to 3 hours at 450 to 750 ℃, the solid obtained by roasting is crushed, graphite is added into the obtained powder and is uniformly mixed, and a tablet machine is used for tabletting and molding the powder mixed with the graphite to obtain the dearsenifying catalyst.

Technical Field

The invention belongs to the field of preparation of dearsenic agents, and particularly relates to a dearsenic agent and a preparation method thereof.

Background

The pyrolysis gas fraction and the C3 fraction of the arsenic-containing naphtha after steam pyrolysis contain impurities such as arsenide, and the like, and in the subsequent reaction of removing acetylene, propyne, propadiene and the like by selective hydrogenation, the activity of a hydrogenation catalyst is seriously affected by arsenic, so that catalysts such as palladium, nickel, copper, platinum and the like are poisoned and inactivated. Therefore, in order to protect the noble metal hydrogenation catalyst, a dearsenization reactor is arranged in front of the hydrogenation reactor, and the dearsenization agent is used for removing the arsenide in the gaseous or liquid material.

Currently, the common dearsenization agents in the prior art include copper-based dearsenization agents and lead-based dearsenization agents. However, the conventional copper-based dearsenifying agent has small arsenic content and poor dearsenifying precision, for example, the arsenic content of the copper-based dearsenifying agent is only 1.3% as provided in patent CN201510940759.2, and the arsenic content at the dearsenifying agent outlet in patent CN106833723A is about 10ppm, which causes frequent replacement of the dearsenifying agent or increase of the loading of the dearsenifying agent to avoid frequent replacement.

Disclosure of Invention

In order to solve the technical defects of small arsenic capacity and poor arsenic removal precision of the arsenic removal agent in the prior art, the invention provides the arsenic removal agent and a preparation method thereof.

The specific technical scheme is as follows:

a dearsenicating agent, the difference being that the dearsenicating agent comprises: active components, dispersing aids and loading bodies;

the active components comprise zinc oxide and copper oxide, and the dispersing auxiliary agent is manganese oxide;

the active component accounts for 20-80% of the dearsenic agent by mass, the loading component accounts for 15-70% of the dearsenic agent by mass, and the dispersing auxiliary agent accounts for 1-10% of the dearsenic agent by mass.

Further, the load body is macroporous pseudo-boehmite.

Further, the dearsenic agent is prepared by the following steps:

step S1, adding the load, a precipitator and a solvent into a reaction container, and uniformly mixing to obtain a first suspension, wherein the precipitator is soluble carbonate or bicarbonate;

step S2: adding soluble zinc salt into the first suspension liquid in the step S1, and precipitating the zinc salt on the load to obtain a second suspension liquid;

step S3: adding soluble copper salt and soluble manganese salt into the second suspension for reaction to generate precipitate, and filtering, washing and drying the precipitate in sequence to obtain a dearsenic agent precursor;

step S4: and roasting the dearsenic agent precursor, crushing, and tabletting to obtain the dearsenic agent.

Further, the dearsenic agent comprises the following components in percentage by mass:

zinc oxide: 5% -25%, copper oxide: 10% -65%, manganese oxide: 1% -10% and a carrier: 15 to 70 percent.

The preparation method of the dearsenic agent is characterized in that the dearsenic agent is prepared by the following steps:

step S1, adding the load, a precipitator and a solvent into a reaction container, and uniformly mixing to obtain a first suspension, wherein the precipitator is soluble carbonate or bicarbonate;

step S2: adding soluble zinc salt into the first suspension liquid obtained in the step S1 for reaction, and precipitating the zinc salt on the load to obtain a second suspension liquid;

step S3: adding soluble copper salt and soluble manganese salt into the second suspension for reaction to generate precipitate, and filtering, washing and drying the precipitate in sequence to obtain a dearsenic agent precursor;

step S4: and roasting the dearsenic agent precursor, crushing, and tabletting to obtain the dearsenic agent.

Further, in the step S1, adding the load and water into a reaction kettle, stirring and pulping, heating to 50-70 ℃, keeping the temperature constant, adding the precipitant aqueous solution into the kettle, stirring for 20-40 min, and uniformly mixing to obtain a first suspension, wherein the load is macroporous pseudo-boehmite.

Further, dropwise adding the soluble zinc salt solution into the reaction kettle for 10-30 min, and stirring at the constant temperature of 55-70 ℃ for 10-30 min to obtain the second suspension.

Further, dripping a soluble copper salt solution and a soluble manganese salt solution into the second suspension, and after dripping is finished within 30-60 min, using K₂CO₃And/or Na₂CO₃Adjusting the pH value of the solution to 8-9, continuously stirring at 55-70 ℃, aging for 3-5 h, filtering, washing, drying at 120-130 ℃ for 2-3 h to ensure that the water content in the precipitate is less than 5 percent, and obtaining the dearsenic agent precursor.

Further, the dearsenization agent precursor is placed into a roasting furnace to be roasted for 1.5 to 3 hours at the temperature of 450 to 750 ℃, the obtained solid is crushed, graphite is added into the obtained powder and is uniformly mixed, and a tablet machine is used for tabletting and forming, so that the dearsenization catalyst is obtained.

Compared with the prior art, the invention has the beneficial effects that: the macroporous pseudo-boehmite is used as a carrier, has large pore channels and large specific surface area, is favorable for the diffusion of reactants in the dearsenifying agent, and improves the outlet precision; the synergistic effect among the components is increased by adopting a fractional precipitation method, and the dispersibility of the active components is further improved by adopting a dispersing auxiliary agent.

Drawings

FIG. 1 is a process diagram of the present invention.

Detailed Description

The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.