TWI684481B - Co-removing reagent having layers of carbonates including copper and manufacturing method thereof - Google Patents

Abstract

A CO-removing reagent having layers of carbonates including copper and a manufacturing method thereof are provided. The CO-removing reagent is a mixture of layers of carbonates including copper and zeolites. The Manufacturing method includes preparing acid solution with copper precursor and aluminum nitrate, preparing alkaline solution with sodium hydroxide and sodium carbonate, mixing and filtrating the acid solution with the alkaline solution to form a solid, dehydrating the solid and incinerating to form Cu-Al carbonate powders, mixing the Cu-Al carbonate powders with zeolite powders to form the CO-removing reagent.

Description

Copper-containing layered carbonate carbon monoxide adsorbent and manufacturing method

The invention relates to a carbon monoxide adsorbent, a mixture used for adsorbing carbon monoxide, and a method for manufacturing a carbon monoxide adsorbent.

The development of gas separation technology can promote the efficient use of energy. Taking my country’s industrial residual hydrogen as an example, the National Energy Conference has pointed out that about 6 billion cubic meters have not been effectively used, and most of them are emitted by combustion, resulting in huge waste of energy and environmental pollution. The recovery and utilization of CO and H2 in available gas has not been popularized in my country.

Industrial gas CO is widely used, and its attributes are one of the necessary elements. According to purity, such as electronics (semiconductor), chemical industry, clean energy, steel, etc., it is an important basic material in various countries, and its price also affects cost and industrial competitiveness.

Existing CO adsorption technologies such as solution absorption, low temperature distillation and other international technologies are mature, but the cost is relatively high. Recent researches on environmentally friendly, low energy consumption, high adsorption capacity adsorbent separation technology are the current international development trend. Solid CO adsorbents based on van der Waals force, such as zeolite materials, have lower adsorption capacity at room temperature and pressure. Based on the above, the existing CO adsorption technology has room for improvement.

In view of this, the object of the present invention is to provide a carbon monoxide adsorbent, a mixture for adsorbing carbon monoxide, and a method for manufacturing a carbon monoxide adsorbent, which can efficiently adsorb carbon monoxide.

A carbon oxide adsorbent according to the present invention contains copper and aluminum carbonate ([Cu ²⁺ _1-x Al ³⁺ _x (OH) ₂ ] ^x+ (CO ₃ ^2- ) _x/2 ‧mH ₂ O) powder and zeolite (zeolite) powder .

In the embodiments of the present invention, the copper aluminum carbonate powder is a layered double hydroxide (Layered Double Hydroxide, LDH).

In the embodiments of the present invention, the molar ratio of copper to aluminum in the copper-aluminum carbonate powder ranges from 1 to 10.

In the embodiment of the present invention, the weight mixing ratio of the copper-aluminum carbonate powder and the zeolite powder ranges from 1:5 to 5:1.

In the embodiment of the present invention, the weight mixing ratio of the copper aluminum carbonate powder and the zeolite powder is 1:3.

The mixture of the invention is used for adsorbing carbon monoxide, wherein the mixture comprises zeolite powder and copper aluminum carbonate powder.

In the embodiments of the present invention, the copper aluminum carbonate powder is a layered double hydroxide (Layered Double Hydroxide, LDH).

In the embodiments of the present invention, the molar ratio of copper to aluminum in the copper-aluminum carbonate powder ranges from 1 to 10.

In the embodiments of the present invention, the weight mixing ratio of the copper-aluminum carbonate powder and the zeolite powder ranges from 1:5 to 5:1.

In the embodiment of the present invention, the weight mixing ratio of the copper aluminum carbonate powder and the zeolite powder is 1:3.

A method for manufacturing a carbon oxide adsorbent according to the present invention includes: using copper precursors and aluminum nitrate to produce an acid solution; using sodium hydroxide and sodium carbonate to produce an alkaline solution; mixing and stirring the acid solution and alkali Liquid and filter to produce a solid; the solid is dried and calcined to produce a copper aluminum carbonate powder; the copper aluminum carbonate powder is mixed with zeolite powder to form the carbon oxide adsorbent.

In an embodiment of the present invention, the copper precursor includes copper nitrate.

In the embodiments of the present invention, in the step of manufacturing the acid solution, the molar ratio of copper to aluminum in the copper precursor and aluminum nitrate ranges from 1 to 10.

In an embodiment of the present invention, in the step of generating copper aluminum carbonate powder, the calcination temperature is less than 400°C.

In the embodiments of the present invention, the copper aluminum carbonate powder is a layered double hydroxide (Layered Double Hydroxide, LDH).

In the embodiments of the present invention, the weight mixing ratio of the copper-aluminum carbonate powder and the zeolite powder ranges from 1:5 to 5:1.

In the embodiment of the present invention, the weight mixing ratio of the copper aluminum carbonate powder and the zeolite powder is 1:3.

A method for manufacturing a carbon monoxide adsorbent according to the present invention further includes placing the carbon monoxide adsorbent in an inert gas at a pretreatment temperature for pretreatment.

In the embodiment of the present invention, the pretreatment temperature is 370°C.

In an embodiment of the invention, the inert gas is nitrogen.

1000‧‧‧Step

2000‧‧‧step

3000‧‧‧Step

4000‧‧‧Step

5000‧‧‧Step

6000‧‧‧Step

1 is a schematic flow chart of an embodiment of a method for manufacturing a carbon monoxide adsorbent according to the present invention; FIG. 2 is an SEM photograph of copper and aluminum carbonate powder in a carbon monoxide adsorbent according to the present invention; Fig. 3 is an XRD test chart of copper and aluminum carbonate powder in a carbon monoxide adsorbent of the present invention; Fig. 4 is a test result chart of carbon monoxide adsorption amount of an embodiment with different pretreatment temperatures; Fig. 5 is a diagram of different copper and aluminum carbonate powders and zeolite powders The graph of the test result of the carbon monoxide adsorption amount of the weight mixing ratio example.

As shown in the flowchart of the embodiment shown in FIG. 1, a method for manufacturing a carbon oxide adsorbent according to the present invention includes, for example, the following steps.

Step 1000, using copper precursor and aluminum nitrate to make acid solution. More specifically, an acid solution is manufactured using a copper precursor containing copper nitrate and aluminum nitrate. Among them, the molar ratio of copper to aluminum of the copper precursor and aluminum nitrate is preferably 1-10.

In step 2000, sodium hydroxide and sodium carbonate are used to produce lye. More specifically, it is preferable to use 1.6M sodium hydroxide and 0.1M sodium carbonate to produce the lye.

Step 3000: Mix and stir the acid solution and alkali solution and filter to generate solid. More specifically, the acid solution and the alkali solution are preferably in a volume ratio of 1:1. During the mixing process, the stirring speed is appropriately adjusted to make it uniform. The solid produced after the mixing is filtered using 100 mesh filter paper to obtain a solid.

At step 4000, the solid is dried and calcined to produce copper aluminum carbonate ([Cu ²⁺ _1-x Al ³⁺ _x (OH) ₂ ] ^x+ (CO ₃ ^2- ) _x/2 ‧mH ₂ O) powder. More specifically, the drying equipment (brand: CHANNEL, model: DM-30) is set at 105°C, and the drying time is 8~24hr; the calcination equipment (brand: NABERTHERM, model: P330) is set at 200~450°C, forging Time 1~4 hours. According to a preferred embodiment, the calcination temperature is less than 400°C.

As shown in the scanning electron microscope (SEM) (Hitachi brand, model: S-4800 type, operating parameters: 15kV, magnification 100,000 times) of the photon in Figure 2, the generated copper aluminum carbonate powder is layered structure. In addition, as shown in Figure 3 X-ray diffraction analysis (X-ray Diffraction, XRD) (brand: Bruker, model: D8-ADVENCE, operating parameters: 40kV, 40mA, 5 ° ~ 70 °, scanning speed per second 1step) As shown in the test chart, the generated copper-aluminum carbonate powder has peaks at 2 θ equal to 11.5° (mark 003), 23.6° (mark 006), and 35.5° (mark 009). From this, it can be seen that the produced copper aluminum carbonate powder is a layered double hydroxide (Layered Double Hydroxide, LDH).

In step 5000, copper aluminum carbonate powder is mixed with zeolite powder to form a carbon oxide adsorbent. More specifically, the two powders are mixed by simple grinding, and the mixing time should be more than 1 hour to ensure uniform mixing. Among them, the weight mixing ratio of copper aluminum carbonate powder and zeolite powder ranges from 1:5 to 5:1.

According to a preferred embodiment, a method for manufacturing a carbon oxide adsorbent of the present invention further includes step 6000, placing the carbon monoxide adsorbent in an inert gas at a pretreatment temperature for pretreatment. Among them, the inert gas contains nitrogen, but not limited to this. Among them, the processing time is 1 to 10 hours.

Further, at normal temperature and pressure, the carbon monoxide adsorbent formed by mixing the copper-aluminum carbonate powder and the zeolite powder in a weight mixing ratio of 1:1 is placed in nitrogen at different pretreatment temperatures for pretreatment , And then perform the carbon monoxide adsorption test. Among them, the carbon monoxide adsorption test adopts the gravimetric method, that is, the weight percentage difference of the adsorption amount is calculated according to the weight difference of the adsorbent before and after adsorption, and the result is shown in FIG. 4. Among them, the test result of zeolite powder without copper and aluminum carbonate powder at a temperature of 390°C on the leftmost side of FIG. 4. As can be seen from Figure 4, the pre-treatment temperature is 370 At ℃, carbon monoxide adsorbent has a larger adsorption capacity.

In different embodiments, the pretreatment temperature is 370° C., and the weight mixing ratio of the copper aluminum carbonate powder and the zeolite powder is adjusted, and then the carbon monoxide adsorbent formed by the mixing is subjected to a carbon monoxide adsorption test. The results are shown in Table 1.

It can be seen from Table 1 that the weight mixing ratio of the copper-aluminum carbonate powder and the zeolite powder is 1:3, and one of the formed carbon oxide adsorbents has a better carbon monoxide adsorption capacity.

On the other hand, the carbon monoxide adsorbent of the present invention is further compared with the conventional carbon monoxide adsorbent. More specifically, the carbon monoxide adsorbent, CuCl, CuAl, and zeolite of the present invention with a pretreatment temperature of 370°C and a weight mixing ratio of copper aluminum carbonate powder and zeolite powder of 1:3 were subjected to carbon monoxide adsorption test, the test results As shown in Figure 5.

It can be seen from FIG. 5 that one of the carbon oxide adsorbents of the present invention has a better carbon monoxide adsorption effect than CuCl, CuAl, and zeolite. From this, it can be confirmed that the mixture containing zeolite powder and copper aluminum carbonate powder can be used for adsorbing carbon monoxide.

Based on the above, one of the carbon oxide adsorbents of the present invention contains copper aluminum carbonate ([Cu ²⁺ _1-x Al ³⁺ _x (OH) ₂ ] ^x+ (CO ₃ ^2- ) _x/2 ‧mH ₂ O) powder and zeolite ( zeolite) powder. Among them, the copper aluminum carbonate powder is layered double hydroxide (Layered Double Hydroxide, LDH). In other words, in a preferred embodiment, the carbon monoxide adsorbent is a mixture of copper-containing layered carbonate and zeolite. Among them, the molar ratio of copper to aluminum in the copper-aluminum carbonate powder ranges from 1 to 10. The weight mixing ratio of the copper aluminum carbonate powder and the zeolite powder ranges from 1:5 to 5:1, and preferably 1:3.

Although the foregoing description and drawings have disclosed preferred embodiments of the present invention, it must be understood that various additions, many modifications and substitutions may be used in the preferred embodiments of the present invention without departing from the scope as defined in the appended patent application The spirit and scope of the principles of the present invention. Those of ordinary skill in the art to which the present invention pertains will appreciate that the present invention can be used in many forms, structures, arrangements, ratios, materials, elements, and component modifications. Therefore, the embodiments disclosed herein should be considered to illustrate the present invention, rather than to limit the present invention. The scope of the present invention should be defined by the scope of the attached patent application and cover its legal equivalents, not limited to the previous description.

1000‧‧‧Step

2000‧‧‧step

3000‧‧‧Step

4000‧‧‧Step

5000‧‧‧Step

6000‧‧‧Step

Claims (18)

A carbon monoxide adsorbent includes: a copper aluminum carbonate powder, wherein the copper aluminum carbonate powder is a layered double hydroxide (LDH); and a zeolite powder. The carbon monoxide adsorbent according to claim 1, wherein the molar ratio of copper to aluminum in the copper aluminum carbonate powder ranges from 1 to 10. The carbon monoxide adsorbent according to claim 1, wherein the weight mixing ratio of the copper aluminum carbonate powder and the zeolite powder ranges from 1:5 to 5:1. The carbon monoxide adsorbent according to claim 3, wherein the weight mixing ratio of the copper aluminum carbonate powder and the zeolite powder is 1:3. A mixture is used for adsorbing carbon monoxide, wherein the mixture comprises: a zeolite (zeolite) powder; and a copper aluminum carbonate powder, wherein the copper aluminum carbonate powder is layered double hydroxide (Layered Double Hydroxide, LDH). The use of the mixture as claimed in claim 5 for adsorbing carbon monoxide, wherein the molar ratio of copper to aluminum in the copper-aluminum carbonate powder ranges from 1 to 10. The mixture according to claim 5 is used for adsorbing carbon monoxide, wherein the weight mixing ratio of the copper-aluminum carbonate powder and the zeolite powder ranges from 1:5 to 5:1. The mixture according to claim 7 is used for adsorbing carbon monoxide, wherein the weight mixing ratio of the copper aluminum carbonate powder and the zeolite powder is 1:3. A method for manufacturing carbon monoxide adsorbent, comprising Use a copper precursor and aluminum nitrate to make an acid solution; use a sodium hydroxide and sodium carbonate to make an alkaline solution; mix and stir the acid solution and the alkaline solution and filter to produce a solid; dry the solid and Calcination to produce a copper aluminum carbonate powder; the copper aluminum carbonate powder is mixed with a zeolite powder to form the carbon monoxide adsorbent. The method for manufacturing a carbon monoxide adsorbent according to claim 9, wherein the copper precursor includes copper nitrate. The method for manufacturing a carbon monoxide adsorbent according to claim 9, wherein in the step of manufacturing the acid solution, the molar ratio of copper to aluminum of the copper precursor and the aluminum nitrate ranges from 1 to 10. The method for manufacturing a carbon monoxide adsorbent according to claim 9, wherein in the step of generating the copper aluminum carbonate powder, the calcination temperature is less than 400°C. The method for manufacturing a carbon monoxide adsorbent according to claim 12, wherein the copper aluminum carbonate powder is a layered double hydroxide (LDH). The method for manufacturing a carbon monoxide adsorbent according to claim 9, wherein the weight mixing ratio of the copper aluminum carbonate powder and the zeolite powder ranges from 1:5 to 5:1. The method for manufacturing a carbon monoxide adsorbent according to claim 14, wherein the weight mixing ratio of the copper aluminum carbonate powder and the zeolite powder is 1:3. The method for manufacturing a carbon monoxide adsorbent according to claim 9, further comprising placing the carbon monoxide adsorbent in an inert gas at a pretreatment temperature to perform a pretreatment. The method for manufacturing a carbon monoxide adsorbent according to claim 16, wherein the pretreatment temperature is 370°C. The method for manufacturing a carbon monoxide adsorbent according to claim 16, wherein the inert gas is nitrogen.

Images