KR102051033B1 - Composite for the removal of VOC and the preparing method thereof - Google Patents

Abstract

Activated carbon, spent FCC catalyst, bentonite, and silica sol (SiO ₂ ) are mixed to form a molded body, and a hydro-synthesized composite molded body for removing volatile organic compounds (VOC) formed, the content of the silica sol is greater than 0 and less than 15 wt% Disclosed is a composite molded article for volatile organic compound (VOC) removal.
Moreover, as a manufacturing method of the composite molded object containing activated carbon, a waste catalyst, bentonite, and a silica sol,
Molding and drying a sample mixed with activated carbon, spent catalyst, bentonite and silica sol;
Heat-treating the shaped sample in an inert atmosphere; And
Hydrothermally synthesizing the heat-treated sample at a temperature of 80 to 100 ° C. for 10 to 14 hours;
Disclosed is a method of manufacturing a composite molded article for volatile organic compound (VOC) removal, comprising:

Description

Composite molded article for VOC removal and its manufacturing method {Composite for the removal of VOC and the preparing method

The present invention relates to a composite molded body for removing VOC (Volatile Organic Compound) and a method for manufacturing the same, and more particularly, to a composite molded body for VOC removal using activated carbon and waste Catalytic Cracking (FCC) catalyst, etc. The invention relates to.

Spent equilibrium FCC catalysts from FCC processes are currently used or buried as cement raw materials due to their impurity and low specific surface area, and thus their low utilization. Research needs to be actively used in various ways.

On the other hand, activated carbon has the advantage that it can be used in various adsorptive separation / removal processes from gas to liquid phase, but it is widely used in such a process. There is a disadvantage that a fire may occur. In addition, due to the risk of fire during desorption, the situation is that water is used instead of air as a regeneration material, but water can not only destroy the shape of activated carbon, but also require further processing such as separation or condensation at the end of the process. Is holding.

In such a situation, the applicant intends to use as a raw material of the zeolite which is a useful substance by utilizing the components such as Si and Al in the waste FCC catalyst, and hydrothermal synthesis is possible by utilizing the waste FCC catalyst and activated carbon. In addition, the present invention was to develop a composite molded article having excellent adsorption performance and improved fire stability.

Accordingly, an object of the present invention is to provide a composite molded body for removing volatile organic compounds (VOC) formed by mixing activated carbon, spent catalyst, bentonite and silica sol (SiO ₂ ) to make a molded body, and hydrothermally synthesizing it.

Another object of the present invention is to form a molded body by mixing activated carbon, waste catalyst, bentonite and silica sol (SiO ₂ ), and a composite molded body for removing volatile organic compounds (VOC) formed by hydrothermal synthesis, the waste catalyst is a fluid catalytic decomposition ( It is produced in the FCC) process, the content of the silica sol is to provide a composite molded body for removing volatile organic compounds (VOC), characterized in that more than 0 and less than 15 wt%.

Still another object of the present invention is to provide a composite molded body comprising activated carbon, spent catalyst, bentonite and silica sol,

Molding and drying a sample mixed with activated carbon, spent catalyst, bentonite and silica sol;

Heat-treating the shaped sample in an inert atmosphere; And

Hydrothermally synthesizing the heat-treated sample at a temperature of 80 to 100 ° C. for 10 to 14 hours;

It provides a method for producing a composite molded body for removing volatile organic compounds (VOC) comprising a.

The composite molded body for VOC removal according to an aspect of the present invention includes an activated carbon and a waste FCC catalyst, and thus has a high specific surface area, excellent adsorption performance, excellent strength, and improved ignition stability compared to activated carbon. Moreover, the waste catalyst from the FCC process is recycled as a raw material of zeolite rather than simply used as a cement raw material or landfill, and is advantageous in terms of cost and resource efficiency, and is also environmentally friendly.

Figure 1 shows the results of measuring the temperature change of each sample while increasing the temperature with time in the tower.

Hereinafter, the present invention will be described in detail.

An aspect of the present invention provides a composite molded body for removing volatile organic compounds (VOC) formed by mixing activated carbon, spent catalyst, bentonite, and silica sol (SiO ₂ ) to make a molded body, and hydrothermally synthesizing it.

In particular, the waste catalyst included in the composite molded body is produced in a fluid catalytic cracking (FCC) process, and since the waste FCC catalyst contains components such as Si and Al, it can be used as a zeolite raw material, which is a useful material. It is preferable to use from such spent FCC catalysts.

Further, the content of activated carbon included in the composite molded body for removing volatile organic compounds (VOC) may be more than 25 to 40 wt%, specifically, more than 26 to less than 35 wt%, more specifically, based on the total mass ratio of the composite molded body. May be greater than 27 and less than 30. When the content of activated carbon is in the range of more than 25 wt%, the VOC adsorption performance is excellent, and in the case of less than 40 wt%, the ignition stability of the composite molded product is excellent.

In addition, the content of the spent catalyst included in the composite molded product for removing volatile organic compounds (VOC) may be greater than 40 and less than 60 wt%, more specifically greater than 42 and less than 55 wt%, based on the total mass ratio of the composite molded product. Specifically, it may be greater than 43 and less than 50 wt%.

The ignition stability of the composite molded body is excellent in the range of more than 40 wt% of the waste catalyst, and VOC adsorption performance is excellent in the range of less than 60 wt%.

In addition, the content of bentonite included in the composite molded body for removing volatile organic compounds (VOC) may be greater than 15 and less than 25 wt%, more specifically greater than 16 and less than 23 wt%, more specifically, relative to the total mass ratio of the composite molded body. And more than 17 and less than 20 wt%.

If the content of bentonite is more than 15 wt%, it is excellent in strength of the composite molded body, and in terms of VOC adsorption performance in the range of less than 25 wt%.

The content of the silica sol (SiO ₂ ) included in the composite molded body for removing the volatile organic compound (VOC) may be greater than 0 and less than 15 wt%, specifically, greater than 0 and less than 13 wt%, more specifically greater than 0 10. It may be wt% or less.

When the content of silica sol is 0 wt%, the specific surface area, porosity, and strength may all be low among the characteristics of the molded article including the same, and the specific surface area and pore characteristics may be reduced in the range of less than 15 wt%. Can be kept high.

In the composite compact for removing volatile organic compounds (VOC) including activated carbon, spent catalyst, bentonite and silica sol according to one aspect of the present invention, the mass ratio (wt%) of activated carbon: waste catalyst: bentonite is 3: 5: 2 Can be.

In another aspect of the present invention, a method for producing a composite molded article comprising activated carbon, spent catalyst, bentonite and silica sol,

Molding and drying a sample mixed with activated carbon, spent catalyst, bentonite and silica sol;

Heat-treating the shaped sample in an inert atmosphere; And

Hydrothermally synthesizing the heat-treated sample at a temperature of 80 to 100 ° C. for 10 to 14 hours;

It provides a method for producing a composite molded body for removing volatile organic compounds (VOC) comprising a.

The silica sol content in the drying step may be greater than 0 and less than 15 wt%, more specifically greater than 0 and less than 13 wt%, more specifically greater than 0 and less than 10 wt%, based on the total mass of the composite molded body.

When the content of silica sol is 0 wt%, the composite molded product for removing volatile organic compounds (VOC) prepared by the above method may exhibit low specific surface area, pore characteristics, and strength, and the content is 15 In the range of less than wt%, the specific surface area and pore characteristics can be kept high.

In addition, the heat treatment in the heat treatment step may be performed for 2 to 4 hours at a temperature of 650 to 800 ℃.

Further, in connection with hydrothermal synthesis of the heat-treated sample at a temperature of 80 to 100 ° C. for 10 to 14 hours, specifically, the heat-treated sample is placed in a 3M sodium hydroxide (NaOH) solution and subjected to hydrothermal treatment for 12 hours. Can be. In view of hydrothermal synthesis, it is most preferable to heat for 12 hours at this temperature.

Thereafter, the hydrothermally synthesized sample is sufficiently washed with distilled water, and the washed water sample can be sufficiently dried at a temperature of about 110 ° C. through an oven or the like. Within the range that can be carried out for sufficient drying, the temperature range is not particularly limited.

 The sample sufficiently dried as described above may be heat-treated at a temperature of 200 to 550 ° C. for at least 3 hours in an inert atmosphere in a subsequent step, and specifically, at least 3 hours at a temperature of 350 ° C. .

According to an aspect of the present invention, the composite molded body for removing volatile organic compounds (VOC) prepared as described above and a method for preparing the same have a high specific surface area, excellent adsorption performance, excellent strength, and improved fire stability compared to activated carbon. In addition, by recycling the waste catalyst from the FCC process as a raw material of zeolite, rather than simply using it as a cement raw material or landfill, it is environmentally friendly and can exhibit a desirable effect in terms of cost and resource efficiency.

Hereinafter, the present invention will be described in detail by the following production examples and experimental examples. However, these are merely illustrative of the present invention and the scope of the invention is not limited by these examples and experimental examples.

< Example >

One. Production Example  : VOC  Removal compound Molded  Produce

(1) forming of pellets

Activated carbon (AC), spent catalyst (waste FCC), bentonite and silica sol (SiO ₂ ) were mixed using a granulator (Lodige Co.) according to the ratio of Table 1 below, and the mixed sample was mixed with Pelletizer (Fuji Paudal Co. Molding using). Thereafter, the molded sample is dried in an oven at 110 ° C. for 12 hours or more.

Sample AC ( wt% ) Waste FCC ( wt% ) Bentonite ( wt% ) SiO ₂ ( wt% ) A 30.0 50.0 20.0 0 B 28.5 47.5 19.0 5.0 C 27.9 46.5 18.6 7.0 D 25.5 42.5 17 15

(2) heat treatment

The molded sample is heat treated at an inert atmosphere at a temperature of 650 to 800 ° C. for 2 hours.

(3) hydrothermal synthesis

i) Heat-treated samples were placed in a Nalgene bottle in a weight ratio of 1: 10 in 3M NaOH solution and sealed, and aged at 120 rpm at room temperature for 24 hours.

ii) After aging, hydrothermal synthesis for 12 hours (optimum time) at 90 ℃ and 80 rpm in a thermostat.

iii) After the hydrothermally synthesized sample is sufficiently washed with distilled water, the washed sample is sufficiently dried in an oven at 110 ° C.

iv) The dried sample is heat treated at 350 ° C (optimum temperature) for at least 3 hours in an inert atmosphere.

2. Experimental Example

end. Characterization

(1) Porosity

After the prepared sample is pretreated (vacuum) at 350 ° C. for 3 hours or more, porosity is measured using a volumetric adsorption apparatus (Tristar, Micromeritics Co.).

(2) strength

One of the prepared samples is placed on a compressive strength tester (lab-made), and a force is applied until the sample is broken. The strength of the sample at this time is measured in kgf / unit.

The properties of (1) porosity and (2) strength are shown in Table 2 below.

Heat treatment temperature
(℃) Sample Surface area
(㎡ / g) Total pore volume
(Cm 3 / g) Strength
( kgf Of ea ) 750 A 605 0.29 1.42 B 636 0.31 4.95 C 665 0.32 5.81 D 635 0.30 6.42 800 B 642 0.31 5.1 C 650 0.32 6.31

As shown in Table 2, the porosity and strength is excellent when SiO _{2 is} added (Sample B, C, D), but when the SiO ₂ is added 15 wt% or more (Sample D), the pore characteristics are rather reduced. You can see that

I. Ignition stability measurement

(Top: outer diameter = 1/2 inch, inner diameter = 10 mm, height = 2.5 cm), (Feed: Air, 500 ml / min), (sample size: # 16-40)

i) After filling the tower with sample, increase the tower temperature up to 900 ℃ at 10 ℃ / min with air and measure the temperature of adsorbent using TC (thermocouple).

ii) Select the ignition point when the temperature is at least 5% higher than the tower temperature (without adsorbent).

The results are shown in Table 3 below and FIG. 1.

sample Ignition Temperature (℃) Difference with activated carbon
(℃) Crushed activated carbon 394 0 750 heat treatment 523 129 750 hydrothermal synthesis 512 118 800 heat treatment 545 151

(In the above table, '750 heat treatment' means a sample heat-treated at 750 ℃, '750 hydrothermal synthesis' means a sample subjected to hydrothermal synthesis after the heat treatment at 750 ℃, '800 heat treatment' means a heat treatment at 800 ℃ Means the sample.)

As shown in Table 3 and Figure 1, it can be seen that the composite molded article of the present invention significantly increased the ignition stability compared to the existing activated carbon.

All. Breakthrough

(Top: outer diameter = 1/2 inch, inner diameter = 10 mm, height = 10 cm), (Feed: 500 ppm benzene / Air, 2 L / min), (sample size: # 16-40)

i) After the sample is filled in the tower, He is flown at the top of the tower at 350 ° C for at least 3 hours and vacuumed at the bottom of the tower for pretreatment.

ii) Cool the tower to room temperature, feed the feed, and use GC-FID to adsorb benzene to detect the breakthrough benzene of the adsorbent reaching the max performance. At this time, the breakthrough time is measured by measuring the time point at which the benzene concentration is discharged at 1% concentration (5 ppm) of the feed.

la. Control Porosity of the sample and  Strength characterization

Said 'a. In the same way as in the 'characteristic analysis', the porosity and strength were analyzed, and the results and the above'. The results for breakthrough 'are shown in Table 4 below.

Control sample Surface area
(㎡ / g) Total pore volume
(Cm 3 / g) Strength
( kgf Of ea ) Breakthrough
(time) Activated carbon 1226 0.52 - 408 Waste FCC 128 0.13 - 21 Waste FCC Regeneration (Synthesis) 299 0.16 1.02 208 Activated Carbon + Waste FCC (Synthetic) 846 0.41 0.13 242 Activated Carbon + Waste FCC + Bentonite
(Sample A) 605 0.29 1.42 211

As shown in Table 4, activated carbon has excellent porosity characteristics, but poor ignition stability, and also has a disadvantage of being relatively expensive. In contrast, spent FCC catalysts have very low pore characteristics.

On the other hand, a sample regenerated from only the spent FCC catalyst or a regenerated sample synthesized from activated carbon + spent FCC catalyst has low strength and thus is difficult to be used in the actual process. Although the overall strength and fire safety is excellent, it can be seen that the pore characteristics are somewhat lower than the present invention to which a certain amount of SiO ₂ is added (see Table 2), and the activated carbon + waste catalyst + bentonite + silicaazole of the present invention It can be seen that the composite molded article is highly applicable as a VOC adsorbent.

hemp. Changes in Porosity and Strength Characteristics According to Annealing Temperature

The composition of Sample B (AC: waste FCC: bentonite: SiO ₂ = 47.5: 28.5: 19.0: 5.0) was subjected to a heat treatment temperature of 650 ° C, 700 ° C, 750 ° C, and 800 ° C, respectively, to analyze porosity and strength. Subsequently, the surface area and strength of the hydrothermal synthesis at 90 ° C. were investigated, and the change thereof was observed.

The results before hydrothermal synthesis are shown in Table 5 below, and the results after hydrothermal synthesis are shown in Table 6 below.

Heat treatment temperature
(℃) Surface area
(㎡ / g) Total pore volume
(Cm 3 / g) Strength
( kgf Of ea ) 650 394 0.25 3.7 700 389 0.24 3.85 750 390 0.24 4.41 800 379 0.24 4.72

Heat treatment temperature
(℃) Surface area
(㎡ / g) Total pore volume
(Cm 3 / g) Strength
( kgf Of ea ) 650 649 0.32 4 700 656 0.32 4.51 750 636 0.31 4.95 800 642 0.31 5.1

As shown in Table 5 and Table 6, it can be seen that the specific surface area after hydrothermal synthesis is greatly increased, the porosity is similar but the strength is increased with increasing the heat treatment temperature.

Claims (12)

More than 27 and less than 30 wt% activated carbon, more than 43 and less than 50 wt% spent catalyst, more than 17 and less than 20 wt% bentonite and more than 0 and less than 10 wt% silica sol (SiO ₂ ) were mixed to form a shaped body, which was hydrothermal Composite molded body for removing volatile organic compounds (VOC) formed by synthesis.
The method of claim 1,
The waste catalyst is a composite molded body for removing volatile organic compounds (VOC) is produced in the fluid catalytic cracking (FCC) process.
delete delete delete delete As a method for producing a composite molded body comprising activated carbon, spent catalyst, bentonite and silica sol,
Molding and drying a sample mixed with greater than 27 and less than 30 wt% activated carbon, more than 43 and less than 50 wt% spent catalyst, more than 17 and less than 20 wt% bentonite and greater than 0 and less than 10 wt% silica sol;
Heat-treating the shaped sample in an inert atmosphere; And
Hydrothermally synthesizing the heat-treated sample at a temperature of 80 to 100 ° C. for 10 to 14 hours;
Method for producing a composite molded body for removing volatile organic compounds (VOC) comprising a.
delete The method of claim 7, wherein
Method for producing a composite molded body for removing volatile organic compounds (VOC) that the heat treatment of the heat treatment step is performed for 2 to 4 hours at a temperature of 650 to 800 ℃.
The method of claim 7, wherein
In the hydrothermal synthesis step, the heat-treated sample is put in 3M sodium hydroxide (NaOH) solution, and hydrothermally synthesized for 12 hours.
The method of claim 7, wherein
After the hydrothermal synthesis step, washing with distilled water and drying step of producing a composite molded body for removing volatile organic compounds (VOC).
The method of claim 11,
After washing with distilled water and drying, the composite sample for volatile organic compound (VOC) removal comprising the heat treatment of the dried sample for 3 hours at a temperature of 200 to 550 ℃ in an inert atmosphere (inert) Manufacturing method.

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