KR102313559B1 - All-in-one Device for Preparing of Sodium Bicarbonate Combined Bubble Reactor with Packed Tower and Method for Preparing The Same - Google Patents

Abstract

The present invention relates to a device for manufacturing sodium bicarbonate in an integrated gas-liquid contact by making a sodium carbonate aqueous solution react with carbon dioxide gas contained in the exhaust gas and a method for manufacturing the same. The device for manufacturing the integrated sodium bicarbonate and the method for manufacturing the same of the present invention integrate a packed tower and a bubble reactor into one unit and make the sodium carbonate aqueous solution react with carbon dioxide gas to produce sodium bicarbonate, thereby maximizing carbon dioxide gas utilization, shortening reaction time, reducing facility costs and the like.

Description

All-in-one Device for Preparing of Sodium Bicarbonate Combined Bubble Reactor with Packed Tower and Method for Preparing The Same

The present invention relates to an apparatus for manufacturing an integrated sodium bicarbonate in which a packed tower and a bubble reactor are combined, and a method for manufacturing the same. _{More specifically, an apparatus for producing sodium bicarbonate (NaHCO 3} ) by reacting an aqueous sodium carbonate solution with carbon dioxide contained in exhaust gas by gas-liquid contact in an integrated reactor combining a packed tower and a bubble reactor, and an apparatus and the same The invention relates to a manufacturing method.

Recently, global warming due to an increase in the amount of carbon dioxide emitted has emerged as a problem, and a technology for recovering carbon dioxide contained in exhaust gas emitted from factories, etc. is receiving attention.

Sodium bicarbonate (NaHCO ₃ , sodium bicarbonate) is industrially manufactured by recrystallizing a product by the ammonia soda method in hot water. It is used as an antacid, an alkali agent, etc. for pharmaceuticals, and is used as an alkali agent, swelling agent, buffering agent, and carbon dioxide generator for soft drinks in food. Industrially, it has excellent abrasive power, neutralization, deodorization, foaming, and softening ability, so it is widely used as a cleaning agent and deodorant. In addition, recently, as a dry sulfur oxide (SO _x ) remover, it is also used in steel mills and thermal power plants, and its application range is increasing.

Problems in the production of sodium bicarbonate in the prior art using low-concentration carbon dioxide gas (about 14 Vol%) from power plants, etc. are as follows.

First, when producing sodium bicarbonate by gas-liquid reaction of soda ash solution and low-concentration carbon dioxide gas as raw materials, the efficiency of the device is not good, so about 60% of carbon dioxide gas is not utilized and is discharged to the outside. Accordingly, there are disadvantages that 1) the reaction yield is lowered, 2) the reaction time is long, and 3) the reactor becomes very large.

Second, the technology of collecting the exhaust gas of a power plant and concentrating the concentration of carbon dioxide to about 90% and then reacting has a disadvantage in that the investment cost increases and the economic feasibility decreases because a collection and concentration facility is added.

Third, the technology to increase the solubility of carbon dioxide by increasing the specific surface area by using low-concentration carbon dioxide as microbubbles also improves the utilization rate of carbon dioxide to about 70%, but has a disadvantage in that a significant amount of carbon dioxide is discharged to the outside.

Therefore, there is an urgent need for technology development that can solve the above problems.

: Korean Patent Registration No. 10-1571251 (2015. 11. 17.) : Korean Patent Registration No. 10-2095865 (2020. 3. 26.)

The present invention is to solve the above problems, and the efficiency is greatly improved, such as shortening the reaction time and maximizing the reaction rate by reacting the sodium carbonate aqueous solution with the carbon dioxide gas by integrating the conventional packed tower and the bubble reactor as an integral type To provide an apparatus for manufacturing sodium bicarbonate and a method for manufacturing the same.

In order to achieve the object as described above, the present invention is a reactor comprising: a reactor including a packed tower and a bubble reactor, which generates sodium bicarbonate by reacting an aqueous sodium carbonate solution with carbon dioxide gas; a mixing mixer for generating fine bubbles from carbon dioxide gas and supplying a fluid produced by mixing with an aqueous sodium carbonate solution to the gas separator; a gas separator for separating liquid and gas from the fluid supplied from the mixing mixer and supplying them to the bubble reactor; a dehydrator for separating sodium bicarbonate in a slurry state produced in the reactor by centrifugation; It includes; a dryer for drying the sodium bicarbonate separated in the dehydrator, wherein the mixing mixer provides an integrated sodium bicarbonate manufacturing apparatus, characterized in that it is a vortex collision type.

In addition, the present invention is a first step of producing sodium bicarbonate by mixing carbon dioxide gas into an aqueous sodium carbonate solution as bubbles and then reacting with each other; The sodium bicarbonate in the slurry state produced in the first step includes a second step of being dried after centrifugation, wherein the reaction in the first step is performed in a one-step reaction method in which a packed tower and a bubble reactor are combined, In the second step, the filtrate obtained by centrifuging sodium bicarbonate in a slurry state provides a method for producing sodium bicarbonate, characterized in that it is recycled to the packed column.

On the other hand, the means for solving other specific problems according to the present invention are described in the detailed description of the invention.

In the integrated sodium bicarbonate manufacturing apparatus and method for combining a packed tower and a bubble reactor of the present invention, a packed tower and a bubble reactor are integrated, and a sodium carbonate aqueous solution and carbon dioxide gas are reacted to produce sodium bicarbonate, thereby carbon dioxide gas utilization rate It has great advantages such as maximization of efficiency, shortening of reaction time, and reduction of facility cost.

1 is a schematic manufacturing apparatus for integrated sodium bicarbonate in which a packed tower and a bubble reactor of the present invention are combined.
2 is a schematic view of a mixing mixer in the apparatus for producing integrated sodium bicarbonate of the present invention.
3 is a schematic view of the generation of primary bubbles in the mixing mixer of the integrated sodium bicarbonate production apparatus of the present invention.
4 is a schematic view of mixing using a secondary rotational force in a mixing mixer among the integrated sodium bicarbonate manufacturing apparatus of the present invention.
5 is a schematic view of mixing using a tertiary collision in a mixing mixer among the integrated production apparatus of sodium hydrogen carbonate of the present invention.

Hereinafter, embodiments of the present invention will be described in more detail with reference to the accompanying drawings. Embodiments of the present invention may be modified in various forms, and the scope of the present invention should not be construed as being limited to the following embodiments. This embodiment is provided to more completely explain the present invention to a person with average knowledge in the relevant technical field. Accordingly, shapes and detailed configurations of elements in the drawings are simplified for explanation. And it should be noted that the terms used in this specification are terms used to properly express preferred embodiments of the present invention.

As used herein, “fine bubbles” means bubbles having an average diameter of 0.1 mm or less. Also, the term “liquid” refers to comprising at least one of an aqueous sodium carbonate solution, an intermediate product of a reaction to form sodium bicarbonate, and a product of a reaction to form sodium bicarbonate.

Hereinafter, detailed features of an apparatus for manufacturing an integrated sodium bicarbonate in which a packed tower and a bubble reactor are combined will be described in detail with reference to the drawings. The apparatus for manufacturing an integrated sodium bicarbonate combining a packed tower and a bubble reactor of the present invention is not limited thereto, and in addition, it can be used without limitation in various devices requiring the structure of an integrated sodium bicarbonate manufacturing apparatus combining a packed tower and a bubble reactor. of course there is

1 is a schematic view for explaining an apparatus for manufacturing an integrated sodium bicarbonate in which a packed tower and a bubble reactor are combined according to the present invention.

First, the apparatus for manufacturing an integrated sodium bicarbonate in which a packed tower and a bubble reactor are combined according to the present invention comprises: a reactor including a packed tower and a bubble reactor for generating sodium bicarbonate by reacting an aqueous sodium carbonate solution with carbon dioxide gas; a mixing mixer for generating fine bubbles from carbon dioxide gas and supplying a fluid produced by mixing with an aqueous sodium carbonate solution to the gas separator; a gas separator for separating liquid and gas from the fluid supplied from the mixing mixer and supplying them to the bubble reactor; a dehydrator for separating sodium bicarbonate in a slurry state produced in the reactor by centrifugation; A dryer for drying the sodium bicarbonate separated in the dehydrator; includes, but the mixing mixer is characterized in that it is a rotating collision type.

Hereinafter, each configuration of the integrated sodium bicarbonate manufacturing apparatus will be described in detail.

First, the reactor 02 generates sodium bicarbonate by reacting an aqueous sodium carbonate solution with carbon dioxide gas, and is integrally configured including a packed tower 03 and a bubble reactor 05 .

The charging tower 03 is connected to an inlet 01 for dissolving sodium carbonate in water to receive an aqueous sodium carbonate solution having an appropriate concentration at the top thereof, and a filler is filled therein. In addition, a bubble reactor 05 is connected to the lower portion of the packed tower 03 . Each of the upper portions of the bubble reactor 05 is connected to the gas separator 12 and a pipe (no reference numeral).

The sodium carbonate aqueous solution supplied from the inlet 01 located at the upper part of the packed tower 03 flows through the gap of the irregular packing filled in the packed tower 03 in a thin film state. (05) After being stored in the inner floor, it is supplied to the mixing mixer 08 through the distribution line 07.

The bubble reactor 05 is coupled to the packed tower 03 at its upper portion, so that the aqueous sodium carbonate solution flowing down from the top is pooled at the inner bottom. From the gas separator 12, the liquid sodium carbonate aqueous solution, the intermediate product and product of the sodium bicarbonate production reaction, and the gas carbon dioxide and air are respectively separated and supplied to the upper part of the bubble reactor 05, respectively. In addition, at the lower end of the bubble reactor 05, a distribution line 07 for supplying an aqueous sodium carbonate solution or the like to the mixing mixer 08 is connected.

The combustion exhaust gas generated by the combustion of fossil fuels in thermal power plants, etc. contains about 14 vol% of carbon dioxide. The carbon dioxide gas obtained from the combustion exhaust gas is supplied to the orbital impact type mixing mixer 08 through the inlet 09 .

As shown in FIGS. 2 to 5, the orbital collision type mixing mixer 08 is installed by inserting a gas pipe (no reference numeral) into which carbon dioxide gas is injected into the center of the liquid pipe (no reference numeral) first, and the discharge part By forming a number of holes (without reference numerals), carbon dioxide gas is evenly sprayed to generate fine bubbles. Second, the fluid in which the microbubbles and the aqueous sodium carbonate solution are mixed is injected into the side of the cylindrical body (no reference numeral) and rotates by the rotational force, and the sodium carbonate aqueous solution is mixed with the microbubbles to become a fluid. At this time, the light fluid containing a lot of carbon dioxide moves to the inner upper part by the rotational force, and the carbon dioxide gas that is not mixed is mixed with the liquid at the upper part and becomes heavy, so it descends, and mainly the mixed fluid is separated and moves to the upper part. do. As the mixture is mixed with the rotational motion and the difference in the weight of the particles, the pressure loss is small. And thirdly, the fluid collides with a circular perforated plate (without reference numeral) several times to make it finer while mixing. The vortex generated at the time of collision is used to mix well and to make it finer, so that the pressure loss is small, so that the mixing efficiency can be maximized.

And the carbon dioxide gas fine bubbles supplied to the bubble reactor 05 react with the sodium carbonate aqueous solution to produce sodium bicarbonate, and the reaction formula is as follows.

[Reaction formula] Na ₂ CO ₃ + CO ₂ + H ₂ O → 2NaHCO ₃

In addition, unreacted fine bubbles in the bubble reactor 05 rise and react as above again in the packed tower 03 to produce sodium bicarbonate.

In this way, the sodium carbonate aqueous solution and the fine bubbles of carbon dioxide gas react with each other while passing through the bubble reactor 05 and the packed tower 03 in sequence to generate sodium bicarbonate, so that about 90% of the carbon dioxide gas can be utilized.

On the other hand, the gas separator 12 is configured to separate the liquid and gas generated in the mixing mixer 08, respectively, and supply them to the bubble reactor 05. More specifically, the liquid sodium carbonate aqueous solution generated by the mixing mixer 08, the intermediate product and product of the sodium bicarbonate production reaction, liquid carbon dioxide, gaseous carbon dioxide gas, and air are separated from each other. Next, the liquid sodium carbonate aqueous solution, the intermediate product and product of the sodium bicarbonate production reaction, and the liquid carbon dioxide go to the lower inlet (no reference numeral) at the top of the bubble reactor 05, and the gas carbon dioxide gas and air the bubble reactor 05 ) is supplied to the upper inlet (no reference sign), respectively.

In addition, after the carbon dioxide gas reacts with the sodium carbonate aqueous solution secondary to generate sodium bicarbonate in the packed tower 03 , the off gas mostly composed of nitrogen and oxygen may be discharged to the outside through the outlet 04 .

The dehydrator 10 separates sodium bicarbonate in a slurry state generated in the reactor 02 into a cake and a filtrate by centrifugal force. The cake can be extracted with powdered sodium bicarbonate after a significant amount of moisture has been removed using a device such as a steam heater. At this time, the filtrate may be recycled to the packed tower 03 through the circulation pipe 06 with about 10% by weight of sodium bicarbonate to improve the yield of the product.

After that, the sodium bicarbonate with some moisture remaining may be transferred to the dryer 11 and dried to a desired level, and finally shipped as a solid sodium bicarbonate product.

Hereinafter, the method for producing sodium bicarbonate according to the present invention will be described in detail.

The method for producing sodium bicarbonate according to the present invention comprises: 1) a first step of mixing carbon dioxide gas as fine bubbles in an aqueous sodium carbonate solution and then reacting them with each other to produce sodium bicarbonate; 2) A second step of drying the sodium bicarbonate in a slurry state produced in the first step after centrifugation:

In the first step, the reaction is carried out in a way in which a packed column and a bubble reactor are combined in an integrated manner, and the filtrate obtained by centrifuging sodium bicarbonate in a slurry state in the second step is recycled to the packed tower. do.

The first step is a step of producing sodium bicarbonate by mixing carbon dioxide gas as fine bubbles in an aqueous sodium carbonate solution and then reacting with each other. Specifically, the sodium carbonate aqueous solution is supplied to the inlet 01 after dissolving sodium carbonate in water to obtain a sodium carbonate aqueous solution having an appropriate concentration. At this time, the sodium carbonate aqueous solution is preferably added into the packed tower 03 through the inlet 01 after mixing 100 parts by weight of water with 6.6 parts by weight of sodium carbonate. In addition, about 14 Vol% of carbon dioxide gas obtained from the combustion exhaust gas is supplied to the mixing mixer 08 through the inlet 09.

The sodium carbonate aqueous solution supplied to the inlet 01 and the carbon dioxide gas rising from the bubble reactor 05 meet and react with each other to produce sodium bicarbonate. Subsequently, the unreacted carbon dioxide gas rises to cause a secondary reaction with the sodium carbonate aqueous solution coming down from the packed tower (03).

At this time, the temperature of the reaction conditions is preferably 30 ~ 35 ℃ in both the bubble reactor (05) and the adsorption tower (03). When the temperature is less than 30°C, energy cost increases due to the exothermic reaction, and when the temperature exceeds 35°C, a problem occurs in that the reaction rate is lowered. In addition, the pressure is preferably maintained at 4Bar in both the bubble reactor (05) and the adsorption tower (03).

In the second step, the sodium bicarbonate in the slurry state produced in the first step is centrifuged and then dried. Specifically, the sodium bicarbonate produced in the first step is in the form of a slurry, and since it contains a significant amount of water, it must be removed. Water may be removed from sodium bicarbonate in a slurry state by centrifugation in the dehydrator 10 . Subsequently, it is passed through a dryer 11 in order to remove the trace amount of moisture remaining in the sodium bicarbonate, and the moisture is dried and then commercialized.

On the other hand, since the filtrate separated from sodium bicarbonate in a slurry state contains 10 wt% of sodium bicarbonate, it is preferable to circulate it to the packed tower 03 through the circulation pipe 06 in order to improve the yield.

A carbon dioxide analyzer (not shown) may be installed on the upper portion of the bubble reactor 05 to measure the content of carbon dioxide introduced through the gas separator 12 . In addition, a carbon dioxide analyzer (not shown) may be installed at the outlet 04 to measure the carbon dioxide content emitted after carbon dioxide gas is converted into sodium bicarbonate product. The carbon dioxide utilization rate can be calculated from the carbon dioxide content measured at these two locations.

Hereinafter, preferred embodiments will be presented to help the understanding of the present invention be described in detail.

<Example 1>

The aqueous sodium carbonate solution was mixed with 6.6 kg of sodium carbonate and 100 L of water through the inlet 01 of the packed tower 03, in which the inside of the tower was filled with atypical packing (Random Packing), and put into the mixing mixer 08. In addition, 14 vol% carbon dioxide gas was introduced through the inlet 09 at a rate of 10 m 3 /hr. Then, the sodium carbonate aqueous solution is mixed with the carbon dioxide gas in fine bubbles in the mixing mixer 08, separated in the gas separator 12, and then supplied to the bubble reactor 05, and reacts with the sodium carbonate aqueous solution to primarily produce sodium bicarbonate. . The unreacted aqueous sodium carbonate solution and carbon dioxide gas rise and react in the packed tower to secondarily produce sodium bicarbonate. All reactions in the bubble reactor 05 and the packed tower 03 are performed at 33° C. and 4 bar. The sodium bicarbonate in the slurry state generated in the bubble reactor 05 was centrifuged in the dehydrator 10, and 11 kg of the filtrate obtained was recirculated through the circulation pipe 06. The carbon dioxide content was measured from the carbon dioxide gas analyzer installed on the outlet 04 and the upper part of the bubble reactor 05, and the results obtained therefrom are shown in Table 1.

<Example 2>

Compared with Example 1, the reactions in the bubble reactor 05 and the packed tower 03 are all the same except that the reaction is performed at 40° C., 4 bar instead of 33° C. and 4 bar, and the rest are the same. The results obtained therefrom are shown in Table 1.

<Comparative example>

A sodium bicarbonate production apparatus in which the primary reactor and the secondary reactor are connected by a two-stage reaction method was used (same as Patent No. 10-2095865). The sodium carbonate aqueous solution was supplied to the primary reactor by mixing 6.6 kg of sodium carbonate with 100 L of water. 14 vol% carbon dioxide gas was introduced into the primary and secondary reactors at rates of 10 m3/hr and 2.5 m3/hr, respectively. The aqueous sodium carbonate solution was reacted with carbon dioxide gas through the primary and secondary reactors in sequence to produce sodium bicarbonate. The results are shown in Table 1.

Driving data comparison hour
(min) importance CO ₂ (%) conversion rate
arrival time Entrance exit utilization rate Example 1 0 1.128 14.0 1.2 89.8 65 minutes 15 1.120 13.9 1.5 30 1.104 13.7 1.4 45 1.094 13.8 1.3 65 1.085 13.6 1.5 Example 2 0 1.128 14.0 1.9 86.1 75 minutes 15 1.122 13.9 1.9 30 1.108 13.7 2.0 45 1.101 13.7 1.9 60 1.093 13.7 1.9 75 1.085 13.8 1.9 comparative example 0 1.129 14.0 8.5 48.3 135 minutes 15 1.127 13.5 8.1 30 1.123 13.4 8.2 45 1.119 13.6 8.3 60 1.115 13.6 8.3 75 1.111 13.6 8.4 90 1.106 13.7 8.2 105 1.101 13.7 8.4 120 1.091 13.7 4.1 135 1.085 13.6 4.1

* In the comparative example, 0 to 105 minutes is the operation of the primary reactor, and 120 to 135 minutes is the operation of the secondary reactor.

From the above [Table 1], the method for producing integrated sodium bicarbonate, which is a preferred embodiment 1 according to the present invention, has a very high carbon dioxide gas utilization rate of 89.8% and a very short time to reach the conversion rate of only 65 minutes, in Example 2 and It was found that there was a very superior effect than the sodium bicarbonate production method using the two-stage reaction method according to the comparative example.

Although the present invention has been described with reference to the drawings and examples, it will be understood that these are exemplary, and that various modifications and equivalent other embodiments are possible therefrom by those of ordinary skill in the art. will be. Therefore, it will be obvious that the true technical protection scope of the present invention is defined by the following claims.

01: inlet 02: reactor
03: charging tower 04: off-gas outlet
05: bubble reactor 06: circulation pipe
07: distribution line 08: mixing mixer
09: inlet 10: dehydrator
11: dryer 12: gas separator

Claims (9)

a reactor including a packed tower and a bubble reactor for generating sodium bicarbonate by reacting an aqueous sodium carbonate solution with carbon dioxide gas;
a mixing mixer for generating fine bubbles from carbon dioxide gas and mixing the resulting fluid with an aqueous sodium carbonate solution to a gas separator;
a gas separator for separating liquid and gas from the fluid supplied from the mixing mixer and supplying them to the bubble reactor;
a dehydrator for separating sodium bicarbonate in a slurry state produced in the reactor by centrifugation;
A dryer for drying the sodium bicarbonate separated in the dehydrator;
The mixing mixer is an integrated sodium bicarbonate manufacturing apparatus, characterized in that the rotating impact type.
The method of claim 1,
An integrated apparatus for manufacturing sodium bicarbonate, characterized in that the average diameter of the microbubbles is 0.1 mm or less.
The method of claim 1,
The liquid separated in the gas separator is an integrated sodium bicarbonate production apparatus, characterized in that at least one of an aqueous sodium carbonate solution, an intermediate product and a product of the sodium bicarbonate production reaction.
The method of claim 1,
The gas separated in the gas separator is carbon dioxide gas, an integrated production apparatus for sodium bicarbonate, characterized in that air.
The method of claim 1,
The filtrate obtained by centrifuging sodium bicarbonate in a slurry state in the dehydrator is recycled to the packed tower through a circulation pipe.
The method of claim 1,
The rotational collision type is firstly installed by inserting a gas pipe in the center of the liquid pipe, forming a number of holes in the discharge part to evenly spray carbon dioxide gas to generate fine bubbles, and secondly, it is input to the side of the cylindrical body to generate rotational force After mixing the sodium carbonate aqueous solution with the microbubbles to form a fluid, the fluid collides with the circular perforated plate a number of times in the tertiary manner so as to be mixed.
The sodium carbonate aqueous solution supplied through the inlet and the carbon dioxide gas supplied through the inlet are mixed with fine bubbles in the vortex-impact mixing mixer to form a fluid, then separated from the gas separator and supplied to the bubble reactor, and then reacted with each other to primarily sodium bicarbonate a first step of producing sodium bicarbonate secondarily by generating a , and then reacting the unreacted aqueous sodium carbonate solution with carbon dioxide gas in a packed tower;
A second step of drying the sodium bicarbonate in a slurry state produced in the first step after centrifugation in a dehydrator includes:
The reaction of the first step is made in a reactor configured in an integrally coupled manner, including a packed tower and a bubble reactor,
The method for producing sodium bicarbonate, characterized in that the filtrate obtained by centrifuging the sodium bicarbonate in the slurry state in the second step is recycled to the packed column.
8. The method of claim 7,
The microbubbles of the first step have an average diameter of 0.1 mm or less.
8. The method of claim 7,
The reaction of the first step is a method for producing sodium bicarbonate, characterized in that both 30 ~ 35 ℃, 4 bar in a packed tower and a bubble reactor.

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