KR102121408B1 - Odor removal method of strong basic anion ecxhange resin - Google Patents
Odor removal method of strong basic anion ecxhange resin Download PDFInfo
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- KR102121408B1 KR102121408B1 KR1020200015781A KR20200015781A KR102121408B1 KR 102121408 B1 KR102121408 B1 KR 102121408B1 KR 1020200015781 A KR1020200015781 A KR 1020200015781A KR 20200015781 A KR20200015781 A KR 20200015781A KR 102121408 B1 KR102121408 B1 KR 102121408B1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/04—Processes using organic exchangers
- B01J41/05—Processes using organic exchangers in the strongly basic form
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Abstract
Description
개시된 내용은 강염기성 음이온 교환수지의 취기 제거방법, 더욱 상세하게는 유해가스의 흡착력이 우수하면서도, 음이온교환수지 제품의 취기가 발생하지 않는 강염기성 음이온 교환수지의 취기 제거방법에 관한 것이다. Disclosed is a method for removing odor of a strong basic anion exchange resin, and more particularly, a method for removing an odor of a strong basic anion exchange resin that does not generate odor of an anion exchange resin product, while having excellent adsorption power of harmful gases.
본 명세서에서 달리 표시되지 않는 한, 이 식별항목에 설명되는 내용은 이 출원의 청구항들에 대한 종래기술이 아니며, 이 식별항목에 포함된다고 하여 종래기술이라고 인정되는 것은 아니다. Unless otherwise indicated in this specification, the contents described in this identification item are not prior art to the claims of this application, and being included in this identification item is not recognized as a prior art.
일반적으로 이온교환수지에는 미반응 고분자물질등 미량의 불순물이 있으며, 특히 아민기를 가지고 있는 음이온 교환수지는 냄새가 발생하게 된다. 종래에는 이의 냄새나 맛 또는 유기물질 유출을 예방하기 위하여 전처리를 실시하였다.In general, the ion exchange resin has a trace amount of impurities such as unreacted polymer materials, and in particular, an anion exchange resin having an amine group generates odor. In the related art, pretreatment was performed to prevent the smell or taste or the leakage of organic substances.
일반적으로는 통액전에 해당 재생제로 재생작업을 하는것으로 충분하지만 좀더 "정밀한" 용도에는 4∼8% HCl과 4% NaOH용액으로 교차 세척 후 120분간 SV 5로 수세한 다음 수온 70˚C의 열수로 120분간 SV 5로 온수수세를 한 후 배량 재생작업을 하고, 특히 강염기성 음이온교환수지의 Amine 취기(臭氣)의 제거하기 위하여 NaCl 10% 용액을 70℃로 2∼3BV 가한 후 70℃의 온수로 수세하는 전처리 방법이 있다.In general, it is sufficient to regenerate with the appropriate regeneration agent before passing through, but for a more "precise" use, cross-wash with 4-8% HCl and 4% NaOH solution, wash with SV 5 for 120 minutes, and then use hot water at 70˚C. After washing with hot water for 5 minutes with SV 5 for 120 minutes, the volume is regenerated. Especially, in order to remove Amine odor of strong basic anion exchange resin, NaCl 10% solution is added to 2~3BV at 70℃ and hot water at 70℃. There is a pretreatment method of washing with.
하지만, OH형이나 Free-base형의 음이온 교환수지에는 상기의 전처리 방법은 부적합하며, 전처리 과정이 복잡하고 경제적이지 않다는 문제점이 있다. However, the above pretreatment method is not suitable for the OH type or the free-base anion exchange resin, and there is a problem that the pretreatment process is complicated and not economical.
시간이 지나도 이온교환성능이 유지되어 유해가스의 흡착력이 우수하면서도, 음이온교환수지 제품의 냄새가 발생하지 않는 강염기성 음이온 교환수지의 취기 제거방법을 제공하고자 한다.It is an object of the present invention to provide a method for removing odor of a strongly basic anion exchange resin that does not generate an odor of an anion exchange resin product, while maintaining excellent ion adsorption performance due to the maintenance of ion exchange performance over time.
또한 상술한 바와 같은 기술적 과제들로 한정되지 않으며, 이하의 설명으로부터 또 다른 기술적 과제가 도출될 수도 있음은 자명하다.In addition, it is obviously not limited to the above-described technical problems, and another technical problem may be derived from the following description.
하나의 일 실시예로서, 강염기성 음이온 교환수지 전처리 단계,상기 전처리 단계를 거친 강염기성 음이온 교환수지의 수분함량을 낮추는 건조단계 및 상기 건조단계를 거친 강염기성 음이온 교환수지에 취기제거원료를 투입하는 혼합단계를 포함하는 강염기성 음이온 교환수지의 취기 제거방법에 대해 기술하고 있다.As one embodiment, a strong basic anion exchange resin pre-treatment step, a drying step of lowering the moisture content of the strong basic anion exchange resin that has been subjected to the pre-treatment step, and a strong basic anion exchange resin that has undergone the drying step are added with an odor removal raw material. Describes a method for removing odor of a strong basic anion exchange resin including a mixing step.
이상에서와 같은 강염기성 음이온 교환수지의 취기 제거방법은 시간이 지남에 따라서도 이온교환 성능이 유지되고, 아민의 냄새가 발생하지 않아 작업환경을 개선시키는 효과를 제공할 수 있다.The odor removal method of the strong basic anion exchange resin as described above can maintain the ion exchange performance over time and provide an effect of improving the working environment because no amine odor is generated.
본 실시 예들의 효과는 이상에서 언급한 효과들로 제한되지 않으며, 언급되지 않은 또 다른 효과들은 청구범위의 기재로부터 통상의 기술자에게 명확하게 이해될 수 있을 것이다.The effects of the present embodiments are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description of the claims.
이하에는, 본 발명의 바람직한 실시예와 각 성분의 물성을 상세하게 설명하되, 이는 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 발명을 용이하게 실시할 수 있을 정도로 상세하게 설명하기 위한 것이지, 이로 인해 본 발명의 기술적인 사상 및 범주가 한정되는 것을 의미하지는 않는다.Hereinafter, a preferred embodiment of the present invention and the physical properties of each component will be described in detail, but this is intended to be described in detail so that a person skilled in the art to which the present invention pertains can easily implement the invention. This does not mean that the technical spirit and scope of the present invention is limited.
강염기성 음이온 교환수지의 취기 제거방법은 강염기성 음이온 교환수지를 전처리하는 전처리 단계와, 전처리 단계를 거친 강염기성 음이온 교환수지의 수분함량을 낮추는 건조단계와, 건조단계를 거친 강염기성 음이온 교환수지에 취기제거원료를 투입하는 혼합단계를 포함한다.The odor removal method of the strong basic anion exchange resin is a pretreatment step of pre-treating the strong basic anion exchange resin, a drying step of lowering the moisture content of the strong basic anion exchange resin after the pretreatment step, and a strong basic anion exchange resin after the drying step. And a mixing step of adding an odor removing raw material.
더욱 상세하게는 제품의 원료가 되는 강염기성 음이온 교환수지의 수분 함유량은 55 내지 65 중량% 정도인데, 이를 30 내지 60℃ 온도하에서 강염기성 음이온 교환수지의 수분함량을 30 내지 35 중량%로 낮추는 전처리 작업을 한다.More specifically, the water content of the strong basic anion exchange resin as a raw material of the product is about 55 to 65% by weight, which is pre-treatment to reduce the moisture content of the strong basic anion exchange resin to 30 to 35% by weight under the temperature of 30 to 60℃. Work.
전처리 작업은 강염기성 음이온 교환수지를 건조기를 통해 건조하는 것이 아니라 30 내지 60℃ 온도로 실내가 유지되는 건조실의 바닥 또는 다단적층선반에 투입되어 이루어질 수 있다. 전처리 작업은 1일 내지 3일의 시간에 걸쳐 이루어질 수 있다.The pre-treatment may be performed by putting the strong basic anion exchange resin in the floor or multi-layer lathe of the drying room where the room is maintained at a temperature of 30 to 60° C. rather than drying through a dryer. The pre-treatment can take place over a period of 1 to 3 days.
전처리 단계를 거친 원료는 건조기 내부에 투입되어, 18 시간 내지 24 시간 동안의 건조단계를 거쳐, 강염기성 음이온 교환수지의 수분함량을 16 내지 22 중량%로 낮추게 된다.The raw material that has undergone the pre-treatment step is introduced into the dryer, and after 18 to 24 hours of drying, the moisture content of the strong basic anion exchange resin is reduced to 16 to 22% by weight.
강염기성 음이온 교환수지는 전처리 작업과 건조단계 즉 2단계를 거쳐 건조되면서 물성의 큰 변화없이 요구되는 수분함량, 즉 16 내지 22 중량%의 수분함량으로 감소될 수 있게 된다.The strong basic anion exchange resin can be reduced to a required moisture content, that is, a moisture content of 16 to 22% by weight without significant change in physical properties as it is dried through a pre-treatment operation and a drying step, that is, a second step.
건조단계가 끝난 후에는, 건조기에서 인출하여 소분을 한 후에, 강염기성 음이온 교환수지 100 중량부 대비, 취기제거원료를 0.05 내지 20 중량부를 투입하는상기 혼합단계를 거친다. 바람직하게는 취기제거 원료를 3 내지 10 중량부 투입하는 것이고, 더 바람직하게는 0.8 중량부를 투입하는 것이다. 취기제거 원료를 0.05 미만으로 넣게 되면 취기를 제거하는 효과가 미미하고, 20 중량부 이상을 투입하게 되면 이온교환수지의 성능을 떨어뜨리게 된다.After the drying step is completed, the mixture is drawn out from the dryer and subjected to the mixing step of adding 0.05 to 20 parts by weight of the odor removing raw material, compared to 100 parts by weight of the strong basic anion exchange resin. Preferably, 3-10 parts by weight of the odor removing raw material is added, and more preferably 0.8 parts by weight is added. If the raw material for removing odor is added to less than 0.05, the effect of removing odor is negligible, and when more than 20 parts by weight is added, the performance of the ion exchange resin is deteriorated.
이온교환수지는 관능기에 따라 강산성 양이온 교환수지, 약산성 양이온 교환수지, 강염기성 음이온 교환수지 및 약염기성 음이온 교환수지로 분류되며, 제조방법에 따라서는 GEL형과 POROUS형으로 나뉜다. Ion exchange resins are classified into strong acid cation exchange resins, weak acid cation exchange resins, strong basic anion exchange resins, and weak basic anion exchange resins according to functional groups, and are classified into GEL type and POROUS type depending on the manufacturing method.
그 중에서 강염기성 음이온 교환수지는 시간이 지남에 따라서 냄새를 발산하게 되는데, 이 취기(臭氣)는 트리메틸아민에 결합된 수산기(OH-)가 쉽게 탈락하면서 제품에 그룹으로 형성되어 있는 트리메틸기가 열 분해에 의해 발생하는 것이다. 이로인해 이온교환수지를 사용하는 근로자들의 작업환경을 저해하고, 이온교환수지 성능의 급격한 저하로 경제적 손실과 이온교환수지를 이용한 실험 데이터 등에 악영향을 주게 된다. Among them, there is the strongly basic anion exchange resins give off the smell with time, the odor (臭氣) is a hydroxyl group (OH -) coupled to the trimethylamine group is easily eliminated with heat trimethylamine formed as a group in the product It is caused by decomposition. As a result, the working environment of workers using ion exchange resins is hindered, and the rapid decrease in the performance of ion exchange resins adversely affects economic loss and experimental data using ion exchange resins.
개시된 발명은 OH-의 강염기성 음이온 교환수지가 상온에서 서서히 분해되어 Amine 냄새를 발산하는 것을 방지하기 위하여, 취기 제거를 위한 원료로 약산성 양이온 교환 수지를 투입하게 된다. 투입된 약산성 양이온 교환수지가, OH-가 탈락된 트리메틸기에 결합하여 아민기의 열분해를 방지하는 역할을 한다. In the disclosed invention, a weakly acidic cation exchange resin is introduced as a raw material for removing odor in order to prevent the strong basic anion exchange resin of OH − from slowly decomposing at room temperature to emit the odor of amine. The introduced weakly acidic cation exchange resin binds to the trimethyl group from which OH - is eliminated, and serves to prevent thermal decomposition of the amine group.
개시된 발명에서 적용되는 음이온 교환수지와 취기제거 원료의 상세한 물성은 하기와 같다. Detailed properties of the anion exchange resin and the odor removal raw material applied in the disclosed invention are as follows.
<강염기성 음이온 교환수지><strong basic anion exchange resin>
1. 제품형태:OH-형1. Product type: OH-type
2. 제품Type:Gel-타입/Ⅰ형또는.Porous-타입/Ⅰ2. Product Type:Gel-type/Ⅰtype or .Porous-type/Ⅰ
3. 제품의입상상태:둥근알갱이 또는 Bead 모양3. Product granularity: Round grain or bead shape
4. 제품의입자및색상:담황색투명구상 및 둥근입자모양4. Particles and color of the product: light yellow transparent sphere and round particle shape
5. 제품입자의크기:150㎛~1,250㎛5. Product particle size: 150㎛~1,250㎛
6. 제품사용온도:20~60℃6. Product use temperature: 20~60℃
7. 제품의조성비율:디비닐벤젠(2~25%),스틸렌모노머.(50~100%)7. Composition ratio of product: divinylbenzene (2~25%), styrene monomer. (50~100%)
8. 강염기성 음이온교환수지(Ⅰ-Gel타입/OH-형)구조식은 아래 표 1과 같다.8. Strong basic anion exchange resin (Ⅰ-Gel type/OH-type) structural formula is as shown in Table 1 below.
구조모형
Structure model
트리메틸아민기를 도입하여 교환기를 붙임
Trimethylamine group is introduced to attach the exchange group
9. 강염기성 음이온 교환수지 물성치는 아래 표 2와 같다9. The properties of strong basic anion exchange resin are shown in Table 2 below.
<취기(臭氣) 제거 원료><Raw material for removing odor>
1. 취기제거하는원료형태:COOH1. Raw material type to remove odor: COOH
2. 취기제거하는원료Type:Gel-타입2. Raw material type to remove odor: Gel-type
3. 취기제거하는원료의입상상태:둥근.알갱이또는Bead 모양3. Granular state of raw material to remove odor: round, granular or bead shape
4. 취기제거하는원료의.입자및색상: 담갈색~담황색투명구상의둥근입자모양4. Particles and color of raw material to remove odor: Light brown to light yellow transparent spherical shape
5. 취기제거하는원료입자의.크기:150㎛~1,250㎛5. Size of raw material particles to remove odor: 150㎛~1,250㎛
6. 취기제거하는원료사용온도:25~120℃↓6. Raw material temperature to remove odor: 25~120℃↓
7. 취기제거하는원료.조성비율:디비닐벤젠(2~15%), 스틸렌모노머(98~85%)7. Raw material and composition ratio to remove odor: Divinylbenzene (2~15%), Styrene monomer (98~85%)
8. 취기제거하는원료명:약산성양이온교환수지.(COOH) 구조식은 아래 표 3과 같다8. Raw material name to remove odor: Weak acidic cation exchange resin. (COOH) Structural formula is shown in Table 3 below.
구조모형
Structure model
9. 취기 제거하는 원료 항목 및 규격(DRY 상태)은 아래 표 4와 같다9. Items and specifications (DRY status) of raw materials to be removed are shown in Table 4 below.
상기 제조된 수지의 사용분야는 SOx, NOX 의 물질을 제거하는 매체로 사용되며, 특히 반도체 공장의 크린룸이나 또는 LCD 반도체 크린룸 등에 사용되는 필터로 제품을 생산하여 외부로부터 불순물을 차단하여 제품의 불량을 줄이고 또 근로자들에게 내부의 작업 환경의 개선으로 인해 산업 안전 보건법을 준수할 수 있게 된다.The field of use of the manufactured resin is used as a medium for removing substances of SO x and NO X. In particular, the product is produced with a filter used in a clean room of a semiconductor factory or an LCD semiconductor clean room to block impurities from the outside to produce a product. Reducing defects and improving internal working conditions for workers will enable them to comply with occupational safety and health laws.
Claims (6)
상기 전처리 단계를 거친 강염기성 음이온 교환수지의 수분함량을 낮추는 건조단계; 및
상기 건조단계를 거친 강염기성 음이온 교환수지에 취기제거원료를 투입하는 혼합단계;를 포함하고,
상기 취기제거원료는 약산성 양이온 교환수지로,
COOH 형이며,
디빌닐 벤젠 2 내지 15 중량부와 스틸렌 모노머 85 내지 98 중량부의 구상 중합물로,
교환 용량이 1.1 내지 4.5Meq/ml-R이고,
입도 범위가 0.15 내지 0.85mm인 것을 특징으로 하는 강염기성 음이온 교환수지의 취기 제거방법.
A pretreatment step of pre-treating the strong basic anion exchange resin;
A drying step of lowering the moisture content of the strong basic anion exchange resin after the pretreatment step; And
Including the mixing step of adding the odor removal raw material to the strong basic anion exchange resin after the drying step;
The odor removal raw material is a weakly acidic cation exchange resin,
COOH Brother,
As a spherical polymer of 2 to 15 parts by weight of divinyl benzene and 85 to 98 parts by weight of styrene monomer,
The exchange capacity is 1.1 to 4.5 Meq/ml-R,
A method for removing odor of a strong basic anion exchange resin, characterized in that the particle size range is 0.15 to 0.85 mm.
상기 전처리 단계는,
30 내지 60℃ 온도하에서 상기 강염기성 음이온 교환수지의 수분함량을 30 내지 35 중량%로 낮추는 것을 특징으로 하는 강염기성 음이온 교환수지의 취기 제거방법.
The method according to claim 1,
The pre-treatment step,
A method for removing odor of a strong basic anion exchange resin, characterized in that the moisture content of the strong basic anion exchange resin is reduced to 30 to 35% by weight under a temperature of 30 to 60°C.
상기 건조단계는 강염기성 음이온 교환수지의 수분함량은 16 내지 22 중량%로 낮추는 것을 특징으로 하는 강염기성 음이온 교환수지의 취기 제거방법.
The method according to claim 1,
In the drying step, the odor removal method of the strong basic anion exchange resin is characterized in that the moisture content of the strong basic anion exchange resin is lowered to 16 to 22% by weight.
상기 혼합단계는 강염기성 음이온 교환수지 100 중량부 대비, 취기제거원료를 0.05 내지 20 중량부를 투입하는 것을 특징으로 하는 강염기성 음이온 교환수지의 취기 제거방법.
The method according to claim 1,
In the mixing step, the odor removal method of the strong basic anion exchange resin is characterized in that 0.05 to 20 parts by weight of the odor removal raw material is added, compared to 100 parts by weight of the strong basic anion exchange resin.
상기 강염기성 음이온 교환수지는,
OH- 형으로,
디비닐 벤젠 2 내지 25 중량부와 스틸렌 모노머 50 내지 100중량부의 구상 중합물로,
교환 용량이 0.9 Meq/ml-R 이상이고,
입도 범위가 0.315 내지 1.25mm인 것을 특징으로 하는 강염기성 음이온 교환수지의 취기 제거방법. The method according to any one of claims 1 to 4,
The strong basic anion exchange resin,
OH -in the form,
As a spherical polymer of 2 to 25 parts by weight of divinyl benzene and 50 to 100 parts by weight of styrene monomer,
The exchange capacity is 0.9 Meq/ml-R or more,
A method for removing odor of a strong basic anion exchange resin having a particle size range of 0.315 to 1.25 mm.
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| KR102267687B1 (en) | 2020-07-22 | 2021-06-22 | 오염희 | Processing Method for Strongly Basic Anion Exchange Resin and Processing System thereof |
| KR102357399B1 (en) * | 2020-12-22 | 2022-02-09 | 경민워터컴(주) | A composition for mixed ion exchange polymers and bad odor removal method |
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