KR100297321B1 - Synthesis of Zeolite A from Serpentine - Google Patents
Synthesis of Zeolite A from Serpentine Download PDFInfo
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- KR100297321B1 KR100297321B1 KR1019990006110A KR19990006110A KR100297321B1 KR 100297321 B1 KR100297321 B1 KR 100297321B1 KR 1019990006110 A KR1019990006110 A KR 1019990006110A KR 19990006110 A KR19990006110 A KR 19990006110A KR 100297321 B1 KR100297321 B1 KR 100297321B1
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- serpentine
- zeolite
- distilled water
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- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 title claims abstract description 49
- 239000010457 zeolite Substances 0.000 title claims abstract description 49
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 41
- 230000015572 biosynthetic process Effects 0.000 title abstract description 8
- 238000003786 synthesis reaction Methods 0.000 title abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000012153 distilled water Substances 0.000 claims abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 14
- 238000002386 leaching Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 5
- 239000011707 mineral Substances 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001308 synthesis method Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 11
- 239000012535 impurity Substances 0.000 abstract description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract description 2
- 238000010298 pulverizing process Methods 0.000 abstract description 2
- 238000005303 weighing Methods 0.000 abstract description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910052898 antigorite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052620 chrysotile Inorganic materials 0.000 description 1
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052899 lizardite Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/14—Type A
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
본 발명은 사문석으로부터 제올라이트 A 의 합성방법에 관한 것으로, 그 목적은 국내에 부존 되어 있는 사문석을 황산이나 염산으로 습식처리하여 불순물을 제거한 활성화된 침출잔사로부터 제올라이트 A를 합성하는데 있으며 실리카원료로 물유리나 실리카졸, 화이트 카본(white carbon) 등 시약급을 사용한 경우 보다 비교적 저온에서 제올라이트 A의 합성이 가능함과 동시에, 단시간 내에 반응이 종료될 수 있는 사문석으로부터 제올라이트 A 의 합성방법을 제공하는 것이다.The present invention relates to a method for synthesizing zeolite A from serpentine, the purpose of which is to synthesize zeolite A from activated leach residues obtained by wet treatment of serpentine existing in Korea with sulfuric acid or hydrochloric acid to remove impurities. In the case of using reagent grades such as silica sol and white carbon, zeolite A can be synthesized at a relatively low temperature, and a method for synthesizing zeolite A from serpentine can be completed in a short time.
본 발명은 A 타입(type) 제올라이트 합성방법에 있어서; SiO236∼37%, MgO 34∼36%를 함유하는 사문석을 -200mesh로 분쇄 및 자력선별하는 제 1 단계와, 상기 200mesh로 분쇄 및 자력선별된 사문석을 광액농도 5∼300g/ℓ범위에서 반응온도 80∼100℃인 침출제에 주입한 후, 약 1∼12 시간동안 300rpm의 속도로 교반하고, 침출처리하는 제 2 단계와, 상기 침출처리된 산물을 고/액분리하여 활성화처리된 사문석 침출잔사를 회수하고, 이를 증류수로 세척하여 침출잔사에 잔류하는 산을 제거하는 제 3 단계와, 상기 세척된 사문석 침출잔사를 110℃에서 24시간 건조하는 제 4 단계와, 상기 건조된 침출잔사 일정량을 일정량의 증류수가 들어있는 비이커에 넣고, 다시 50% 수산화나트륨(NaOH)용액 일정량을 가한 후, 투명하게 용해될 때 까지 가열하는 제 5 단계와, 상기 제 5 단계와 동일한 양의 증류수가 들어있는 동일한 용량의 비이커에 수산화알루미늄(Al(OH)3) 일정량을 넣고, 다시 50% 수산화나트륨(NaOH)용액 일정량을 가한 후 투명하게 용해될 때 까지 가열하는 제 6 단계와, 상기 제 5 단계 및 제 6 단계에 의해 가열된 두 용액을 각각 냉각시킨 후 무게를 측정하고, 소모된 양만큼의 증류수를 다시 가하는 제 7 단계와, 상기 두 용액을 둥근바닥 플라스크에 넣고 히팅 맨틀(heating mantle)에 장치한 후, 반응온도 60∼90℃에서 100rpm 속도로 교반하면서 1∼4시간동안 반응시키는 제 8 단계와, 상기 반응이 완료된 산물을 여과를 통해 고/액 분리하고, 이를 증류수로 수회 세척하는 제 9 단계와, 상기 세척된 분말을 110℃에서 24시간 건조하는 제 10 단계에 의해 aNa2O·bAl2O3·cSiO2·dH2O ( a/c : 0.5∼2.0, c/b : 0.5∼4.0, d/a : 20∼40 )의 조성비를 구비하는 제올라이트 A를 합성하는 사문석으로부터 제올라이트 A 의 합성방법을 제공함에 있다.The present invention provides a method for synthesizing A type zeolite; The first step of pulverizing and magnetically sorting serpentine containing 36 to 37% SiO 2 and 34 to 36% MgO to -200mesh, and reacting the serpentine pulverized and magnetically selected to 200mesh in the range of 5 to 300 g / l of mineral solution After injecting a leaching agent having a temperature of 80 to 100 ° C., stirring at a speed of 300 rpm for about 1 to 12 hours, and leaching the second step, and solidifying / liquid-separating the leached product, activated serpentine leaching Recovering the residue, washing it with distilled water to remove acid remaining in the leach residue, a fourth step of drying the washed serpentine leach residue at 110 ° C. for 24 hours, and a predetermined amount of the dried leach residue Put in a beaker containing a certain amount of distilled water, add a predetermined amount of 50% sodium hydroxide (NaOH) solution, and then heat until it is dissolved transparently, the same as the fifth step containing the same amount of distilled water Capacity Beaker Aluminum hydroxide (Al (OH) 3) amount were placed again in the sixth step of heating after adding 50% sodium hydroxide (NaOH) solution, a certain amount until it is transparent to dissolve, and the fifth step and the heating by the sixth step After cooling each of the two prepared solutions, weighing them, and adding the distilled water as much as the consumed amount, and putting the two solutions in a round bottom flask and placing them in a heating mantle, the reaction temperature 60 An eighth step of reacting for 1 to 4 hours while stirring at a speed of 100 rpm at -90 ° C, a ninth step of solid / liquid separation of the product from which the reaction is completed through filtration, and washing with distilled water several times; ANa 2 O.bAl 2 O 3 .cSiO 2 .dH 2 O (a / c: 0.5-2.0, c / b: 0.5-4.0, d / a: by the tenth step of drying the powder at 110 ° C for 24 hours. Zeolite from serpentine for synthesizing zeolite A having a composition ratio of 20 to 40 It is the synthesis of the A to provide.
Description
본 발명은 사문석으로부터 제올라이트 A 의 합성방법에 관한 것으로, 국내에 부존 되어 있는 사문석을 황산 또는 염산으로 습식처리하여 불순물이 제거된 침출잔사로부터 A-타입(type) 제올라이트를 제조하는 사문석으로부터 제올라이트 A 의 합성방법에 관한 것이다.The present invention relates to a method for synthesizing zeolite A from serpentine, wherein zeolite A is prepared from serpentine to prepare A-type zeolite from a leaching residue from which impurities are removed by wet treatment of serpentine existing in Korea with sulfuric acid or hydrochloric acid. It relates to a synthesis method.
일반적으로 제올라이트(zeolite)는 SiO4와 AlO4의 사면체가 기하학적 형태로 결합하여 규칙적인 삼차원적 골격 구조를 갖는 알루미나-실리카의 결정분자체로, 상기 사면체들은 산소를 서로 공유하여 연결되며 골격은 홈(channel)을 갖고또한 서로 연결된 공동(cavity)을 갖는 특징이 있다. 다른 알루미노규산염 (aluminosilicate)의 결정에 비하여 공동이 크고, 이온교환성이 우수하기 때문에 촉매, 흡착제, 분자체, 이온교환제 등 다양한 용도로 사용되고 있다.In general, zeolites are crystallites of alumina-silica having tetrahedral structures of SiO 4 and AlO 4 , which have a regular three-dimensional skeletal structure, and the tetrahedrons share oxygen to each other, and the skeleton is a groove. It is characterized by having channels and cavities connected to each other. Compared with other crystals of aluminosilicate, the cavities are larger and have excellent ion exchange properties. Therefore, they are used in various applications such as catalysts, adsorbents, molecular sieves and ion exchangers.
제올라이트는 천연에서 산출되는 제올라이트와 합성된 제올라이트가 있는데 순도나 구조적인 제약으로 인하여 천연산 제올라이트의 용도는 특별한 부분에 제한되어 있는 반면 합성 제올라이트의 용도는 더욱 확대되고 있는 실정이다. 합성된 제올라이트가 다양한 용도로 응용되기 위해서는 경제적인 합성방법뿐 아니라 합성된 제올라이트의 결정크기, 분포 및 형태를 임의대로 조절할 수 있어야 하기 때문에 제올라이트의 합성에 관한 많은 특허와 연구결과가 발표된 바 있다.Zeolites include zeolites produced in nature and zeolites synthesized. Due to purity and structural constraints, the use of natural zeolites is limited to a particular part, but the use of synthetic zeolites is being expanded. In order to apply the synthesized zeolite for various applications, many patents and researches on the synthesis of zeolite have been published since it is necessary to arbitrarily control the crystal size, distribution, and shape of the synthesized zeolite as well as an economical synthesis method.
본 발명에서 제조하고자 하는 A 타입(type) 제올라이트는 현재 주로 세제지지체(detergent builder)로 사용되고 있으며, 상기 A 타입(type) 제올라이트는 1940년대에 합성되었기 때문에 기본적인 제조방법은 이미 널리 알려져 있다. 제올라이트는 주로 수열합성에 의해 제조되며, 발표된 논문마다 방법적인 면과 조성에서 약간씩의 차이를 보인다. 일반적인 제올라이트 A의 수열합성시 조성은 aNa2O·bAl2O3·cSiO2·dH2O ( a/c : 0.3∼4.0, c/b : 0.3∼3.0, d/a : 20∼40 ), 온도는 70∼95℃범위, 1∼7일간 숙성하고 1∼24시간동안 반응을 시킨다. 반응이 완료되면 여과 및 세척한 다음, 110℃에서 24시간 건조한다. 제올라이트 A의 합성시 SiO2원료로는 대부분 물유리나 실리카졸, 화이트 카본(White Carbon) 등을 사용하고 있다.The type A zeolite to be prepared in the present invention is currently mainly used as a detergent builder, and since the A type zeolite was synthesized in the 1940's, a basic manufacturing method is already widely known. Zeolites are mainly manufactured by hydrothermal synthesis, and there are some differences in method and composition between published articles. In the hydrothermal synthesis of general zeolite A, the composition is aNa 2 O.bAl 2 O 3 .cSiO 2 .dH 2 O (a / c: 0.3-4.0, c / b: 0.3-3.0, d / a: 20-40), The temperature is in the range of 70-95 ° C., aged for 1-7 days and allowed to react for 1-24 hours. After the reaction is completed, the mixture is filtered and washed, and then dried at 110 ° C for 24 hours. In the synthesis of zeolite A, most of SiO 2 materials are water glass, silica sol, and white carbon.
최근에는 천연 실리카 광물을 활용하여 A 타입(type) 제올라이트를 경제적으로 합성하기 위한 연구가 활발히 수행되고 있으며, 고령토로부터 제올라이트 합성에 관한 연구결과는 상당수 보고된 바 있으나, 고령토 이외의 천연 실리카 광물은 불순물과 경제성 때문에 제올라이트의 원료로는 부적당한 것으로 알려져 있다.Recently, studies on economically synthesizing A-type zeolites using natural silica minerals have been actively conducted, and many studies on the synthesis of zeolites from kaolin have been reported, but natural silica minerals other than kaolin are impurities. It is known to be inadequate as a raw material for zeolite due to its economy and economy.
본 발명의 상기와 같은 문제점을 고려하여 이루어진 것으로, 그 목적은 국내에 부존 되어 있는 사문석을 황산이나 염산으로 습식처리하여 불순물을 제거한 활성화된 침출잔사로부터 제올라이트 A를 합성하여 실리카 원료로 물유리나 실리카졸, 화이트 카본(white carbon) 등 시약급을 사용한 경우 보다 비교적 저온에서 제올라이트 A 합성이 가능하고, 숙성시간이 필요 없으며, 단시간 내에 반응이 종료될 수 있는 사문석으로부터 제올라이트 A 의 합성방법을 제공하는 것이다.In view of the above problems of the present invention, the object of the present invention is to synthesize zeolite A from activated leach residues by removing impurities by wet treating serpentine existing in Korea with sulfuric acid or hydrochloric acid, and using water glass or silica sol as a silica raw material. It is to provide a method for synthesizing zeolite A from serpentine, which can be synthesized zeolite A at a relatively low temperature, does not require a aging time, and the reaction can be terminated within a short time when using a reagent grade such as white carbon.
본 발명은 A 타입(type) 제올라이트 합성방법에 있어서; SiO236∼37%, MgO 34∼36%를 함유하는 사문석을 -200mesh로 분쇄 및 자력선별하는 제 1 단계와, 상기 200mesh로 분쇄 및 자력선별된 사문석을 광액농도 5∼300g/ℓ범위에서 반응온도 80∼100℃인 침출제에 주입한 후, 약 1∼12 시간동안 300rpm의 속도로 교반하고, 침출처리하는 제 2 단계와, 상기 침출처리된 산물을 고/액분리하여 활성화처리된 사문석 침출잔사를 회수하고, 이를 증류수로 세척하여 침출잔사에 잔류하는 산을 제거하는 제 3 단계와, 상기 세척된 사문석 침출잔사를 110℃에서 24시간 건조하는 제 4 단계와, 상기 건조된 침출잔사 일정량을 일정량의 증류수가 들어있는 비이커에 넣고, 다시 50% 수산화나트륨(NaOH)용액 일정량을 가한 후, 투명하게 용해될 때 까지 가열하는 제 5 단계와, 상기 제 5 단계와 동일한 양의 증류수가 들어있는 동일한 용량의 비이커에 수산화알루미늄(Al(OH)3) 일정량을 넣고, 다시 50% 수산화나트륨(NaOH)용액 일정량을 가한 후 투명하게 용해될 때 까지 가열하는 제 6 단계와, 상기 제 5 단계 및 제 6 단계에 의해 가열된 두 용액을 각각 냉각시킨 후 무게를 측정하고, 소모된 양만큼의 증류수를 다시 가하는 제 7 단계와, 상기 두 용액을 둥근바닥 플라스크에 넣고 히팅 맨틀(heating mantle)에 장치한 후, 반응온도 60∼90℃에서 100rpm 속도로 교반하면서 1∼4시간동안 반응시키는 제 8 단계와, 상기 반응이 완료된 산물을 여과를 통해 고/액 분리하고, 이를 증류수로 수회 세척하는 제 9 단계와, 상기 세척된 분말을 110℃에서 24시간 건조하는 제 10 단계에 의해 aNa2O·bAl2O3·cSiO2·dH2O ( a/c : 0.5∼2.0, c/b : 0.5∼4.0, d/a : 20∼40 )의 조성비를 구비하는 제올라이트 A를 합성하는 사문석으로부터 제올라이트 A 의 합성방법을 제공함에 있다.The present invention provides a method for synthesizing A type zeolite; The first step of pulverizing and magnetically sorting serpentine containing 36 to 37% SiO 2 and 34 to 36% MgO to -200mesh, and reacting the serpentine pulverized and magnetically selected to 200mesh in the range of 5 to 300 g / l of mineral solution After injecting a leaching agent having a temperature of 80 to 100 ° C., stirring at a speed of 300 rpm for about 1 to 12 hours, and leaching the second step, and solidifying / liquid-separating the leached product, activated serpentine leaching Recovering the residue, washing it with distilled water to remove acid remaining in the leach residue, a fourth step of drying the washed serpentine leach residue at 110 ° C. for 24 hours, and a predetermined amount of the dried leach residue Put in a beaker containing a certain amount of distilled water, add a predetermined amount of 50% sodium hydroxide (NaOH) solution, and then heat until it is dissolved transparently, the same as the fifth step containing the same amount of distilled water Capacity Beaker Aluminum hydroxide (Al (OH) 3) amount were placed again in the sixth step of heating after adding 50% sodium hydroxide (NaOH) solution, a certain amount until it is transparent to dissolve, and the fifth step and the heating by the sixth step After cooling each of the two prepared solutions, weighing them, and adding the distilled water as much as the consumed amount, and putting the two solutions in a round bottom flask and placing them in a heating mantle, the reaction temperature 60 An eighth step of reacting for 1 to 4 hours while stirring at a speed of 100 rpm at -90 ° C, a ninth step of solid / liquid separation of the product from which the reaction is completed through filtration, and washing with distilled water several times; ANa 2 O.bAl 2 O 3 .cSiO 2 .dH 2 O (a / c: 0.5-2.0, c / b: 0.5-4.0, d / a: by the tenth step of drying the powder at 110 ° C for 24 hours. Zeolite from serpentine for synthesizing zeolite A having a composition ratio of 20 to 40 It is the synthesis of the A to provide.
도 1 은 사문석으로부터 제조한 제올라이트 A(a,b,c)와 표준시료(d,미국, PQ사)의 XRD 분석결과도1 is an XRD analysis of zeolite A (a, b, c) prepared from serpentine and a standard sample (d, PQ, USA)
사문석은 Mg3Si2O5(OH)4의 조성을 갖는 마그네슘의 함수규산염으로서, 산화마그네슘이 32∼38%, 실리카가 35∼40% 정도 포함되어 있으며, 국내에는 약 75,000천톤이 매장되어 있는 광물이다. 사문석에 함유된 SiO2는 MgO와 서로 층상구조를 갖고 있기 때문에 산으로 MgO를 제거할 경우 원래 약 20㎡/g 인 사문석의 비표면적이250∼410㎡/g 정도로 증가하여 표면이 활성화된 비정질 실리카를 회수할 수 있다. 본 발명은 이와 같은 원리를 이용하는 것으로, 먼저 사문석을 분쇄하여 자력선별한 후, 염산이나 황산 등으로 습식처리하여 활성화된 침출잔사와 NaOH 그리고 Al(OH)3를 사용하여 제올라이트를 합성하였다.Serpentine is a hydrous silicate of magnesium having a composition of Mg 3 Si 2 O 5 (OH) 4 , containing 32 to 38% of magnesium oxide and 35 to 40% of silica, and a mineral containing about 75,000 tons in Korea to be. Since SiO 2 contained in the serpentine has a layered structure with MgO, when the MgO is removed with acid, the specific surface area of the serpentine, which is about 20 m 2 / g, is increased to about 250 to 410 m 2 / g, thereby making the surface activated amorphous silica. Can be recovered. The present invention uses the same principle, first, the serpentine was pulverized by magnetic screening, and then wet treatment with hydrochloric acid or sulfuric acid was used to synthesize zeolite using activated leach residue, NaOH and Al (OH) 3 .
즉, 본 발명은 사문석(SiO2: 36∼37%, MgO : 34∼36%)을 -200mesh로 분쇄 및 자력선별한 후, 80∼100℃의 황산 또는 염산용액에서 약 1∼12 시간 침출처리한다. 이때 상기 황산과 염산용액의 농도는 각각 5∼30% 와 5∼20%이었으며, 광액농도는 5∼300g/ℓ, 교반속도는 300rpm으로 설정하였다.That is, according to the present invention, the serpentine (SiO 2 : 36-37%, MgO: 34-36%) is pulverized and magnetically screened to -200mesh, and then leached in sulfuric acid or hydrochloric acid solution at 80 to 100 ° C. for about 1 to 12 hours. do. At this time, the concentration of sulfuric acid and hydrochloric acid solution was 5-30% and 5-20%, respectively, the mineral liquid concentration was set to 5 ~ 300g / ℓ, the stirring speed was set to 300rpm.
상기와 같이 황산 또는 염산용액으로 침출처리하면 마그네슘, 철 및 알루미늄 산화물은 70∼90% 침출되어 용액중에 존재하고, 침출잔사에는 80∼90% SiO2, 수분 및 기타 불순물이 함유되어 있다. 이를 고/액 분리한 다음 증류수로 여러 번 세척하여 침출잔사에 잔류하고 있는 산을 완전히 제거한다. 그리고 침출잔사로부터 A 타입(type) 제올라이트를 제조하기 위하여 aNa2O·bAl2O3·cSiO2·dH2O (a/c : 0.5∼2, c/b : 0.5∼4, d/a : 20∼40)의 조성비로 출발용액을 만들고 60∼90℃에서 100rpm의 속도로 교반하면서 1∼4시간동안 반응시키면 분말상태의 제올라이트 A 가 제조된다.When leaching with sulfuric acid or hydrochloric acid solution as described above, magnesium, iron and aluminum oxides are leached 70 to 90% in the solution, the leaching residue contains 80 to 90% SiO 2 , water and other impurities. This is separated into solids and liquids and washed several times with distilled water to completely remove the acid remaining in the leach residue. And for the production of type A (type) zeolite from the leach residue aNa 2 O · bAl 2 O 3 · cSiO 2 · dH 2 O (a / c: 0.5~2, c / b: 0.5~4, d / a: A starting solution is prepared at a composition ratio of 20 to 40), and the mixture is reacted for 1 to 4 hours with stirring at a speed of 100 rpm at 60 to 90 ° C., thereby preparing a powdery zeolite A.
상기 제올라이트 A 는 세제용으로 사용되기 때문에 백색도가 중요하다. 그러나, 사문석 침출잔사에 남아있는 미량의 불순물, 특히 철분에 의해 백색도가 떨어지는데 이를 보완하기 위해 처음 침출잔사를 용해시키는 단계에서 여과에 의해 불순물을 제거하면, 백색도가 우수한 제올라이트를 얻을 수가 있다.Since the zeolite A is used for detergents, whiteness is important. However, a small amount of impurities remaining in the serpentine leach residue, in particular, iron is reduced in whiteness. To compensate for this, if the impurities are removed by filtration at the first dissolving leach residue, a zeolite having excellent whiteness can be obtained.
이하 본 발명을 실시예에 의거하여 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail with reference to Examples.
실시예 1Example 1
사문석 100g을 25% 황산용액 1000㎖에 넣고 80∼100℃에서 1∼12시간 동안 가열하여 침출처리한다. 1∼12시간 경과 후 고/액 분리를 행하여 사문석 침출잔사를 회수한다. 사문석 침출잔사를 물로 여러 번 세척하여 남아있는 산 용액을 완전히 제거한다. 세척한 사문석 침출잔사를 110℃에서 24시간 건조하였다. 200㎖ 비이커에 증류수 66.4㎖를 넣고 마그네틱 바(magnetic bar)를 이용해 교반하면서 사문석 침출잔사 10.6g을 서서히 넣어준다. 다시 50% NaOH용액을 21.4㎖ 가한 후 가열한다. 또 다른 200㎖ 비이커에 증류수 66.4㎖를 넣고 마그네틱바(magnetic bar)로 교반하면서 Al(OH)3를 13.9g 넣어준다. 다시 50% NaOH용액을 21.4㎖ 가하고 가열한다. 두 용액이 모두 투명하게 용해될 때까지 가열한 후 냉각시킨다. 냉각된 상태에서 무게를 재고 소모된 양만큼의 증류수를 채워준다. 500㎖ 둥근바닥 플라스크에 두 용액을 넣으면 백색의 고형겔이 형성된다. 상기 플라스크를 히팅 맨틀(heating mantle)에 장치한 후 반응온도 90℃에서 교반하면서 1시간동안 반응을 시킨다. 반응이 완료되면 여과를 통해 고/액 분리를 하고 증류수로 수회 세척한다. 세척한 분말을 110℃에서 24시간 건조하여 제올라이트 A를 얻었다. 합성된 제올라이트 A는 XRD를 이용하여 확인하였다. (도 1-a 참조)100 g of serpentine is added to 1000 ml of 25% sulfuric acid solution and heated at 80 to 100 ° C. for 1 to 12 hours to leach out. After 1 to 12 hours, solid / liquid separation is performed to recover the serpentine leach residue. The serpentine leach residue is washed several times with water to completely remove the remaining acid solution. The washed serpentine leach residue was dried at 110 ° C. for 24 hours. 66.4 ml of distilled water was added to a 200 ml beaker and 10.6 g of serpentine leach residue was slowly added while stirring using a magnetic bar. 21.4 ml of a 50% NaOH solution was further added, followed by heating. 66.4 ml of distilled water was added to another 200 ml beaker and 13.9 g of Al (OH) 3 was added while stirring with a magnetic bar. Again 21.4 mL of 50% NaOH solution was added and heated. Both solutions are heated and cooled until they dissolve transparently. It is weighed in the cool state and filled with the amount of distilled water consumed. Two solutions are added to a 500 ml round bottom flask to form a white solid gel. The flask was placed in a heating mantle, and then reacted for 1 hour while stirring at a reaction temperature of 90 ° C. After the reaction is completed, the solids / liquids are separated by filtration and washed several times with distilled water. The washed powder was dried at 110 ° C. for 24 hours to obtain zeolite A. The synthesized zeolite A was confirmed using XRD. (See Figure 1-a)
실시예 2Example 2
사문석 100g을 25% 황산용액 1000㎖에 넣고 80∼100℃에서 1∼12시간 동안 가열하여 침출처리한다. 1∼12시간 경과 후 고/액 분리를 행하여 사문석 침출잔사를 회수한다. 사문석 침출잔사를 물로 여러 번 세척하여 남아있는 산 용액을 완전히 제거한다. 세척한 사문석 침출잔사를 110℃에서 24시간 건조하였다. 200㎖ 비이커에 증류수 66.4㎖를 넣고 마그네틱 바(magnetic bar)를 이용해 교반하면서 사문석 침출잔사 10.6g을 서서히 넣어준다. 다시 50% NaOH용액을 21.4㎖ 가한 후 가열한다. 또 다른 200㎖ 비이커에 증류수 66.4㎖를 넣고 마그네틱 바(magnetic bar)로 교반하면서 Al(OH)3를 13.9g 넣어준다. 다시 50% NaOH용액을 21.4㎖ 가하고 가열한다. 두 용액이 모두 투명하게 용해 될 때까지 가열한 후 냉각시킨다. 냉각된 상태에서 무게를 재고 소모된 양만큼의 증류수를 채워준다. 500㎖ 둥근바닥 플라스크에 두 용액을 넣으면 백색의 고형겔이 형성된다. 플라스크를 히팅 맨틀(heating mantle)에 장치한 후 반응온도 80℃에서 교반하면서 2시간동안 반응을 시킨다. 반응이 완료되면 여과를 통해 고/액 분리를 하고 증류수로 수회 세척한다. 세척한 분말을 110℃에서 24시간 건조하여 제올라이트 A를 얻었다. 합성된 제올라이트 A는 XRD를 이용하여 확인하였다. (도 1-b 참조)100 g of serpentine is added to 1000 ml of 25% sulfuric acid solution and heated at 80 to 100 ° C. for 1 to 12 hours to leach out. After 1 to 12 hours, solid / liquid separation is performed to recover the serpentine leach residue. The serpentine leach residue is washed several times with water to completely remove the remaining acid solution. The washed serpentine leach residue was dried at 110 ° C. for 24 hours. 66.4 ml of distilled water was added to a 200 ml beaker and 10.6 g of serpentine leach residue was slowly added while stirring using a magnetic bar. 21.4 ml of a 50% NaOH solution was further added, followed by heating. 66.4 ml of distilled water was added to another 200 ml beaker and 13.9 g of Al (OH) 3 was added while stirring with a magnetic bar. Again 21.4 mL of 50% NaOH solution was added and heated. Heat until both solutions are transparent and then cool. It is weighed in the cool state and filled with the amount of distilled water consumed. Two solutions are added to a 500 ml round bottom flask to form a white solid gel. The flask was placed in a heating mantle, and then reacted for 2 hours while stirring at a reaction temperature of 80 ° C. After the reaction is completed, the solids / liquids are separated by filtration and washed several times with distilled water. The washed powder was dried at 110 ° C. for 24 hours to obtain zeolite A. The synthesized zeolite A was confirmed using XRD. (See Figure 1-b)
실시예 3Example 3
사문석 100g을 25% 황산용액 1000㎖에 넣고 80∼100℃에서 1∼12시간 동안 가열하여 침출처리한다. 1∼12시간 경과 후 고/액 분리를 행하여 사문석 침출잔사를 회수한다. 사문석 침출잔사를 물로 여러 번 세척하여 남아있는 산 용액을 완전히 제거한다. 세척한 사문석 침출잔사를 110℃에서 24시간 건조하였다. 200㎖ 비이커에 증류수 66.4㎖를 넣고 마그네틱 바(magnetic bar)를 이용해 교반하면서 사문석 침출잔사를 10.6g 서서히 넣어준다. 다시 50% NaOH용액을 21.4㎖ 가한 후 가열한다. 또 다른 200㎖비이커에 증류수 66.4㎖를 넣고 마그네틱 바(magnetic bar)로 교반하면서 Al(OH)3를 13.9g 넣어준다. 다시 50% NaOH용액을 21.4㎖ 가하고 가열한다. 두 용액이 모두 투명하게 용해 될 때까지 가열한 후 냉각시킨다. 냉각된 상태에서 무게를 재고 소모된 양만큼의 증류수를 채워준다. 500㎖ 둥근바닥 플라스크에 두 용액을 넣으면 백색의 고형겔이 형성된다. 플라스크를 히팅 맨틀(heating mantle)에 장치한 후 반응온도 60℃에서 교반하면서 4시간동안 반응을 시킨다. 반응이 완료되면 여과를 통해 고/액 분리를 하고 증류수로 수회 세척한다. 세척한 분말을 110℃에서 24시간 건조하여 제올라이트 A를 얻었다. 합성된 제올라이트 A는 XRD를 이용하여 확인하였다. (도 1-c 참조)100 g of serpentine is added to 1000 ml of 25% sulfuric acid solution and heated at 80 to 100 ° C. for 1 to 12 hours to leach out. After 1 to 12 hours, solid / liquid separation is performed to recover the serpentine leach residue. The serpentine leach residue is washed several times with water to completely remove the remaining acid solution. The washed serpentine leach residue was dried at 110 ° C. for 24 hours. 66.4 ml of distilled water is added to a 200 ml beaker, and 10.6 g of serpentine leach residue is slowly added while stirring using a magnetic bar. 21.4 ml of a 50% NaOH solution was further added, followed by heating. 66.4 ml of distilled water was added to another 200 ml beaker and 13.9 g of Al (OH) 3 was added while stirring with a magnetic bar. Again 21.4 mL of 50% NaOH solution was added and heated. Heat until both solutions are transparent and then cool. It is weighed in the cool state and filled with the amount of distilled water consumed. Two solutions are added to a 500 ml round bottom flask to form a white solid gel. The flask was placed in a heating mantle, and then reacted for 4 hours while stirring at a reaction temperature of 60 ° C. After the reaction is completed, the solids / liquids are separated by filtration and washed several times with distilled water. The washed powder was dried at 110 ° C. for 24 hours to obtain zeolite A. The synthesized zeolite A was confirmed using XRD. (See Figure 1-c)
이와 같이 본 발명은 국내 매장량이 약 75,000 천톤이나 되는 사문석을 황산 또는 염산으로 습식처리하여 불순물이 제거된 침출잔사로부터 제올라이트 A를 제조할 수 있어 사문석의 부가가치와 활용분야를 확대할 수 있으며 비교적 저온에서 합성이 가능하고, 단시간내에 반응이 종료되므로 합성공정의 경제성이 확보되는 등 많은 효과가 있다.As such, the present invention can prepare zeolite A from leaching residues from which impurities are removed by wet treatment of serpentine having a domestic reserve of about 75,000 thousand tons with sulfuric acid or hydrochloric acid, thereby expanding the added value and application of serpentine at a relatively low temperature. Since the synthesis is possible and the reaction is completed within a short time, there are many effects such as securing the economics of the synthesis process.
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| JPH01261219A (en) * | 1988-04-13 | 1989-10-18 | Agency Of Ind Science & Technol | Production of a type zeolite |
| KR940006640A (en) * | 1992-09-17 | 1994-04-25 | 김용태 | Method for manufacturing adsorbent based on serpentine |
| US5595716A (en) * | 1994-08-23 | 1997-01-21 | Japan As Directed By Director General Of Agency Of Industrial Science And Technology | Synthetic mixed-layer silicate and method for the preparation thereof |
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| JPH01261219A (en) * | 1988-04-13 | 1989-10-18 | Agency Of Ind Science & Technol | Production of a type zeolite |
| KR940006640A (en) * | 1992-09-17 | 1994-04-25 | 김용태 | Method for manufacturing adsorbent based on serpentine |
| US5595716A (en) * | 1994-08-23 | 1997-01-21 | Japan As Directed By Director General Of Agency Of Industrial Science And Technology | Synthetic mixed-layer silicate and method for the preparation thereof |
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| DE102010004103A1 (en) | 2009-08-17 | 2011-03-03 | Epel Co., Ltd. | Catalyst for the conversion of light oil and production process thereof |
| US9061914B2 (en) | 2009-08-17 | 2015-06-23 | Epel Co., Ltd | Catalyst for recovering light oil and preparation method thereof |
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