KR100310661B1 - Technique of snythesis of Zeolite Na-A from Pyrophyllite - Google Patents
Technique of snythesis of Zeolite Na-A from Pyrophyllite Download PDFInfo
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- KR100310661B1 KR100310661B1 KR1019990023379A KR19990023379A KR100310661B1 KR 100310661 B1 KR100310661 B1 KR 100310661B1 KR 1019990023379 A KR1019990023379 A KR 1019990023379A KR 19990023379 A KR19990023379 A KR 19990023379A KR 100310661 B1 KR100310661 B1 KR 100310661B1
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- 239000010457 zeolite Substances 0.000 title claims abstract description 45
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 42
- 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 42
- 238000000034 method Methods 0.000 title abstract description 15
- 229910052903 pyrophyllite Inorganic materials 0.000 title description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- 239000012153 distilled water Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000010433 feldspar Substances 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000003599 detergent Substances 0.000 abstract description 3
- 238000005342 ion exchange Methods 0.000 abstract description 3
- 238000010517 secondary reaction Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229910021532 Calcite Inorganic materials 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000010808 liquid waste Substances 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000006063 cullet Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- -1 Al (OH) 3 Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910000144 sodium(I) superoxide Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 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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- 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 납석을 이용한 제올라이트 Na-A 제조법에 관한 것으로서, 더욱 상세하게는 자연산 납석으로부터 세제용 빌더 및 이온교환용 소재로 쓰일 수 있는 물질인 제올라이트류의 화합물 합성법으로 특히 Na-A에 대한 합성법에 관한 것이다.The present invention relates to a method for preparing zeolite Na-A using leadstone, and more particularly, to a method for synthesizing a compound of zeolite, which is a substance that can be used as a detergent builder and an ion exchange material from natural leadstone, in particular, a method for synthesizing Na-A. It is about.
본 발명은 납석을 150 매쉬 정도로 분쇄한 후 NaOH 2N ∼ 3N의 용액에 3 ∼ 4g:20cc의 비율로 섞어서 적절한 용량의 압력용기에 40±5％ 정도를 채운다. 그 후, 제 1 차 합성반응으로서 약 100 ∼ 130℃에서 교반시키면서 6 ∼ 10시간 이내로 가열하면 제올라이트 P가 순수한 물질로서 만들어진다. 제올라이트 P가 상온으로 냉각되면 제 2 차 반응으로서 제 1 차 반응결과물의 양을 1:1의 비율로 3M 이상의 NaAlO2 시약을 넣고 100℃ 이하에서 교반시키면서 하루 6 ∼ 10시간 이내로 가열하면 순수한 물질로서 제올라이트 Na-A가 만들어진다. 이렇게 하여 제조된 순수한 물질을 증류수로 세척하여 pH 10 정도가 되도록 하고 오븐에 넣어 90±5℃에서 건조시키는 제올라이트 Na-A 백색 분말 제조법이다.In the present invention, pulverized calcite is about 150 mesh, and then mixed with NaOH 2N-3N solution at a ratio of 3-4g: 20cc to fill a pressure vessel of the appropriate capacity about 40 ± 5%. Thereafter, the zeolite P is formed as a pure substance by heating within 6 to 10 hours with stirring at about 100 to 130 ° C. as the first synthesis reaction. When the zeolite P is cooled to room temperature, the amount of the first reaction product as a secondary reaction is added to the NaAlO2 reagent of 3M or more in a ratio of 1: 1, and the mixture is heated within 6 to 10 hours with stirring at 100 ° C. or less. Na-A is made. The pure material thus prepared is washed with distilled water to have a pH of about 10 and put in an oven to dry at 90 ± 5 ° C. to prepare a zeolite Na-A white powder.
Description
본 발명은 납석을 이용한 제올라이트 Na-A 제조법에 관한 것으로서, 더욱 상세하게는 자연산 납석으로부터 세제용 빌더 및 이온교환용 소재로 쓰일 수 있는 물질인 제올라이트류의 화합물 합성법으로 특히 Na-A에 대한 합성법에 관한 것이다.The present invention relates to a method for preparing zeolite Na-A using leadstone, and more particularly, to a method for synthesizing a compound of zeolite, which is a substance that can be used as a detergent builder and an ion exchange material from natural leadstone, in particular, a method for synthesizing Na-A. It is about.
일반적으로, 납석이란 딕카이트질(dickite-rich), 도석질(silicious) 납석과 엽납석(pyrophyllite)으로 구분되지만 어떠한 경우도 제올라이트 A로 합성이 가능하다.Generally, feldspar is divided into dickite-rich, sillicious feldspar and pyrophyllite, but in any case, it can be synthesized with zeolite A.
종래의 국내제조업체에 의한 제올라이트 Na-A 제조법은 SiO2+NaOH를 1200℃에서 반응시켜 만든 소위 Cullet를 수입하여 고온고압하에서 우선 물유리인(NaO2 3SiO2nHeO)를 만들고(7kb, 200℃), Al(OH)3와 SiO2 등을 사용하여 NaAlO2을 만들어서 이를 물유리와 열수반응시켜 제조하였다.The conventional method of manufacturing zeolite Na-A by a domestic manufacturer imports the so-called Cullet made by reacting SiO2 + NaOH at 1200 ° C to make water glass (NaO2 3SiO2nHeO) first under high temperature and high pressure (7kb, 200 ° C), and Al (OH) NaAlO2 was prepared using 3 and SiO2 and prepared by hydrothermal reaction with water glass.
그러나, 본 발명은 상기한 내용과 다른 점은 SiO2+NaOH를 1200℃에서 반응시켜 만들고(소위 Cullet) 이를 다시 고온고압에서 물유리로 만드는 대신에 약 100℃, 상압에서 자연산 납석과 NaOH 액상 폐기물을 반응시켜 우선 제올라이트 P를 만들고 이로부터 제올라이트 Na-A를 만들므로써 생산원가가 저렴하다.However, the present invention differs from the above in that it is reacted with SiO 2 + NaOH at 1200 ° C. (so-called Cullet) and reacts with natural feldspar and NaOH liquid waste at about 100 ° C. and atmospheric pressure instead of making it into water glass at high temperature and high pressure. The production cost is low by making zeolite P first and then forming zeolite Na-A.
본 발명은 상기한 내용과 같은 점은 Al(OH)3와 SiO2 등을 사용하여 원료의 하나인 NaAlO2을 만든다는 점이다.In the present invention, the same point as described above is that Al (OH) 3 and SiO 2 are used to make NaAlO 2, which is one of the raw materials.
본 발명은 상기한 문제점을 해결하기 위하여 안출한 것으로서, 그 목적은 NaOH, Al(OH)3, SiO2 등을 사용하여 좀더 복잡한 공정에 의해 제조하는 종래의 제올라이트 Na-A 제조법과는 달리 자연산 원료비중을 높이고 또한 폐기물을 사용함으로써 공정을 다소 단순화하고 제조원가를 낮출 수 있는 방법을 제공한다.The present invention has been made in order to solve the above problems, the purpose of which is unlike the conventional zeolite Na-A manufacturing method prepared by a more complex process using NaOH, Al (OH) 3, SiO 2, etc. The use of waste and the use of waste also provide a way to simplify the process somewhat and reduce manufacturing costs.
또한, 상기한 물질이 자연산 제올라이트에 비해 물리, 화학적으로 우수한 물질로서 현재 세재용 빌더(builder) 등으로 쓰이는 제올라이트 Na-A의 제조법과는 다르고(특히, 제조때 쓰이는 원료물질) 확실히 더 경제적으로 제조할 수 있으며 제올라이트 Na-A 만으로 이루어진 순수한 물질이나 제올라이트 Na-A와 제올라이트Na-X가 적절히 혼합된 물질을 합성할 수 있는 방법을 제공하는 것이다.In addition, the above-mentioned materials are physically and chemically superior to natural zeolites, and are different from the method of preparing zeolite Na-A, which is currently used as a builder for cleaners (particularly, raw materials used in manufacturing), and is manufactured more economically. It is possible to provide a method for synthesizing a pure material consisting of zeolite Na-A alone or a material in which zeolite Na-A and zeolite Na-X are properly mixed.
본 발명은 상기한 목적을 달성하기 위하여 납석을 150 매쉬 정도로 분쇄한 후 NaOH 2N ∼ 3N의 용액(혹은 NaOH 액상폐기물)에 3 ∼ 4g : 200cc의 비율로 섞어서 적절한 용량의 압력솥(autoclave)에 40±5％ 정도를 채운 후 제 1 차 합성반응으로서 약 100 ∼ 130℃에서 교반(stirring)시키면서 6 ∼ 10시간 이내로 가열하면 제올라이트 P가 순수한 물질로서 만들어지게 되며 제올라이트 P가 상온으로 냉각되면 제 2 차 반응으로서 제 1 차 반응결과물의 양을 1:1의 비율로 3M NaAlO2 시약을 추가하여 넣고 100℃ 이하에서 교반시키면서 하루 6 ∼ 10시간 이내로 가열하면 순수한 물질로서 제올라이트 Na-A가 만들어 진다. 이렇게 하여 제조된 순수한 물질을 증류수로 세척하여 pH 10 정도가 되도록 하고 오븐에 넣어 90±5℃에서 건조시키는 제올라이트 Na-A 백색 분말 제조법을 제공함에 의해 달성된다.In order to achieve the above object, the present invention grinds feldspar to about 150 mash, and then mixes it in a solution of NaOH 2N-3N (or NaOH liquid waste) at a ratio of 3 to 4 g: 200 cc to a 40 ± autoclave. After filling about 5% and heating within 6 to 10 hours while stirring at about 100 to 130 ° C. as the first synthetic reaction, zeolite P is made of pure substance, and when zeolite P is cooled to room temperature, secondary reaction As a primary reaction product, 3M NaAlO2 reagent is added at a ratio of 1: 1, and the mixture is heated within 6 to 10 hours with stirring at 100 ° C. or lower to make zeolite Na-A as a pure substance. This is achieved by providing a method for preparing a zeolite Na-A white powder which is washed with distilled water to a pH of about 10 and placed in an oven to dry at 90 ± 5 ℃.
도 1 은 본 발명의 제올라이트 Na-A 분말 제조 공정도1 is a process chart of manufacturing zeolite Na-A powder of the present invention
이하, 첨부된 도면을 참조하여 본 발명의 구성 및 작용을 설명하면 다음과 같다.Hereinafter, the configuration and operation of the present invention with reference to the accompanying drawings.
도 1 은 본 발명의 제올라이트 Na-A 분말 제조 공정도를 도시한 것으로서,1 is a process chart showing the zeolite Na-A powder of the present invention,
본 발명은 자연산 납석으로부터 세제용 빌더 및 이온교환용 소재로 쓰일 수 있는 물질인 제올라이트류의 화합물 합성법, 특히 제올라이트 4-A와 제올라이트 P에 대한 합성법으로,The present invention is a method for synthesizing a compound of zeolites, which is a substance that can be used as a detergent builder and an ion exchange material from natural leadstone, in particular, for synthesis of zeolite 4-A and zeolite P,
1) 제 1 차 열수합성반응(제올라이트 P 합성법)은 NaOH 2N 이상의 용액(혹은NaOH 액상폐기물)에 자연산 납석을 분쇄하여 3 ∼ 4g : 20cc의 비율로 섞어서 약 100 ∼ 130℃에서 교반(Stirring)시키면서 6 ∼ 10시간 이내로 가열 후 냉각하는 것이다.1) The first hydrothermal synthesis reaction (zeolite P synthesis method) is pulverized natural leadstone in a solution of NaOH 2N or more (or NaOH liquid waste), mixed at a ratio of 3 to 4g: 20cc, and stirred at about 100 to 130 ° C. It cools after heating in 6 to 10 hours.
2) 제 2 차 열수합성반응(제올라이트 Na-A 합성법)은 제 1 차 열수합성반응물 제올라이트 P의 양과 1:1의 비율로 증류수와 함께 3M NaAlO2 시약을 넣고 100℃이하에서 교반시키면서 하루 6 ∼ 10시간 이내로 가열(숙성) 후 서서히 냉각한다.2) The second hydrothermal synthesis reaction (zeolite Na-A synthesis method) is carried out at a rate of 1: 1 with the amount of the first hydrothermal reactant zeolite P in a ratio of 1 to 3M NaAlO2 with distilled water and stirred at 100 ° C. or lower for 6-10 days. Cool slowly after heating (aging) within hours.
또한, 가열반응시간을 조절하면 입도 및 결정형태를 조절할 수 있으며 혹은 제올라이트 Na-A와 제올라이트 Na-X가 1:1 등으로 적절히 혼합된 물질을 합성할 수 있다.In addition, by controlling the heating reaction time, it is possible to adjust the particle size and crystal form, or to synthesize a material in which zeolite Na-A and zeolite Na-X are mixed properly, such as 1: 1.
상기, 납석을 150 매쉬 정도로 분쇄한 후 NaOH 2N 이상의 용액에 3 ∼ 4g : 20cc의 비율로 섞어서 적절한 용량의 압력솥(autoclave)에 40±5％ 정도를 채운다.After pulverizing the feldspar about 150 mash, the solution is mixed with a NaOH 2N or higher solution at a ratio of 3 to 4 g: 20 cc and filled in an autoclave of about 40 ± 5% with an appropriate capacity.
그 후, 다음과 같은 제 1 차 열수합성반응을 실시한다. 제 1 차 열수합성반응은 약 100 ∼ 130℃에서 교반(stirring)시키면서 하루 6 ∼ 10시간 이내로 가열하면 소위 제올라이트 P(자연산 제올라이트 Gismondine에 해당)가 순수한 물질로서 만들어 진다. 이때, 제올라이트 P란 Na3.6Al3.6Si12.4O3214H2O 혹은 Na6Al6Si10O3212H2O를 의미하지만 제올라이트는 화학조성이 일반적인 경우에 비해 매우 다양하므로 다소의 오차가 수반될 수 있다. 합성된 제올라이트 P가 상온으로 냉각되면 그 후 제 2 차 열수합성반응을 실시한다. 제 1 차 열수합성반응물의 양과 1:1의 비율로 3M NaAlO2 시약을 넣고 100℃ 이하에서 교반시키면서 6 ∼ 10시간 이내로 가열하면 순수한 물질로서 소위 제올라이트 Na-A가 만들어 진다. 이렇게 하여 제조된 순수한 물질들은 오븐에 넣어 90±5℃에서 건조시킨다.Thereafter, the following first hydrothermal synthesis reaction is carried out. In the first hydrothermal synthesis reaction, when heated within about 6 to 10 hours with stirring at about 100 to 130 ° C., so-called zeolite P (corresponding to natural zeolite Gismondine) is made as a pure substance. In this case, zeolite P means Na 3.6 Al 3.6 Si 12.4 O 32 14H 2 O or Na 6 Al 6 Si 10 O 32 12H 2 O, but since zeolites are more diverse in chemical composition than general cases, some errors may be involved. have. When the synthesized zeolite P is cooled to room temperature, a second hydrothermal synthesis reaction is then performed. 3M NaAlO2 reagent is added at a ratio of 1: 1 with the amount of the first hydrothermal reactant, and heated to within 6 to 10 hours with stirring at 100 ° C. or lower to form a so-called zeolite Na-A as a pure substance. Pure materials thus prepared are placed in an oven and dried at 90 ± 5 ° C.
또한, 가열시간을 조절하면 입도 및 결정형태를 조절할 수 있다. 상기한 제올라이트 Na-A는 결정학적으로 입방정계에 속하며 Na96Al96Si96O384216H2O의 화학조성을 갖는다.In addition, by controlling the heating time it is possible to control the particle size and crystal form. Zeolite Na-A is crystallographically belongs to the cubic system and has a chemical composition of Na 96 Al 96 Si 96 O 384 216H 2 O.
교반속도는 50 ∼ 100rpm으로 변화가 가능하다. 특히, 도석질(silicious) 납석의 경우 제올라이트 Na-A와 함께 석영이 다량 합성되지만 선광에 의해 분리시키면 순수한 제올라이트 Na-A를 얻을 수 있다.Stirring speed can be changed to 50 ~ 100rpm. In particular, in the case of silicious feldspar, a large amount of quartz is synthesized together with zeolite Na-A, but pure zeolite Na-A can be obtained by separating by beneficiation.
본 발명은 제올라이트 Na-A는 현재 Na 대신에 K 등의 알카리 원소로 치환이 가능하므로 해당되는 각종 산업분야에서 실용화시킬 수 있는 매우 유용한 발명인 것이다. 제조원가가 종래의 제조법에 비해 저렴(약 60∼70％)하므로 임가공 형태로 생산중인 현재의 Na-A를 대체할 수 있으며 따라서 100％ 국산화와 수입대체가 가능하다.The present invention is a zeolite Na-A is a very useful invention that can be put to practical use in various industrial fields because it can be replaced by an alkali element such as K instead of Na at present. Since the manufacturing cost is cheaper (about 60 to 70%) than the conventional manufacturing method, it is possible to replace the present Na-A produced in the form of forestry, and thus 100% localization and import substitution are possible.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2992068A (en) * | 1959-02-20 | 1961-07-11 | Minerals & Chem Philipp Corp | Method for making synthetic zeolitic material |
| US3663164A (en) * | 1968-10-11 | 1972-05-16 | Air Prod & Chem | Crystalline zeolite and method of preparation |
| KR800000334Y1 (en) * | 1979-03-17 | 1980-04-02 | 함영찬 | Timer of watch |
| JPH05310416A (en) * | 1991-07-25 | 1993-11-22 | Nantou Opaale Kk | Production of zeolite |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2992068A (en) * | 1959-02-20 | 1961-07-11 | Minerals & Chem Philipp Corp | Method for making synthetic zeolitic material |
| US3663164A (en) * | 1968-10-11 | 1972-05-16 | Air Prod & Chem | Crystalline zeolite and method of preparation |
| KR800000334Y1 (en) * | 1979-03-17 | 1980-04-02 | 함영찬 | Timer of watch |
| JPH05310416A (en) * | 1991-07-25 | 1993-11-22 | Nantou Opaale Kk | Production of zeolite |
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