KR100509395B1 - Process for preparation of aluminum alkoxide from aluminum waste - Google Patents
Process for preparation of aluminum alkoxide from aluminum waste Download PDFInfo
- Publication number
- KR100509395B1 KR100509395B1 KR10-2002-0068239A KR20020068239A KR100509395B1 KR 100509395 B1 KR100509395 B1 KR 100509395B1 KR 20020068239 A KR20020068239 A KR 20020068239A KR 100509395 B1 KR100509395 B1 KR 100509395B1
- Authority
- KR
- South Korea
- Prior art keywords
- aluminum
- waste
- waste aluminum
- alkoxide
- catalyst
- Prior art date
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 73
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000002699 waste material Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 13
- -1 aluminum alkoxide Chemical class 0.000 title abstract description 23
- 239000011888 foil Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims description 26
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 claims description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- 150000004703 alkoxides Chemical class 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000003973 paint Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- HEJPGFRXUXOTGM-UHFFFAOYSA-K iron(3+);triiodide Chemical compound [Fe+3].[I-].[I-].[I-] HEJPGFRXUXOTGM-UHFFFAOYSA-K 0.000 claims 1
- 239000000049 pigment Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract 2
- 238000005516 engineering process Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 238000004090 dissolution Methods 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 229960002523 mercuric chloride Drugs 0.000 description 4
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- QKEOZZYXWAIQFO-UHFFFAOYSA-M mercury(1+);iodide Chemical compound [Hg]I QKEOZZYXWAIQFO-UHFFFAOYSA-M 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229960003671 mercuric iodide Drugs 0.000 description 2
- YFDLHELOZYVNJE-UHFFFAOYSA-L mercury diiodide Chemical compound I[Hg]I YFDLHELOZYVNJE-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FGRBYDKOBBBPOI-UHFFFAOYSA-N 10,10-dioxo-2-[4-(N-phenylanilino)phenyl]thioxanthen-9-one Chemical compound O=C1c2ccccc2S(=O)(=O)c2ccc(cc12)-c1ccc(cc1)N(c1ccccc1)c1ccccc1 FGRBYDKOBBBPOI-UHFFFAOYSA-N 0.000 description 1
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- WSNMPAVSZJSIMT-UHFFFAOYSA-N COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 Chemical compound COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 WSNMPAVSZJSIMT-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 1
- 208000034809 Product contamination Diseases 0.000 description 1
- 102000001708 Protein Isoforms Human genes 0.000 description 1
- 108010029485 Protein Isoforms Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229940030980 inova Drugs 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000000371 solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/20—Waste processing or separation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
본 발명은 폐 알루미늄 캔이나 폐 알루미늄 호일과 같은 폐 알루미늄 자원을 이용하여 고순도의 알루미늄 알콕사이드를 합성하는 방법에 관한 발명으로 지금까지 알루미늄 재활용을 통해 만들어내는 알루미늄 괴의 형태는 처리과정에서 알루미늄 드로스의 발생으로 인해 알루미늄 금속의 재활용율이 매우 떨어지는 실정이었다. 본 발명은 이러한 기존의 알루미늄 처리공정을 거치지 않고 알루미늄 알콕사이드를 제조하는 발명이다. 또한 처리공정이 매우 단순하여 종래의 공정비용이 절감되고, 또한 알루미늄 알콕사이드 생산에 버려진 폐알루미늄 캔이나 호일을 이용하므로 생산비용을 크게 절감시킬 수 있는 기술이다. 본 발명은 폐 알루미늄 캔이나 폐 알루미늄 호일을 고부가가치 산업으로 활용 할 수 있어 자원 리사이클링은 물론 환경친화적인 기술로 환경산업에 미치는 파급효과는 대단히 클 것으로 기대된다.The present invention relates to a method of synthesizing high purity aluminum alkoxide using waste aluminum resources such as waste aluminum cans or waste aluminum foil. Due to the occurrence of a very low recycling rate of aluminum metal. The present invention is an invention for producing aluminum alkoxide without going through the existing aluminum treatment process. In addition, since the treatment process is very simple, the conventional process cost is reduced, and since the waste aluminum cans or foils discarded in aluminum alkoxide production are used, the production cost can be greatly reduced. According to the present invention, waste aluminum cans or waste aluminum foils can be utilized as high value-added industries, and thus the ripple effect on the environmental industry is expected to be very large due to resource recycling as well as environmentally friendly technologies.
Description
종래에 알루미늄 알콕사이드 물질은 γ-알루미나 촉매나 지지체 등과 같이 여러 알루미나 화학제품을 위한 출발물질로 사용되고 있는 물질이다. 알루미늄 알콕사이드는 다양한 고순도 알루미나 제품에 원료로 폭넓게 사용되는 물질이나 복잡한 제조 생산공정으로 인해 고가의 반응물로 인식되어 지금까지 주로 정확성을 요하는 실험실 수준에서 출발물질로 이용되고 있으며 산업적인 제품 생산을 위한 원료로의 이용은 특수한 경우에 제한적으로 이루어져 왔다.Aluminum alkoxide materials are conventionally used as starting materials for various alumina chemicals such as γ-alumina catalysts and supports. Aluminum alkoxide is widely used as a raw material for various high-purity alumina products or it is recognized as an expensive reactant due to complex manufacturing and production process. It has been used as a starting material at the laboratory level, which requires accuracy, and is a raw material for producing industrial products. The use of furnaces has been limited in special cases.
본 발명은 이러한 고가의 알루미늄 알콕사이드를 생산하는 데, 폐알루미늄 캔, 폐알루미늄 호일 및 기타 폐 알루미늄과 같은 폐 알루미늄 자원을 이용하므로서 저가의 원료비용으로 알루미늄 알콕사이드를 생산할 수 있는 기술이다. 지금까지 이러한 알루미늄 알콕사이드 생산에 폐 알루미늄 캔이나 호일의 이용은 전세계적으로 전무한 실정으로 본 발명에 의하여 폐 알루미늄 자원을 활용하고, 종래에 알루미늄 알콕사이드의 가격을 크게 낮출 수 있을 것으로 기대된다. The present invention utilizes waste aluminum resources such as waste aluminum cans, waste aluminum foils, and other waste aluminum to produce such expensive aluminum alkoxides, thereby producing aluminum alkoxides at low raw material costs. Until now, the use of waste aluminum cans or foils in the production of such aluminum alkoxides is unprecedented in the world, and the present invention is expected to utilize waste aluminum resources and to significantly lower the price of aluminum alkoxides.
본 발명에서는 폐알루미늄 캔, 폐 호일 또는 기타 페 알루미늄 자원을 수거한다. 폐 알루미늄 캔을 그대로 또는 폐 알루미늄 캔의 경우 잘게 부수어 알루미늄 조각으로 만든다. 이렇게 얻어진 폐 알루미늄 캔이나 호일에 부착되어진 락커, 도료, 플라스틱 또는 기타 오염물을 제거하기 위하여 300～1200℃ 범위로 가열한다. 가열을 통해 폐 알루미늄 자원에 부착된 불순물을 연소시켜서 제거가 이루어지게 된다. 가열 후 알루미늄 캔의 형태나 조각을 알루미늄 알콕사이드의 반응원료로 그대로 이용한다. In the present invention, waste aluminum cans, waste foils or other waste aluminum resources are collected. The waste aluminum cans are left as-is or, in the case of waste aluminum cans, crushed into pieces of aluminum. In order to remove the lacquer, paint, plastic or other contaminants attached to the waste aluminum can or foil thus obtained, it is heated to a range of 300 to 1200 ° C. The heating is accomplished by burning off impurities attached to the waste aluminum resources. After heating, the form or flake of the aluminum can is used as a reaction raw material of the aluminum alkoxide.
알루미늄 알콕사이드의 합성반응은 알루미늄과 메탄올, 에탄올, 프로판올, n-부탄올 또는 이소프로판올과 같은 저급 알칸올의 용해반응을 통해 합성된다. 그 반응식은 다음과 같다.Synthesis of aluminum alkoxides is accomplished through the dissolution reaction of aluminum with lower alkanols such as methanol, ethanol, propanol, n-butanol or isopropanol. The scheme is as follows.
Al + 3ROH ↔Al(OR)3 + 3/2 H2 ↑Al + 3ROH ↔Al (OR) 3 + 3/2 H 2 ↑
상기식에서 R은 탄소수 1-4의 저급 알킬기이다.R is a lower alkyl group having 1-4 carbon atoms.
알루미늄 금속과 알코올과의 용해반응은 무촉매의 조건하에서도 반응하지만 그 반응속도가 너무 느려 염화수은(HgCl2, mercuric chloride), 요오드(I2, iodine), 요오드화수은(mercuric iodide), 염화제이철(FeCl3, ferric chloride)와 같은 다양한 촉매의 이용이 불가피하다. 그러나 촉매의 첨가는 생성물의 오염, 독성(toxicity) 그밖에 부식성(corrosiveness)을 유발할 수 있어 촉매의 선택시 촉매 성분의 휘발성의 유무, 합성 수율, 반응속도 등 여러 가지 변수를 고려하여 선택해야만 할 것이다. 특히 용해 반응시 발생되는 높은 반응열과 수소가스의 발생은 폭발의 위험이 있을 수 있으며, 공기 중의 수분이 반응기내로 침투되면 알루미늄 산화물 또는 알루미늄 수산화물이 생성되어 고순도 알루미늄 저급 알콕사이드의 합성에 장애가 될 수 있으므로 주의해야만 한다.The dissolution reaction between aluminum metal and alcohol reacts even under non-catalytic conditions, but the reaction rate is too slow, so mercuric chloride (HgCl 2 , mercuric chloride), iodine (I 2 , iodine), mercuric iodide, ferric chloride Various catalysts such as (FeCl 3 , ferric chloride) are inevitable. However, the addition of the catalyst may cause product contamination, toxicity and other corrosiveness, so the choice of the catalyst should be selected in consideration of various variables such as the presence or absence of volatility of the catalyst component, the synthesis yield, and the reaction rate. In particular, high heat of reaction and hydrogen gas generated during the dissolution reaction may cause an explosion, and when moisture in the air penetrates into the reactor, aluminum oxide or aluminum hydroxide may be generated, which may interfere with the synthesis of high-purity aluminum lower alkoxide. You must be careful.
본 연구에서는 염화수은, 요오드, 요오드화수은, 염화제이철 촉매의 이용에 따른 영향을 고찰하고 높은 수율을 얻기 위한 제반 공정변수의 영향을 고찰하였다. 본 연구는 고가의 알루미늄 알콕사이드 원료비용을 대폭 절감할 수 있을 뿐만 아니라 관련 알루미나 제품의 활용을 촉진시키는 계기가 될 것으로 기대한다.In this study, the effects of mercuric chloride, iodine, mercury iodide, and ferric chloride catalysts were investigated, and the effects of various process variables to obtain high yields were investigated. This study is expected to significantly reduce the cost of expensive aluminum alkoxide raw materials and promote the utilization of related alumina products.
최초의 증류과정에서 얻어지는 trimer 구조를 갖는 시럽형 용해된 알루미늄 이소프로폭사이드(sirupy and molten AIP)는 수일 동안의 느린 결정화(slow crystallization) 과정을 거치면서 과냉각되어 tetramer 구조를 갖는 고체 분말형 알루미늄 이소프로폭사이드로 전환된다. Mehrotra[ Mehrotra, R.C.: J. Non-crystalline solids, 100, 1(1988)]에 의하면 벤젠에 용해된 molten AIP의 분자량 측정 결과, 평균 중합의 정도는 2.83으로 주로 trimer 구조를 가지며 느린 결정화에 의해 서서히 재배열 과정을 거치면서 tetramer 구조의 고체 분말 AIP(soilid AIP)로 전환된다고 하였다. 또한 Bradley[Bradley, D.C.: Batyrem 182, 1211(1958)]는 바로 증류시켜 얻은 molten AIP의 경우, 배위수가 4에서 6으로 증가하여 분자량이 서서히 증가하고 있다는 사실을 제안하였다.Syrup-type molten aluminum isopropoxide (sirupy and molten AIP) having a trimer structure obtained during the first distillation process was subjected to slow crystallization for several days and then supercooled to give a solid powdery aluminum isoform having a tetramer structure. Converted to propoxide. According to Mehrotra [Mehrotra, RC: J. Non-crystalline solids, 100, 1 (1988)], the molecular weight of molten AIP dissolved in benzene showed that the average degree of polymerization was 2.83. The rearrangement process is said to convert the tetramer structure into solid powder AIP (soilid AIP). Bradley [Bradley, D.C .: Batyrem 182, 1211 (1958)] also suggested that the molten AIP obtained by direct distillation increased its molecular weight slowly from 4 to 6 with a coordination number.
이처럼 알루미늄 알콕사이드의 복잡한 분자구조는 올리고머(oligomerization)화 정도에 주로 의존한다. 입체적으로 부피가 큰 secondary, tertiary-OR기들은 dimer나 trimer와 같이 구속력이 약한 직선의 형태로 유도되어 4배위 Al원자들이 5배위나 6배위 원자로의 전환을 방해한다. The complex molecular structure of aluminum alkoxides depends mainly on the degree of oligomerization. Three-dimensionally bulky secondary and tertiary-OR groups are induced in the form of weakly constrained straight lines, such as dimers and trimers, to prevent the conversion of the 4th coordinating Al atoms to the 5th and 6th coordination reactors.
Ulich와 Nespital은 알루미늄 알콕사이드의 구조는 분자량이나 쌍극자모멘트와 같은 물리적 성질에 의해 결정되고 특히 알루미늄 이소프로폭사이드는 tetrameric 구조 I를 갖는다고 제안하였다. 반면에 Wardlaw는 알킬기의 가지(branching)에 의해 금속 알콕사이드의 중합 정도(degree of polymerization)가 결정됨을 보였으며, Bradley는 알콕사이드는 금속의 최대 공유결합을 위한 최소 중합을 갖게 되어 tetrameric 알루미늄 이소프로폭사이드의 경우, II의 구조를 띠게 된다고 주장하였다.Ulich and Nespital suggested that the structure of aluminum alkoxides is determined by physical properties such as molecular weight and dipole moment, and especially aluminum isopropoxide has tetrameric structure I. Wardlaw, on the other hand, showed that the degree of polymerization of the metal alkoxide was determined by the branching of the alkyl group, and Bradley showed that the alkoxide had a minimum polymerization for the maximum covalent bonding of the metal, resulting in tetrameric aluminum isopropoxide. In case of, it is claimed to have the structure of II.
구조 I 구조 IIStructure I Structure II
Tetrameric Structures of Aluminum Isopropoxide. Tetrameric Structures of Aluminum Isopropoxide.
고체상의 알루미늄 이소프로폭사이드는 벤젠, 톨루엔, 사염화탄소, 이소프로필 알코올, dioxane, carbon disulfide, mesitylene 등의 유기용매에 용해되고, Bradley가 제안한 바와 같이 tetrameric 구조를 갖는다. 또한 고온이나 melting 또는 용액 내에서 알루미늄 이소프로폭사이드는 cyclic trimeric 구조로 전환된다. 그리고 저온의 과냉각된 melting 상에서나 용액 내에서 cyclic trimeric 구조에서 tetrameric 구조로 서서히 전환된다. 또한 제조된 알루미늄 이소프로폭사이드가 trimeric 구조인지 tetrameric 구조인지는 용해도 과정에 의해서도 판별이 가능하다. Trimeric 구조의 알루미늄 이소프로폭사이드는 피리딘에 용해도가 높고, tetrameric 구조는 피리딘에 용해도가 낮기 때문이다.Solid aluminum isopropoxide is dissolved in organic solvents such as benzene, toluene, carbon tetrachloride, isopropyl alcohol, dioxane, carbon disulfide, mesitylene, and has a tetrameric structure as proposed by Bradley. In addition, aluminum isopropoxide is converted to a cyclic trimeric structure at high temperature, melting or in solution. It then slowly converts from cyclic trimeric structures to tetrameric structures in low temperature supercooled melting or in solution. In addition, it is possible to determine whether the manufactured aluminum isopropoxide has a trimeric structure or a tetrameric structure by a solubility process. The aluminum isopropoxide of the trimeric structure has high solubility in pyridine and the tetrameric structure has low solubility in pyridine.
다음은 본 발명의 방법에 의한 폐 알루미늄 자원으로부터 알루미늄 알콕사이드를 합성하는 훌로우 챠트이다.The following is a hollow chart for synthesizing aluminum alkoxide from waste aluminum resources by the method of the present invention.
본 훌로우 챠트에 의해 알루미늄 이소프로폭사이드의 합성 실험 방법 및 기기를 나타내면 다음과 같다.The experimental method and apparatus for synthesizing aluminum isopropoxide by this hollow chart are as follows.
상기 후로우 챠트는 폐 알루미늄 캔이나 폐 알루미늄 호일을 이용한 알루미늄 알콕사이드 합성단계를 나타낸 흐름도이다. The flow chart is a flow chart showing the aluminum alkoxide synthesis step using a waste aluminum can or waste aluminum foil.
또한 도 1은 폐 알루미늄 캔이나 폐 알루미늄 호일을 이용한 알루미늄 이소프로폭사이드 합성을 위한 용해반응 실험 장치도이다. 1 is a dissolution reaction experimental apparatus for the synthesis of aluminum isopropoxide using waste aluminum cans or waste aluminum foil.
도 2는 폐 알루미늄 캔이나 호일을 용해시킨 슬러리 용액상에서 순수한 알루미늄 알콕사이드 성분만을 추출하기 위한 분리정제장치도이다. 2 is a separation and purification apparatus for extracting only pure aluminum alkoxide component from a slurry solution in which waste aluminum cans or foils are dissolved.
폐 알루미늄 캔이나 폐 알루미늄 호일중 알루미늄 성분과 이소프로판올과의 용해반응시 다량의 반응열이 발생하게 되므로 가해지는 촉매는 개시제로서 초기 순간에만 필요한 수준이어서 소량의 촉매 첨가만으로도 충분히 반응을 진행시킬 수 있다. 따라서 본 실험에서는 10-3mol catalyst/1mol Al의 촉매 량을 가하여 용해반응을 진행하였다. 또한 도 1에서 보는 바와 같이 용해반응시 수소가스의 발생으로 인한 폭발의 위험을 피하기 위하여 응축기 말단부를 반드시 개방시켜야 한다.Since a large amount of heat of reaction is generated during the dissolution reaction between the aluminum component and isopropanol in the waste aluminum can or waste aluminum foil, the added catalyst is required only at an initial instant as an initiator, and thus the reaction can be sufficiently proceeded even with the addition of a small amount of catalyst. Therefore, in this experiment, a dissolution reaction was performed by adding a catalyst amount of 10 -3 mol catalyst / 1mol Al. Also, as shown in FIG. 1, the condenser end must be opened to avoid the risk of explosion due to the generation of hydrogen gas during the dissolution reaction.
폐 알루미늄 자원을 300 ～ 1200℃의 온도로 처리하여 불순물을 제거하고, 이를 그대로 사용하거나 또는 조각을 절단하여 촉매량의 촉매존재하에 상압 또는 가압하에 사용되는 저급 알칸올의 비등점이상의 온도에서 반응시킨다. The waste aluminum source is treated at a temperature of 300 to 1200 ° C. to remove impurities and used as it is or the pieces are cut and reacted at a boiling point of lower alkanol used under normal pressure or pressure in the presence of a catalytic amount of catalyst.
알루미늄 이소프로폭사이드 합성 조건은 표 1과 같다. Al 1mol에 대해 화학양론적 비를 초과하는 4mol C3H7OH/1mol Al의 이소프로판올(C3H7OH, Showa Chem. Inc., > 99.5%)을 반응기에 넣고 항온조를 이용하여 이소프로판올의 비등점(82.5℃) 이상의 온도로 가열한 후, 알루미늄 금속과 촉매를 가하고 교반시키면서 반응을 진행시켰다. 본 실험에 이용된 촉매로는 염화수은(HgCl2, Fluka, >99.5%), 요오드(I2, Fluka, >99.5%), 요오드화수은(HgI2, Fluka, >99.0%), 염화제이철(FeCl3, Ferric chloride anhydrous, Fluka, ≥98%)을 이용하였으며 여러 촉매에 따른 반응시간, 합성 수율 그리고 순도 등의 영향을 고찰하였다.Aluminum isopropoxide synthesis conditions are shown in Table 1. Isopropanol (C 3 H 7 OH, Showa Chem. Inc.,> 99.5%) of 4 mol C 3 H 7 OH / 1 mol Al, which exceeds the stoichiometric ratio for 1 mol of Al, is placed in a reactor and the boiling point of isopropanol using a thermostat After heating to the temperature (82.5 degreeC) or more, reaction was advanced, adding and stirring an aluminum metal and a catalyst. The catalysts used in this experiment were mercury chloride (HgCl 2 , Fluka,> 99.5%), iodine (I 2 , Fluka,> 99.5%), mercury iodide (HgI 2 , Fluka,> 99.0%), ferric chloride (FeCl 3 , Ferric chloride anhydrous, Fluka, ≥98%), and the effects of reaction time, synthesis yield and purity on the various catalysts were investigated.
용해반응이 끝난 후, 용액 내에는 여러 불순물이 포함되어 있다. 따라서 순수한 알루미늄 이소프로폭사이드만을 얻기 위해서 도 4와 같이 알루미늄 이소프로폭사이드의 150℃ 비등점 온도 범위에서 감압 증류에 의해 분리 회수하였다. 이때 공기 중에 존재하고 있는 수분이 감압 증류 조건시 반응기로 침투되어 생성된 알루미늄 알콕사이드가 물과 반응하여 알루미늄 하이드록사이드를 생성을 차단하는 것이 필수적이다. 감압 증류 조건하에서 얻어진 알루미늄 이소프로폭사이드는 투명한 시럽형 액상으로 진공오븐 내에서 서서히 결정화시켜 백색의 고체분말 상을 최종적으로 얻었다. After the dissolution reaction is completed, various impurities are contained in the solution. Therefore, in order to obtain only pure aluminum isopropoxide, it was separated and recovered by vacuum distillation in the 150 ° C. boiling point temperature range of aluminum isopropoxide as shown in FIG. 4. At this time, it is essential that the water present in the air penetrates into the reactor under reduced pressure distillation conditions, and the produced aluminum alkoxide reacts with water to block the formation of aluminum hydroxide. The aluminum isopropoxide obtained under reduced pressure distillation conditions was gradually crystallized in a vacuum oven in a transparent syrup-like liquid phase to finally obtain a white solid powder phase.
다양한 촉매조건하에서 합성된 알루미늄 이소프로폭사이드의 특성을 고찰하기 위하여 다음의 제 분석을 수행하였다. 알루미늄 이소프로폭사이드의 결정도는 X선회절분석기(X-ray diffraction analyzer, Rigaku)에 의해 CuKα Filter, scanning speed 2°/min, 30㎸, 20㎃, 10°≤2θ≤90°scanning range 조건하에서 분석하였다. 또한 알루미늄 이소프로폭사이드의 구조내 결합기를 분석하기 위하여 액체 적외선 흡광분석(FTS-60, BIO-RAD)을 400～4000 cm-1 파수 범위에서 분석하였다. 또한 합성된 알루미늄 이소프로폭사이드의 Al 배위체를 확인을 위하여 27Al magic angle spinning NMR(200MHz Solid-State NMR spectrometer B, Unity Inova 200, Varian사, 자기장: 4.7 Tesla, max. spinning rate: 6kHz)을 분석하였다. NMR 분석에 사용한 표준물질은 Al(NO3)3 수용액 0.1M으로 보정한 상태에서 chemical shift가 나타날 때까지 scanning 하였다. 또한 합성한 알루미늄 이소프로폭사이드의 순도 분석을 위하여 용매추출 후 micro-filtering시킨 후, 건조하여 무게 측정으로 순도분석을 수행하였다.In order to investigate the properties of aluminum isopropoxide synthesized under various catalytic conditions, the following analysis was performed. The crystallinity of aluminum isopropoxide was measured by X-ray diffraction analyzer (Rigaku) under the conditions of CuKα Filter, scanning speed 2 ° / min, 30㎸, 20㎃, 10 ° ≤2θ≤90 ° scanning range. Analyzed. In addition, liquid infrared absorption spectrometry (FTS-60, BIO-RAD) was analyzed in the range of 400 ~ 4000 cm -1 wavenumber to analyze the in-structure coupler of aluminum isopropoxide. In addition, 27 Al magic angle spinning NMR (200 MHz Solid-State NMR spectrometer B, Unity Inova 200, Varian, Magnetic Field: 4.7 Tesla, max. Spinning rate: 6 kHz) to confirm the Al ligand of the synthesized aluminum isopropoxide Was analyzed. The standard used for NMR analysis was scanned until the chemical shift appeared in the state of 0.1M aqueous solution of Al (NO 3 ) 3 . In addition, for purity analysis of the synthesized aluminum isopropoxide, after solvent extraction, micro-filtering, and drying, purity analysis was performed by weight measurement.
상기와 같은 실험에 의해 다음의 합성실험결과를 얻었다.The following synthesis experiment results were obtained by the above experiment.
본 연구에서 알루미늄 알콕사이드를 합성하기 위하여 알루미늄 금속과 이소프로판올을 반응물로 이용하여 염화수은, 요오드, 요오드화수은, 염화제이철을 촉매로 이용하여 알루미늄 금속의 용해반응과 감압증류를 통하여 순수한 알루미늄 이소프로폭사이드를 합성하였다.In order to synthesize aluminum alkoxides, pure aluminum isopropoxide was prepared by dissolution reaction and distillation under reduced pressure using aluminum metal and isopropanol as reactants and mercury chloride, iodine, mercuric iodide, and ferric chloride as catalysts. Synthesized.
실험 결과, 알루미늄 금속 성분의 용해반응 시간은 표 2에서 보는 바와 같이 촉매의 종류에 따라 3～48시간이 소요되었다. 또한 용해반응 후, 최종적으로 감압증류 공정을 거쳐 얻은 알루미늄 이소프로폭사이드의 수율을 측정한 결과, 약 90% 수준의 반응 수율을 얻을 수 있었다. As a result, the dissolution reaction time of the aluminum metal component was 3 to 48 hours depending on the type of catalyst as shown in Table 2. After the dissolution reaction, the yield of aluminum isopropoxide obtained through the vacuum distillation process was finally measured. As a result, a reaction yield of about 90% was obtained.
제조된 알루미늄 이소프로폭사이드에 대하여 순도분석 결과, 표 3의 결과를 얻었다. 분석은 알루미늄 이소프로폭사이드를 사염화탄소 유기용매로 용해 추출하여 무기막에 의해 감압 조건하에서 여과 후, 여과 막 위에 남은 성분에 대하여 이소프로판올을 완전히 제거한 후, 중량을 측정하여 알루미늄 이소프로폭사이드의 순도를 측정하였다. 알루미늄 이소프로폭사이드의 순도 측정 결과, 표 3과 같이 Fluka사 알루미늄 이소프로폭사이드(≥97%, Fluka)의 경우, 97.6%의 순도를 보였으며, 본 실험에서 촉매를 변화시켜 제조된 알루미늄 이소프로폭사이드의 경우, 95.5～97.4% 순도를 보였다. 이 결과는 1회의 분리 정제 후 얻은 순도로 만약 분리 정제를 반복한다면 시약급 이상의 고순도 알루미늄 이소프로폭사이드의 제조는 가능하리라 판단된다.Purity analysis of the prepared aluminum isopropoxide afforded the results of Table 3. The analysis was carried out by dissolving and extracting aluminum isopropoxide with a carbon tetrachloride organic solvent, filtering under reduced pressure with an inorganic membrane, completely removing isopropanol from the remaining components on the filtration membrane, and then measuring the weight to determine the purity of aluminum isopropoxide. Measured. As a result of the purity measurement of aluminum isopropoxide, as shown in Table 3, the purity of Fluka aluminum isopropoxide (≥97%, Fluka) was 97.6%. In case of propoxide, the purity was 95.5∼97.4%. This result is a purity obtained after one separation purification, if the separation purification is repeated, it is determined that the production of high-purity aluminum isopropoxide higher than the reagent grade.
도 3은 Fluka-AIP와 Syn-AIPs의 X선회절분석 결과를 나타낸 것으로 Fluka-AIP와 Syn-AIPs의 결정구조나 결정도가 동일하게 나타남을 알 수 있다. Figure 3 shows the results of X-ray diffraction analysis of Fluka-AIP and Syn-AIPs can be seen that the crystal structure or crystallinity of Fluka-AIP and Syn-AIPs are the same.
도 4는 적외선 흡광 분석결과로서 Fluka-AIP와 Syn-AIPs의 결합기의 종류가 일치하고 있음을 알 수 있다. 이로서 알루미늄 이소프로폭사이드가 합성되었음을 알 수 있다. 4 shows that the types of the couplers of Fluka-AIP and Syn-AIPs are the same as the results of infrared absorption analysis. This shows that aluminum isopropoxide was synthesized.
도 5는 합성된 알루미늄 이소프로폭사이드 분말의 형상을 관찰하기 위하여 주사전자 현미경 분석 결과, 상용 Fluka사 시약의 경우, 응집된 분말상을 보이고 있으며, 합성시킨 알루미늄 이소프로폭사이드의 경우 염화수은, 요오드, 요오드화 수은 촉매를 이용하여 제조한 시약의 경우 육각형의 고체 입자상을 보이고 있다. 반면에 용해반응시간이 긴 염화제이철 촉매를 사용하여 제조한 시약의 경우 응집된 미분말 상임을 관찰할 수 있었다. FIG. 5 shows the result of scanning electron microscopy to observe the shape of the synthesized aluminum isopropoxide powder. In the case of a commercial Fluka reagent, the aggregated powder was shown. In the case of the synthesized aluminum isopropoxide, mercuric chloride and iodine In the case of a reagent prepared using a mercury iodide catalyst, the solid particles are hexagonal. On the other hand, reagents prepared using a ferric chloride catalyst having a long dissolution reaction time were observed to be aggregated fine powder phase.
본 발명은 폐 알루미늄 캔이나 폐 알루미늄 호일과 같은 알루미늄 폐자원을 이용하여 고순도의 알루미늄 저급알킬알콕사이드를 제조하는 방법에 관한 것으로, 본 발명의 방법에 의하여 폐 알루미늄 자원을 활용하여 생산비용을 크게 절감시킬 수 있고, 환경친화적으로 고순도의 알루미늄 저급 알콕사이드를 제조할 수 있다. The present invention relates to a method for producing a high purity aluminum lower alkyl alkoxide using aluminum waste resources such as waste aluminum cans or waste aluminum foil, and significantly reduces the production cost by utilizing waste aluminum resources by the method of the present invention. It is possible to produce an environmentally friendly high purity aluminum lower alkoxide.
도 1은 폐 알루미늄 캔이나 폐 알루미늄 호일을 이용한 알루미늄 이소프로폭사이드 합성을 위한 용해반응 실험 장치도,1 is a dissolution reaction experimental apparatus for the synthesis of aluminum isopropoxide using waste aluminum cans or waste aluminum foil,
도 2는 폐 알루미늄 캔이나 호일을 용해시킨 슬러리 용액상에서 순수한 알루미늄 알콕사이드 성분만을 추출하기 위한 분리정제장치도,2 is a separation and purification device for extracting only pure aluminum alkoxide component from a slurry solution in which waste aluminum cans or foils are dissolved.
여기에서 1은 실리카겔, 2는 온도조절기, 3은 콘덴서, 4는 AIP Recovery chamber, 5는 진공펌프를 각각 나타낸다.Here, 1 denotes a silica gel, 2 denotes a temperature controller, 3 denotes a condenser, 4 denotes an AIP recovery chamber, and 5 denotes a vacuum pump.
도 3은 Fluka-AIP와 Syn-AIPs의 X선회절분석 결과를 나타낸 그래프,3 is a graph showing the results of X-ray diffraction analysis of Fluka-AIP and Syn-AIPs,
도 4는 적외선 흡광 분석결과로서 Fluka-AIP와 Syn-AIPs의 결합기의 종류가 일치하고 있음을 보여주는 그래프,FIG. 4 is a graph showing that the types of the combiners of Fluka-AIP and Syn-AIPs match as infrared absorption analysis results.
도 5는 합성된 알루미늄 이소프로폭사이드 분말의 형상을 관찰하기 위하여 주사전자 현미경 분석 결과이며, 5 is a scanning electron microscope analysis result to observe the shape of the synthesized aluminum isopropoxide powder,
여기에서 (a)는 Fluka,(b)는 HgCl2,(c)는 I2,(d)는 HgI2,(e)는 FeCl3 를 촉매로 사용한 경우를 각각 나타낸다.Here, (a) represents Fluka, (b) represents HgCl 2 , (c) represents I 2 , (d) represents HgI 2 , and (e) uses FeCl 3 as a catalyst.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2002-0068239A KR100509395B1 (en) | 2002-11-05 | 2002-11-05 | Process for preparation of aluminum alkoxide from aluminum waste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2002-0068239A KR100509395B1 (en) | 2002-11-05 | 2002-11-05 | Process for preparation of aluminum alkoxide from aluminum waste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20040039976A KR20040039976A (en) | 2004-05-12 |
| KR100509395B1 true KR100509395B1 (en) | 2005-08-22 |
Family
ID=37337484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR10-2002-0068239A KR100509395B1 (en) | 2002-11-05 | 2002-11-05 | Process for preparation of aluminum alkoxide from aluminum waste |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100509395B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101341182B1 (en) | 2011-11-28 | 2013-12-13 | 재단법인 포항산업과학연구원 | Manufacturing Method Of High Purity Aluminum Alkoxide |
-
2002
- 2002-11-05 KR KR10-2002-0068239A patent/KR100509395B1/en not_active IP Right Cessation
Non-Patent Citations (1)
| Title |
|---|
| The Merck Index, 12th Edition, p357-358, Published by Merck Research Laboratories Division of MERCK & CO.,INC., 1996 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101341182B1 (en) | 2011-11-28 | 2013-12-13 | 재단법인 포항산업과학연구원 | Manufacturing Method Of High Purity Aluminum Alkoxide |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20040039976A (en) | 2004-05-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100983349B1 (en) | Chemical process for recycling polyethylene terephthalate (pet) wastes | |
| US4542001A (en) | Fine particulate crystalline aluminum orthophosphate and method for preparing same | |
| CN101462746B (en) | Method for preparing anhydrous magnesium chloride from bischofite | |
| AU2011317371A1 (en) | Process for producing a lactic acid-amine complex | |
| CN110294712B (en) | Preparation method of high-purity imidazole acetate ionic liquid | |
| CN113845446B (en) | Preparation method of trifluoromethanesulfonic acid | |
| KR100509395B1 (en) | Process for preparation of aluminum alkoxide from aluminum waste | |
| Yoo et al. | Synthesis of aluminum isopropoxide from aluminum dross | |
| US3000703A (en) | Manufacture of zirconium oxide | |
| CN112209853A (en) | Synthesis method of N, N' -dicyclohexylcarbodiimide | |
| CN114315728B (en) | Imidazole ionic liquid and application thereof in alcoholysis polymerization of 2, 5-furandicarboxylic acid ester | |
| KR20190049478A (en) | Method for producing 2,6-naphthalene dicarboxylic acid | |
| CN101429210B (en) | Synthesis of esterifiable fluorene diborate | |
| CN114478606A (en) | Synthetic method of tributyl borate | |
| CN113563169A (en) | Preparation method of tris (2,2,6, 6-tetramethyl-3, 5-heptanedionate) aluminum | |
| EP0079392B1 (en) | Composite oxyalkoxides and derivatives thereof | |
| US3886264A (en) | Process for hydrolyzing aluminum alkoxides using sulfurous acid | |
| Zhang et al. | Alumina recovery from spent Bayer liquor by methanol | |
| RU2784345C1 (en) | Method for producing a zirconium-based organometallic framework | |
| CN114014346B (en) | Preparation method of anhydrous magnesium chloride | |
| CN115286506B (en) | Method for synthesizing matrithrin by one-step oxidation esterification with metal organic framework material as catalyst | |
| CN112552338B (en) | Comprehensive recycling method of phosphorus-containing composite salt as byproduct in organic phosphine production | |
| CN1300098C (en) | Method for synthesizing N-butyl-glucosamine | |
| CN103183391B (en) | Preparation method of high-purity rhodium iodide | |
| WO2012100555A1 (en) | A method for the preparation of lower aluminum alkoxide by gas-solid phase reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20120806 Year of fee payment: 8 |
|
| FPAY | Annual fee payment |
Payment date: 20130704 Year of fee payment: 9 |
|
| FPAY | Annual fee payment |
Payment date: 20150104 Year of fee payment: 10 |
|
| LAPS | Lapse due to unpaid annual fee |