CN100431699C - Activated carbon carried cuprous iodide catalyst, and its preparing method and use - Google Patents
Activated carbon carried cuprous iodide catalyst, and its preparing method and use Download PDFInfo
- Publication number
- CN100431699C CN100431699C CNB2006100843991A CN200610084399A CN100431699C CN 100431699 C CN100431699 C CN 100431699C CN B2006100843991 A CNB2006100843991 A CN B2006100843991A CN 200610084399 A CN200610084399 A CN 200610084399A CN 100431699 C CN100431699 C CN 100431699C
- Authority
- CN
- China
- Prior art keywords
- cuprous iodide
- activated carbon
- catalyst
- ethanol
- iodide catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910021595 Copper(I) iodide Inorganic materials 0.000 title claims abstract description 42
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 title claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 44
- 239000003054 catalyst Substances 0.000 title claims description 30
- 238000000034 method Methods 0.000 title claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 8
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001868 water Inorganic materials 0.000 claims abstract description 7
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims abstract description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 claims abstract description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 4
- 239000011630 iodine Substances 0.000 claims abstract description 4
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 8
- -1 alkylthio group aromatic compound Chemical class 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims 2
- 238000009388 chemical precipitation Methods 0.000 claims 1
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 abstract description 12
- 229910000365 copper sulfate Inorganic materials 0.000 abstract description 6
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 abstract 1
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 5
- 238000006053 organic reaction Methods 0.000 description 5
- JTBAOJVLBMPVBV-UHFFFAOYSA-N [2,4-diamino-5-methyl-3-(sulfanylmethyl)phenyl]methanethiol Chemical compound CC1=CC(CS)=C(N)C(CS)=C1N JTBAOJVLBMPVBV-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 3
- TXDBDYPHJXUHEO-UHFFFAOYSA-N 2-methyl-4,6-bis(methylsulfanyl)benzene-1,3-diamine Chemical compound CSC1=CC(SC)=C(N)C(C)=C1N TXDBDYPHJXUHEO-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000007336 electrophilic substitution reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 235000010269 sulphur dioxide Nutrition 0.000 description 3
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- CETBSQOFQKLHHZ-UHFFFAOYSA-N Diethyl disulfide Chemical compound CCSSCC CETBSQOFQKLHHZ-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- XVSJTVAPLGSCSK-UHFFFAOYSA-N 2,3,6-trimethylbenzenethiol Chemical compound CC1=CC=C(C)C(S)=C1C XVSJTVAPLGSCSK-UHFFFAOYSA-N 0.000 description 1
- WLHCBQAPPJAULW-UHFFFAOYSA-N 4-methylbenzenethiol Chemical compound CC1=CC=C(S)C=C1 WLHCBQAPPJAULW-UHFFFAOYSA-N 0.000 description 1
- ODHAQPXNQDBHSH-UHFFFAOYSA-N Dicyclohexyl disulfide Chemical compound C1CCCCC1SSC1CCCCC1 ODHAQPXNQDBHSH-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- SWJBITNFDYHWBU-UHFFFAOYSA-N [I].[I] Chemical compound [I].[I] SWJBITNFDYHWBU-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供的活性炭负载腆化亚铜可用作二烷基二硫与芳烃化合物之间的烷硫基化反应的催化剂，它是用活性炭浸渍在硫酸铜和碘或硫酸铜和碘化钾的乙醇/水溶剂中，由甲醛、氧化硫、亚硫酸钠或硫代硫酸钠还原而制成的。The gac-supported cuprous iodide provided by the invention can be used as the catalyzer of the alkylthiolation reaction between dialkyl disulfide and aromatic compound, and it is impregnated in the ethanol/ethanol of copper sulfate and iodine or copper sulfate and potassium iodide with gac In water solvent, it is made by reduction of formaldehyde, sulfur oxide, sodium sulfite or sodium thiosulfate.
Description
技术领域 technical field
本发明是属于化学反应催化剂领域。特别涉及用于二烷基二硫与芳烃化合物反应，制备烷硫基芳烃化合物的活性炭负载碘化亚铜催化剂。The invention belongs to the field of chemical reaction catalysts. In particular, it relates to an active carbon supported cuprous iodide catalyst used for the reaction of dialkyl disulfide and aromatic compound to prepare alkylthio aromatic compound.
技术背景technical background
许多烷硫基芳烃(例如苯甲硫醚、对甲硫基苯酚、2，4-二氨基-3，5-二甲硫基甲苯、2，6-二氨基-3，5-二甲硫基甲苯等)是重要的精细合成中间体原料，广泛应用于农药和橡塑助剂的合成。二烷基二硫与芳烃的亲电取代反应是制备烷硫基芳烃的重要方法之一，其中的二烷基二硫主要包括二甲基二硫、二乙基二硫、二苄基二硫、二环己基二硫等，芳烃主要包括由推电子基团活化的芳香族化合物，例如苯酚、苯胺、2，4-二氨基甲苯、2，6-二氨基甲苯、2，4(2，6)-甲苯二胺混合物、对甲基苯胺等。最为重要的是Lewis酸作为上述反应的催化剂是必不可少的，常用的Lewis酸催化剂有碘化亚铜、氯化锌、三氯化铝等，碘化亚铜的催化效果最好。美国专利US4594453、US5015770、US5210304、US5302755等报道了二甲基二硫与2，4(2，6)-甲苯二胺混合物反应，制备2，4-二氨基-3，5-二甲硫基甲苯和2，6-二氨基-3，5-二甲硫基甲苯混合物的方法，使用的催化剂都是碘化亚铜。Many alkylthioaromatics (such as sulfide anisole, p-methylthiophenol, 2,4-diamino-3,5-dimethylthiotoluene, 2,6-diamino-3,5-dimethylthio Toluene, etc.) are important fine synthetic intermediate raw materials, widely used in the synthesis of pesticides and rubber and plastic additives. The electrophilic substitution reaction between dialkyl disulfide and arene is one of the important methods to prepare alkylthio arene, wherein dialkyl disulfide mainly includes dimethyl disulfide, diethyl disulfide, dibenzyl disulfide , dicyclohexyl disulfide, etc. Aromatics mainly include aromatic compounds activated by electron-pushing groups, such as phenol, aniline, 2,4-diaminotoluene, 2,6-diaminotoluene, 2,4(2,6 )-toluenediamine mixture, p-methylaniline, etc. The most important thing is that Lewis acid is indispensable as the catalyst of the above reaction. Commonly used Lewis acid catalysts include cuprous iodide, zinc chloride, aluminum trichloride, etc., and cuprous iodide has the best catalytic effect. U.S. Patents US4594453, US5015770, US5210304, US5302755, etc. have reported the reaction of dimethyl disulfide and 2,4 (2,6)-toluenediamine mixture to prepare 2,4-diamino-3,5-dimethylthiotoluene and 2,6-diamino-3,5-dimethylthiotoluene mixture, the catalyst used is cuprous iodide.
市售碘化亚铜产品通常为20目的大颗粒粉体，由于碘化亚铜大颗粒粉体比重较大，所以用在二烷基二硫与芳烃的亲电取代反应制备烷硫基芳烃化合物的过程中，反应体系中出现碘化亚铜大颗粒粉沉降严重，催化效能低，造成碘化亚铜催化剂的耗量增大等问题。为了能够减少碘化亚铜催化剂的用量，提高其催化效能，工业一般是采用将20目大颗粒粉体碘化亚铜粉碎为200～400目微细粉体的方法。但是，碘化亚铜催化剂是一种光敏感化合物，微细粉体碘化亚铜在粉碎和催化应用两过程中的感光分解损失比较严重。碘化亚铜的价格又比较高，所以碘化亚铜作为催化剂的损耗高，所占2，4-二氨基-3，5-二甲硫基甲苯和2，6-二氨基-3，5-二甲硫基甲苯混合物的生产成本比例高。Commercially available cuprous iodide products are usually 20-mesh large-particle powders. Due to the large specific gravity of cuprous iodide large-particle powders, they are used in the electrophilic substitution reaction of dialkyl disulfide and aromatic hydrocarbons to prepare alkylthio aromatic compounds. During the process, serious settling of copper iodide large-particle powder occurs in the reaction system, and the catalytic efficiency is low, which causes problems such as increased consumption of cuprous iodide catalyst. In order to reduce the consumption of cuprous iodide catalyst and improve its catalytic efficiency, the industry generally adopts the method of pulverizing cuprous iodide with 20-mesh large particle powder into 200-400-mesh fine powder. However, the cuprous iodide catalyst is a photosensitive compound, and the photosensitive decomposition loss of the fine powder cuprous iodide in the two processes of pulverization and catalytic application is relatively serious. The price of cuprous iodide is relatively high, so the loss of cuprous iodide as a catalyst is high, accounting for 2,4-diamino-3,5-dimethylthiotoluene and 2,6-diamino-3,5 - A high proportion of production costs for dimethylthiotoluene mixtures.
发明内容 Contents of the invention
本发明提供的活性炭负载碘化亚铜催化剂，目的在于减小催化剂与有机反应体系之间的密度差，提高碘化亚铜在有机反应体系中的分散度，提高其催化效能；利用活性炭的黑色保护碘化亚铜，避免碘化亚铜在使用和储存过程中的感光分解损失，以降低烷硫基芳烃化合物的生产成本。The active carbon-supported cuprous iodide catalyst provided by the present invention aims to reduce the density difference between the catalyst and the organic reaction system, improve the dispersion of cuprous iodide in the organic reaction system, and improve its catalytic performance; Protect the cuprous iodide, avoid the photosensitive decomposition loss of the cuprous iodide in the process of use and storage, so as to reduce the production cost of the alkylthio arene compound.
本发明提供的活性炭负载碘化亚铜催化剂的制备方法是活性炭浸渍在硫酸铜和碘化钾的水中，由甲醛、二氧化硫、亚硫酸钠或硫代硫酸钠等还原剂还原而制成的。或者活性炭浸渍在硫酸铜和碘的乙醇水混合溶剂中，由甲醛、二氧化硫、亚硫酸钠或硫代硫酸钠等还原剂还原而制成。The preparation method of the activated carbon supported cuprous iodide catalyst provided by the invention is that the activated carbon is soaked in the water of copper sulfate and potassium iodide, and then reduced by reducing agents such as formaldehyde, sulfur dioxide, sodium sulfite or sodium thiosulfate. Or activated carbon is impregnated in a mixed solvent of copper sulfate and iodine in ethanol and water, and is made by reducing with reducing agents such as formaldehyde, sulfur dioxide, sodium sulfite or sodium thiosulfate.
本发明提供的活性炭负载碘化亚铜催化剂的制备方法所述的活性炭可以是球状、柱状、圆桶状、无定形颗粒状，也可以是粉末状的。为了提高碘化亚铜在活性炭表面上或空腔中的分散度，活性炭浸渍在硫酸铜和碘化钾的水溶液中或活性炭浸渍在硫酸铜和碘的乙醇水混合溶剂中，应先加热煮沸1～4小时，然后再加入还原剂甲醛、二氧化硫、亚硫酸钠或硫代硫酸钠等，这样生成的碘化亚铜就可以在活性炭中分散均匀。The preparation method of the activated carbon-supported cuprous iodide catalyst provided by the invention The activated carbon can be spherical, columnar, drum-shaped, amorphous granular, or powdery. In order to improve the dispersion of cuprous iodide on the surface of activated carbon or in the cavity, activated carbon is impregnated in an aqueous solution of copper sulfate and potassium iodide or activated carbon is impregnated in a mixed solvent of ethanol and water of copper sulfate and iodine. It should be heated and boiled for 1 to 4 Hours, and then add the reducing agent formaldehyde, sulfur dioxide, sodium sulfite or sodium thiosulfate, etc., so that the generated cuprous iodide can be evenly dispersed in the activated carbon.
本发明提供的活性炭负载碘化亚铜作为二烷基二硫与芳烃的亲电取代反应催化剂具有以下的优点：活性炭负载碘化亚铜催化剂相对有机反应体系的密度差减小，活性炭负载碘化亚铜催化剂在有机反应体系的均分散性高，相等重量的活性炭负载碘化亚铜催化活性相比碘化亚铜催化剂的催化活性中心多；利用活性炭的黑色可以有效保护碘化亚铜免于感光分解，提高活性炭负载碘化亚铜催化剂的循环使用效率，降低烷硫基芳烃化合物生产中催化剂的消耗量：活性炭负载碘化亚铜催化剂与有机反应物体系和有机反应产物体系的过滤分离方便，简化了活性炭负载碘化亚铜催化剂分出过程。The activated carbon-supported cuprous iodide provided by the present invention has the following advantages as a catalyst for the electrophilic substitution reaction of dialkyl disulfide and aromatic hydrocarbons: the density difference of the activated carbon-supported cuprous iodide catalyst relative to the organic reaction system is reduced, and the activated carbon-supported iodide The uniform dispersion of cuprous catalyst in the organic reaction system is high, and the catalytic activity of equal weight of activated carbon supported cuprous iodide is more than that of cuprous iodide catalyst; the black color of activated carbon can effectively protect cuprous iodide from Photodecomposition, improving the recycling efficiency of activated carbon-supported cuprous iodide catalysts, reducing the consumption of catalysts in the production of alkylthio aromatic compounds: the filtration and separation of activated carbon-supported cuprous iodide catalysts from organic reactant systems and organic reaction product systems is convenient , which simplifies the separation process of activated carbon-supported cuprous iodide catalyst.
以下实施例进一步说明本发明提供的活性炭负载碘化亚铜催化剂、制备方法以及应用。The following examples further illustrate the activated carbon supported cuprous iodide catalyst, preparation method and application provided by the present invention.
实施例1Example 1
活性炭负载碘化亚铜催化剂及制备方法Activated carbon supported cuprous iodide catalyst and preparation method
在装有搅拌器、回流冷凝器、滴液漏斗的反应烧瓶中，加入0.21摩尔五水硫酸铜、0.2摩尔碘化钾、200克60目活性炭、去离子水200毫升，搅拌下，升温至沸腾保持2小时。冷却至室温，搅拌滴入0.22摩尔亚硫酸钠的饱和水溶液，反应1小时后，收集滤饼，滤饼先用去离子水洗涤3～5次，后用无水乙醇洗涤3～5次，抽空干燥，即可制得活性炭负载碘化亚铜催化剂。In the reaction flask equipped with stirrer, reflux condenser, and dropping funnel, add 0.21 mole of copper sulfate pentahydrate, 0.2 mole of potassium iodide, 200 grams of 60 mesh activated carbon, and 200 milliliters of deionized water. Hour. Cool to room temperature, stir and drop 0.22 mole of sodium sulfite in a saturated aqueous solution, react for 1 hour, collect the filter cake, wash the filter cake with deionized water for 3 to 5 times, then wash with absolute ethanol for 3 to 5 times, and vacuum dry. The activated carbon-supported cuprous iodide catalyst can be prepared.
实施例2Example 2
活性炭负载碘化亚铜催化剂及制备方法Activated carbon supported cuprous iodide catalyst and preparation method
在装有搅拌器、回流冷凝器、滴液漏斗的反应烧瓶中，加入0.21摩尔五水硫酸铜、0.2摩尔精碘、200克60目活性炭、乙醇100毫升、去离子水100毫升，搅拌下均匀，升温至沸腾2小时。冷却至室温，搅拌滴入37％的甲醛水溶液20克，反应1小时后，收集滤饼，滤饼先用去离子水洗涤3～5次，后用无水乙醇洗涤3～5次，抽空干燥，即可制得活性炭负载碘化亚铜催化剂。In a reaction flask equipped with a stirrer, a reflux condenser, and a dropping funnel, add 0.21 moles of copper sulfate pentahydrate, 0.2 moles of iodine iodine, 200 grams of 60-mesh activated carbon, 100 milliliters of ethanol, and 100 milliliters of deionized water. , heated to boiling for 2 hours. Cool to room temperature, stir and drop in 20 grams of 37% formaldehyde solution, react for 1 hour, collect the filter cake, wash the filter cake with deionized water for 3 to 5 times, then wash with absolute ethanol for 3 to 5 times, and then vacuum dry , the activated carbon-supported cuprous iodide catalyst can be prepared.
实施例3Example 3
活性炭负载碘化亚铜催化剂的应用Application of Activated Carbon Supported Cuprous Iodide Catalyst
在装有搅拌器、回流冷凝器、滴液漏斗的反应烧瓶中，加入刚蒸馏过的2，4-二氨基甲苯和2，6-二氨基甲苯混合物(80∶20)100克和实施例1所制备的活性炭负载碘化亚铜催化剂30克。N2保护下，搅拌升温至130～135℃，3小时内滴入二甲基二硫160克，滴完二甲基二硫继续保持130～135℃反应2小时。冷却至50℃附近，真空抽滤，滤液真空蒸馏可分出2，4-二氨基-3，5-二甲硫基甲苯和2，6-二氨基-3，5-二甲硫基甲苯混合物231克，产率94.4％。滤饼循环使用可达8次以上，依然保持高产率。In the reaction flask equipped with agitator, reflux condenser and dropping funnel, add 100 grams of 2,4-diaminotoluene and 2,6-diaminotoluene mixture (80:20) and Example 1 Prepared activated carbon supported cuprous iodide catalyst 30 grams. Under the protection of N 2 , the temperature was raised to 130-135°C with stirring, and 160 grams of dimethyl disulfide was added dropwise within 3 hours, and the reaction was continued at 130-135°C for 2 hours after the addition of dimethyl disulfide was completed. Cool to around 50°C, vacuum filter, and vacuum distill the filtrate to separate the mixture of 2,4-diamino-3,5-dimethylthiotoluene and 2,6-diamino-3,5-dimethylthiotoluene 231 g, 94.4% yield. The filter cake can be recycled for more than 8 times and still maintain a high yield.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100843991A CN100431699C (en) | 2006-05-23 | 2006-05-23 | Activated carbon carried cuprous iodide catalyst, and its preparing method and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100843991A CN100431699C (en) | 2006-05-23 | 2006-05-23 | Activated carbon carried cuprous iodide catalyst, and its preparing method and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1891338A CN1891338A (en) | 2007-01-10 |
| CN100431699C true CN100431699C (en) | 2008-11-12 |
Family
ID=37596687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100843991A Expired - Fee Related CN100431699C (en) | 2006-05-23 | 2006-05-23 | Activated carbon carried cuprous iodide catalyst, and its preparing method and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100431699C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105825990B (en) * | 2016-03-30 | 2017-11-14 | 淮北师范大学 | A kind of CuI Fe3O4The preparation method of magnetic nanocomposites |
| CN105883895A (en) * | 2016-05-25 | 2016-08-24 | 浙江汇能生物股份有限公司 | Preparation method of copper iodide |
| CN106115764B (en) * | 2016-06-23 | 2017-12-12 | 淮北师范大学 | The method that one pot of ball milling solid phase method prepares CuI nano-powders |
| CN106187823B (en) * | 2016-07-04 | 2018-06-22 | 江苏省原子医学研究所 | A kind of method for preparing meta iodobenzyl guanidine |
| CN115612857B (en) * | 2022-10-25 | 2023-10-20 | 昆明理工大学 | Method for selectively recycling gold (III) in waste circuit board leaching solution |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0132915A1 (en) * | 1983-07-20 | 1985-02-13 | Hidefumi Hirai | Method of preparing solid adsorbent for unsaturated hydrocarbon and process for separation of unsaturated hydrocarbon from gas mixture |
| US5210304A (en) * | 1991-03-11 | 1993-05-11 | Ethyl Corporation | Process for preparing hydrocarbyl aromatic amines |
| US5302755A (en) * | 1991-05-31 | 1994-04-12 | Ethyl Corporation | Method for DMTDA production |
| CN1388117A (en) * | 1998-06-18 | 2003-01-01 | 弗·哈夫曼－拉曼切有限公司 | Process for prodcing 3-aryl sulfate iso-hydroximic acid |
| US6638489B2 (en) * | 2000-09-28 | 2003-10-28 | Japan Pionics Co., Ltd. | Cleaning process and cleaning agent for harmful gas |
-
2006
- 2006-05-23 CN CNB2006100843991A patent/CN100431699C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0132915A1 (en) * | 1983-07-20 | 1985-02-13 | Hidefumi Hirai | Method of preparing solid adsorbent for unsaturated hydrocarbon and process for separation of unsaturated hydrocarbon from gas mixture |
| US5210304A (en) * | 1991-03-11 | 1993-05-11 | Ethyl Corporation | Process for preparing hydrocarbyl aromatic amines |
| US5302755A (en) * | 1991-05-31 | 1994-04-12 | Ethyl Corporation | Method for DMTDA production |
| CN1388117A (en) * | 1998-06-18 | 2003-01-01 | 弗·哈夫曼－拉曼切有限公司 | Process for prodcing 3-aryl sulfate iso-hydroximic acid |
| US6638489B2 (en) * | 2000-09-28 | 2003-10-28 | Japan Pionics Co., Ltd. | Cleaning process and cleaning agent for harmful gas |
Non-Patent Citations (2)
| Title |
|---|
| A general method for the formation of diaryl selenides usingcopper(I) catalysts. Rttan K. Gujadhur et al.Tetrahedron Letters,Vol.44 . 2003 |
| A general method for the formation of diaryl selenides usingcopper(I) catalysts. Rttan K. Gujadhur et al.Tetrahedron Letters,Vol.44 . 2003 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1891338A (en) | 2007-01-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100431699C (en) | Activated carbon carried cuprous iodide catalyst, and its preparing method and use | |
| CN104724734B (en) | A kind of manufacture lightweight, high-specific surface area, the method for bouquet type nano-sized magnesium hydroxide | |
| CN105753022B (en) | A kind of preparation method of magnesium-base layer-shaped complex hydroxide | |
| CN104324762B (en) | A kind of trielement composite material preparation method and application | |
| CN104324761B (en) | The Synthesis and applications that a kind of porous rare earth organic coordination compound is catalyst based | |
| CN106334568A (en) | Method for adopting solvothermal one-step method to synthesize Bi/BiOCl composite nanostructure | |
| CN102773110A (en) | Preparation method of coin-shaped hollow structure SnS2/SnO2 composite photocatalyst material | |
| CN108176392A (en) | Composite catalyst of amine salt and preparation method thereof is catalytically decomposed, prepares the method for MDA | |
| CN102009959A (en) | Preparation method of organic acid anion intercalation hydrotalcite | |
| CN114213251B (en) | Process for catalytic synthesis of dimethyl carbonate | |
| CN102531037A (en) | Chemical preparation method of nanoscale zinc oxide powder | |
| CN108097277A (en) | A kind of BiOCl/ZnO hetero-junctions high visible light catalytic activity material and preparation method thereof | |
| CN115716918A (en) | A method for preparing metal-organic framework materials by ball milling and solution blending | |
| Kalita et al. | CuWO4 Reinforced Co‐doped HAp Nanocomposite: Improved Photocatalytic Activity Towards Degradation of Eosin Y and Catalytic Activity in Crossed Aldol Condensation Reaction | |
| CN105776311B (en) | A kind of preparation method of copper oxide nano material | |
| CN108212187A (en) | Fe adulterates Bi2O2CO3Preparation method and Fe the doping Bi of photochemical catalyst2O2CO3Photochemical catalyst | |
| CN102603540B (en) | A kind of preparation method of diethyldiaminotoluene | |
| CN104741112B (en) | A kind of TiO2/WO3The preparation method of composite granule | |
| CN104477869A (en) | Method for synthesizing bismuth phosphate nano particles by room-temperature solid-phase chemical method | |
| CN100411735C (en) | A kind of solid superacid catalyst and preparation method thereof | |
| CN101318945B (en) | Method for preparing furfural from waste crops containing pentosan | |
| CN104418763A (en) | Method for preparation of aryl amides by aromatic carboxylic acid amination | |
| CN101792371B (en) | Method for catalytically synthesizing p-ethylphenol | |
| CN102337555B (en) | Method for synthesizing 2,4-dimethylanisole | |
| CN102627264B (en) | Square monodisperse ferric phosphate and its preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081112 |