CN1302792A - 减少工业生产物流中碘化物的方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 35
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 150000001351 alkyl iodides Chemical class 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 carboxylate salt Chemical class 0.000 claims abstract description 10
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 10
- 239000011630 iodine Substances 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 7
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910052768 actinide Inorganic materials 0.000 claims abstract 3
- 150000001255 actinides Chemical class 0.000 claims abstract 3
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 3
- 229910052802 copper Inorganic materials 0.000 claims abstract 3
- 239000010949 copper Substances 0.000 claims abstract 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 16
- 229940071870 hydroiodic acid Drugs 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 claims 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- 229910052728 basic metal Inorganic materials 0.000 claims 1
- 150000003818 basic metals Chemical class 0.000 claims 1
- 150000007942 carboxylates Chemical class 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 229910001505 inorganic iodide Inorganic materials 0.000 abstract 1
- 229910052747 lanthanoid Inorganic materials 0.000 abstract 1
- 150000002602 lanthanoids Chemical class 0.000 abstract 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 35
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- ANOOTOPTCJRUPK-UHFFFAOYSA-N 1-iodohexane Chemical compound CCCCCCI ANOOTOPTCJRUPK-UHFFFAOYSA-N 0.000 description 25
- 238000010521 absorption reaction Methods 0.000 description 23
- 239000003795 chemical substances by application Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 15
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 13
- 235000011056 potassium acetate Nutrition 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 8
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- UWLHSHAHTBJTBA-UHFFFAOYSA-N 1-iodooctane Chemical compound CCCCCCCCI UWLHSHAHTBJTBA-UHFFFAOYSA-N 0.000 description 4
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- YLYBTZIQSIBWLI-UHFFFAOYSA-N octyl acetate Chemical compound CCCCCCCCOC(C)=O YLYBTZIQSIBWLI-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229940043232 butyl acetate Drugs 0.000 description 2
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 150000002497 iodine compounds Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910013594 LiOAc Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- IAQLJCYTGRMXMA-UHFFFAOYSA-M lithium;acetate;dihydrate Chemical compound [Li+].O.O.CC([O-])=O IAQLJCYTGRMXMA-UHFFFAOYSA-M 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
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- 230000000717 retained effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
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- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
- C07C51/493—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification whereby carboxylic acid esters are formed
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
一种减少混合物中,特别是羧酸类和/或羧基酐与烷基碘和/或氢碘酸的混合物中碘含量的方法,包括在高温下于汽相中将有机介质与分散在活性炭中的金属盐接触。金属盐可以是羧酸盐类、碳酸盐、氧化物、氢氧化物以及可以与有机介质起化学反应产生金属羧酸盐的其他盐类。金属可以为主族元素、镧系元素、锕系元素、锌和铜。此方法使烷基碘化合物转化为它们相应的羧酸酯类,同时碘以无机碘化物形式粘结在纯化物质上。
Description
本发明涉及从含碘化合物如烷基碘等中除碘的方法，该含碘化合物是含在与其他化合物(更具体地是羧酸和/或羧酐)混合的混合物中。特别地，本发明适合于由铑或铱催化、甲基碘加速使甲醇和/或二甲醚和/或乙酸甲酯羰基化制备的乙酸和/或乙酸酐的纯化。
在工业乙酸的制造中，大家都知道在很多情况下，为了满足用户的需要，最终产品中碘化物的含量必须极其低(不到十亿分之六重量(ppb))。大约50％的全球生产的乙酸产品用于以催化工艺生产乙酸乙烯酯。即使碘化物浓度极低也会严重地损害此方法的催化剂。乙酸中的碘化物源自在甲醇和/或二甲醚和/或乙酸甲酯的羰基化中使用了甲基碘和/或氢碘酸作为助催化剂。在粗制的乙酸中大部分碘以甲基碘形式存在，少量碘以氢碘酸和较高的烷基碘形式存在。甲基碘容易地经过蒸馏分离和回收到反应器区段。大部分氢碘酸也可以回收。残余在产品中的碘化物，主要是较高(C2-C8)的烷基碘，更难被除去。常常提到己基碘，因为由于它的沸点非常接近乙酸的沸点，所以特别难以经过蒸馏除去此化合物。较高的烷基碘的浓度一般为100-1000ppb(0.1-1ppm)的数量级。
已经描述了几种纯化粗制的羧酸类和/或乙酸和/或其衍生物的方法。然而，大多数方法涉及在液相中的纯化。因此，一些专利(美国专利号4,975,155、5,220,058、5,227,524、5,300,685和5,801,279)提出在液相中使用银、钯、汞和/或铑离子交换树脂以减少羧酸酯物流中碘的含量。提出加入氧化剂来纯化，例如美国专利号5,387,713描述了在液相中使用过氧化氢，和美国专利号5,155,265描述了在液相中使用臭氧作为纯化剂。与本发明更相关的是美国专利号4,246,195，其提出了使用乙酸铯、乙酸钾和乙酸钠纯化与碘污染相关的羰基化产品。然而，所说的专利仅仅涉及在液相中的操作。
本发明的一个目的是提供在汽相中减少混合物，特别是乙酸与烷基碘和/或氢碘酸的混合物中碘含量的方法。
根据本发明，令人惊讶地发现：当在高温和常压下在汽相中将被浓度为0.1到3000ppm的烷基碘污染的乙酸与分散在特殊的载体材料中的金属乙酸盐类接触的时候，烷基碘转变为相应的乙酸烷基酯，而碘化物以无机(不挥发的)碘化物形式粘结在吸收剂上。所说的特殊载体材料是活性炭。对于其他载体例如氧化铝和硅石来说，几乎不转化。
因此，发现当在189±6℃的温度和33±8克/小时的流速下，通过活性炭上的乙酸钾床蒸发乙酸中258ppb己基碘溶液(总体积7ml)时，在再浓缩的乙酸溶液中己基碘的浓度已降低到低于6ppb己基碘(低于4ppb碘)。在20、40、60、120和140分钟之后测量物流中己基碘的浓度，并发现在所有的情况下都低于6ppb己基碘。
而且，本发明烷基碘由于一些色谱的影响并不仅仅保留在吸收剂上。下列例子将说明烷基碘转化为它们相应的乙酸酯类，这已经由气相色谱分析确认。为了说明本发明的范围，制备7种不同的吸收剂(实施例1-7)。因为本发明可以具体应用于乙酸生产和纯化工艺中，所以试验一些吸收剂对己基碘含量为100-300ppb的乙酸溶液的性能(实施例8-14)。也试验一些在乙酸中具有更浓的烷基碘溶液的比较实施例(实施例15-32)。这些比较实施例不是对乙酸中己基碘溶液进行试验，而是对乙酸中甲基碘、丁基碘和辛基碘的混合物进行试验。
实施例1
制备在活性炭上的钾的吸收剂(KOAc/A.C.)。
将乙酸钾(1.96克，0.02摩尔)溶于去离子水(4ml)中，并用去离子水稀释到7.5ml得到透明的、无色溶液。在密闭容器中将2.5毫米颗粒形式的活性炭(10.00克)(Merck,QBET表面积为1190m2/克，其中470m2/克是多微孔的表面积)与水溶液接触，并充分地摇动，直到材料变干或几乎变干。然后将该材料在烘箱中于100℃下干燥16小时，之后记录其重量为13.10克，总体积为28ml。然后将此材料等重分成四份，因此每份含有0.005摩尔钾，并分别贮藏这四份。接着此步骤制备吸收剂。
实施例2
除用乙酸铯(3.84克，0.02摩尔)代替乙酸钾之外，按照实施例1所述方法制备吸收剂。
实施例3
除用乙酸锂二水合物(2.04克，0.02摩尔)代替乙酸钾之外，按照实施例1所述方法制备吸收剂。
实施例4
除用乙酸锌二水合物(4.39克，0.02摩尔)代替乙酸钾之外，按照实施例1所述方法制备吸收剂。
实施例5
除用乙酸镁四水合物(4.29克，0.02摩尔)代替乙酸钾之外，按照实施例1所述方法制备吸收剂。
实施例6
除了使用10.00克煅烧氧化铝(QBET表面积为270m2/克)代替10.00克活性碳之外，按照实施例1所述方法制备吸收剂。
实施例7
除了使用10.00克硅石(Merck,100目)代替10.00克活性碳之外，按照实施例1所述方法制备吸收剂。
实施例8
将按照实施例1所述方法制备的一份吸收剂(体积7毫升，0.005摩尔乙酸钾)装入内径为1.0厘米的玻璃反应器中。将该玻璃反应器放入一管式炉中。将该玻璃反应器的下端连接到置于加热罩中的完全隔离的250毫升圆底烧瓶中，而顶端安装到Claisen冷凝器和收集器烧瓶中。该圆底烧瓶安装有温度计。通过该玻璃反应器顶部引入热电偶，在蒸馏过程中该热电偶固定在该金属乙酸盐床的中心。该管式炉被加热到250℃，然后打开加热罩。用蠕动泵将乙酸中正己基碘(HxI)溶液引入热的圆底烧瓶中。在整个实验期间乙酸盐床的温度测得为189℃±6℃。流速保持为33±8克/小时。每隔一定时间，从收集器烧瓶中取出冷凝物，记录它的重量以便测量流速，并用气相色谱-质谱联用法按标准化方法分析样品(充分均匀的)中HxI的含量。在未经处理的溶液中HxI的浓度测得为258ppb(每千克溶液258微克己基碘)。之后20分钟收集并分析净化溶液。HxI的浓度总计为5.4ppb。继续试验140分钟，在试验过程中定期取出样品。在各个样品中测量HxI的浓度，结果显示在表1中。此实施例表明在189℃的温度和33克/小时的流速下，按照实施例1所述方法制备的体积为7毫升的吸收剂使乙酸物流中己基碘含量从258ppb减少到6ppb以下。而且，此实施例说明在140分钟连续时间生产中在处理的溶液中己基碘的浓度保持不变。
实施例9-12
除了按照表1所示的改变吸收剂、和/或改变温度、和/或改变流速、和/或改变在未经处理的乙酸溶液中己基碘浓度之外，重复实施例8所述的步骤。通过改变管式炉的设定值和/或改变流速来改变温度。对每个实施例，在处理的样品中己基碘含量也显示在表1中。实施例9证明按照实施例2所述方法制备的吸收剂在表1规定的条件下也能有效地减少己基碘浓度。实施例10说明实施例1制备的吸收剂在较低的温度和高流速下不如实施例8。然而，与在未经处理的溶液中己基碘浓度相比，仍然大大减少了己基碘浓度。实施例11清楚地证明在实质上较低的温度(155℃，与实施例8中的189℃相比)下，按照实施例1所述方法制备的吸收剂不如在高温下降低己基碘浓度。实施例12证明用14毫升柱床体积(两份按照实施例1所述方法制备的吸收剂)代替实施例8中使用的7ml柱床体积，降低己基碘浓度更大。
实施例13
除了单独使用活性炭代替在活性炭上的乙酸钾作为吸收剂之外，重复实施例8描述的步骤。将温度、流速、未经处理的溶液中HxI的含量记录在表1中。对每个实施例，在处理的样品中己基碘含量也显示在表1中。此实施例证明单独的活性炭显然在降低乙酸物流中己基碘的含量方面与活性炭和金属乙酸盐类一起使用时同样有效。然而，后面的实施例将说明：单独使用活性炭仅仅将烷基碘的小部份转化为乙酸烷基酯，在该实施例中观察到的在乙酸物流中降低己基碘含量的结果主要是一种色谱效应。
实施例14
除了在活性炭上的乙酸钾床的顶部(14)放置另一个未浸渍的活性炭的床(7毫升)之外，重复实施例8描述的步骤。将温度、流速、未经处理的溶液中HxI的含量记录在表1中。对每个实施例，在处理的样品中己基碘含量也显示在表1中。此实施例证明可以将己基碘的含量减少到我们方法的检测极限以下的水平(＜0.5ppb)。
实施例15-32
下列实施例全部按照实施例8所述进行，除了下列不同：(ⅰ)在乙酸中使用甲基碘、丁基碘和辛基碘的混合物代替己基碘/乙酸混合物；(ⅱ)在大多数情况下在未经处理的溶液中碘的总浓度为0.037-0.040摩尔(37-40毫摩尔)，而有时为0.0037摩尔(3.7毫摩尔)；(ⅲ)吸收剂的种类和数量、温度、流速和甲基碘、丁基碘和辛基碘的比浓度按照表2所示来改变。对于每个实验来说包括在表2中的数值是每个烷基碘和每个乙酸烷基酯测量三次到五次的数值。对于每个时间点，计算使用的吸收层的容量(表2中的Cap(％))，按照如下计算：
Cap(％)=(n(MeOAc)+n(BuOAc)+n(OctOAc))/n(M)*100％
其中
n(MeOAc)是当时形成的乙酸甲酯的摩尔总数；
n(BuOAc)是当时形成的乙酸丁酯的摩尔总数；
n(OctOAc)是当时形成的乙酸辛酯的摩尔总数；
n(M)是在表2中标明的吸收剂中金属的摩尔数。
同样地，按照下式计算每个时间点三种烷基碘转化为乙酸盐的平均转化率(表2中的Con(％))：
Con(％)=(([MeOAc]/[MeI]tot)+([BuOAc]/[BuI]tot)+([OctOAc]/[OctI]tot)/3*100％，
其中
(MeOAc)是在净化的混合物中乙酸甲酯的实测浓度；
(BuOAc)是在净化的混合物中乙酸丁酯的实测浓度；
(OctOAc)是在净化的混合物中乙酸辛酯的实测浓度；
(MeI)tot是在未纯化的混合物中甲基碘的浓度；
(BuI)tot是在未纯化的混合物中丁基碘的浓度；
(OctI)tot是在未纯化的混合物中辛基碘的浓度。
表1
表2
表2(续)
表2(续)
| 时间(分钟) | PpbHxI | 时间(分钟) | PpbHxI | ||
| 实施例8 231199AKOAc/A.C.(7ml)F=33±8g/hT=189±6℃5毫摩尔K | --- | 258 | 实施例12 091299CKOAc/A.C.(14ml)F=43±4g/hT=191±4℃10毫摩尔K | --- | 130 |
| 20 | 5.4 | 20 | ＜0.5 | ||
| 40 | 2.7 | 40 | ＜0.5 | ||
| 60 | 4.0 | 80 | 0.9 | ||
| 120 | 3.2 | 120 | 1.7 | ||
| 140 | 5.9 | 140 | 2.2 | ||
| 实施例9 241199ACsOAc/A.C.(7ml)F=43±4g/hT=200±5℃5毫摩尔Cs | --- | 258 | 实施例13 091299AA.C.(7ml)F=42±6g/hT=179±2℃0毫摩尔 金属 | --- | 215 |
| 21 | 3.7 | 20 | ＜00.6.5 | ||
| 86 | 5.1 | 40 | ＜0.51.3 | ||
| 121 | 3.1 | 80 | 0.90.9 | ||
| 140 | 3.6 | 120 | 1.71.9 | ||
| 167 | 4.2 | 140 | 2.22.7 | ||
| 实施例10 251199AKOAc/A.C.(7ml)F=42±3g/hT=183±3℃5毫摩尔K | --- | 258 | 实施例14 101299AKOAc/A.C.(14ml)+A.C.(7ml)F=41±4g/hT=209±2℃10毫摩尔K | --- | 109 |
| 20 | 3.9 | 41 | ＜0.5 | ||
| 40 | 5.7 | 60 | ＜0.5 | ||
| 80 | 12.4 | 100 | ＜0.5 | ||
| 120 | 16.3 | 120 | ＜0.5 | ||
| 140 | 7.2 | 140 | ＜0.5 | ||
| 实施例11 261199AKOAc/A.C.(7ml)F=38±8g/hT=155±3℃5毫摩尔K | --- | 258 | |||
| 41 | 100 | ||||
| 60 | 116 | ||||
| 80 | 93 | ||||
| 120 | 125 | ||||
| 140 | 114 |
| 时间(分钟) | ppmMeI | ppmMeA | ppmBuI | ppmBuA | ppmOctI | ppmOctA | Cap(％) | Con(％) | |
| 实施例15 151099ACsOAc/A.C.(14ml)F=29±8g/hT=179±3℃10毫摩尔Cs[I]=37.0毫摩尔 | --- | 1750 | --- | 2250 | --- | 3000 | --- | --- | --- |
| 43 | 0 | 509 | 794 | 931 | 0 | 1565 | 6 | 65 | |
| 86 | 0 | 573 | 462 | 1172 | 0 | 1810 | 11 | 76 | |
| 113 | 0 | 572 | 438 | 1161 | 0 | 1680 | 15 | 74 | |
| 123 | 0 | 566 | 444 | 1158 | 0 | 1640 | 16 | 73 | |
| 实施例16 151099BLiOAc/A.C.(14ml)F=35±10g/hT=162±5℃10毫摩尔Li[I]=36.8毫摩尔 | --- | 1739 | --- | 2236 | --- | 2981 | --- | --- | --- |
| 41 | 826 | 289 | 1476 | 454 | 0 | 221 | 1 | 25 | |
| 81 | 1187 | 102 | 1948 | 102 | 480 | 922 | 3 | 21 | |
| 102 | 1182 | 65 | 1962 | 65 | 820 | 965 | 4 | 17 | |
| 130 | 1273 | 85 | 1987 | 85 | 722 | 1037 | 6 | 22 | |
| 150 | 1238 | 101 | 1920 | 101 | 559 | 1203 | 7 | 25 | |
| 实施例17 181099AZn(OAc)2/A.C.(14ml)F=44±3g/hT=170±3℃10毫摩尔Zn[I]=36.7毫摩尔 | --- | 1739 | --- | 2253 | --- | 2939 | --- | --- | --- |
| 40 | 940 | 322 | 1123 | 688 | 0 | 238 | 3 | 32 | |
| 81 | 1071 | 294 | 1126 | 719 | 0 | 751 | 7 | 40 | |
| 100 | 1086 | 292 | 1188 | 673 | 0 | 1022 | 10 | 43 | |
| 122 | 1157 | 258 | 1244 | 636 | 0 | 1251 | 12 | 44 | |
| 141 | 1091 | 236 | 1303 | 605 | 0 | 1368 | 15 | 44 | |
| 实施例18 191099AMg(OAc)2/A.C.(14ml)F=30±14g/hT=170±5℃10毫摩尔Mg[I]=37.5毫摩尔 | --- | 1775 | --- | 2300 | --- | 3000 | --- | --- | --- |
| 40 | 1100 | 308 | 1492 | 486 | 0 | 164 | 3 | 25 | |
| 61 | 968 | 403 | 1169 | 695 | 0 | 266 | 4 | 35 | |
| 80 | 946 | 528 | 1125 | 751 | 0 | 396 | 5 | 42 | |
| 125 | 1166 | 276 | 1672 | 413 | 0 | 695 | 7 | 30 | |
| 145 | 1321 | 307 | 1852 | 297 | 91 | 1003 | 9 | 33 |
| 实施例19 191099BKOAc/A.C.(14ml)F=41±7g/hT=179±9℃10毫摩尔K[I]=37.5毫摩尔 | --- | 1775 | --- | 2300 | --- | 3000 | --- | --- | --- |
| 40 | 486 | 560 | 1019 | 727 | 0 | 953 | 4 | 52 | |
| 130 | 619 | 496 | 1167 | 720 | 0 | 1637 | 15 | 60 | |
| 151 | 595 | 510 | 1103 | 695 | 0 | 1928 | 18 | 64 | |
| 实施例20 201099AA.C.(7ml)F=34±3g/hT=162±2℃0毫摩尔 金属[I]=37.5毫摩尔 | --- | 1775 | --- | 2300 | --- | 3000 | --- | --- | --- |
| 42 | 1324 | 88 | 1514 | 380 | 0 | 0 | --- | 15 | |
| 80 | 1574 | 199 | 1866 | 258 | 0 | 0 | --- | 13 | |
| 102 | 1691 | 207 | 1938 | 134 | 0 | 0 | --- | 11 | |
| 121 | 1775 | 125 | 2059 | 99 | 0 | 34 | --- | 7 | |
| 140 | 1579 | 190 | 2029 | 81 | 0 | 61 | --- | 10 | |
| 比较实施例21 151099AA.C.(7ml)F=31±2g/hT=172±3℃0毫摩尔金属[I]=37.5毫摩尔 | --- | 1775 | --- | 2300 | --- | 3000 | --- | --- | --- |
| 43 | 1008 | 286 | 1042 | 710 | 0 | 0 | --- | 27 | |
| 60 | 1317 | 245 | 1286 | 597 | 0 | 0 | --- | 23 | |
| 81 | 1372 | 264 | 1536 | 474 | 0 | 0 | --- | 20 | |
| 119 | 1568 | 311 | 1753 | 335 | 0 | 0 | --- | 19 | |
| 143 | 1627 | 350 | 1848 | 279 | 0 | 0 | --- | 19 |
| 时间(分钟) | ppmMeI | ppmMeA | ppmBuI | ppmBuA | ppmOctI | ppmOctA | Cap(％) | Con(％) | |
| 实施例22 281099AKOAc/A.C.(7ml)F=44±4g/hT=150±1℃5毫摩尔K[I]=39.0毫摩尔 | --- | 1791 | --- | 2348 | --- | 3024 | --- | --- | --- |
| 80 | 1205 | 243 | 1943 | 146 | 622 | 1346 | 12 | 33 | |
| 140 | 1261 | 190 | 1996 | 126 | 709 | 1336 | 22 | 30 | |
| 179 | 1378 | 179 | 2026 | 108 | 739 | 1217 | 29 | 28 | |
| 220 | 1386 | 144 | 2069 | 101 | 814 | 1229 | 35 | 26 | |
| 255 | 1411 | 123 | 2091 | 92 | 833 | 1225 | 40 | 25 | |
| 实施例23 281099DKOAc/A.C.(7ml)F=45±3g/hT=166±2℃5毫摩尔K[I]=37.9毫摩尔 | --- | 1753 | --- | 2351 | --- | 3068 | --- | --- | --- |
| 42 | 1019 | 293 | 1801 | 302 | 516 | 1274 | 9 | 37 | |
| 80 | 1035 | 262 | 1836 | 302 | 492 | 1409 | 17 | 38 | |
| 100 | 1011 | 275 | 1750 | 338 | 431 | 1468 | 21 | 40 | |
| 120 | 1029 | 285 | 1756 | 354 | 407 | 1524 | 26 | 41 | |
| 140 | 1092 | 277 | 1797 | 338 | 424 | 1492 | 31 | 40 | |
| 实施例24 291099AKOAc/A.C.(7ml)F=40±2g/hT=194±2℃5毫摩尔K[I]=37.9毫摩尔 | --- | 1753 | --- | 2351 | --- | 3068 | --- | --- | --- |
| 40 | 437 | 673 | 736 | 929 | 0 | 1119 | 12 | 62 | |
| 80 | 443 | 761 | 658 | 984 | 0 | 1364 | 26 | 70 | |
| 101 | 489 | 743 | 703 | 956 | 0 | 1343 | 33 | 69 | |
| 124 | 536 | 716 | 759 | 927 | 0 | 1307 | 41 | 67 | |
| 138 | 546 | 693 | 804 | 899 | 0 | 1257 | 46 | 64 | |
| 实施例25 041199ACsOAc/A.C.(7ml)F=35±3g/hT=162±1℃5毫摩尔Ca[I]=39.9毫摩尔 | --- | 2051 | --- | 2350 | --- | 3047 | --- | --- | --- |
| 40 | 608 | 701 | 1109 | 776 | 139 | 1614 | 11 | 64 | |
| 80 | 814 | 607 | 1298 | 679 | 177 | 1904 | 23 | 63 | |
| 100 | 796 | 602 | 1238 | 716 | 139 | 1896 | 29 | 64 | |
| 120 | 832 | 594 | 1244 | 730 | 115 | 1800 | 34 | 62 | |
| 140 | 854 | 577 | 1262 | 709 | 117 | 1758 | 40 | 61 |
| 实施例26 041199CZn(OAc)2/A.C.(7ml)F=41±2g/hT=155±2℃5毫摩尔Zn[I]=39.9毫摩尔 | --- | 2051 | --- | 2350 | --- | 3047 | --- | --- | --- |
| 60 | 1313 | 249 | 1584 | 503 | 230 | 709 | 8 | 30 | |
| 80 | 1505 | 147 | 1846 | 320 | 376 | 1215 | 11 | 30 | |
| 100 | 1598 | 120 | 1935 | 189 | 450 | 1490 | 14 | 31 | |
| 120 | 1624 | 93 | 1933 | 262 | 474 | 1672 | 18 | 34 | |
| 140 | 1502 | 0 | 1923 | 233 | 518 | 1573 | 21 | 29 | |
| 实施例27 111199AKOAc/Al2O3/A.C.(4ml)F=34±3g/hT=157±2℃5毫摩尔K[I]=39.9毫摩尔 | --- | 2051 | --- | 2350 | --- | 3047 | --- | --- | --- |
| 40 | 1813 | 0 | 2308 | 0 | 2961 | 155 | 1 | 2 | |
| 80 | 1774 | 0 | 2264 | 0 | 3041 | 65 | 1 | 1 | |
| 100 | 1856 | 0 | 2302 | 0 | 3058 | 40 | 1 | 1 | |
| 126 | 1765 | 0 | 2239 | 0 | 3091 | 32 | 1 | 0 | |
| 145 | 1781 | 0 | 2273 | 0 | 3082 | 31 | 1 | 0 | |
| 比较实施例28 151099AKOAc/A.C.(7ml)F=45±2g/hT=152±2℃5毫摩尔K[I]=3.7毫摩尔 | --- | 178 | --- | 230 | --- | 298 | --- | --- | --- |
| 60 | 117 | 44 | 205 | 34 | 99 | 165 | 2 | 49 | |
| 80 | 121 | 43 | 204 | 0 | 98 | 172 | 2 | 42 | |
| 100 | 115 | 26 | 202 | 37 | 105 | 177 | 2 | 45 | |
| 120 | 121 | 32 | 201 | 0 | 103 | 177 | 3 | 39 | |
| 140 | 131 | 41 | 211 | 0 | 104 | 161 | 3 | 40 |
| 时间(分钟) | ppmMeI | ppmMeA | ppmBuI | ppmBuA | ppmOctI | ppmOctA | Cap(％) | Con(％) | |
| 实施例29 121199AKOAc/A.C.(7ml)F=394-3g/hT=174±2℃5毫摩尔K[I]=3.7毫摩尔 | --- | 178 | --- | 230 | --- | 298 | --- | --- | --- |
| 40 | 61 | 77 | 113 | 107 | 0 | 153 | 1 | 76 | |
| 81 | 68 | 83 | 121 | 106 | 15 | 215 | 3 | 88 | |
| 101 | 67 | 52 | 125 | 74 | 20 | 223 | 4 | 70 | |
| 120 | 73 | 77 | 129 | 73 | 20 | 217 | 4 | 78 | |
| 140 | 66 | 73 | 119 | 61 | 20 | 213 | 5 | 73 | |
| 实施例30 171199AKOAc/A.C.(7ml)F=47±3g/hT=191±2℃5毫摩尔K[I]=3.7毫摩尔 | --- | 178 | --- | 230 | --- | 298 | --- | --- | --- |
| 40 | 0 | 70 | 42 | 212 | 35 | 117 | 1 | 92 | |
| 80 | 0 | 75 | 83 | 155 | 22 | 209 | 3 | 95 | |
| 100 | 0 | 74 | 55 | 148 | 14 | 226 | 4 | 96 | |
| 120 | 40 | 73 | 88 | 110 | 25 | 231 | 5 | 87 | |
| 140 | 46 | 73 | 108 | 126 | 34 | 240 | 6 | 93 | |
| 实施例31 181199AKOAc/S2O2(4ml)F=41±2g/hT=161±2℃5毫摩尔K[I]=40.0毫摩尔 | --- | 2086 | --- | 2404 | --- | 2940 | --- | --- | --- |
| 40 | 1578 | 110 | 2253 | 0 | 2430 | 242 | 2 | 7 | |
| 80 | 1699 | 95 | 2337 | 0 | 2501 | 214 | 4 | 6 | |
| 100 | 1713 | 89 | 2342 | 0 | 2491 | 202 | 4 | 6 | |
| 120 | 1661 | 79 | 2300 | 0 | 2544 | 197 | 5 | 6 | |
| 140 | 1766 | 77 | 2354 | 0 | 2478 | 183 | 5 | 5 | |
| 实施例32 181199BCsOAc/A.C.(7ml)F=45±1g/hT=174±2℃5毫摩尔Cs[I]=40.0毫摩尔 | --- | 2086 | --- | 2404 | --- | 2940 | --- | --- | --- |
| 60 | 341 | 1072 | 555 | 1295 | 0 | 1722 | 32 | 88 | |
| 100 | 429 | 933 | 623 | 864 | 0 | 1543 | 53 | 72 | |
| 120 | 534 | 885 | 720 | 1096 | 38 | 1360 | 62 | 73 | |
| 140 | 656 | 787 | 821 | 1001 | 48 | 1276 | 70 | 66 | |
Claims (8)
1．一种在工业生产混合物中减少碘含量的方法，包括在100℃-300℃的温度下于汽相中将有机介质与分散在活性炭中的金属盐接触。
2．权利要求1的方法，其中金属盐是选自羧酸盐、碳酸盐、氧化物、氢氧化物和/或能与有机介质起化学反应产生金属羧酸盐的盐类。
3．权利要求1的方法，其中金属盐包括选自主族元素、镧系元素、锕系元素、锌、铜和银的一种元素。
4．权利要求1所述的方法，其中金属盐包括选自主族元素、镧系元素、锕系元素、锌、铜、碱金属和碱土金属的一种元素以及它们的混合元素。
5．权利要求1所述的方法，其中金属盐包括Na、K和/或Cs。
6．权利要求1所述的方法，其中在所说的混合物中按重量计算的主要成分为羧酸和/或羧酸酐和/或羧酸酯和/或亚烷基二羧酸酯。
7．权利要求1所述的方法，其中在所说的混合物中按重量计算的主要成分是乙酸。
8．根据在前的任一权利要求的方法，其中工业生产混合物包括羧酸类和/或羧基酐与烷基碘和/或氢碘酸的混合物。
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| CN1769252B (zh) * | 2003-07-02 | 2010-05-26 | 日宝化学株式会社 | 碘化烷烃的回收方法以及碘化烷烃的回收装置 |
| CN102249190A (zh) * | 2011-07-25 | 2011-11-23 | 国药集团化学试剂有限公司 | 一种氢碘酸的纯化方法 |
| CN103214361A (zh) * | 2013-04-28 | 2013-07-24 | 天津渤海化工有限责任公司天津碱厂 | 一种低负荷下含碘甲醇再生循环利用方法 |
| CN110732352A (zh) * | 2019-09-23 | 2020-01-31 | 江苏大学 | 一种过渡金属离子交换树脂脱碘剂的制备方法 |
| CN110743493A (zh) * | 2019-11-07 | 2020-02-04 | 江苏索普化工股份有限公司 | 一种分子筛脱碘剂的制备方法及分子筛脱碘剂 |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE288617T1 (de) * | 2001-11-29 | 2005-02-15 | Coding Tech Ab | Wiederherstellung von hochfrequenzkomponenten |
| US7915470B2 (en) | 2006-09-08 | 2011-03-29 | Board Of Regents, The University Of Texas System | Coupled electrochemical method for reduction of polyols to hydrocarbons |
| CN100581646C (zh) * | 2006-12-28 | 2010-01-20 | 中国科学院化学研究所 | 一种载银高分子衍生碳除碘吸附剂及制法和应用 |
| CN103071457B (zh) * | 2013-01-15 | 2014-12-24 | 中国科学院青海盐湖研究所 | 凝胶型碘离子吸附剂、其制备方法及应用 |
| CN106782504B (zh) * | 2016-12-29 | 2019-01-22 | 百度在线网络技术（北京）有限公司 | 语音识别方法和装置 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE791577A (fr) * | 1971-11-19 | 1973-05-17 | Monsanto Co | Purification de courants d'acide carboxylique |
| US4246195A (en) * | 1978-10-06 | 1981-01-20 | Halcon Research And Development Corporation | Purification of carbonylation products |
| DE2901359A1 (de) * | 1979-01-15 | 1980-07-24 | Basf Ag | Verfahren zur entfernung von jod aus organischen verbindungen |
| GB8822661D0 (en) * | 1988-09-27 | 1988-11-02 | Bp Chem Int Ltd | Removal of iodine/iodide impurities |
| US5300685A (en) * | 1991-11-25 | 1994-04-05 | Hoechst Celanese Corporation | Removal of halide impurities from organic liquids |
| KR950013467B1 (ko) * | 1993-03-31 | 1995-11-08 | 포항종합제철주식회사 | 초산중의 요오드 화합물의 제거방법 |
-
2000
- 2000-12-18 EP EP00127663A patent/EP1114814A3/en not_active Withdrawn
- 2000-12-21 US US09/740,822 patent/US20020010363A1/en not_active Abandoned
- 2000-12-27 JP JP2000397943A patent/JP2001187342A/ja not_active Withdrawn
- 2000-12-28 CA CA002329817A patent/CA2329817A1/en not_active Abandoned
- 2000-12-28 RU RU2000132899/04A patent/RU2268873C2/ru not_active IP Right Cessation
- 2000-12-29 CN CN00137385A patent/CN1302792A/zh active Pending
- 2000-12-29 KR KR1020000085714A patent/KR20010070379A/ko not_active Application Discontinuation
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1769252B (zh) * | 2003-07-02 | 2010-05-26 | 日宝化学株式会社 | 碘化烷烃的回收方法以及碘化烷烃的回收装置 |
| CN102249190A (zh) * | 2011-07-25 | 2011-11-23 | 国药集团化学试剂有限公司 | 一种氢碘酸的纯化方法 |
| CN102249190B (zh) * | 2011-07-25 | 2013-03-13 | 国药集团化学试剂有限公司 | 一种氢碘酸的纯化方法 |
| CN103214361A (zh) * | 2013-04-28 | 2013-07-24 | 天津渤海化工有限责任公司天津碱厂 | 一种低负荷下含碘甲醇再生循环利用方法 |
| CN103214361B (zh) * | 2013-04-28 | 2015-07-15 | 天津渤海化工有限责任公司天津碱厂 | 一种低负荷下含碘甲醇再生循环利用方法 |
| CN110732352A (zh) * | 2019-09-23 | 2020-01-31 | 江苏大学 | 一种过渡金属离子交换树脂脱碘剂的制备方法 |
| CN110743493A (zh) * | 2019-11-07 | 2020-02-04 | 江苏索普化工股份有限公司 | 一种分子筛脱碘剂的制备方法及分子筛脱碘剂 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001187342A (ja) | 2001-07-10 |
| RU2268873C2 (ru) | 2006-01-27 |
| CA2329817A1 (en) | 2001-06-29 |
| EP1114814A3 (en) | 2003-01-22 |
| KR20010070379A (ko) | 2001-07-25 |
| US20020010363A1 (en) | 2002-01-24 |
| EP1114814A2 (en) | 2001-07-11 |
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