CN101506092B - 氧化溴化物制备溴的方法及其中使用的催化剂 - Google Patents
氧化溴化物制备溴的方法及其中使用的催化剂 Download PDFInfo
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title claims abstract description 53
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 27
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- 150000001649 bromium compounds Chemical class 0.000 title 1
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- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 4
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- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
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- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 1
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
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- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/09—Bromine; Hydrogen bromide
- C01B7/096—Bromine
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
提供一种制备溴的方法，其中，由至少溴源、氧化剂、以及包含第1主族阳离子和过渡金属氧化物的催化剂形成水溶液。
Description
背景技术
溴在工业领域广泛应用。例如，溴用于制造耐火剂，1，2-二溴乙烷(CH2BrCH2Br)(其用于汽油添加剂防止铅在气缸中沉淀)；用于摄影(例如，银溴化物，AgBr，其是胶片中的感光物质)、染料和药物的化合物；在分析试验室用于检测有机化合物的不饱和性，其中溴加成到不饱和化合物的多键上；作为消毒剂；以及用于生产熏蒸剂、水净化的化合物、染料、医药中；和消毒杀菌剂。溴可以利用过氧化氢作为氧化剂通过氧化溴化物的方法制备。例如，下面的反应是合适的：H2O2+2HBr→Br2+2H2O(反应(1))。溴还可以利用氯作为氧化剂通过氧化溴化物的方法制备。例如，下面的反应是合适的：
(反应(2))。
US 5,266,295描述了当利用过氧化氢作为氧化剂将溴化氢氧化成溴时，利用强酸，例如硫酸或磷酸，来提高效率。然而，酸的加入影响了制备过程的经济性，并且，在一些情况下酸源不容易得到。反应(1)和(2)的任何一个均能受益于通过添加催化剂提高溴化物向溴的转化率。钼酸铵((NH4 +)2MoO4 -)是众所周知的氧化反应催化剂，可以使用碘量法滴定H2O2。然而，在商业溴的塔设备中NH4 +不能作为添加剂中阳离子的选择。
这样考虑到目前可采用的技术，仍然需要商业可行的方法来提高用氧化溴化物制备溴时的转化率，以及其中使用的催化剂。
发明内容
本发明实现了上述需要，提供制备溴的方法，所述方法包括由至少溴源、氧化剂、和包含第1主族的阳离子和过渡金属的含氧物的催化剂形成水溶液。进一步，提供的方法包含(i)由至少溴源、氧化剂、无机酸、和包含第1主族的阳离子和过渡金属氧化物的催化剂形成水溶液，所述水溶液的pKa小于约-1.74；和(ii)制备溴。还提供了制备溴的方法，包含由至少溴源、氧化剂、氯化氢、和根据本发明的催化剂形成水溶液。根据本发明的方法可以以连续的方式或间歇的方式实施。本发明还提供了这样的制备溴的方法，其中，该水溶液的pKa小于约-1.74。
催化剂
用于根据本发明的方法的催化剂包含第1主族的阳离子和包含过渡金属阴离子的阴离子。第1主族阳离子可以包含Na+，K+，Rb+，Cs+，Fr+，Li+或H+。阴离子可以包含源自一种或多种过渡金属例如钒，铈，铬，锰，铌，钼，钌，钨，铼，和/或锇的氧化物。例如，所述阴离子可以包含MoO4 -2。根据本发明的催化剂的例子包含钼酸钠(Na2MoO4)。包含能促进过氧化氢分解的过渡金属氧化物阴离子的催化剂可用于本发明的方法中，因为催化剂中的阴离子能向氧化溴化物的方向活化过氧化氢，这样基于过氧化氢得到的溴的产率至少为90重量％(或至少为95重量％或98重量％)。
溴源
在本发明的方法中，溴源可以包含溴化氢(HBr)或溴化钠(NaBr)。所述HBr可以由原位分解较不稳定的(例如仲和叔)脂肪族烷基溴化物来产生。其他合适的溴源包括溴化钾(KBr)和溴化锂(LiBr)。适合本发明的另一个溴源包括氢溴酸水溶液、溴化氢气体、或与盐酸结合的第1主族的金属溴化物。第1主族金属包含锂(Li)、钠(Na)、和钾(K)。
氧化剂
在本发明的方法中，氧化剂可以包含过氧化氢(H2O2)，氯(Cl2)，或氧(O2)。所述氧化剂可以包含过氧化氢的盐，例如，过氧化锂。氯作为氧化剂可以以气体引入或由氯离子和过氧化物原位产生，所述过氧化物包含过氧化氢。氧，一种经济上有益的溴离子氧化剂，为了活化一般需要温度高于室温，而所述氧可以以气体形式使用。可以使用氧的输送体例如氧化铈或五氧化钒。其他合适的氧化剂包括有机过氧化物，例如，过氧化苯甲酰，其在加热时分解。
无机酸
在本发明的方法中，无机酸可以提高形成的水溶液的酸性。合适的无机酸包括盐酸、硫酸和/或磷酸。
溴化物氧化为溴
根据本发明将溴化物氧化成溴一般在添加了反应物和蒸汽的商业化的填料塔环境中，以过氧化氢作为氧化剂在连续体系中来制备溴，然而，对本领域技术人员来讲可以进行变化。
本发明提供的溴可以源自约0.01重量％至约60重量％的HBr，约3重量％至约70重量％的H2O2，约0.03重量％至约0.5重量％的根据本发明的催化剂和约5重量％至约20重量％的HCl，全部基于用于制备溴之前的HBr、H2O2、催化剂和HCl的总重量。通常，所述溴源、氧化剂和催化剂，以及当有氯化氢或无机酸时，均在水溶液中。本发明还提供了溴源和根据本发明的催化剂的摩尔比是从约150∶1至约1200∶1，或者约200∶1至约1000∶1，或者约400∶1至约900∶1，或者约600∶1至约850∶1，或者约658∶1至约831∶1。
实施例
以下实施例是说明本发明的原理。应理解为本发明并不限制于此处例示的任何一个特定的具体例子。
实施例1：将HBr(357.20g 7.46重量％的水溶液；0.33molHBr)和Na2MoO4(2.04g 4重量％的水溶液；0.4mmol Na2MoO4)与HCl(16.08g 12M的HCl；0.13molHCl)和H2O2(2.84g 70重量％的水溶液；0.06mol H2O2)一起加入到500mL的锥形瓶中。搅拌混合物，冷却，保持在15-20℃以10mL/min加入12”×1”的塔顶部的回流物流中，该塔安装有24/40料器(glassware)，进入500mL注有新鲜蒸汽的三颈圆底烧瓶中。过量的冷凝物和HBr用泵除去，且塔顶部产品包括溴和水，其被4-7℃的含水乙二醇冷却的弗雷德里契(Friedrich’s)冷凝器冷凝。冷凝物和所有不冷凝的物质转入300mL(15重量％)Na2SO3溶液中，在该溶液中溴还原成溴离子，并用0.1N的AgNO3滴定定量。得到总量为9.27g的溴，基于H2O2溴的产率为99.04重量％。
实施例2：如实施例1的过程，使用HBr(356.77g 8.96重量％的水溶液；0.40molHBr)，HCl(11.40g 12M的HCl；0.09molHCl)，Na2MoO4(3.09g 4重量％的水溶液；0.6mmol Na2MoO4)和H2O2(2.91g 70重量％的水溶液；0.06molH2O2)。得到总量为8.99g的溴，基于H2O2溴的产率为93.91重量％。
实施例3(比较实施例)：如实施例1的过程，使用HBr(356.54g 7.52重量％的水溶液；0.33molHBr)，HCl(17.90g 12M的HCl；0.15molHCl)，和H2O2(2.80g 70重量％的水溶液；0.06mol H2O2)。不添加根据本发明的催化剂，得到总量为7.32g的溴，基于H2O2溴的产率为79.38重量％。
实施例4(比较实施例)：如实施例1的过程，用HBr(360.80g 6.19重量％的水溶液；0.28molHBr)，HCl(19.27g 12M的HCl；0.16molHCl)，和H2O2(3.39g 70重量％的水溶液；0.07mol H2O2)添加到原料HBr中。不添加根据本发明的催化剂，得到总量为5.19g的溴，基于H2O2溴的产率为46.43重量％。
实施例5(比较实施例)：如实施例1的过程，使用HBr(355.68g 7.46重量％的水溶液；0.33molHBr)，HCl(159.02g 30重量％的水溶液；1.14molHCl)，和H2O2(2.65g 70重量％的水溶液；0.06mol H2O2)。不添加根据本发明的催化剂，得到总量为8.30g的溴，基于H2O2溴的产率为95.09重量％。
实施例6(比较实施例)：如实施例1的过程，使用HBr(356.65g 17.20重量％的水溶液；0.76molHBr)，HCl(通过滴定法22.04重量％；46.10g(0.28mol)HCl)，和H2O2(14.98g 70重量％的水溶液；0.31mol H2O2)；另外，使用循环利用的酸源。不添加根据本发明的催化剂，得到总量为45.65g的溴，基于H2O2溴的产率为92.50重量％。
如上述实施例中看出(数据概括于表1中)，在溴的氧化反应中使用本发明的催化剂能提高Br2的产率。比较实施例3的氧化反应，其中使用0.15molHCl和0.06mol H2O2氧化0.33molHBr，结果基于H2O2Br2的产率为79.38重量％，而实施例1的反应中，使用0.13mol HCl，0.06mol H2O2和0.4mmol根据本发明的催化剂(Na2MoO4)氧化0.33molHBr，结果基于H2O2Br2的产率为99.04重量％(相对比较实施例3的79.38重量％的产率)。同样将实施例3与实施例2比较，实施例2中稍稍减少使用HCl(0.09mol对0.15mol)，并且使用0.6mmol根据本发明的催化剂(Na2MoO4)，结果基于H2O2Br2的产率为93.91重量％(相对比较实施例3的79.38重量％的产率)。上述实施例还表明，增加HCl的量可以提高溴氧化反应的效率。例如，将实施例3与实施例5比较，将HCl从0.15mol增加到1.14mol能导致基于氧化剂溴(Br2)的产率从79.38重量％增加到95.09重量％。
表1
| 实施例编号 | HBr(mols) | HCl(mols) | H2O2(mols) | Na2MoO4(mmols) | 基于H2O2的Br2的产率(wt％) |
| 1 | 0.33 | 0.13 | 0.06 | 0.4 | 99.04 |
| 2 | 0.40 | 0.09 | 0.06 | 0.6 | 93.91 |
| 3 | 0.33 | 0.15 | 0.06 | - | 79.38 |
| 4 | 0.28 | 0.16 | 0.07 | - | 46.43 |
| 5 | 0.33 | 1.14 | 0.06 | - | 95.09 |
| 6 | 0.76 | 0.28 | 0.31 | - | 92.50 |
已经根据一个或多个优选的实施方式表述了本发明，应该理解为可以做不背离本发明的其他修改，这已经在权利要求中阐明。
Claims (5)
1.一种制备溴的方法，包括：
(i)由至少溴源、过氧化氢、无机酸、以及包含第1主族阳离子和包含过渡金属阴离子的阴离子的催化剂形成水溶液，其中，所述阴离子包含MoO4 -2，所述水溶液具有小于-1.74的pKa；
(ii)使该水溶液与蒸汽通过以连续方式操作的填料塔；和
(iii)基于过氧化氢，以产率至少为90重量％来制备溴。
2.根据权利要求1所述的方法，其中，该第1主族阳离子包含Na+或K+。
3.根据权利要求1所述的方法，其中，该催化剂包含Na2MoO4。
4.根据权利要求1所述的方法，其中，该溴源包含溴化氢或溴化钠。
5.根据权利要求3所述的方法，其中，该溴源与催化剂的摩尔比是150∶1至1200∶1。
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| CN106928038A (zh) * | 2017-03-20 | 2017-07-07 | 江苏工程职业技术学院 | 一种过氧化氢常温氧化环己醇制备环己酮的方法 |
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| US8642822B2 (en) | 2004-04-16 | 2014-02-04 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor |
| US20080275284A1 (en) | 2004-04-16 | 2008-11-06 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
| US8282810B2 (en) | 2008-06-13 | 2012-10-09 | Marathon Gtf Technology, Ltd. | Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery |
| WO2010089750A1 (en) * | 2009-02-09 | 2010-08-12 | Bromine Compounds Ltd. | Process and apparatus for preparing molecular bromine |
| KR20120020155A (ko) * | 2009-05-08 | 2012-03-07 | 써던 리서취 인스티튜트 | 수은 방출을 감소시키기 위한 시스템들 및 방법들 |
| US8198495B2 (en) | 2010-03-02 | 2012-06-12 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
| US8367884B2 (en) | 2010-03-02 | 2013-02-05 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
| US8815050B2 (en) * | 2011-03-22 | 2014-08-26 | Marathon Gtf Technology, Ltd. | Processes and systems for drying liquid bromine |
| CN102774812A (zh) * | 2011-05-09 | 2012-11-14 | 郭建利 | 废氢溴酸提取溴素新技术 |
| US8436220B2 (en) | 2011-06-10 | 2013-05-07 | Marathon Gtf Technology, Ltd. | Processes and systems for demethanization of brominated hydrocarbons |
| US8829256B2 (en) | 2011-06-30 | 2014-09-09 | Gtc Technology Us, Llc | Processes and systems for fractionation of brominated hydrocarbons in the conversion of natural gas to liquid hydrocarbons |
| US8802908B2 (en) | 2011-10-21 | 2014-08-12 | Marathon Gtf Technology, Ltd. | Processes and systems for separate, parallel methane and higher alkanes' bromination |
| US9193641B2 (en) | 2011-12-16 | 2015-11-24 | Gtc Technology Us, Llc | Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems |
| US20130156681A1 (en) * | 2011-12-19 | 2013-06-20 | Marathon Gtf Technology, Ltd. | Processes and Systems for Oxidizing Aqueous Metal Bromide Salts |
| CN104627964B (zh) * | 2015-01-14 | 2017-01-25 | 崔鑫 | 利用卤水制取溴的方法 |
| ITUB20160454A1 (it) * | 2016-01-28 | 2017-07-28 | Univ Degli Studi Di Palermo | Metodo per la produzione di bromo |
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