CN101100286B - 稳定的高温硼氢化物制剂 - Google Patents
稳定的高温硼氢化物制剂 Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 238000009472 formulation Methods 0.000 title description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 81
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 46
- 239000012279 sodium borohydride Substances 0.000 claims description 46
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- 239000000126 substance Substances 0.000 claims description 7
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- -1 metal hydroxide compound Chemical class 0.000 abstract description 3
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- 239000012267 brine Substances 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
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- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229920002785 Croscarmellose sodium Polymers 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920003110 Primojel Polymers 0.000 description 1
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- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
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- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000013011 aqueous formulation Substances 0.000 description 1
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- 229910010277 boron hydride Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229960000540 polacrilin potassium Drugs 0.000 description 1
- 235000013809 polyvinylpolypyrrolidone Nutrition 0.000 description 1
- 229920000523 polyvinylpolypyrrolidone Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- WVWZXTJUCNEUAE-UHFFFAOYSA-M potassium;1,2-bis(ethenyl)benzene;2-methylprop-2-enoate Chemical compound [K+].CC(=C)C([O-])=O.C=CC1=CC=CC=C1C=C WVWZXTJUCNEUAE-UHFFFAOYSA-M 0.000 description 1
- 229940069328 povidone Drugs 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
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- 239000007885 tablet disintegrant Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
- C01B6/10—Monoborane; Diborane; Addition complexes thereof
- C01B6/13—Addition complexes of monoborane or diborane, e.g. with phosphine, arsine or hydrazine
- C01B6/15—Metal borohydrides; Addition complexes thereof
- C01B6/19—Preparation from other compounds of boron
- C01B6/21—Preparation of borohydrides of alkali metals, alkaline earth metals, magnesium or beryllium; Addition complexes thereof, e.g. LiBH4.2N2H4, NaB2H7
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
- C01B6/10—Monoborane; Diborane; Addition complexes thereof
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
一种稳定化的水性混合物，其包含至少一种硼氢化物和至少一种金属氢氧化物。所述混合物具有提高的防止硼氢化物分解的稳定性，尤其是在升高的温度下的稳定性。
Description
技术领域
本发明涉及具有提高的稳定性、特别是提高的高温稳定性的水性硼氢化钠混合物。
背景技术
具有较好的稳定性的硼氢化物水溶液是人们已知的。例如，包含大约12％的硼氢化钠和大约40％的氢氧化钠的溶液在市场上有售。在一些应用中，例如在氢燃料电池中需要包含较少的氢氧化钠的稳定的含硼氢化物的溶液。在美国专利第6866689号中描述了这样的溶液；其包含约44％的硼氢化钠和约0.2％的氢氧化钠。但是该溶液在升高的温度下具有较高的硼氢化钠分解速率。
本发明所解决的问题是发现一种在升高的温度下具有改进的稳定性的硼氢化钠水性制剂(formulation)。
发明内容
本发明提供一种水性混合物，该混合物包含：(a)15-65％的至少一种硼氢化物；(b)1-10％的至少一种金属氢氧化物；(c)0.1-20％的至少一种吸收剂聚合物或赋形剂。本发明还涉及一种通过加入至少一种吸收剂聚合物或赋形剂使水性硼氢化物混合物稳定的方法。
具体实施方式
除非另外说明，百分数是重量百分数，温度单位为℃。“硼氢化物”是包含硼氢阴离子BH4 -的化合物。“吸收剂聚合物”是能够吸收水的聚合物。较佳的是，吸收剂聚合物选自水溶性聚合物(水中溶解度至少为1％、或至少5％的聚合物)、纤维素及其衍生物和交联的聚合物。交联的聚合物优选具有羧基、酰胺基、羟基、氨基或醚基、或者它们的组合，以利于在水中分散。“赋形剂”是如《药物赋形剂手册(Handbook of Pharmaceutical Excipients)》，A.Wade&P.J.Weller(1964)中所述的药物赋形剂。特别优选的赋形剂是用作片剂崩解剂的赋形剂，例如聚丙烯酸、当归酸、藻酸钙、羧甲基纤维素(例如钙盐或钠盐)、壳聚糖、交联羧甲基纤维素钠、交聚维酮、多库酯钠、瓜耳胶、聚克立林钾、聚乙烯吡咯酮、藻酸钠、淀粉羟乙酸钠和淀粉。在本发明的一个实施方式中，赋形剂的水溶解度至少为0.5％，或者至少为1％。在本发明的一个实施方式中，优选的吸收剂聚合物包括聚丙烯酸、聚丙烯酰胺-共聚-聚丙烯酸、丙烯酸共聚物(例如聚丙烯酸-共聚-聚环氧乙烷)、聚乙烯基吡咯烷酮、聚乙烯基吡啶、聚乙烯基吡啶N-氧化物、聚乙烯基咪唑、乙氧基化的聚氮丙啶、纤维素酯(例如乙酸酯、丁酸酯)、羟烷基纤维素和羧甲基纤维素。本发明的水性混合物可以是在温度至少为40℃下为溶液、浆液、凝胶或任意其它流体混合物的物质。具有较高硼氢化物浓度(例如至少50％)的混合物在大约25℃的常温下为固体或稠的浆液，但是在更高的温度下变成流体。
在一个实施方式中，硼氢化物的量至少为20％，或者至少为25％。在一个实施方式中，金属氢氧化物的量不大于8％，或者不大于6％，或者不大于4％。在本发明的一个实施方式中，金属氢氧化物的量至少为2％，或者至少为3％。在一个实施方式中，硼氢化物的量不大于55％，或者不大于50％，或者不大于45％，或者不大于40％。较佳的是，所述硼氢化物是来自元素周期表中第1、2、4、5、7、11、12或13族的金属阳离子的金属盐，或者它们的混合物。在一个实施方式中，所述硼氢化物是碱金属硼氢化物或其组合，或者包括硼氢化钠(SBH)或硼氢化钾或其混合物，或者包括硼氢化钠。较佳的是，所述金属氢氧化物是碱金属氢氧化物或其组合；或者是钠、锂或钾的氢氧化物或其混合物；或者是氢氧化钠或氢氧化钾；或者是氢氧化钠。其中可包含一种以上的碱金属硼氢化物和一种以上的金属氢氧化物。
在本发明的一个实施方式中，吸收剂聚合物和/或赋形剂的含量至少为0.2％，或者至少为0.4％，或者至少为1％，或者至少为2％。在本发明的一个实施方式中，吸收剂聚合物和/或赋形剂的量不大于15％，或者不大于12％，或者不大于10％，或者不大于8％。在本发明的一个实施方式中，需要极少量的吸收剂聚合物和/或赋形剂：至少0.1％，但是不大于1％，或者不大于0.5％。例如，部分中和的聚丙烯酸，或者包含至少20％、或者至少30％、或者至少50％、或者至少75％丙烯酸单体单元的共聚物可能仅需要极少量的吸收剂聚合物和/或赋形剂。加入硼氢化物中的聚丙烯酸的中和度并不关键，这是由于所述水性混合物包含另外的碱，使得水性混合物中的酸通常会被完全中和。对于用于本发明的聚合物，优选重均分子量至少为1500，或者至少为3000，或者至少为5000。
在本发明的一个实施方式中，水性混合物基本不含能够催化硼氢化物水解的物质，例如Co、Ru、Ni、Fe、Rh、Pd、Os、Ir、Pt之类的过渡金属的盐或其混合物；以及Co和/或Ni的硼化物。
本发明的水性混合物还可用于合成和金属回收领域。
实施例
表1：包含25％的SBH、3％的NaOH和添加剂的溶液在室温和60℃的分解速率。
| 25％SBH，3％NaOH，包含添加剂 | 添加剂重量％ | 在室温下的分解速率，SBH％/天 | 在60℃的分解速率，SBH％/天 | 在60℃的分解速率减小％ |
| 无，25％NaBH4，3％NaOH | N/A | -0.12 | -0.958 | N/A |
| 聚丙烯酸部分钠盐，略微交联的(固态)CAS#76774-25-9 | 0.5 | -0.05 | -0.564 | 41 |
| 聚丙烯酰胺-共聚-丙烯酸部分钠盐(固态)Mw＝15000000 | 0.5 | -0.074 | -0.662 | 31 |
| 聚丙烯酸-共聚-聚环氧乙烷(固态)CAS#27599-59-56-0 | 0.5 | -0.012 | -0.614 | 36 |
| 聚乙烯基吡咯烷酮(固态)Mw＝10000；CAS#9003-39-0 | 0.5 | -0.004 | -0.734 | 23 |
| 羧甲基纤维素钠盐(固态)Mw＝70000；CAS#9004-39-4 | 0.5 | -0.032 | -0.728 | 24 |
将聚丙烯酸部分交联的部分钠盐加入较高浓度的硼氢化钠制剂还会造成40重量％和50重量％制剂的水解速率减小。当对这些制剂进行长期加热的时候观察到出人意料的现象。在初始的引发期之后，硼氢化物的水解速率几乎减小到0。
表2：包含40％的SBH、5％的NaOH和添加剂的溶液在室温和50℃的分解速率(“DR”)。
| 40％SBH，5％NaOH，包含添加剂 | 添加剂重量％ | 在室温下的分解速率，SBH％/天 | 在50℃的分解速率，SBH％/天 | 在50℃的分解速率减小％ | 在50℃、引发期之后的分解速率，SBH％/天 |
| 无，40％NaBH4，5％NaOH | N/A | 0.0549 | 0.3604 | N/A | N/A |
| 聚丙烯酸部分钠盐，略微交联的(固态)CAS#76774-25-9 | 0.5 | 0.0333 | 0.1139 | 68 | 0.0547 |
| 聚丙烯酸部分钠盐(液态)Mw＝30000；CAS#9003-04-07 | 4％ | 0.0339 | 0.1716 | 52 | 0.0084 |
表3：包含50％的SBH、5％的NaOH和添加剂的溶液在室温和58℃的分解速率。
| 50％SBH，5％NaOH，包含添加剂 | 添加剂重量％ | 在室温下的分解速率，SBH％/天 | 在58℃的分解速率，SBH％/天 | 分解速率减小％ | 在58℃、引发期之后的分解速率，SBH％/天 |
| 无，50％NaBH4，5％NaOH | N/A | 0.0031 | 0.35 | N/A | N/A |
| 聚丙烯酸部分钠盐，略微交联的(固态)CAS#76774-25-9 | 0.5％ | － | 0.03121 | 91 | 0.01165 |
| 聚丙烯酸部分钠盐(液态)Mw＝30000；CAS#9003-04-07 | 4％ | － | 0.01715 | 95 | 0.01388 |
表4：包含25％SBH、5％NaOH、不同重量％的聚丙烯酸部分钠盐固体的溶液在22℃的分解速率。
| 温度℃ | 添加剂重量％ | 分解速率SBH％/天 | 差异％ |
| 22 | 0 | 0.026 | N/A |
| 22 | 0.5 | 0.011 | 57.7 |
| 22 | 1 | 0.0485 | |
| 22 | 1.5 | 0.0473 | |
| 22 | 2 | 0.0473 | |
| 22 | 4 | 0.025 | 3.8 |
表5：包含25％SBH、5％NaOH、不同重量％的聚丙烯酸部分钠盐固体的溶液在60℃的分解速率。
| 温度℃ | 添加剂重量％ | 分解速率SBH％/天 | 差异％ |
| 60 | 0 | 0.4334 | N/A |
| 60 | 0.5 | 0.3764 | 13.2 |
| 60 | 1 | 0.409 | 5.6 |
| 60 | 1.5 | 0.424 | 2.1 |
| 60 | 2 | 0.4114 | 5.1 |
| 60 | 4 | 0.4201 | 3.1 |
表6：包含25％的SBH、5％的NaOH、不同重量％的30％的聚(丙烯酸钠盐)水溶液(Mw＝15000)的溶液在22℃下的分解速率。(本表和以下各表中所示重量％的添加剂基于聚合物/水制剂总重)
| 温度℃ | 添加剂重量％ | 分解速率SBH％/天 | 标样分解速率，SBH％/天 | 差异％ |
| 22 | 0 | |||
| 22 | 10 | 0.1161 | 0.0114 | |
| 22 | 5 | 0.0019 | 0.1029 | 98.1 |
| 22 | 1 | 0.046 | 0.0421 |
表7：包含25％的SBH、5％的NaOH、不同重量％的30％的聚(丙烯酸钠盐)水溶液(Mw＝15000)的溶液在60℃下的分解速率。
| 温度℃ | 添加剂重量％ | 分解速率SBH％/天 | 标样分解速率，SBH％/天 | 差异％ |
| 60 | 0 | |||
| 60 | 10 | 0.3982 | 0.4993 | 20.2 |
| 60 | 5 | 0.4301 | 0.4964 | 13.3 |
| 60 | 1 | 0.4236 | 0.4399 | 3.7 |
表8：包含25％SBH、5％NaOH、15重量％的80％乙氧基化的聚氮丙啶的溶液在22℃的分解速率
| 温度℃ | 添加剂重量％ | 分解速率SBH％/天 | 差异％ | |
| 标样 | 0 | 0.0585 | N/A | |
| 22 | 80％乙氧基化的聚氮丙啶的37％水溶液，Mw＝50000；CAS#26558-46-8 | 15 | 0.0116 | 80.1 |
| 22 | 80％乙氧基化的聚氮丙啶的35-40％水溶液，Mw＝70000；CAS#26558-46-8 | 15 | 0.0321 | 45.1 |
表9：包含25％SBH、5％NaOH、15重量％的80％乙氧基化的聚氮丙啶的溶液在60℃的分解速率
| 温度℃ | 添加剂重量％ | 分解速率SBH％/天 | 差异％ | |
| 标样 | 0 | 0.5782 | N/A | |
| 60 | 80％乙氧基化的聚氮丙啶的37％水溶液，Mw＝50000；CAS#26558-46-8 | 15 | 0.5096 | 11.8 |
| 60 | 80％乙氧基化的聚氮丙啶的35-40％水溶液，Mw＝70000；CAS#26558-46-8 | 15 | 0.5052 | 12.6 |
表10：包含25％SBH、5％NaOH、15重量％的不同MW聚丙烯酸钠盐的溶液在22℃的分解速率
| 温度℃ | 添加剂重量％ | 分解速率SBH％/天 | 差异％ | |
| 标样 | 0 | 0.0585 | N/A | |
| 22 | 45％的聚丙烯酸钠盐水溶液，Mw＝1200；CAS#9003-04-7 | 15 | 0.06493 | 大于10 |
| 22 | 45％的聚丙烯酸钠盐水溶液，Mw＝8000；CAS#9003-04-7 | 15 | 0.0257 | 56.0 |
| 22 | 40％的聚丙烯酸钠盐水溶液，Mw＝30000；CAS#9003-04-7 | 15 | 0.0091 | 84.4 |
表11：包含25％SBH、5％NaOH、15重量％的不同MW聚丙烯酸钠盐的溶液在60℃的分解速率
| 温度℃ | 添加剂重量％ | 分解速率SBH％/天 | 差异％ | |
| 标样 | 0 | 0.5782 | N/A | |
| 60 | 45％的聚丙烯酸钠盐水溶液，Mw＝1200；CAS#9003-04-7 | 15 | 0.3812 | 34.0 |
| 60 | 45％的聚丙烯酸钠盐水溶液，Mw＝8000；CAS#9003-04-7 | 15 | 0.3607 | 37.6 |
| 60 | 40％的聚丙烯酸钠盐水溶液，Mw＝30000；CAS#9003-04-7 | 15 | 0.3736 | 35.38 |
Claims (10)
1.一种水性混合物，其包含：
(a)15-65％的至少一种硼氢化物；
(b)1-10％的至少一种金属氢氧化物；
(c)0.1-20％的至少一种吸收剂聚合物或赋形剂，
其中所述百分数为重量百分数。
2.如权利要求1所述的水性混合物，其特征在于，所述至少一种硼氢化物是硼氢化钠、硼氢化钾或其组合；所述至少一种金属氢氧化物是氢氧化钠、氢氧化锂或氢氧化钾、或者它们的组合。
3.如权利要求2所述的水性混合物，其特征在于，所述至少一种吸收剂聚合物或赋形剂选自：水溶性聚合物、纤维素、以及交联的聚合物。
4.如权利要求3所述的水性混合物，其特征在于，所述硼氢化物是硼氢化钠，金属氢氧化物是氢氧化钠。
5.如权利要求4所述的水性混合物，其特征在于，所述水性混合物包含2-8％的氢氧化钠和20-50％的硼氢化钠。
6.如权利要求5所述的水性混合物，其特征在于，所述至少一种吸收剂聚合物或赋形剂是聚丙烯酸、或者包含至少50％的丙烯酸单体单元的丙烯酸共聚物。
7.如权利要求6所述的水性混合物，其特征在于，所述水性混合物包含0.1-1％的聚丙烯酸或丙烯酸共聚物，所述聚丙烯酸或丙烯酸共聚物的重均分子量至少为1500。
8.一种对包含15-65％的至少一种硼氢化物和1-10％的至少一种金属氢氧化物的水性硼氢化物混合物进行稳定化的方法；所述方法包括加入0.1-20％的至少一种吸收剂聚合物或赋形剂，其中所述百分数为重量百分数。
9.如权利要求8所述的方法，其特征在于，所述至少一种金属氢氧化物是氢氧化钠，所述至少一种硼氢化物是硼氢化钠。
10.如权利要求9所述的方法，其特征在于，所述水性硼氢化物混合物包含2-8％的氢氧化钠和20-50％的硼氢化钠。
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| KR101245914B1 (ko) * | 2010-12-21 | 2013-03-20 | 황보창수 | 건조오징어의 가공장치 |
| US20170158390A1 (en) * | 2015-12-04 | 2017-06-08 | Mead Johnson Nutrition Company | Powder dosing closure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3933676A (en) * | 1974-04-08 | 1976-01-20 | Ventron Corporation | Stabilized aqueous solutions of sodium borohydride |
| US5354478A (en) * | 1993-06-09 | 1994-10-11 | Morton International, Inc. | Alkali metal borohydride/anionic polymer solutions |
| US20030108832A1 (en) * | 2001-11-13 | 2003-06-12 | Lumsden Charles A. | Aqueous borohydride compositions |
| CN1778678A (zh) * | 2004-10-18 | 2006-05-31 | 罗门哈斯公司 | 固体氢氧化钠生产中减少腐蚀的方法 |
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| US2970114A (en) * | 1958-01-27 | 1961-01-31 | Metal Hydrides Inc | Stabilized aqueous solutions of sodium borohydride |
| DE1567554A1 (de) * | 1966-04-02 | 1970-07-09 | Goerrig Dipl Chem Dr Rer Nat D | Festkoerper,enthaltend Alkalihydroxydhydrat,Alkaliboranat und gegebenenfalls Katalysatoren |
| US5169555A (en) * | 1990-11-09 | 1992-12-08 | Morton International, Inc. | Pulp bleaching solution |
| FR2746328B1 (fr) * | 1996-03-21 | 1998-05-29 | Stmi Soc Tech Milieu Ionisant | Gel organomineral de decontamination et son utilisation pour la decontamination de surfaces |
| JP2001019401A (ja) * | 1999-07-05 | 2001-01-23 | Seijiro Suda | 水素発生剤及びそれを用いる水素発生方法 |
| JP2002201001A (ja) * | 2000-12-28 | 2002-07-16 | Toyota Motor Corp | 錯金属水素化物水溶液の安定化方法 |
| JP2003146604A (ja) * | 2001-11-08 | 2003-05-21 | Sekisui Chem Co Ltd | 水素発生用圧縮成形体と、それを用いた水素発生方法及び装置 |
| JP2004196634A (ja) * | 2002-12-20 | 2004-07-15 | Honda Motor Co Ltd | 水素貯蔵・放出システムに用いられる水素化物粉末 |
| JP4276854B2 (ja) * | 2003-01-30 | 2009-06-10 | ウチヤ・サーモスタット株式会社 | 水素発生材料、水素発生方法及び水素発生装置 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3933676A (en) * | 1974-04-08 | 1976-01-20 | Ventron Corporation | Stabilized aqueous solutions of sodium borohydride |
| US5354478A (en) * | 1993-06-09 | 1994-10-11 | Morton International, Inc. | Alkali metal borohydride/anionic polymer solutions |
| US20030108832A1 (en) * | 2001-11-13 | 2003-06-12 | Lumsden Charles A. | Aqueous borohydride compositions |
| CN1778678A (zh) * | 2004-10-18 | 2006-05-31 | 罗门哈斯公司 | 固体氢氧化钠生产中减少腐蚀的方法 |
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| EP1876141A3 (en) | 2008-01-23 |
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