CN102180443B - 包含碱金属和碱金属合金的硅胶组合物 - Google Patents
包含碱金属和碱金属合金的硅胶组合物 Download PDFInfo
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- CN102180443B CN102180443B CN201010614833.9A CN201010614833A CN102180443B CN 102180443 B CN102180443 B CN 102180443B CN 201010614833 A CN201010614833 A CN 201010614833A CN 102180443 B CN102180443 B CN 102180443B
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- metal
- silica gel
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- sodium
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 256
- 239000000741 silica gel Substances 0.000 title claims abstract description 226
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 226
- 239000000203 mixture Substances 0.000 title claims abstract description 146
- 229910000573 alkali metal alloy Inorganic materials 0.000 title abstract description 16
- 229910052783 alkali metal Inorganic materials 0.000 title abstract description 15
- 150000001340 alkali metals Chemical class 0.000 title abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 206
- 239000002184 metal Substances 0.000 claims abstract description 206
- 239000011734 sodium Substances 0.000 claims abstract description 106
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 58
- 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 claims abstract description 55
- 239000007788 liquid Substances 0.000 claims abstract description 45
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 38
- 239000000956 alloy Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 36
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 22
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011591 potassium Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 15
- 108091064702 1 family Proteins 0.000 claims description 144
- 150000003818 basic metals Chemical class 0.000 claims description 51
- 229910052728 basic metal Inorganic materials 0.000 claims description 50
- 238000006722 reduction reaction Methods 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 239000001257 hydrogen Substances 0.000 claims description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims description 37
- 229910000574 NaK Inorganic materials 0.000 claims description 28
- 150000002894 organic compounds Chemical class 0.000 claims description 18
- 229910052792 caesium Inorganic materials 0.000 claims description 16
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 15
- 238000006027 Birch reduction reaction Methods 0.000 claims description 10
- NSIKFNOYIGGILA-UHFFFAOYSA-N [Na].[Na].[K] Chemical compound [Na].[Na].[K] NSIKFNOYIGGILA-UHFFFAOYSA-N 0.000 claims description 8
- 238000005695 dehalogenation reaction Methods 0.000 claims description 6
- 229910052701 rubidium Inorganic materials 0.000 claims description 6
- 150000002896 organic halogen compounds Chemical class 0.000 claims description 5
- 238000006621 Wurtz reaction Methods 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 4
- 230000006872 improvement Effects 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 184
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- 230000008018 melting Effects 0.000 abstract description 28
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- 238000010521 absorption reaction Methods 0.000 abstract description 8
- 150000002739 metals Chemical class 0.000 abstract description 7
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 abstract description 4
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- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 60
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- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 15
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229940073608 benzyl chloride Drugs 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
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- 239000002781 deodorant agent Substances 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- 239000001307 helium Substances 0.000 description 6
- 229910052734 helium Inorganic materials 0.000 description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 5
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- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 5
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- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 4
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- 229910003251 Na K Inorganic materials 0.000 description 3
- 229910019443 NaSi Inorganic materials 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 3
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- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
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- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
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- BDCIZVMGTWOOIY-UHFFFAOYSA-N 1,10-dihydroanthracene Chemical compound C1=CC=C2C=C3CC=CC=C3CC2=C1 BDCIZVMGTWOOIY-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- OFQCQIGMURIECL-UHFFFAOYSA-N 2-[2-(diethylamino)ethyl]-2',6'-dimethylspiro[isoquinoline-4,4'-oxane]-1,3-dione;phosphoric acid Chemical compound OP(O)(O)=O.O=C1N(CCN(CC)CC)C(=O)C2=CC=CC=C2C21CC(C)OC(C)C2 OFQCQIGMURIECL-UHFFFAOYSA-N 0.000 description 1
- WPDAVTSOEQEGMS-UHFFFAOYSA-N 9,10-dihydroanthracene Chemical compound C1=CC=C2CC3=CC=CC=C3CC2=C1 WPDAVTSOEQEGMS-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
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- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B01J35/30—
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/14—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
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Abstract
本发明涉及包含硅胶和碱金属或碱金属合金的1族金属/硅胶组合物。本发明的组合物描述为0、I、II和III段材料。这些材料的区别在于它们的制备方法和化学活性。可直接使用下述方法或由更早阶段的材料制备各连续的阶段。例如0段材料可在等温条件(优选在室温下或刚刚超过室温)下使用被硅胶(多孔SiO2)快速吸收的Na和K的液体合金制备,以形成疏松的黑色粉末,保留母体金属的大部分还原能力。当低熔点1族金属吸收在硅胶内时,温和的放热反应制备I段材料,为疏松的黑色粉末,在干燥的空气中长时间稳定。随后加热至400℃,制备II段材料,该材料也是疏松的黑色粉末。再次加热超过400℃,形成III段材料,释放某些1族金属。认为I、II和III段材料代表了吸收1族金属后硅胶的还原。本发明的1族金属/硅胶组合物优选为那些包含钠、钾或钠-钾合金的组合物,最优选钠和钠-钾合金。本发明各阶段的1族金属/硅胶组合物采用与碱金属及其合金相同的方法,作为还原剂与多种可还原的有机物质反应。
Description
本申请是以下申请的分案申请:申请日:2004年11月24日;申请号:200480040616.6(PCT/US2004/039304);发明名称:“包含碱金属和碱金属合金的硅胶组合物”。
相关申请数据
本申请要求保护以下临时申请系列号的优先权:2003年11月24日提交的60/524,038、2004年4月14日提交的60/561,886、2004年6月14日提交的60/578,818、2004年9月22日提交的60/611,701和2004年9月22日提交的60/611,700,所述临时申请所公开的全部内容通过引用结合到本文中来。
技术领域
本发明涉及通过碱金属或这些金属的合金与硅胶相互作用制备的硅胶组合物。所述组合物具有改进的操作特性并保持中性碱金属或合金的活性。
背景技术
那些在周期表中1族的碱金属和碱金属的合金在其金属态或中性状态下是非常活性的。碱金属及其合金对空气和湿气是非常活性的,当暴露于这些试剂时会自发着火。为了避免因其活性而引起的固有的危险,中性金属或合金必须储存在真空下或者在惰性液体(例如油)中,以使其免于与大气接触而导致氧化或其他反应。例如金属钠通常储存在液体石蜡油中,为了避免不必要的杂质,在用于化学反应之前必需将该液体石蜡油除去。这点严重限制了其运输和应用。
在许多实验室中已广泛研究了碱金属与二氧化硅沸石(例如ZSM-5)的组合。例如,最近的研究表明,纯的二氧化硅沸石可吸收最高达12%摩尔的气相铯和可比量的其他碱金属(锂除外)。以前有关将碱金属包封在整个二氧化硅沸石中的研究表明,这种组合物与水进行放热反应,产生定量的氢。(例如参见“Toward Inorganic Electrides”,A.S.Ichimura,J.L.Dye,M.A.Camblor和L.A.Villaescusa,J.Am.Chem.Soc.,124,1170-1171(2002)以及“Inorganic Electrides Formed byAlkali Metal Addition to Pure Silica Zeolites”,D.P.Wernette,A.S.Ichimura,S.A.Urbin和J.L.Dye,Chem.Mater.15,1441-1448(2003))。但是,所述沸石组合物吸收的钠含量太低,以至于是不适用的。此外,所述反应较慢,钠在有限的沸石孔径中扩散较慢。
钾金属分散在二氧化硅上作为试剂在有机合成中的应用报道于Levy等的Angew.Chem.Int.Ed.Engl.20(1981)第1033页。钾金属分散在硅胶上(CAS登记号7631-86-9:实际上是胶态二氧化硅,没有内表面积)制备无定形材料。如下所示,所述材料的活性用水和二苯酮说明。还参见Russel等的Organometallics(有机金属化合物)2002,21,4113-4128,方案3。
因此,需要得到形式易操作不显著失去金属活性的碱金属及其合金。本发明满足这些需求。
发明内容
本发明涉及1族金属/硅胶组合物,所述组合物包含在惰性气氛、足以将液体1族金属吸收在硅胶孔内的等温条件下,液体1族金属与硅胶混合的产物。所制备的1族金属/硅胶组合物与干燥的O2发生反应。该材料称为“0段”材料。
本发明还涉及1族金属/硅胶组合物,所述组合物包含在足以将液体1族金属吸收在硅胶孔内的放热条件下,液体1族金属与硅胶混合的产物。所制备的1族金属/硅胶组合物不与干燥的O2发生反应。该材料称为“I段”材料。
此外,本发明还涉及1族金属/硅胶组合物,所述组合物包含在足以将液体1族金属吸收在硅胶孔内的条件下,并将所得到的混合物加热至约215℃-约400℃,液体1族金属与硅胶混合的产物。所制备的1族金属/硅胶组合物不与干燥的O2发生反应。该材料称为“II段”材料。
本发明还涉及1族金属/硅胶组合物,所述组合物包含在足以将液体1族金属吸收在硅胶孔内的条件下,并将所得到的混合物加热至超过约400℃,液体1族金属与硅胶混合的产物。所制备的1族金属/硅胶组合物不与干燥的O2发生反应。该材料称为“III段”材料。
附图说明
图1表示1∶1NaK/硅胶试样(8.9mg)的差示扫描量热法(DSC)图。
图2表示1∶1Na3K/硅胶试样(5.7mg)的差示扫描量热法(DSC)图。
图3表示1∶1铯/硅胶试样(6.7mg)的差示扫描量热法(DSC)图。
图4表示涂有Na2K的合金组合物的硅胶颗粒转化为疏松、有光泽的黑色I段粉末。
图5表示与3.9mg硅胶混合的2.4mg Na的差示扫描量热法(DSC)图。
图6表示向II型钠/硅胶材料中加入水后氢气球的吹胀。
图7表示在真空或惰性气氛下,于约140℃下将0段材料加热过夜结果的差示扫描量热法(DSC)图。
图8表示用本发明的I段材料还原蒽制得的蒽自由基阴离子的光谱。
图9表示将蒽的THF溶液通过本发明的1族金属/硅胶组合物的混合床柱的伯奇(Birch)还原反应产物的1H NMR谱。
图10A-10C表示间歇法中苄基氯还原产物的分析结果。
图11A-11C表示二苯硫醚与本发明的I段材料过夜间歇反应产物的分析结果。
具体实施方式
1族金属:碱金属和碱金属合金
碱金属为周期表的1族金属。本文使用的术语“1族金属”是指可用于本发明的硅胶组合物的碱金属和碱金属的合金。所述碱金属包括钠(Na)、钾(K)、铷(Rb)和铯(Cs)。在这些碱金属中,优选钠和钾用于本发明的硅胶组合物,特别优选钠。
碱金属合金也可用于本发明的硅胶组合物。优选所述碱金属合金为两种或多于两种碱金属的合金,例如特别优选钠-钾(NaK)合金。其他优选的碱金属合金为那些包含钾、铯和铷的合金,特别是这些元素与钠的合金。所述碱金属合金在本说明书和权利要求书的“1族金属”定义范围内。
在制备本发明的1族金属/硅胶组合物中,通常将1族金属与硅胶混合。液体1族金属的粘度应至少低至足以被硅胶吸收。一种实现方法为在与硅胶混合之前在惰性气氛下加热该碱金属。或者根据待制备的材料的阶段,1族金属可作为固体与硅胶混合,随后加热该混合物以熔融碱金属。
向硅胶中引入1族金属的另一种方法为由气相状态与沸石混合。(参见A.S.Ichimura,J.L.Dye,M.A.Camblor和L.A.Villaescusa,J.Am.Chem.Soc.,124,1170-1171(2002)以及D.P.Wernette,A.S.Ichimura,S.A.Urbin和J.L.Dye,Chem.Mater.15,1441-1448(2003))。在另一种方法中,可由金属-氨溶液将1族金属淀积在硅胶上。(参见M.Makesya和K.Grala,Syn.Lett.1997,第267-268页,“ConvenientPreparation of‘High Surface Sodium’in Liquid Ammonia:Use inAcyloin Reaction”)。可使用金属-氨溶液以避免在与硅胶混合时金属附聚,并且制备金属与硅胶的均质混合物。但是,在实践金属-氨溶液法混合1族金属与硅胶时,伴随有金属-氨溶液显著分解,形成酰胺。但是,如本发明优选的,将液体1族金属与硅胶简单地接触,以避免耗时的蒸气淀积或金属-氨路线。
如下所述,对于至少0段材料,通常优选1族金属的熔点在室温(25℃)的约15℃范围内。例如铯和铷的熔点分别为28.5℃和38.5℃。通常两种或多于两种碱金属的合金在室温或近室温下为并优选为液体。优选的低熔点合金为各种摩尔比率的钠和钾(NaK),Na∶K的摩尔比率为0.5-3.0,更优选为2∶1摩尔比率的Na2K。摩尔比率在0.5-2.5之间的所有的Na-K合金在-12.6℃低共熔温度下开始熔融。对于摩尔比率为约0.12和3.1的Na-K合金在25℃下完成熔融。碱金属的其他二元合金,例如Cs与Rb、K或Na,以及Rb与Na或K也在低于或仅稍高于室温下熔融,因此适用于该目的。由这四种碱金属中的三种制备的三元合金或所有四种金属的合金也在足以形成本发明的1族金属/硅胶组合物的低温下熔融。
硅胶
硅胶为多孔形式的无定形二氧化硅。其为自由流动的粉末,列为99+%的SiO2。硅胶易得且廉价。硅胶的孔体积通常为约0.6-约1.2cm3/g,表面积为约300-约750m2/g。通常可用的硅胶为以下目大小:3-8、6-16、14-20、14-42、30-60、28-200以及小至325目。由于其多孔的性质,硅胶可吸收大量的被吸收材料。用于本发明的硅胶组合物的硅胶的孔径优选为优选孔径可为更优选硅胶的平均孔径为约硅胶的优选形式包括DavisilTM 646级和50级,均为30-60目,购自化学供应商例如Aldrich,并直接购自DavisonChemical Division of WR Grace Company,(即孔径,颗粒,30-60目,素白色,无指示剂)。这种硅胶的另一个供应商为Eagle ChemicalDivision of Multisorb。
虽然硅胶在购买时为自由流动的粉末,但它通常包含大量的气态物质,例如水和空气。优选在硅胶与碱金属或合金混合以形成本发明的组合物之前将这些气态物质除去。可使用本领域已知的方法对硅胶进行脱气。例如,为了除去这些气态物质,可在真空下,在可抽真空的烧瓶中加热硅胶,首先使用热空气干燥器,随后使用火炬。这种加热达到的温度约为300℃。还可并且实际上优选在空气中将硅胶加热至600℃或更高(900℃)(煅烧),以更容易地除去这些气体质并钝化活性部位。认为将硅胶加热至600℃或更高引起孔或硅胶晶格中的至少部分Si-OH部位形成硅氧烷Si-O-Si基团,伴随着失去水。在较低的温度下加热硅胶也可制备可用的原料,但是一部分碱金属可能通过与缺陷Si-OH基团反应而变得惰性。通常将硅胶冷却至室温,随后制备本发明的1族金属/硅胶组合物。
包含碱金属和碱金属合金的硅胶组合物
在化学工业和氢气生产界持续需要能以方便的形式利用碱金属或其等价物。为了满足这些需求,本发明涉及包含硅胶和碱金属或碱金属合金的1族金属/硅胶组合物。本发明的组合物描述为0、I、II和III段材料。这些材料的区别在于它们的制备方法和化学活性。可直接使用下述方法或由更早阶段的材料制备各连续的阶段。例如0段材料可在等温条件(优选在室温下或刚刚超过室温)下使用被硅胶(多孔SiO2)快速吸收的Na和K的液体合金制备,以形成疏松的黑色粉末,保留母体金属的大部分还原能力。认为0段材料含有吸收在硅胶孔内的小簇中性1族金属。与其母体1族金属相比,0段材料在空气中自燃但不易爆炸。可于140℃下将0段材料加热过夜制备1段材料。I段材料为疏松的黑色粉末,在干燥的空气中长时间稳定。随后加热至400℃,制备II段材料,该材料也是疏松的黑色粉末。再次加热超过400℃,形成III段材料,释放某些1族金属。认为I、II和III段材料代表了吸收1族金属后硅胶的还原性。优选本发明的1族金属/硅胶组合物为那些包含钠、钾或钠-钾合金的组合物,最优选钠和钠-钾合金。
如下所述,用差示扫描量热法(DSC)测试含有各种负载和质量比率的NaK和铯的这种材料的多个试样。于-25℃至0℃下熔融硅胶孔内的NaK所吸收的热量用于确定在硅胶内保持为金属的已包封金属的量。随后在5-650℃之间有宽的放热峰。冷却并再次加热相同的试样时,未观察到明显的热量峰。这点表明,热处理引起孔内的已包封金属与硅胶反应,产生II段材料,随后产生III段材料,但是峰的边界不尖锐。这种向II段和III段材料的转化不明显地改变该材料产生氢的能力。
本发明的1族金属/硅胶组合物包含吸收1族金属的硅胶。1族金属的负载量取决于实际使用的硅胶的孔径和孔密度。通常存在于本发明组合物中的1族金属最高达约50%重量。优选金属的量为30-40%重量。在本发明的I、II和III段材料中,负载高于约40%重量导致某些游离的金属保留在硅胶孔内。
本发明的1族金属/硅胶组合物与水快速反应,约定量收率(通常约95%收率)地产生气体氢气。以下所述的本发明的1族金属/硅胶组合物的制备和性能表明,所述组合物有前途作为清洁氢气的易运输和操作来源以及作为各种有机化合物反应的强有力的还原剂。下表I总结了0、I、II和III段材料的制备方法及用途。
表I
0、I、II和III段材料概述
如上所述,为了制备本发明所有的1族金属/硅胶组合物,优选在与1族金属混合之前将硅胶脱气和钝化。通常在制备本发明的材料时,首先在空气中将硅胶加热至约600℃或更高以除去水,对硅胶脱气,使缺陷部位最小化。还可使用本领域已知的其他方法来干燥、脱气和/或钝化硅胶。
0段材料
显然本发明的0段材料包含吸收在硅胶孔内的低熔点1族金属,该金属不反应或在硅胶晶格中再分布。因此,可看作是在敞开的孔和沟槽中吸收在硅胶内的纳米级的碱金属或碱金属合金颗粒。本发明的0段材料为1族金属/硅胶组合物,所述组合物包含在足以将液体1族金属或液体1族金属合金吸收在硅胶孔内的等温条件下,液体1族金属或液体1族金属合金(例如Na2K)与硅胶混合的产物。优选用于0段材料的1族金属包括低熔点1族金属,例如铯或NaK合金。所述0段1族金属/硅胶组合物与干燥的O2反应,这点与I、II和III段材料不同。由于0段材料对干燥的空气具有活性,因此应在真空下、在不含氧的气氛(优选在惰性气氛下,例如在氮气或惰性气体下)下操作。虽然0段材料在空气中自燃,但在这种条件下可储存在封闭的容器(例如口上有螺纹的管形瓶)中。
为了制备0段材料,在等温条件下(优选在室温下或稍高于室温),将1族金属与硅胶在惰性气氛中混合足够的时间,使得碱金属或合金吸收在二氧化硅内。所述混合必须在惰性气氛中进行,例如在手套箱或手套袋中进行。在制备优选的0段材料的过程中,于室温下可将液体1族金属(例如Na2K)倒在硅胶床上。搅动(优选搅拌或摇动)该混合物使混合充分。优选液体1族金属吸收在多孔硅胶内没有明显的反应热或明显的放热。
根据使用的1族金属,吸收液体1族金属形成0段材料优选在室温(25℃)的15℃范围内进行。在通常的方法中,涉及这么少的热量以至于所述试样不明显变热,但是转化为自由流动的无定形黑色粉末产物,其中各颗粒具有有光泽的表面。将所述混合物搅动足够的时间使得碱金属或合金被硅胶吸收或“全部吸收”。混合时间通常取决于待制备材料的批量大小,可为数分钟至数小时。(制备本发明的任何1族金属/硅胶组合物的混合时间均如此。)
当制备0段材料时,应控制或散失反应产生的任何热量或对反应施加的热量。应避免在制备过程中有明显的温度上升。在优选的实施方案中,0段材料在近室温(25℃)下形成。加热远远超过该温度通常导致形成I段材料。可将硅胶铺展(例如在金属盘上)、搅拌硅胶或冷却反应器来控制温度。但是,应保持反应温度使得1族金属保持为液体,使其可被硅胶吸收。还应注意的是,当保存在室温下时,0段材料长时间后可缓慢转化为I段材料,但是如下所述,不加热时不会进一步转化为II段材料。
0段材料为有光泽的黑色粉末,与水反应放热。0段材料的DSC表明,在硅胶内存在中性状态的碱金属。虽然目前不知道0段材料的确切组成,但0段材料的熔点低于最常见的1族合金(例如NaK)的熔点,因此说明硅胶孔内存在1族合金的小颗粒。
图4说明室温下硅胶吸收Na2K合金,形成疏松有光泽的黑色0段粉末。如图4所示,(A)中所示的烧瓶包含刚刚混合后涂覆Na2K合金的硅胶。(B)中所示的烧瓶包含将烧瓶(A)中的试样摇动几分钟后最终的疏松黑色材料。外观上是均匀、易倒出的黑色粉末。
0段材料为本发明的1族金属/硅胶组合物中最活性的材料。由于向硅胶中加入低熔点碱金属或合金产生0段材料没有明显的放热,因此0段材料保持碱金属的大多数还原能力。由于其对空气和湿气具有活性,因此必需仔细操作,且不能与大量的空气和湿气接触。尽管有这些限制,0段材料可用于高度还原色谱法。本发明的1族金属/硅胶组合物的填充柱的孔隙率提供了还原环境,而母体金属或合金不能满足该还原能力。如下所述,这使得0段材料可用于与水一起产生氢气以及采用与纯的碱金属类似的方式,作为还原剂与大量可还原的有机物质反应。
I段材料
本发明的I段材料为1族金属/硅胶组合物,所述组合物包含在足以将液体1族金属吸收在硅胶孔内的放热条件下,液体1族金属与硅胶混合的产物。所制备的I段1族金属/硅胶组合物不与干燥的O2反应。在I段材料中,看起来碱金属或合金已转化为失去本体金属性质的形式,例如熔融。分散有所述活性还原材料的骨架看起来主要为SiO2。对I段材料的对分布函数实验说明主要为硅和氧的峰,没有结晶度,这说明一种或多种碱金属已离子化形成碱性阳离子,电子释放至二氧化硅骨架或空隙空间。参见Billinge等的Chem.Commun.2004,第749-760页有关对分布函数的讨论。
可在惰性气氛下,在液体1族金属的熔点温度下或刚刚高于其熔点下,将液体1族金属与硅胶混合,使得1族金属被硅胶的孔吸收,形成本发明的I段材料。还可使用上述的一种可选的方法(例如以蒸气形式加入1族金属)将1族金属与硅胶混合。随后将混合物保持在或稍高于1族金属的熔点(即约70-150℃)下搅动数分钟至数小时。总的来说,反应温度越高,材料的转化时间越短。形成I段材料的反应为温和的放热反应,在大规模生产时,优选所述方法如下进行,将液体金属或合金加至金属盘中的硅胶中,使得热量一经产生就被移除。所述反应看起来形成碱金属-硅胶晶格。I段材料反应放热的性质与0段材料不同。根据加热的温度,加热超过放热量可将I段材料转化为II段材料或III段材料。
当将低熔点1族金属加至密闭环境(例如锥形瓶)中的已煅烧和除气的硅胶时,因为碱金属与硅胶或其缺陷部位反应放热,通常体系变热。这样可导致形成0段和I段材料的混合物。最简单和最直接制备I段材料的方法为在惰性气氛、140℃下将0段试样加热过夜。其他时间和温度也可制备I段材料,但应小心以避免过热而形成II段材料。为了确保得到均匀的产物,在加热过程中应当搅动。
I段材料为无定形、有光泽的黑色粉末,不立即与干燥的空气反应,但与水发生放热反应。I段材料的DSC表明几乎没有或没有1族金属残留在硅胶内。I段材料和0段材料的差别在于前者可在干燥的空气中操作,甚至在普通实验室空气中可快速转移而不会着火或快速变劣。当保存在干燥的氧气气氛下数小时至数天,I段材料(与和干燥的O2反应的0段材料相比)不变化,在与液体水反应反应时产生与新鲜试样相同量的氢气。
I段材料作为活性还原剂在反应化学中有许多用处,比起下述的II段材料,为更好的还原剂。可为本体还原和色谱还原可选的试剂。
II段材料
本发明的II段材料为1族金属/硅胶组合物,所述组合物包含在足以将液体1族金属或液体1族金属合金吸收在硅胶孔内的放热条件下,并将所得到的混合物加热至约215-约400℃,液体1族金属与硅胶混合的产物。例如熔融在钠和硅胶的混合物中的钠,随后于400℃下在密闭的容器中加热过夜,完成了钠掺杂在硅胶孔内并形成II段钠/硅胶组合物。对钠II段材料的预对分布函数实验表明,在所述硅胶组合物中存在纳米晶体硅化钠(一种化学计量的NaSi化合物,例如Na4Si4)。看起来不存在金属钠。
在加热至约215℃-约400℃的过程中,开始放热反应并形成II段材料。I段材料可转化为II段材料。所有的1族金属掺入硅胶中,所得到材料的空气敏感性下降。较高熔点的1族金属(例如钠和钾)在形成0段或I段材料的温度下通常不润湿硅胶。则钠、钾和其他高熔点1族金属形成II段材料。所述反应形成碱金属-硅胶晶格,例如上述实例中的硅化钠。加热I段试样制备的II段材料的稳定性和活性与加热较高熔点的碱金属(例如钠或钾)与硅胶形成的材料相似。
如上所述,II段材料可由在惰性气氛下,将0段或I段材料缓慢加热或逐步加热至400℃制备。对于较高熔点的碱金属Na和K,在已煅烧、除气的硅胶存在下,可将该金属加热至超过其熔点,随后缓慢加热至400℃,偶尔需要摇动。在典型的加热方法中,将在密封的派热克斯锥形瓶中的材料各在150、200、250和300℃下加热1-3小时,随后于400℃下加热过夜。每一加热阶段后,将烧瓶剧烈摇动已防止过分“丛生”。产物为疏松的黑色粉末,当所述制剂均匀时易倒出。如果加热太快或者已熔融的金属未与硅胶剧烈混合,产物可结块,必须手动压碎。
纯Na+SG的差示扫描量热法(DSC)曲线示于图5。图5说明2.4mg Na+3.9mg SG的DSC曲线。反应的全部(放热)热量为约-90±10kJ/mol Na。注意到吸热熔融Na(113J/g Na)的放热峰在初始曲线(510)中于98℃处出现,但在重复曲线(520)中不存在了。这表明在第一次加热时Na与硅胶反应,可能形成硅化物NaSi。钠与硅胶的II段反应释放约90kJ热量/mol钠。在初始曲线中98℃处存在的金属Na熔融吸热在随后的加热中不存在,表明金属已与硅胶反应。反应产物未经确定,但Na+SG可能在所用硅胶的15nm直径的孔中形成硅化钠(所有组成的NaSi),伴随着形成硅酸钠。X-射线粉末图说明该产物仍为无定形的。
II段材料为无定形无光泽的黑色粉末。所制备的II段1族金属/硅胶组合物不与干燥的O2或干燥的空气反应。II段材料在含有干燥空气的环境中易操作。II段材料疏松的黑色粉末在敞开的周围环境中易操作,当保存在低湿度存在的环境(例如在密闭的容器中)下长时间后不变化。实际上,II段材料为本发明的1族金属/硅胶组合物中活性最差的。但是,该材料仍与水快速反应,产生几乎定量的纯氢气。
图6表示向本发明的II段钠/硅胶组合物试样中加入水后氢气球的吹胀。所述II段组合物约含30-40%重量的金属。如图(A)所示,在加入水之前,气球在真空下包含干燥的粉末。图(B)表示加入水2分钟后的气球。在该阶段,还原硅胶加上水仍在鼓泡。在1atm和25℃下,1g粉末产生约170cm3的H2。该材料为清洁氢气所需的方便、便携的来源,仅有的气态产物为氢气和水蒸气。
尽管II段材料为本发明的1族金属/硅胶组合物中活性最差的,但II段材料作为钝化还原剂在反应化学中有许多用处并用于生产氢气。由于从空气中吸收湿气,II段材料可缓慢变劣,但是在普通实验室空气中不着火且可很容易地转移。其还原能力看起来不如其他阶段材料的还原能力,但可用于不需要碱金属的全部还原能力的许多还原反应中。例如在质子源存在下,II段材料可将蒽还原为二氢蒽,但是所述还原比I段材料慢。由于II段材料对周围空气不敏感,因此为与水反应制备氢气的优选试剂。
III段材料
本发明的III段材料为1族金属/硅胶组合物,所述组合物包含在足以将液体1族金属吸收在硅胶孔内的放热条件下,并将所得到的混合物加热至超过约400℃,优选超过约500℃,液体1族金属与硅胶混合的产物。所述III段1族金属/硅胶组合物不与干燥的O2反应。
与制备本发明的其他1族金属/硅胶组合物一样,为了制备III段材料,在惰性气氛或真空下将1族金属与硅胶混合。在优选的方法中,首先将混合物加热至约215℃-400℃(形成II段材料),随后在几小时内缓慢加热至约400℃-600℃。当升温超过400℃时,发生强烈的放热。所述反应看起来形成包含富硅硅化物的碱金属-硅胶产物。所述III段材料为无定形、无光泽的黑色粉末,不与干燥的空气反应。如果通过加热实现II段或III段材料的反应,反应的放热性质说明为了防止“失控”的热反应,在大规模生产时需要除去热量。此外,如果不能有效地混合,则加热可释放碱金属蒸气。因此,本领域技术人员应领会对于大规模生产,可能需要封闭的体系。
III段材料作为掺杂材料在反应化学中有许多用处并用于生产氢气。
如上所述,本发明的各阶段1族金属/硅胶组合物可由每一连续阶段顺序制备。例如于25℃下向硅胶中加入1∶1摩尔比率的钠和钾(液体)形成自由流动的黑色粉末0段材料。在这种情况下,随后于400℃下在封闭的容器中加热过夜,进一步反应产生还原性较差的粉末II段材料。再次加热超过400℃引起进一步反应,产生III段材料。图1所示差示扫描量热法(DSC)曲线说明NaK与硅胶的放热反应在至少两步中进行。在图1中,差示扫描量热法(DSC)表示1∶1NaK/硅胶试样(8.9mg)的曲线,其中顶部曲线(110)为新鲜的室温试样,底部曲线(120)为将该试样冷却后重复操作。插入图(130)为第一曲线低温区的放大图,表明熔融吸热相当于加入的金属为约50%。对于该放热过程,总ΔH值相当于-100至-125KJ/mol金属。
图2表示由Na3K和等质量的硅胶制备的1族金属/硅胶组合物的相似的行为。在图2中,DSC图表示1∶1的Na3K/硅胶试样(5.7mg)的曲线,其中顶部曲线(210)为新鲜的室温试样,底部曲线(220)为将该试样冷却后重复操作。插入图(230)为第一曲线低温区的放大图,表明熔融吸热相当于加入的金属仅为约10%。对于该放热过程,总ΔH值相当于-75至-100KJ/mol金属。0段材料于室温下或近室温下制备,没有明显的热量产生。在加热至215-400℃时自发形成II段材料,于400-600℃下加热制得最终产物III段材料。
1族金属/硅胶组合物的反应化学
基于1族金属计算,本发明所有的1族金属/硅胶组合物与水放热反应本质上定量收率地产生氢气。因此,最好本发明的组合物保持1族金属的活性。0段材料可在干燥的空气中短暂操作,但其与氧反应缓慢,与湿气反应快速。而1族金属/硅胶组合物的I、II和III段材料完全不与干燥的氧气反应。
虽然本发明的I、II和III段1族金属/硅胶组合物较无毒并且活性不强烈,但它们确实存在强碱,在与水反应时形成碱金属氢氧化物。当金属含量高(约35%或以上)时,与水的反应产物完全溶解,可能为碱性金属硅酸盐。用酸中和沉淀出二氧化硅。
本发明各阶段的1族金属/硅胶组合物可作为还原剂与各种可还原的有机物质反应,其方式与碱金属及其合金的方式相同。例如1族金属/硅胶组合物可用于将芳族化合物还原为其自由基阴离子,该反应通常称为伯奇还原,,通常与碱金属-氨溶液反应。伯奇还原为用碱金属在液体氨中的溶液还原芳族化合物的通用方法。关于伯奇还原的理论和制备方面在几篇文章中有讨论。参见G.W.Watt,Chem.Rev.,46,317(1950);A.J.Birch,Quart.Rev.(London),4,69(1950);A.J.Birch和H.F.Smith,Quart.Rev.(London),12,17(1958);以及C.D.Gutsche和H.H.Peter,Org.Syntheses,Coll.Vol.4,887(1963)。本发明的1族金属/硅胶组合物可很容易地替代伯奇还原反应中的钠。实施例10说明使用本发明的1族金属/硅胶组合物的伯奇还原反应。
类似地,强烈的还原例如卤代有机化合物(例如PCB)的孚兹(Wurtz)还原可在可控的条件下进行。孚兹反应为用2摩尔的钠处理2摩尔的有机卤化物(RX),两个有机基团(R)的偶联反应:
2RX+2Na→R-R+2NaX
参见A.Wurtz,Ann.Chim.Phys.[3]44,275(1855);Ann.96,364(1855).;J.L.Wardell,Comp.Oranometal.Chem.1,52(1982);W.E.Lindsell,ibid.193;B.J.Wakefield,ibid.7,45;D.C.Billington,Comp.Org.Syn.3,413-423(1991)。本发明的1族金属/硅胶组合物可很容易地替代孚兹反应或其他这种脱卤反应中的钠。本发明的组合物还可用于脱卤无机卤化物。实施例11说明使用本发明的1族金属/硅胶组合物的孚兹还原反应。
可用本发明的1族金属/硅胶组合物进行工业可用的反应,例如石油脱硫。例如本发明的组合物可用于由二苯硫醚除硫制备联苯的改进方法。所述改进包括进行以下反应:
其中M-SG为本发明的1族金属/硅胶组合物。
由于所述组合物比相应的碱金属或合金操作性更安全,因此使用本发明的1族金属/硅胶组合物使得碱金属的反应(例如上述的那些反应)在较安全的条件下进行。使用所述组合物的收率通常也比仅使用1族金属相应反应的收率高。
由于I段材料(例如I段Na2K/硅胶组合物)非常容易制备且保持母体1族金属大部分的还原能力,因此可用作强有力和方便的还原剂。当有机化合物溶解于四氢呋喃(THF)并通过填充I段粉末的小玻璃柱时,该柱能还原各种有机化合物。或者将有机化合物的THF溶液与I段材料简单地搅拌,可进行间歇反应。例如如下所示,二苯酮(1)还原为自由基阴离子(羰游离基);苄基氯(2)进行孚兹还原形成联苄(3);以及二苯并噻吩(4)还原为自由基阴离子,最终为不含原料的产物混合物。其他反应包括二氯苯的孚兹还原形成预期的偶联产物以及蒽伯奇还原为二氢蒽。
如上所述,II段钠/硅胶组合物比I段材料更易在空气中操作。其与水反应制备氢气为定量的,且还能进行许多上述I段材料的有机还原反应。例如可将二苯酮(1)还原为自由基阴离子,且可将苄基氯(2)转化为联苄(3)。I段和II段材料的大量其他反应是可能的。上述有代表性的化合物的还原反应说明本发明的1族金属/硅胶组合物可将芳族化合物还原为自由基阴离子或二价阴离子(dianion),碳-硫键破裂,芳族氯化物完全脱氯。因此所述材料能通过脱氯和进行脱硫反应破坏PCB。所述1族金属/硅胶组合物强有力的还原性还使得可使用填充所述材料的色谱柱来还原目前用Na-K或碱金属-氨溶液还原的有机化合物和无机化合物。
本发明的所有四阶段的还原硅胶组合物的主要用途为用于燃料储存电势和形成汽车燃料电池所需氢气。例如大量的还原硅胶粉末原料可保存在存储槽内的输送盘上。加入水将释放纯氢气和水蒸气。所有阶段的材料产生接近定量的以往由所用的碱金属产生的氢气。所述氢气则可用于驱动汽车燃料电池。例如1族金属/硅胶组合物原料可保存在存储槽内的输送盘上。随后加入水并与水混合将释放氢气,可随后提取和压缩氢气。压缩氢气可用于填充汽车燃料电池。这时余下的粉末仅为硅胶或已溶解的金属硅酸盐,可被新的1族金属再次活化或用于其他用途。
本发明的另一个实施方案涉及使用硅胶来清理1族金属的撒落物和操作后剩余的类似物。该实施方案利用上述制备本发明组合物的硅胶的吸收性质。如实施例8所述,当在手套箱中用金属铯进行实验时,有几克铯撒落在箱底。首先使用Kimwipe纸巾来清理撒落物,但是脏了的拭纸一离开填充氦气的手套箱就着火。于是决定试图用硅胶吸收铯,希望金属铯能足够稳定以在空气中着火之前将其从箱中转移至安全的地方处理。导致当金属为液体或可熔融形成液体时,使用硅胶来清理金属或其他撒落物,特别是活性金属(例如碱金属)。当处理高熔点碱金属时,必须将金属加热为液体使得可进行清理。
美国专利申请10/248,765“System for Delivery of ActiveSubstances”描述了使用碱金属(例如钠、钾等)的组合物释放活性物质,例如蒸发除臭剂组合物中的香料,所述专利通过引用结合到本文中来。由于其稳定性,本发明的I、II和III段组合物与这种活性组分(例如香料)相容。在另一个实施方案中,本发明还涉及包含本发明的1族金属/硅胶组合物的这些组合物。例如除臭剂组合物可包含约5-15%重量的本发明的还原硅胶、10-30%重量的香料和最高达约75%重量的中和剂和/或有机酸。除了香料,除臭剂还可包含其他活性组分,例如消毒剂、表面活性剂、颜料或染料。所述1族金属/硅胶组合物与水的反应分配香料或其他活性组分。
实施例
实施例1
示例性的硅胶Davisil 30-50目购自Grace-Davison,为一种自由流动的粉末,列为99+%的SiO2。但是,该硅胶包含大量的气态物质(可能为水和空气)。为了除去这些气态物质,在真空下,在可抽真空的锥形瓶中加热硅胶,首先使用热风干燥器,随后使用火炬。预计温度达到约300℃。如上所述,在空气中将该材料加热至600℃或更高(煅烧)可更容易地对硅胶除气(钝化活性部位)。
实施例2
本发明的1族金属/硅胶组合物的一个显著的特性为在加入水时能定量地产生纯氢气。向已抽空的试样中加入水并用改进托普勒泵收集氢气来测定1族金属/硅胶组合物的“还原能力”。还原能力定义为产生相同量的氢气使用的碱金属或合金的%重量。通过收集由已知质量的材料与除气的水反应产生的氢气来证实这一点。使用改进托普勒泵(填充汞)将氢气收集在校准吸移管中。产生的氢气的量通常等于单独的一种或多种金属产生的量。对每一个还原二氧化硅试样都进行这种分析,而不管材料的阶段。例如如果40%重量NaK在I段硅胶中的试样产生的氢气的量与单独该量的NaK产生的氢气量相同,则还原能力为40%。随后加入HCl并用氢氧化钠返滴定测定形成的碱金属氢氧化物的总量。滴定得到的总碱金属百分含量与还原能力之间的差异可大概衡量SiOH基团和其他氢源的含量。在试样制备过程中碱金属可与这些基团反应释放氢气。该反应大概为在金属或合金与硅胶混合过程中形成可检测量的气体来源。
实施例3
在填充氦气的手套箱中使用不锈钢盘,14g已除气和煅烧的硅胶与9.7g来自巴斯德吸移管的Na2K混合,产生0段材料。将Na2K滴加至涂覆硅胶的盘的不同区域。合金滴润湿了硅胶,并且可用刮勺“压扁”以帮助合金掺入。产物从不变热,并且看起来具有非常有光泽的表面,这说明在表面上有游离的金属。看来Na2K未完全吸收在硅胶孔内。随后收集试样,将3.6mg试样放入DSC盘中进行差示扫描量热法(DSC)。DSC从约-55℃至60℃操作,保持10分钟,随后再次测定。之后,将试样加热至450℃两次。熔融吸热量相当于约135J/g金属,该热量稍高于基于加入的金属计算预期的量。已称重的质量可能失去一部分(off)或者含量不均匀。当加热至60℃并保持10分钟,随后重复一次,得到熔融ΔH=61.4J/g金属,说明退火效果已存在,将试样转化为下一阶段。向已抽空的试样中加入水并用改进托普勒泵收集氢气来测定试样的“还原能力”。还原能力定义为产生相同量的氢需要的1族金属的量。由21mg相同试样放出的H2得到37%的还原能力。这与标称40%重量含量的金属一致。
实施例4
老化试样或均匀加热均可将0段材料转化为I段材料。在真空下或在惰性气氛下,于约140℃下简单地将0段材料加热过夜同时混合,将其转化为I段形式,DSC(见图7)表明几乎没有或没有熔融吸热。由于粒径小,0段材料于-25℃下开始熔融而不是从本体熔融温度-13℃开始。I段材料的ΔH值(9J/g金属)比0段材料的ΔH(117J/g金属)小,表明大多数金属可能转化为碱金属阳离子。外观上在孔中或硅胶颗粒的表面上不存在游离的碱金属,使得该阶段的材料在干燥的空气中完全不被氧化。
实施例5
连续加热0段和I段材料至400℃或者使用较高熔点的碱金属(例如钠和钾)可制备II段材料。称重13.5g已除气和煅烧的硅胶,随后加入约7.3g金属Na。加热下、于3.5×10-5托对硅胶除气。将硅胶与Na的混合物首先加热至150℃下1小时,随后剧烈摇动,再加热至200℃下1.5小时。约每30分钟将该材料剧烈摇动。最后将该材料加热至300℃下过夜。该粉末看起来疏松并自由流动。随后将温度升至400℃,将该材料再加热3小时。
实施例6
在制备NaK掺入硅胶中,将3.00g 600℃煅烧的硅胶置于含有3.012g NaK的锥形瓶中。用5.562g Na和9.433g K制备NaK合金。该质量的NaK含有约50mmolNa和约50mmol K以及50mmol SiO2。因此,2∶1摩尔比率的金属与Si用于该试样。在室温下,硅胶开始变黑并在数分钟内变成均匀、可倒出的有光泽的黑色粉末,没有明显的放热。从该试样中取走22.6mg用于H2分析。在T=296.6K、Patm=738.9托下放出H2。放出H2后,有176.5μmol的H2相应于353μmol的金属。放出的H2相应于48.4%重量的金属在硅胶中,标称50%重量的初始负载。随后可通过可控的方法加热该试样,得到I段和II材料。但是,应注意的是,在制备过程中加热烧瓶可引发强烈的放热反应,引起金属“暴沸”并涂覆于容器上。
实施例7
变化金属和硅胶的量制备了各种不同的制剂,使得碱金属的含量为20-50%重量。制备了还原能力为45.6%的Na和负载硅胶的一个试样。还原能力通常为基于加入的金属量计算可得到的最大还原能力的94%或更高。剩余的2-6%代表一种或多种碱金属与缺陷部位的反应。在经过各种处理(例如暴露于氧或加热)后测定还原能力,提供了关于该材料稳定性的信息。在48小时内,还原能力仅降至44%,共减少1.6%,说明在不存在湿气下几乎不与氧反应。可使用于室温下或近室温下为液体、具有不同比率Na与K的其他合金。例如使用Na3K制备了结果与实施例5类似的还原二氧化硅。在填充氦的手套箱中,在锥形瓶中向433mg Na3K中加入8412mg硅胶制备该试样。还制备了1∶1质量比率的NaK与硅胶的两个其他试样。最后制备了1∶4质量比率的NaK与硅胶的试样。所有的这些试样形成I段自由流动的黑色粉末,在干燥的空气中稳定。长时间储存在手套箱中没有可发觉的性能改变。
实施例8
在氦手套箱中有液体Cs撒落。使得发现了一种有效清理碱金属的方法。将硅胶倒在Cs撒落物上,用Kimwipe在周围混合。所有的金属Cs吸收在硅胶内,使得硅胶变成黑色。因此,硅胶为低熔点碱金属和低共熔合金(例如NaK)理想的清理材料。
实施例9
如图3所示,纯铯的行为类似于NaK合金。在图3中,DSC图说明1∶1铯/硅胶试样(6.7mg)的曲线,其中顶部曲线(310)为新鲜的室温试样,底部曲线(320)为将该试样冷却后重复操作。该放热过程的总ΔH值相当于约-120kJ/mol金属。注意到不存在金属Cs的熔融放热。但是,由于50%重量的Cs包含少于0.5摩尔Cs/mol二氧化硅,在DSC实验中未观察到金属Cs的熔融吸热。制备了四个负载铯的硅胶试样;两个为通过气相加入制备,一个为向硅胶中直接加入金属铯。所有的三个制剂形成自由流动的粉末。两个气相加入的试样分别在室温下和40℃下制备。气相加入负载轻的铯(<20%重量)形成蓝色的还原二氧化硅。较高的浓度产生自由流动的黑色粉末。加热I段材料形成II段和/或III段含Cs的还原硅胶,同时放热。例如图3说明将1∶1的I段Cs-硅胶加热至650℃,随后再次加热已冷却的试样的DSC结果。可见第一次加热产生放热反应,在再次加热该试样时放热不存在了。这表明I段材料转化为III段材料,而III段材料不再存在该明显的反应。
实施例10
所有的0段-II段碱金属-硅胶粉末能通过伯奇还原将蒽还原为自由基阴离子。形成浓亮蓝色溶液观察到还原反应,通过产物的光学吸收波谱(见图8)证实了该还原反应。图8说明用本发明的I段材料M-SG还原蒽制得的蒽自由基阴离子的光谱。该光谱与该阴离子的已知谱图本质相同。该自由基阴离子足够稳定,能在溶液中保持许多小时。该反应可采用几种反应设置进行,例如间歇反应、层叠式(碱金属-硅胶层叠在市售硅胶上部)色谱柱和混合(碱金属-硅胶与市售硅胶均匀混合)色谱柱,通常为50∶50比率的材料。层叠或混合床色谱柱可与碱金属-硅胶一起使用以还原蒽并用残留的水质子化所得到的自由基阴离子。该产物为预期的9,10-二氢蒽。该反应可说明如下:
图9说明蒽的THF溶液通过本发明的1族金属/硅胶组合物的混合床柱的伯奇还原反应产物的1H NMR谱。在这种情况下,使用I段材料的收率为92%的所需产物,总的洗脱时间小于2分钟。再次实验得到100%的收率。这说明易形成自由基阴离子的反应物的伯奇还原反应的效率。用叔丁醇质子化的本体反应产物的GC-MS分析表明主要只有蒽和9,10-二氢蒽。应注意的是,含有II段材料代替I段材料的柱色谱得到较少的产物,说明该较不活性的还原硅胶还原较慢。图中的数据为用I段Na2K/硅胶材料(约30-40%重量的Na2K)的反应。
实施例11
碱金属与有机化合物最早的反应之一为孚兹反应,其中氯烃脱卤产生偶联,形成新的碳-碳键。但是,当与本体碱金属和纯氯烃一起使用时,该反应可很危险地爆炸。如下所示,用约1.3g I段Na2K/硅胶材料(约30-40%重量的Na2K)还原溶解于10ml THF的约130mg苄基氯进行该偶联反应。当快速通过小柱时发生部分还原(约30%)。但是,当再次实验使用I段和0段Na2K/硅胶材料(约30-40%重量的Na2K)快速通过该柱时,得到完全100%的收率。因此,通过柱的速度改变反应物转化为所需产物的程度。与I段Na2K/硅胶材料搅拌3小时后发生本体还原。GC-MS和1H NMR检测,唯一的产物为联苄(见图10A-10C)。图10A-10C说明在间歇法中苄基氯还原产物的分析结果。图10A说明单一的GC谱线,图10B说明GC产物的质谱,图10C说明该产物的1H NMR。图10B所示的MS与联苄的MS完全相符。注意到完全不存在反应物苄基氯在4.6ppm处的峰。
其他脱卤反应包括1,2-二氯苯脱氯(通过柱部分脱氯,在本体反应中完全脱氯)。这些试验表明本发明的1族金属/硅胶组合物可很容易地对芳族和脂族卤代烃进行脱卤.
实施例12
由烃硫醚脱硫可存在许多问题,并且得到数不清的产物。因此,如下所示,二苯硫醚与I段Na2K/硅胶(约30-40%重量的Na2K)的间歇反应仅得到联苯产物,这点是非常令人吃惊的。GC-MS和1H NMR均证实了这一点(见图11A-11C)。图11A-11C说明二苯硫醚与本发明的I段材料过夜间歇反应产物的分析结果。图11A说明单一的GC峰,图11B说明GC产物的质谱,图11C说明该产物的1H NMR。图11C的NMR主要为联苯的NMR谱。还表明存在得自氘核-氯仿的氯仿以及某些二苯硫醚反应物。产率不能确定,这是由于在约7.3ppm化学位移区域NMR重叠,但是产物主要是联苯。类似地,由二苯并噻吩完全除去硫,在烃脱硫中该方法是特别困难的。GC-MS也表明主要产物为联苯,但是1H NMR表明存在其他产物。
实施例13
使用本发明的1族金属/硅胶组合物开始重要的问题是1族金属是否存在于还原二氧化硅组合物中。为了测试这一点,制备精细分割的钠和硅胶试样。由于钠易附聚,通过蒸发钠在氨中的冷冻溶液的氨来制备钠。该材料的三部分经过差示扫描量热法(DSC)测试。于98℃下熔融钠吸收的热量用于确定试样中钠的量。随后在100℃-490℃之间有宽的放热峰。在280℃处有未知来源的尖锐的吸热峰。当冷却该试样并重新加热时,未观察到热量峰。这表明热处理完全除去了游离的钠,推测起来是由于钠与二氧化硅发生了反应。此外,固态Na的NMR表明在还原硅胶组合物中不存在金属钠。此外,可估计产物“还原二氧化硅”与水的反应热。还原二氧化硅与水的反应热(放热)约为-136±18kJ/mol Na,为纯钠的约75%。因此,本发明的1族金属/硅胶组合物与水反应时释放相当可观的热量。
随后加入HCl并用氢氧化钠返滴定测定形成的氢氧化钠的总量。该结果与还原能力之间的差异可大概衡量SiOH基团的含量。在制备过程中1族金属可与这些基团反应释放氢。该反应大概为在硅胶存在下熔融钠的过程中形成的大量气体的来源。
实施例14-制备50%重量的钠-钾还原硅胶
首先于600℃下将约40g硅胶在空气中加热过夜,以对硅胶除气。在高真空(2×10-5托)下,在适合的长颈锥形瓶中将3.0g该硅胶加热至约300℃,以进一步除气。接着,通过抽真空气门将该烧瓶置于填充氦的手套箱中。随后向装有硅胶的烧瓶中加入3.0g NaK(1∶1摩尔比率),形成50∶50质量比率的硅胶与NaK。这时NaK开始润湿硅胶的表面,使硅胶变成黑色。将烧瓶从手套箱中移走后,将该烧瓶抽真空至约2×10-5托。少量的搅动足以活化整个试样,使其转化为自由流动的黑色粉末(I段)。在反应时,没有可检测到的热量释放。用空气加热枪加热的第二个试样自发放热反应,使得该烧瓶太热而不能触摸。推测I段材料转化为另一种形式(II段或III段)。
实施例15-制备含钠的还原硅胶
首先将2.25g硅胶真空加热以对硅胶除气。不再有气体放出后,则将烧瓶从热源移走,压力达到3×10-5托。接着,通过抽真空气门将该烧瓶置于填充氦的手套箱中。放入手套箱后,向该烧瓶中加入1.135gNa。随后液氨(NH3)一次冷冻泵入并在Na-硅胶粉末上蒸馏,因此引起以下催化剂分解反应:
Na+NH3→NaNH2+1/2H2
由于在催化剂分解反应过程中放出大量的H2,因此该管线渐增抽空。随后除去任何剩余的NH3,将烧瓶抽真空至3×10-5托。接着,在真空条件下用空气加热枪加热该烧瓶。加热后,将烧瓶放回手套箱中。随后将试样分配在5个管形瓶中。第一个管形瓶(449mg)从手套箱中移走并储存于室温下。将第二个、第三个和第四个管形瓶(分别为509mg、603mg和653mg)置于手套箱冷藏箱中。第五个试样(122mg)置于密封的管形瓶中,随后倾倒在1000mL装水的烧杯中。
实施例16-制备含钠的还原硅胶
首先将2.2786g 99+%的硅胶(30-50目)加至锥形瓶中。随后在真空条件下将该烧瓶加热并除气,首先使用空气加热枪,随后使用火炬。调整火炬的燃料(O2)使火炬火焰的尖为黄色。将硅胶加热并除气后,剩余约2.145g硅胶,体积为2.5cm3。随后将烧瓶加热,用泵抽吸至压力为2×10-5托。加热后,将980mg Na滚成圆筒加至烧瓶中。目标Na量为1.0g。当Na在烧瓶中熔融时,压力变为约10-3托。真空下将烧瓶间歇加热90分钟,以放出更多的气体。随后将烧瓶冷却至室温,并于2×10-5托下密封。接着,加热烧瓶直至残留在烧瓶壁上的Na蒸馏至硅胶的表面。最后,将烧瓶放置在210℃的炉子中过夜。随后将试样分配在4个管形瓶中。所有的4个管形瓶(分别为812mg、771mg、823mg和525mg加上任何残余物)置于冷藏箱中。
实施例17-香料测试
以上实施例2的两个Na/硅胶混合物试样得自冷藏箱中。第一个试样重520mg。于2×10-5托压力下,将684mg柑橘属油香料冷冻泵抽3次,置于填充He的手套箱中。随后将第一个Na/硅胶混合物试样加至手套箱中的柑橘属油中。液N2冷却下将该试样抽真空。随后将该试样加热至室温,测定Na/硅胶与柑橘属油反应产生的气体。随后将试样于室温下保持110分钟以观察反应。随后用液氮冷却该试样,让水冷凝在试样上5分钟。随后将试样升温,使试样与水反应。随后收集并测定所有的气体。
第二个试样重109.7mg。于2×10-5托压力下,将161mg柑橘属油香料冷冻泵抽3次,置于填充He的手套箱中。随后将第二个Na/硅胶混合物试样加至手套箱中的柑橘属油中。液N2冷却下将该试样抽真空。随后将该试样加热至室温,测定Na/硅胶与柑橘属油反应产生的气体。随后将试样于室温下保持110分钟以观察反应。随后用液氮冷却该试样,让水冷凝在试样上5分钟。随后将试样升温,使试样与水反应。随后收集并测定所有的气体。
实施例18-除臭剂组合物
第一种除臭剂组合物包含0.8g柠檬酸、0.35g碳酸氢钠、0.11g含钠还原硅胶和0.27g香料。第二种除臭剂组合物包含0.8g柠檬酸、0.35g碳酸氢钠、0.11g含钠还原硅胶和0.35g香料。第三种除臭剂组合物包含0.8g柠檬酸、0.35g碳酸氢钠、0.11g含钠还原硅胶和0.5g香料。
Claims (12)
1.一种1族金属和硅胶的组合物,所述组合物通过以下方法制备:在惰性气氛、足以将液体1族金属吸收在多孔硅胶的孔内的等温条件下,将液体1族金属与所述多孔硅胶混合,其中所述硅胶具有直径的孔,所述1族金属的存在量最高达50%重量,且所制备的1族金属和硅胶的组合物与干燥的O2发生反应。
2.权利要求1的1族金属和硅胶的组合物,其中所述硅胶具有直径的孔,所述1族金属的存在量最高达50%重量,且所述1族金属选自铷、铯和两种或多于两种1族金属的合金。
3.权利要求1的1族金属和硅胶的组合物,其中所述1族金属为钠、钾或钠-钾合金。
4.权利要求1-3中任一项的1族金属和硅胶的组合物,其中所述硅胶具有直径的孔。
5.一种制备0段1族金属和硅胶的组合物的方法,所述方法包括以下步骤:在惰性气氛、足以将液体1族金属吸收在多孔硅胶的孔内的等温条件下,将液体1族金属与所述多孔硅胶混合,其中所述硅胶具有直径的孔,所述1族金属的存在量最高达50%重量。
6.一种有机化合物的碱金属还原方法,改进之处在于使所述有机化合物与权利要求1的1族金属和硅胶的组合物接触。
7.权利要求6的有机化合物的碱金属还原方法,其中所述有机化合物的还原反应是芳族化合物的伯奇还原反应,所述1族金属为钠、钾或钠-钾合金。
8.权利要求6的有机化合物的碱金属还原方法,其中所述有机化合物的还原反应是卤化有机化合物的脱卤反应,所述1族金属为钠、钾或钠-钾合金。
9.权利要求6的有机化合物的碱金属还原方法,其中所述有机化合物的还原反应是卤化有机化合物的孚兹反应,所述1族金属为钠、钾或钠-钾合金。
10.权利要求6的有机化合物的碱金属还原方法,其中所述有机化合物的还原反应是包含硫醚键的有机化合物的脱硫反应,所述1族金属为钠、钾或钠-钾合金。
11.权利要求6的有机化合物的碱金属还原方法,其中所述1族金属为钠、钾或钠-钾合金。
12.一种制备氢气的方法,所述方法包括使权利要求1的1族金属和硅胶的组合物与水接触的步骤。
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Families Citing this family (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2005254551A1 (en) * | 2004-06-14 | 2005-12-29 | Michigan State University | Silicide compositions containing alkali metals and methods of making the same |
US8263808B2 (en) * | 2006-02-13 | 2012-09-11 | Signa Chemistry, Inc. | Method for deprotecting aryl or alkyl sulfonamides of primary or secondary amines |
US7670698B2 (en) * | 2006-04-10 | 2010-03-02 | Honeywell International Inc | Silicide fueled power generators and methods related thereto |
US8197707B2 (en) * | 2006-09-08 | 2012-06-12 | Signa Chemistry Llc | Lithium-porous metal oxide compositions and lithium reagent-porous metal compositions |
WO2008131270A1 (en) * | 2007-04-18 | 2008-10-30 | Signa Chemistry, Llc | Method for generating alkali metal phosphides through reduction of tri-substituted phosphines with alkali metal porous oxide compositions |
US7932329B2 (en) | 2007-09-28 | 2011-04-26 | Signa Chemistry, Inc. | Use of alkali metal-silica gel (M-SG) materials in solvent and monomer drying and purification for their use in anionic polymerization |
EP2268655A4 (en) * | 2008-03-24 | 2013-03-13 | Signa Chemistry Llc | BIRCH REDUCTION OF STEROIDSUBSTRATES ON ALKALIMETAL SILICA GEL MATERIALS |
DE102009008144A1 (de) | 2009-02-09 | 2010-08-19 | Nano-X Gmbh | Verfahren zur Herstellung von Alkali- und Erdalkalilegierungen und Verwendung der Alkali- und Erdalkalilegierungen |
JP5778131B2 (ja) | 2009-03-30 | 2015-09-16 | インテリジェント エナジー リミテッドIntelligent Energy Limited | ナトリウムシリサイドおよびナトリウムシリカゲル物質を使用する水素生成システムおよび方法 |
US9102528B2 (en) | 2009-03-30 | 2015-08-11 | Intelligent Energy Limited | Hydrogen generation systems and methods utilizing sodium silicide and sodium silica gel materials |
WO2011060033A1 (en) | 2009-11-10 | 2011-05-19 | Immunolight, L.L.C. | Up and down coversion systems for production of emitted light from various energy sources including radio frequency, microwave energy and magnetic induction sources for upconversion |
WO2011097198A1 (en) | 2010-02-08 | 2011-08-11 | Eveready Battery Company, Inc. | Fuel cell cartridge |
US8895204B2 (en) | 2010-11-08 | 2014-11-25 | Intelligent Energy Limited | Water reactive hydrogen fuel cell power system |
WO2011150179A2 (en) * | 2010-05-26 | 2011-12-01 | Regents Of The University Of Minnesota | Carbon coated silica particles and methods of making same |
WO2012064749A1 (en) | 2010-11-08 | 2012-05-18 | Signa Chemistry, Inc. | Water reactive hydrogen fuel cell power system |
US8962536B2 (en) | 2010-12-17 | 2015-02-24 | Chevron U.S.A. Inc. | Heat generating system for enhancing oil recovery |
EP2700121B8 (en) | 2011-04-21 | 2015-05-13 | Intelligent Energy Limited | Hydrogen generator with improved volume efficiency |
US9657549B2 (en) | 2011-06-14 | 2017-05-23 | Signa Chemistry, Inc. | Enhanced crude oil recovery using metal silicides |
WO2013002893A1 (en) | 2011-06-28 | 2013-01-03 | Eveready Battery Company, Inc. | Hydrogen gas generator |
US9023122B2 (en) | 2011-07-26 | 2015-05-05 | Intelligent Energy Limited | Hydrogen generator with improved fluid distribution |
CN103906825B (zh) | 2011-12-06 | 2015-08-19 | 英派尔科技开发有限公司 | 载有磷的颗粒及其制备和使用方法 |
US9005321B2 (en) | 2012-03-19 | 2015-04-14 | Intelligent Energy Inc. | Hydrogen generator system with liquid interface |
MX2014015945A (es) | 2012-06-25 | 2015-07-17 | Signa Chemistry Inc | Uso de siliciuros de metal en la produccion y transportacion de hidrocarburo. |
US20130344407A1 (en) | 2012-06-25 | 2013-12-26 | Eveready Battery Company, Inc. | Hydrogen Generator and Method of Controlling Reaction |
US9162201B2 (en) | 2012-08-14 | 2015-10-20 | Intelligent Energy, Inc. | Hydrogen generator having liquid delivery member |
US9051183B2 (en) | 2012-08-24 | 2015-06-09 | Intelligent Energy Inc. | Hydrogen generator having reactant pellet with concentration gradient |
GB201217541D0 (en) * | 2012-10-01 | 2012-11-14 | Lucite Int Uk Ltd | A process for production of a silica-supported alkali metal catalyst |
JP6068907B2 (ja) * | 2012-10-01 | 2017-01-25 | 株式会社 東北テクノアーチ | ケイ素およびアルカリ金属ケイ酸塩の製造方法 |
WO2014152779A1 (en) * | 2013-03-15 | 2014-09-25 | Signa Chemistry, Inc. | Treatment of alkali silica gel and alkali porous metal oxide compositions |
WO2015143080A1 (en) | 2014-03-19 | 2015-09-24 | Intelligent Energy Limited | Flexible fuel cell power system |
JP6980533B2 (ja) * | 2015-02-19 | 2021-12-15 | キャンデサント・バイオメディカル・インコーポレイテッドCandesant Biomedical, Inc. | 熱を発生させるための医療用デバイスおよびこれを用いた治療方法 |
WO2016187326A1 (en) * | 2015-05-18 | 2016-11-24 | The Johns Hopkins University | Thermoelectric polymer composites |
CN105776235A (zh) * | 2016-01-29 | 2016-07-20 | 卓达新材料科技集团有限公司 | 一种利用普通循环流化床粉煤灰制备水玻璃的方法 |
US11034712B2 (en) | 2017-02-28 | 2021-06-15 | Kyushu University, National University Corporation | Method for producing transition metal-isocyanide complex |
RU2678995C2 (ru) * | 2017-06-22 | 2019-02-05 | Общество с ограниченной ответственностью "Химмотолог" | Способ дезодорации углеводородов нефти |
CN108249862B (zh) * | 2018-02-07 | 2020-09-15 | 河南城建学院 | 一种高硬度建筑材料及制备方法 |
FR3096981B1 (fr) * | 2019-06-05 | 2023-02-24 | Sunergy | Composition à base de poudre de silicium pour la production d’hydrogène |
CN112076696A (zh) * | 2020-09-11 | 2020-12-15 | 吉化集团油脂化工有限公司 | 一种聚羧酸减水剂大单体原料起始剂的制备系统及制备方法 |
Family Cites Families (90)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1665264A (en) * | 1923-08-10 | 1928-04-10 | Harry N Holmes | Silica gels and process of making the same |
US1655264A (en) | 1926-02-04 | 1928-01-03 | Clarence E Barrett | Fountain-pen container |
US1939647A (en) * | 1930-07-23 | 1933-12-19 | Du Pont | Method of impregnating porous materials |
US2378290A (en) * | 1941-03-14 | 1945-06-12 | Soceny Vacuum Oil Company Inc | Process of preparing oxide gels |
US2337419A (en) * | 1942-01-06 | 1943-12-21 | Texas Co | Catalytic conversion of hydrocarbons |
US2731326A (en) * | 1951-08-31 | 1956-01-17 | Du Pont | Process of preparing dense amorphous silica aggregates and product |
US2740820A (en) * | 1952-02-29 | 1956-04-03 | Exxon Research Engineering Co | Olefin isomerization process |
US2765242A (en) * | 1952-02-29 | 1956-10-02 | Du Pont | Process of making reinforced silica gel and esterified silica gel |
US2816917A (en) * | 1953-01-26 | 1957-12-17 | Nat Distillers Chem Corp | Selective process for dimerization of unsaturated hydrocarbons |
US2887472A (en) * | 1954-09-30 | 1959-05-19 | Standard Oil Co | Production of solid polyethylene by a catalyst consisting essentially of an alkali metal and an adsorbent alumina-containing material |
US3033801A (en) * | 1958-02-06 | 1962-05-08 | Degussa | Process of forming solid cakes and pellets from metal oxide aerogels |
US3033800A (en) * | 1959-04-10 | 1962-05-08 | Gulf Research Development Co | Impregnation of porous solids |
US3016409A (en) * | 1959-04-27 | 1962-01-09 | Universal Oil Prod Co | Preparation of 1-alkyl-1-cyclohexenes |
US3079234A (en) * | 1959-10-23 | 1963-02-26 | Socony Mobil Oil Co Inc | Process for preparing siliceous aerogels |
US3165379A (en) * | 1962-03-14 | 1965-01-12 | Socony Mobil Oil Co Inc | Preparation of siliceous aerogels |
US3290790A (en) * | 1963-04-02 | 1966-12-13 | Mizusawa Industrial Chem | Method of drying a hydrogel |
US3405196A (en) * | 1964-03-24 | 1968-10-08 | Standard Oil Co | Isomerization of terminal olefins |
US3322495A (en) * | 1964-04-30 | 1967-05-30 | Grace W R & Co | Process for preparing alumina having a narrow pore size distribution |
US3274277A (en) * | 1964-09-28 | 1966-09-20 | Universal Oil Prod Co | Preparation of diphenyl |
US3575885A (en) * | 1965-03-01 | 1971-04-20 | Exxon Research Engineering Co | Supported cuprous halide absorbents and methods for their preparation |
US3527563A (en) * | 1965-04-19 | 1970-09-08 | Dunbar L Shanklin | Process for preparing silica gel granules |
US3347944A (en) | 1965-10-01 | 1967-10-17 | Union Carbide Corp | Production of alkylidenebicycloheptenes |
FR1473239A (zh) * | 1966-01-31 | 1967-05-29 | ||
US3489516A (en) * | 1966-10-19 | 1970-01-13 | Owens Illinois Inc | Art of making silica particles |
US3493641A (en) * | 1967-03-23 | 1970-02-03 | Grubernes Spraengstoffabriker | Method for extrusion of plastic tubes for subsequent forming by blowing or vacuum |
US3507810A (en) * | 1967-05-18 | 1970-04-21 | American Cyanamid Co | Catalyst for oxidation of naphthalene to phthalic acid anhydride |
US3535262A (en) * | 1967-07-05 | 1970-10-20 | Us Army | Gas generation carrier |
US3658724A (en) * | 1967-08-01 | 1972-04-25 | Du Pont | Adsorbent oxidation catalyst |
US3577473A (en) * | 1967-10-25 | 1971-05-04 | Sumitomo Chemical Co | Method for producing 5-isopropylidene-2-norbornene |
US3576891A (en) * | 1967-11-06 | 1971-04-27 | Atlantic Richfield Co | Removal of esters and acids from tertiary-butyl alcohol solutions |
US3670033A (en) * | 1968-05-02 | 1972-06-13 | Asahikasei Kogyo Kk | Process for the preparation of 2,6-dialkylphenols |
US3801705A (en) * | 1968-10-11 | 1974-04-02 | Nat Petro Chem | Preparation of silica gels |
US3656724A (en) | 1970-06-05 | 1972-04-18 | William Greenhalgh | Pakahome |
US3897509A (en) * | 1970-07-02 | 1975-07-29 | Sumitomo Chemical Co | Preparation of alkylidene bicyclic compounds |
FR2098137A5 (zh) * | 1970-07-02 | 1972-03-03 | Sumitomo Chemical Co | |
US3679605A (en) * | 1970-07-17 | 1972-07-25 | Sinclair Research Inc | Extruded alumina catalyst support and the preparation thereof |
IL37367A (en) * | 1970-07-23 | 1975-02-10 | Sumitomo Chemical Co | Isomerization of olefins |
JPS5035075B1 (zh) * | 1970-12-22 | 1975-11-13 | ||
US3794712A (en) * | 1971-10-26 | 1974-02-26 | Nat Petro Chem | Preparation of silica gels |
US3906026A (en) * | 1972-05-16 | 1975-09-16 | Sumitomo Chemical Co | Process for preparing alkyl trans-chrysanthemate |
JPS5612626B2 (zh) * | 1973-03-01 | 1981-03-23 | ||
US3878289A (en) * | 1972-08-24 | 1975-04-15 | Parsons Co Ralph M | Process for the removal of hydrogen cyanide from gas streams |
US3915995A (en) * | 1972-11-03 | 1975-10-28 | Eastman Kodak Co | Production of 2,2-disubstituted propiolactones |
US3926485A (en) | 1973-04-30 | 1975-12-16 | Frost & Son C L | Bearing housing assembly |
JPS5648494B2 (zh) * | 1974-07-02 | 1981-11-16 | ||
US4168247A (en) * | 1976-05-28 | 1979-09-18 | Imperial Chemical Industries Limited | Catalysts for the production of alkylene oxides |
US4087477A (en) * | 1976-11-29 | 1978-05-02 | The Goodyear Tire & Rubber Company | Method of reducing the α-acetylene content of hydrocarbon |
JPS53121753A (en) * | 1977-03-31 | 1978-10-24 | Japan Synthetic Rubber Co Ltd | Preparation of 5-alkylidenenorbornene |
US4229610A (en) * | 1978-11-03 | 1980-10-21 | Phillips Petroleum Company | Olefin double bond isomerization |
US4248741A (en) * | 1979-05-29 | 1981-02-03 | The Dow Chemical Company | Method of making catalysts for the production of ethylene oxide |
US4353815A (en) * | 1979-06-08 | 1982-10-12 | Uop Inc. | Hydrocarbon dehydrogenation with an attenuated superactive multimetallic catalytic composite for use therein |
US4446251A (en) * | 1980-02-15 | 1984-05-01 | Union Carbide Corporation | Process for producing two-carbon atom oxygenated compounds from synthesis gas with minimal production of methane |
US4471075A (en) * | 1979-06-28 | 1984-09-11 | Union Carbide Corporation | Process for producing two-carbon atom oxygenated compounds from synthesis gas with minimal production of methane |
US4366091A (en) * | 1979-08-20 | 1982-12-28 | Uop Inc. | Hydrocarbon dehydrogenation with an attenuated superactive multimetallic catalytic composite for use therein |
US4276279A (en) * | 1980-02-08 | 1981-06-30 | The United States Of America As Represented By The United States Department Of Energy | Thermochemical generation of hydrogen and oxygen from water |
US4313925A (en) * | 1980-04-24 | 1982-02-02 | The United States Of America As Represented By The United States Department Of Energy | Thermochemical cyclic system for decomposing H2 O and/or CO2 by means of cerium-titanium-sodium-oxygen compounds |
US4394302A (en) * | 1981-10-26 | 1983-07-19 | Union Oil Company Of California | Hydrodesulfurization catalyst on lithium-containing support and method for its preparation |
US4435606A (en) * | 1981-12-24 | 1984-03-06 | Conoco Inc. | Process for the preparation of linear olefins from triethylaluminum and tripropylaluminum via growth, isomerization and metathesis |
US4413156A (en) * | 1982-04-26 | 1983-11-01 | Texaco Inc. | Manufacture of synthetic lubricant additives from low molecular weight olefins using boron trifluoride catalysts |
JPS58219293A (ja) * | 1982-06-15 | 1983-12-20 | Chiyoda Chem Eng & Constr Co Ltd | 重質油の水素化分解方法 |
EP0190352B1 (en) * | 1984-05-28 | 1989-10-11 | Mitsui Petrochemical Industries, Ltd. | Alkali metal-carrying substance, and its use as catalyst |
US4508930A (en) * | 1984-07-20 | 1985-04-02 | The Goodyear Tire & Rubber Company | Process for the conversion of terpenes to limonene |
US4633029A (en) * | 1985-02-07 | 1986-12-30 | Phillips Petroleum Company | Apparatus and method for use in thermoelectric power generation |
DE3669668D1 (de) * | 1985-07-31 | 1990-04-26 | Ici Plc | Verfahren zur aktivierung der katalysatoren zur herstellung von alkylenoxiden. |
DE3675327D1 (de) * | 1985-10-21 | 1990-12-06 | Sumitomo Chemical Co | Verfahren zur herstellung von 5-aethyliden-2-norbornen. |
MX169136B (es) * | 1985-12-20 | 1993-06-23 | Sumitomo Chemical Co | Procedimiento para preparar 5-etiliden-2-norborneno de alta calidad |
JPS62207712A (ja) * | 1986-03-05 | 1987-09-12 | Fuji Debuison Kagaku Kk | ビ−ルの安定化処理用含水シリカゲル |
EP0254228A1 (en) * | 1986-07-22 | 1988-01-27 | Idemitsu Petrochemical Co. Ltd. | Process for producing alkylphenols |
US5243119A (en) * | 1988-12-12 | 1993-09-07 | Ethyl Corporation | Alkene dimerization |
US4982044A (en) * | 1989-06-30 | 1991-01-01 | Ethyl Corporation | Alkene coupling |
FR2650825B1 (fr) * | 1989-08-11 | 1991-12-06 | Isochem Sa | Nouvelle pyranone, procede pour sa preparation, son application a la preparation d'une nouvelle pyridinone et son procede de preparation |
US5008480A (en) * | 1990-02-26 | 1991-04-16 | Shell Oil Company | Process for converting toluene and butadiene to styrene and 1-pentene |
US5128291A (en) * | 1990-12-11 | 1992-07-07 | Wax Michael J | Porous titania or zirconia spheres |
CA2103063A1 (en) * | 1991-05-14 | 1992-11-15 | Robert Scott Smith | Isomerization of alkenyl bridged ring compounds to alkylidene bridged ring compounds |
US5292985A (en) * | 1991-05-14 | 1994-03-08 | Exxon Chemical Patents, Inc. | Multi-stage olefin isomerization |
JP2858952B2 (ja) * | 1993-04-09 | 1999-02-17 | エクソン・ケミカル・パテンツ・インク | 多段式のオレフィンの異性化 |
DE19535402A1 (de) * | 1995-09-23 | 1997-03-27 | Basf Ag | Palladium-haltiger Trägerkatalysator zur selektiven katalytischen Hydrierung von Acetylen in Kohlenwasserstoffströmen |
US6022823A (en) * | 1995-11-07 | 2000-02-08 | Millennium Petrochemicals, Inc. | Process for the production of supported palladium-gold catalysts |
WO1998029371A1 (fr) * | 1996-12-25 | 1998-07-09 | Sumitomo Chemical Company, Limited | Procedes de production d'hydrocarbures aromatiques a substitution alcenyle |
JP4063421B2 (ja) * | 1997-09-30 | 2008-03-19 | Agcエスアイテック株式会社 | シリカ−金属酸化物微粒子複合体およびそれに使用するシリカ凝集体粒子の製造方法 |
JP2002530361A (ja) * | 1998-11-25 | 2002-09-17 | インペリアル・ケミカル・インダストリーズ・ピーエルシー | アルドール縮合 |
US6096934A (en) * | 1998-12-09 | 2000-08-01 | Uop Llc | Oxidative coupling of methane with carbon conservation |
DE19911757A1 (de) * | 1999-03-16 | 2000-09-21 | Amann & Soehne | Nähgarn sowie Verfahren zur Herstellung eines Nähgarnes |
US6492014B1 (en) * | 1999-04-01 | 2002-12-10 | The United States Of America As Represented By The Secretary Of The Navy | Mesoporous composite gels an aerogels |
AU1785901A (en) | 1999-12-08 | 2001-06-18 | Dow Global Technologies Inc, The | A process for hydrogenating unsaturated polymers |
GB0011858D0 (en) * | 2000-05-18 | 2000-07-05 | Ici Plc | Aldol condensation reaction and catalyst therefor |
JP3905327B2 (ja) * | 2000-06-08 | 2007-04-18 | 高砂香料工業株式会社 | 2−ビニルシクロドデカノンの製造方法 |
US6638493B2 (en) | 2000-07-20 | 2003-10-28 | Erling Reidar Andersen | Method for producing hydrogen |
US6399528B1 (en) * | 2000-09-01 | 2002-06-04 | Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. | Porous aluminum oxide structures and processes for their production |
GB0130907D0 (en) * | 2001-12-22 | 2002-02-13 | Ineos Silicas Ltd | Amorphous silica |
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