CN106744682A - 一种基于硼氢化物和生物乙醇的醇解/水解制氢方法 - Google Patents
一种基于硼氢化物和生物乙醇的醇解/水解制氢方法 Download PDFInfo
- Publication number
- CN106744682A CN106744682A CN201611142287.7A CN201611142287A CN106744682A CN 106744682 A CN106744682 A CN 106744682A CN 201611142287 A CN201611142287 A CN 201611142287A CN 106744682 A CN106744682 A CN 106744682A
- Authority
- CN
- China
- Prior art keywords
- ethanol
- bio
- hydrogen
- alcoholysis
- boron hydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 48
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000006136 alcoholysis reaction Methods 0.000 title claims abstract description 18
- 229910010277 boron hydride Inorganic materials 0.000 title claims abstract description 14
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 230000003301 hydrolyzing effect Effects 0.000 title claims description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 230000007062 hydrolysis Effects 0.000 claims abstract description 9
- 238000000746 purification Methods 0.000 claims abstract description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 15
- 239000012279 sodium borohydride Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 239000012448 Lithium borohydride Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 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 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims 1
- 229910021393 carbon nanotube Inorganic materials 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 7
- 239000002028 Biomass Substances 0.000 abstract description 3
- 238000000855 fermentation Methods 0.000 abstract description 3
- 230000004151 fermentation Effects 0.000 abstract description 3
- 230000008014 freezing Effects 0.000 abstract description 2
- 238000007710 freezing Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000035484 reaction time Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000036632 reaction speed Effects 0.000 description 3
- 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 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 238000006197 hydroboration reaction Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006140 methanolysis reaction Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- TVJORGWKNPGCDW-UHFFFAOYSA-N aminoboron Chemical compound N[B] TVJORGWKNPGCDW-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 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
- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
本发明涉及一种利用硼氢化物和生物乙醇的醇解/水解反应产生氢气的方法。本发明属于储氢和制氢技术领域。其特点是:将硼氢化物溶解于生物乙醇料液中,在催化剂的作用下,通过醇解/水解反应产生氢气。原料生物乙醇可由生物质通过发酵技术制备,属于可再生资源,环境友好。生物乙醇料液(乙醇浓度为5~15vol%)无需提纯,可直接使用。生物乙醇料液冰点在0℃以下,反应具备较宽的温度适应范围。反应产物无害,通过水解反应和分离后可回收乙醇。本发明方法工艺简单、环境友好、适用温度范围广,在便携式制氢领域应用前景广阔。
Description
技术领域
本发明涉及储氢和制氢技术,具体为一种利用硼氢化物和生物乙醇通过醇解/水解反应产生氢气的方法。
背景技术
氢能是一种清洁的二次能源,发展高效储氢/制氢技术是推动氢能规模化商业应用的关键环节。与高压储氢和低温液氢相比,材料基固态储氢在操作安全性、能源效率及理论储氢密度方面具有显著优势,被公认为最具发展前景的储氢方式。其中,化学氢化物在储氢容量上具有其他材料无法比拟的优势,在完成放氢后可通过集中式化工过程完成再生,实现可逆储氢。
化学氢化物包括碱金属、碱土金属氢化物及其硼氢化物和氨基硼烷等,其中硼氢化钠(NaBH4)最具代表性。硼氢化钠水解制氢技术是一种安全、方便的新型氢气制备技术,与其它制氢储氢技术相比具有环境友好、储氢量高、储存运输安全、使用方便的优点。然而,NaBH4水解制氢在低温环境下是无法应用的。
为满足在低温寒冷条件下制氢的需要,可利用硼氢化钠与甲醇的醇解反应代替水解反应产生氢气(如式1所示)。
NaBH4+4CH3OH→NaB(OCH3)4+4H2 (1)
虽然硼氢化钠与甲醇的醇解反应为低温制氢提供了一种可行的途径,但仍存在以下问题:(1)工业甲醇多来源于化石能源,利用甲醇醇解制氢并不是一种清洁的生产方式;(2)甲醇具有较强的毒性;(3)硼氢化钠与甲醇的醇解反应速率过快,其非催化反应速率超过催化水解反应速率,不利于根据实际氢需求控制反应的进行。
发明内容
针对硼氢化钠甲醇醇解制氢的不足,本发明的目的是利用生物乙醇料液与硼氢化物反应来产生氢气。生物乙醇是指通过微生物的发酵将各种生物质转化获得的乙醇,是一种可再生资源。
为实现上述目的,本发明采用以下技术方案:
本发明利用硼氢化物和生物乙醇的醇解/水解制氢,其特征在于将硼氢化物溶解于生物乙醇料液中,在催化剂的作用下,通过醇解/水解反应产生氢气。
本发明所述的硼氢化物包括硼氢化钠(NaBH4)、硼氢化钾(KBH4)、硼氢化锂(LiBH4)以及它们的组合。
本发明所述的生物乙醇料液(乙醇浓度为5~15vol%)无需提纯,可直接与硼氢化物反应产生氢气。
本发明所述的醇解反应产物无害且能通过水解反应转化为乙醇,经分离后可回收使用。
本发明所述的催化剂为负载型催化剂,活性组分为Pt、Ru、Ni、Fe、Co、Mn其中任意一种金属或两种金属的组合,载体为Al2O3、SiO2、离子交换树脂、活性炭、碳纳米管其中任意一种。
本发明的优点和积极效果是:
(1)原料生物乙醇由生物质通过发酵技术制备,属于可再生资源,环境友好。
(2)生物乙醇料液冰点在0℃以下,反应具备较宽的温度适应范围。
(3)可使用多种催化剂,满足不同反应体系可控制氢的需要。
(4)反应产物无害,通过水解反应可重新转化为乙醇,经过分离后可回收利用。
附图说明
图1为本发明实施例1反应生成氢气体积随反应时间变化情况。
图2为本发明实施例2反应生成氢气体积随反应时间变化情况。
图3为本发明实施例3反应生成氢气体积随反应时间变化情况。
图4为本发明实施例4反应生成氢气体积随反应时间变化情况。
具体实施方式
下面结合附图和具体实施方式对本发明的技术方案作进一步详细的说明,本发明并不限于这些实施例。
实施例1
将加有5ml乙醇水溶液(乙醇含量15vol%)的烧瓶置于温度为60℃的水浴中平衡,向烧瓶中加入0.1g固体硼氢化钠和0.01g催化剂,使混合均匀,产生的气体经水洗后利用排气法计量。该实施例中所用催化剂如下:
体系1:20wt%Co/SiO2;
体系2:12wt%Co/Al2O3;
体系3:0.5wt%Pt/Al2O3;
体系4:0.5wt%Pt/SiO2;
体系5:3wt%Pt/717阴离子交换树脂;
此条件下硼氢化钠催化醇解/水解制氢体积-时间关系如图1。
实施例2
同实施例1的操作,使用3wt%Pt/717阴离子交换树脂作为催化剂,恒温水浴温度分别设定为0℃、20℃、60℃。此条件下硼氢化钠催化醇解/水解制氢体积-时间关系如图2。
实施例3
同实施例2的操作,温水浴温度为60℃,乙醇水溶液的乙醇浓度分别为5vol%、10vol%、15vol%。此条件下的硼氢化钠催化醇解/水解制氢产量-时间关系如图3。
实施例4
除所述硼氢化物为硼氢化钾和催化剂为20wt%Co/SiO2外,其余操作同实施例1。此条件下硼氢化钾催化醇解/水解制氢产量-时间关系如图4。
Claims (5)
1.一种基于硼氢化物和生物乙醇的醇解/水解制氢方法,所述方法包括将硼氢化物溶解于生物乙醇料液中,在催化剂的作用下,通过醇解/水解反应产生氢气。
2.根据权利要求1所述的方法,其中所述的硼氢化物包括硼氢化钠(NaBH4)、硼氢化钾(KBH4)、硼氢化锂(LiBH4)以及它们的组合。
3.根据权利要求1所述的方法,生物乙醇料液(乙醇浓度为5~15vol%)无需提纯,可直接与硼氢化物反应产生氢气。
4.根据权利要求1所述的方法,醇解反应产物无害且能通过水解反应转化为乙醇,经分离后可回收使用。
5.根据权利要求1所述的方法,所述催化剂为负载型催化剂,活性组分为Pt、Ru、Ni、Fe、Co、Mn其中任意一种金属或两种金属的组合,载体为Al2O3、SiO2、离子交换树脂、活性炭、碳纳米管其中任意一种。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611142287.7A CN106744682A (zh) | 2016-12-13 | 2016-12-13 | 一种基于硼氢化物和生物乙醇的醇解/水解制氢方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611142287.7A CN106744682A (zh) | 2016-12-13 | 2016-12-13 | 一种基于硼氢化物和生物乙醇的醇解/水解制氢方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN106744682A true CN106744682A (zh) | 2017-05-31 |
Family
ID=58876008
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201611142287.7A Pending CN106744682A (zh) | 2016-12-13 | 2016-12-13 | 一种基于硼氢化物和生物乙醇的醇解/水解制氢方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106744682A (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107335428A (zh) * | 2017-06-26 | 2017-11-10 | 俞秀英 | 一种制氢催化剂及其制备方法和用途 |
CN108479820A (zh) * | 2018-01-24 | 2018-09-04 | 北京化工大学 | 一种硼氢化钠醇解制氢用块状载体纳米型合金催化剂及其制备方法 |
-
2016
- 2016-12-13 CN CN201611142287.7A patent/CN106744682A/zh active Pending
Non-Patent Citations (3)
Title |
---|
昌晶等: "二氧化钛载钴基催化剂对乙醇废液的催化制氢研究", 《工业安全与环保》 * |
昌晶等: "凹凸棒石载Co-Cd-B催化剂对乙醇废液的催化制氢研究", 《青岛农业大学学报(自然科学版)》 * |
晶昌: "多组多钴基催化剂催化硼氢化钠制氢技术的研究", 《中国博士学位论文全文数据库(工程科技II辑)》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107335428A (zh) * | 2017-06-26 | 2017-11-10 | 俞秀英 | 一种制氢催化剂及其制备方法和用途 |
CN108479820A (zh) * | 2018-01-24 | 2018-09-04 | 北京化工大学 | 一种硼氢化钠醇解制氢用块状载体纳米型合金催化剂及其制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Demirci et al. | Sodium borohydride versus ammonia borane, in hydrogen storage and direct fuel cell applications | |
CN104129755B (zh) | 采用固体硼氢化钠和结晶水合物反应缓释氢气的方法 | |
CN107601431A (zh) | 一种制氢机排气及泄压系统及其控制方法 | |
Filiz et al. | Boron-based hydrogen storage materials towards Power-to-X technology on the path to carbon neutrality | |
CN106744682A (zh) | 一种基于硼氢化物和生物乙醇的醇解/水解制氢方法 | |
CN207435019U (zh) | 一种制氢机排气及泄压系统 | |
CN103121663A (zh) | 氢气产生设备 | |
CN102060265A (zh) | 燃料电池的NaBH4水解制氢生产工艺及其设备 | |
CN101786603A (zh) | 一种水解制氢装置 | |
CN1245329C (zh) | 含氢无机化合物水溶液制氢催化剂及制氢方法 | |
CN101823692A (zh) | 以哌啶为介质的可逆吸放氢方法及装置 | |
CN101456535B (zh) | 一种氢气的制备方法 | |
CN201154897Y (zh) | 一种简易型便携式氢气发生器 | |
Keskin et al. | Recommendations for ammonia borane composite pellets as a hydrogen storage medium | |
TWI405717B (zh) | 以海水摻合硼氫化合物產製氫氣的方法 | |
CN103240099B (zh) | 一种硼氢化钠醇解制氢催化剂及其制备方法 | |
CN100564245C (zh) | 硼氢化钠-肼混合燃料制备氢气的方法 | |
CN104056638A (zh) | 一种硼氢化钠溶液水解制氢催化剂及其制备方法 | |
CN103552982B (zh) | 一种硼氢化钠水解/醇解制氢反应器 | |
Gotovsky et al. | Formate cycle: The third way in green energy | |
CN112429702B (zh) | 一种连续制氢系统及固体燃料 | |
CN106495093B (zh) | 一种高性能硼氢化锂-氢化镁可逆制氢体系及制氢方法 | |
CN111874865B (zh) | 一种无金属参与的催化产氢的方法 | |
CN103303864A (zh) | 硼氢化物水解制备氢气的方法、装置及应用 | |
CN102806087B (zh) | 一种Ni-La-B催化剂及其制备方法和在硼氢化物醇解制氢中的应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170531 |