CN112591708A - Method for preparing hydrogen from borohydride - Google Patents
Method for preparing hydrogen from borohydride Download PDFInfo
- Publication number
- CN112591708A CN112591708A CN202011423835.XA CN202011423835A CN112591708A CN 112591708 A CN112591708 A CN 112591708A CN 202011423835 A CN202011423835 A CN 202011423835A CN 112591708 A CN112591708 A CN 112591708A
- Authority
- CN
- China
- Prior art keywords
- borohydride
- reaction
- hydrogen
- solvent
- conversion rate
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000001257 hydrogen Substances 0.000 title claims abstract description 73
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 156
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 229920005862 polyol Polymers 0.000 claims description 13
- 150000003077 polyols Chemical class 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 8
- -1 hydroxyl compound Chemical class 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- NDEIPVVSKGHSTL-UHFFFAOYSA-N butane-1,1,1,2-tetrol Chemical compound CCC(O)C(O)(O)O NDEIPVVSKGHSTL-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- ICJBPZBRDLONIF-UHFFFAOYSA-N hexane-1,1,1,2,2,3-hexol Chemical compound CCCC(O)C(O)(O)C(O)(O)O ICJBPZBRDLONIF-UHFFFAOYSA-N 0.000 claims description 3
- 150000002972 pentoses Chemical class 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- 150000002402 hexoses Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 150000003641 trioses Chemical class 0.000 claims description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims 2
- 150000003538 tetroses Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 13
- 238000002360 preparation method Methods 0.000 abstract description 13
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract 1
- 239000012279 sodium borohydride Substances 0.000 description 47
- 229910000033 sodium borohydride Inorganic materials 0.000 description 47
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 26
- 239000007789 gas Substances 0.000 description 22
- 239000004386 Erythritol Substances 0.000 description 20
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 20
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 20
- 235000019414 erythritol Nutrition 0.000 description 20
- 229940009714 erythritol Drugs 0.000 description 20
- 239000000376 reactant Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 239000000811 xylitol Substances 0.000 description 4
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 4
- 235000010447 xylitol Nutrition 0.000 description 4
- 229960002675 xylitol Drugs 0.000 description 4
- 238000006136 alcoholysis reaction Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MHIBEGOZTWERHF-UHFFFAOYSA-N heptane-1,1-diol Chemical compound CCCCCCC(O)O MHIBEGOZTWERHF-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 2
- 229930195725 Mannitol Natural products 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000594 mannitol Substances 0.000 description 2
- 235000010355 mannitol Nutrition 0.000 description 2
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- FVGBHSIHHXTYTH-UHFFFAOYSA-N pentane-1,1,1-triol Chemical compound CCCCC(O)(O)O FVGBHSIHHXTYTH-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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
-
- 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)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供了一种硼氢化物制取氢气的方法，该方法采用硼氢化物和多羟基化合物为原料进行制备，首先将硼氢化物、多羟基化合物和溶剂进行混合，然后将该混合物加热进行反应，进行氢气的制备和收集。本发明所述的硼氢化物制取氢气的方法简单，操作方便，可在较低的温度下较完全地进行反应，由于制备过程中不采用催化剂，避免了金属粉末催化剂不易回收、反应装置复杂、价格昂贵和污染环境的缺点，同时使制备成本更低廉，制备过程更绿色环保，且该制备方法具有较高的反应速率和硼氢化物转化率，也为便捷式一次性供氢技术开拓了新思路。The invention provides a method for preparing hydrogen from borohydride. The method adopts borohydride and polyhydroxy compound as raw materials for preparation, firstly mixing borohydride, polyhydroxy compound and solvent, and then heating the mixture to carry out The reaction is carried out for the preparation and collection of hydrogen. The method for producing hydrogen from borohydride is simple, easy to operate, and can be more completely reacted at a lower temperature. Since no catalyst is used in the preparation process, the metal powder catalyst is not easily recovered and the reaction device is complicated. , the disadvantages of high price and environmental pollution, at the same time, the preparation cost is lower, the preparation process is more green and environmentally friendly, and the preparation method has a higher reaction rate and borohydride conversion rate, and also opens up a convenient one-time hydrogen supply technology. new ideas.
Description
Technical Field
The invention relates to the field of hydrogen energy, in particular to a method for preparing hydrogen from borohydride.
Background
The hydrogen fuel cell is a device for directly converting energy released by the reaction of hydrogen and oxygen into electric energy, and has wide application prospect. Hydrogen storage is a key technology for hydrogen fuel cell applications. In the process of utilizing hydrogen energy, various hydrogen storage materials and hydrogen storage methods have been developed to solve the problem of hydrogen storage. Among them, borohydride has received much attention and research because of its advantages such as high hydrogen content, stable property, easy storage, etc., and is a disposable hydrogen supply technology with great application prospects.
Methods for generating hydrogen using borohydride include pyrolysis, hydrolysis, alcoholysis, and the like. For example, sodium borohydride can be reacted with water to produce hydrogen gas, and can also be reacted with an aqueous solution of methanol to produce hydrogen gas. However, these methods have low hydrogen production rate and low reaction conversion rate, and mainly because the alkalinity of the reaction system is continuously increased during the reaction process, and further the reaction is inhibited from proceeding, so that the reaction rate is continuously reduced, and the reaction is not completely performed, so that a catalyst is required to promote the reaction, and the commonly used catalyst includes transition metals such as Co, Ni, and Pt, but the use of a metal catalyst is difficult to recycle, the reaction apparatus is complicated, the price is high, and the environment is polluted.
Therefore, how to reduce the enhancement of the alkalinity of the reaction system in the reaction process, reduce or avoid the use of catalysts, reduce the preparation cost, reduce the environmental pollution, simplify the reaction device, improve the conversion rate of reactants and promote the reaction becomes a problem to be solved urgently at present.
Disclosure of Invention
Based on the above technical background, the present inventors have made a keen search and, as a result, have found that: the method for preparing hydrogen is simple and convenient to operate, avoids the defects of difficult recovery of the catalyst, complex reaction device, high price, environmental pollution and the like because no catalyst is adopted in the preparation process, simultaneously has lower preparation cost and more environment-friendly preparation process, has higher reaction rate and borohydride conversion rate, and develops a new idea for a portable one-time hydrogen supply technology.
The invention provides a method for preparing hydrogen from borohydride, which comprises the following steps:
step 1, mixing borohydride, hydroxyl compound and solvent;
and 3, collecting hydrogen.
The method for preparing hydrogen from borohydride provided by the invention has the following advantages:
(1) the method for preparing hydrogen from borohydride is simple and convenient to operate;
(2) the method for preparing hydrogen from borohydride has the advantages that the polyhydroxy compound adopted by the method is low in price and environment-friendly;
(3) the method for preparing hydrogen from borohydride does not need any catalyst, thereby avoiding the problems of environmental pollution and the like caused by using a transition metal catalyst in the traditional method;
(4) the method for preparing hydrogen from borohydride can realize high borohydride conversion rate and high hydrogen preparation rate;
(5) the method for preparing hydrogen from borohydride has simple reaction device and important application in a portable one-time hydrogen supply technology.
Drawings
FIG. 1 shows the kinetics of the reaction of sodium borohydride with an aqueous solution of a polyol according to the invention in example 1 and examples 7-9 (first 15 minutes);
FIG. 2 shows the kinetics of the reaction of sodium borohydride with an aqueous solution of a polyol in example 1 and examples 7-9 of the present invention (100 minutes for full reaction);
FIG. 3 shows the kinetics of the reaction of sodium borohydride with aqueous ethylene glycol and glycerol solutions in examples 10 and 11 according to the invention;
FIG. 4 shows the kinetic curve of the reaction of sodium borohydride with aqueous methanol in comparative example 1 according to the invention;
FIG. 5 shows an infrared spectrum of a non-gaseous product in example 1 of the present invention.
Detailed Description
The present invention will be described in detail below, and features and advantages of the present invention will become more apparent and apparent with reference to the following description.
In the prior art, water and borohydride are usually used for reacting to prepare hydrogen, but the hydrolysis of borohydride or the alcoholysis of borohydride in a methanol water solution is used for preparing hydrogen, so that the alkalinity in a reaction system is continuously enhanced, the reaction is further inhibited, the reaction rate is continuously reduced, even the reaction is nearly stopped, and the conversion rate of borohydride is reduced.
The invention provides a method for preparing hydrogen from borohydride, which takes borohydride and hydroxyl compounds as raw materials and concretely comprises the following steps:
step 1, mixing borohydride, hydroxyl compound and solvent;
and 3, collecting hydrogen.
This step is specifically described and illustrated below.
Step 1, mixing borohydride, hydroxyl compound and solvent.
According to the invention, the borohydride is selected from M (BH)4)x、M(B3H8)xAnd M (B)10H10)xPreferably selected from M (BH)4)xAnd M (B)3H8)xMore preferably selected from M (BH)4)xOne or more of them.
Wherein M represents an alkali metal element, an alkaline earth metal element, or an aluminum element, preferably one of the alkali metal element and the alkaline earth metal element, and more preferably one of the alkali metals. x represents a positive real number that varies with the valence of M, ensuring that the valence of the borohydride is zero.
According to a preferred embodiment of the invention, the hydroxy compound is a polyhydroxy compound.
Methanol is used as one of hydroxyl compounds, and NaB (OCH) generated in the reaction process of borohydride and methanol3)4In the method, because B-O bonding is not firm, partial methoxyl is ionized, and the alkalinity of the solution is enhanced. Therefore, the carbon atoms of the methoxyl are connected through C-C bonds to form a carbon chain with stronger rigidity, and the obtained alcoholic oxyl is difficult to be separated from the combined boron atom under the limitation of the rigidity of the carbon chain, thereby causing the results that the ionization of products is inhibited and the conversion rate of reactants is increased macroscopically. Therefore, the present invention preferably uses a polyol to react with borohydride to produce hydrogen.
In the present invention, the polyhydroxy compound is selected from one or more of ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, butanetetraol, pentaerythritol, pentanol, hexanehexol, heptanediol, polyvinyl alcohol, starch, cellulose, triose, butanesugar, pentose and hexose, preferably, the polyhydroxy compound is selected from one or more of ethylene glycol, glycerol, butanetetraol, pentaerythritol, pentanol, hexanehexol, heptanediol, polyvinyl alcohol, starch, cellulose and pentose, more preferably, the polyhydroxy compound is selected from one or more of ethylene glycol, glycerol, butanetetraol, pentaerythritol, pentanol, hexaneonol and heptanediol.
Tests show that the reaction of the polyhydroxy compound and the borohydride can realize higher borohydride conversion rate without catalysis of transition metal, the reaction is mild, and compared with the reaction of the borohydride and water and methanol, the reaction has higher hydrogen production rate and reaction conversion rate. Research finds that in the reaction process of borohydride and polyhydroxy compound, the direct reaction rate of borohydride ions and alcohol molecules is far greater than that of borohydride ions and water molecules, which is also the reason for the higher conversion rate and hydrogen production rate of the method of the invention. Meanwhile, the product generated by the reaction of the polyhydroxy compound and the borohydride is less prone to ionization, the product is less alkaline when being dissolved in water, and the reaction inhibition effect is weak, which is another important reason that the method has higher conversion rate and hydrogen production rate.
The solvent is selected from one or more of tetrahydrofuran, dimethylformamide, water, ethylenediamine, benzene and chloroform, preferably selected from one or more of tetrahydrofuran, dimethylformamide and water, and more preferably water.
The inventor finds that water is used as a solvent to achieve higher reaction rate, hydrogen production rate and borohydride conversion rate at lower reaction temperature, while other solvents are adopted to achieve higher reaction temperature and lower reaction rate and conversion rate. This is probably because water in the reaction system of the present invention not only acts as a solvent to dissolve reactants and products, and helps the reactants to diffuse and contact in the system, but also acts as an intermediate mediator of the reaction, which is more favorable for the reaction.
If the polyol is a solid, the polyol and borohydride are first mixed, preferably by grinding, and then a solvent is added to the resulting mixture.
If the polyol is a liquid, the polyol is preferably first mixed with a solvent to form a mixed solution, which is then added to the borohydride.
The mass ratio of the polyhydroxy compound to the borohydride is (0.1-20): 1, preferably (0.5-10): 1, and more preferably (0.7-7): 1.
the reaction degree of the hydrogen production reaction and the conversion rate of borohydride have a direct relation with the addition ratio of polyhydroxy compound and borohydride, if the addition amount of polyhydroxy compound is too small, the conversion rate of borohydride is reduced, and the reaction is incomplete; the conversion of borohydride increases with increasing amounts of polyol added. If the polyol is added in an excessive amount, it is wasted and the overall mass hydrogen storage density of the system is low.
The mass ratio of the solvent to the borohydride is (0.01-20): 1, preferably the mass ratio of (0.1-15): 1, and more preferably the mass ratio of (0.4-10): 1.
it has been found through experiments that when the amount of solvent added is large enough to maintain the system in a fluid state throughout the reaction (e.g., the mass ratio of solvent to borohydride is greater than or equal to 3: 1), the borohydride and the polyol can react sufficiently until one of them is almost completely converted (the conversion rate is more than 97%). If the amount of the solvent added is reduced, the system may become viscous at the latter stage of the reaction, and contact and diffusion of the reactants may be inhibited, thereby reducing the reaction rate and the conversion rate of the reactants. However, when the amount of solvent added is small (e.g., the mass ratio of solvent to borohydride is less than 1: 1), another reaction mode for rapidly producing hydrogen may be initiated at a certain temperature: the mixed solid of borohydride and polyhydroxy compound is wetted by a small amount of solvent, but the system is always in a non-flowing state, and when the temperature reaches the critical temperature, the system can generate violent hydrogen production reaction, and the borohydride conversion rate of 94 percent can be achieved within 5 seconds. The unique hydrogen production system and the hydrogen production mode enable a method for preparing hydrogen by borohydride fast and quantitatively to be obtained.
And 2, heating the mixture obtained in the step 1 for reaction.
The reaction is carried out in a container, which is preferably provided with one or more of a heating device, a temperature control device and a temperature detection device for heating the reaction or detecting the temperature change in the reaction process. After the solid reactant is added, the container is plugged with a rubber plug, and the solvent or the mixed solution is injected by using a syringe inserted on the rubber plug.
The heating mode of the invention is preferably oil bath heating or water bath heating, and more preferably water bath heating.
The reaction temperature is 20-100 ℃, preferably 25-80 ℃, and more preferably 40-60 ℃.
The reaction system can be carried out at the temperature of 20-100 ℃, but has poor reactivity at low temperature (such as room temperature), slow reaction speed and slow hydrogen preparation speed, can fully react in a long time, and achieves high conversion rate. If the reaction temperature is too high, unnecessary energy waste is caused, and simultaneously, water in the reaction system is evaporated and lost, so that the practicability and the use efficiency of the system are reduced. Therefore, the reaction temperature is more preferably 40 to 60 ℃.
And 3, collecting hydrogen.
According to the present invention, the hydrogen gas may be collected by using a drainage gas collection method, but is not limited thereto.
The specific operation method comprises the following steps: a stainless steel pipeline is used for penetrating through the rubber plug, gas generated by reaction in the container is led out, and the gas is collected by a drainage and gas collection method.
The method for preparing hydrogen from borohydride can be completely carried out without a catalyst, the reaction rate is high, the conversion rate of the borohydride in the first 15 minutes can reach more than 60%, and the conversion rate in 100 minutes is 85% -99%.
The invention has the following beneficial effects:
(1) the method for preparing hydrogen from borohydride is simple and convenient to operate, and the required instruments and devices are conventional, so that a new idea is developed for a portable one-time hydrogen supply technology;
(2) compared with a borohydride hydrogen production system catalyzed by transition metal, the method for preparing hydrogen by borohydride has the characteristics of low price and environmental friendliness, particularly, certain polyols used are biomass materials, are environment-friendly and easy to obtain, and simultaneously, the defect that the catalyst is difficult to recover is avoided;
(3) the method for preparing hydrogen from borohydride has high preparation efficiency and reaction rate;
(4) the method for preparing hydrogen from borohydride can realize high borohydride conversion rate, the borohydride conversion rate in the first 15 minutes can reach more than 60%, and the borohydride conversion rate in 100 minutes is 85% -99%.
Examples
The invention is further illustrated by the following specific examples, which are intended to be illustrative only and not limiting to the scope of the invention.
Example 1 mass ratio of sodium borohydride, erythritol and water is 1: 4: 4
100mg of sodium borohydride (NaBH)4) 400mg of erythritol (one of erythritol, molecular formula CH)2(OH)CH(OH)CH(OH)CH2(OH)), after grinding and mixing, the mixture was put into a 20mL round-bottomed flask, a rubber stopper was fitted to the flask, and 400mg of water was injected through a syringe. The flask was heated in a water bath at 50 ℃ while passing a stainless steel pipe through the rubber stopper, and the gas generated in the flask was taken out and collected by drainage and gas collection. Over 90 minutes, 240mL of gas was collected and the sodium borohydride conversion was calculated to be about 96%.
The reaction kinetics curves are shown in fig. 1 and fig. 2, and it can be seen from fig. 1 that after 5 minutes of reaction, the conversion rate of sodium borohydride can reach more than 70%, and after 15 minutes of reaction, the conversion rate can reach about 85%. As can be seen from FIG. 2, the conversion rate can reach about 95% after the reaction is carried out for 90 minutes.
Example 2 the mass ratio of sodium borohydride, xylitol and water is 1: 3.3: 0.4 Take 300mg of sodium borohydride (NaBH)4) 1000mg of xylitol (one of the pentanetriol, molecular formula CH)2(OH)CH(OH)CH(OH)CH(OH)CH2(OH)), after grinding and mixing, the mixture was put into a 50mL round-bottomed flask, a rubber stopper was fitted to the flask, and 120mg of water was poured into the flask. The flask was heated in a water bath at 50 ℃ while passing a stainless steel pipe through the rubber stopper to conduct the gas generated in the flask, and the gas was collected by drainage and gas collection. The temperature in the flask was monitored by inserting a thermocouple through the rubber stopper into the mixture in the flask. When the thermocouple shows burningWhen the temperature of the reactant in the bottle reached 46 ℃, a large amount of hydrogen gas was instantaneously discharged, and the temperature of the reactant was instantaneously raised to about 100 ℃, and 520mL of gas was collected within 5 seconds thereafter. Subsequently, after a total of 3 minutes of reaction, a total of 670mL of gas was collected and the conversion of sodium borohydride was calculated to be about 88%.
Example 3 mass ratio of sodium borohydride, erythritol and water is 1: 4: 2
The procedure of example 1 was repeated except that: the amount of water added was 200 mg. In 90 minutes, 220mL of gas was collected and the conversion of sodium borohydride was calculated to be 88%.
Example 4 mass ratio of sodium borohydride, erythritol and water is 1: 3: 4
The procedure of example 1 was repeated except that: erythritol (one of erythritol, molecular formula CH)2(OH)CH(OH)CH(OH)CH2(OH)) was added in an amount of 300 mg. Over 90 minutes, 212mL of gas was collected and the conversion of sodium borohydride was calculated to be 85%.
Example 5 mass ratio of sodium borohydride, erythritol and water is 1: 3: 2
The procedure of example 1 was repeated except that: erythritol (one of erythritol, molecular formula CH)2(OH)CH(OH)CH(OH)CH2(OH)) was added in an amount of 300mg, and water was added in an amount of 200 mg. In 90 minutes, 205mL of gas was collected and the conversion of sodium borohydride was calculated to be 82%.
Example 6 mass ratio of sodium borohydride, erythritol and water is 1: 2: 2
The procedure of example 1 was repeated except that: erythritol (one of erythritol, molecular formula CH)2(OH)CH(OH)CH(OH)CH2(OH)) was added in an amount of 200mg, and the amount of water was 200 mg. Over 90 minutes, 165mL of gas was collected and the conversion of sodium borohydride was calculated to be 66%.
Example 7 mass ratio of sodium borohydride, sorbitol and water 1: 4: 4
The procedure of example 1 was repeated except that: erythritol is replaced by sorbitol (one of the hexitols) of equal mass.
The reaction kinetics curves are shown in fig. 1 and fig. 2, and it can be seen from fig. 1 that the conversion rate of sodium borohydride reaches more than 70% after 5 minutes of reaction, the conversion rate reaches about 80% after 15 minutes of reaction, and it can be seen from fig. 2 that the conversion rate is about 90% after 90 minutes of reaction.
Example 8 mass ratio of sodium borohydride, mannitol and water is 1: 4: 4
The procedure of example 1 was repeated except that: erythritol is replaced by mannitol (one of the hexitols) of equal mass.
The reaction kinetics curves are shown in fig. 1 and fig. 2, and it can be seen from fig. 1 that the conversion rate of sodium borohydride reaches more than 65% after 5 minutes of reaction, the conversion rate reaches about 75% after 15 minutes of reaction, and it can be seen from fig. 2 that the conversion rate is about 90% after 90 minutes of reaction.
Example 9 mass ratio of sodium borohydride, xylitol and water 1: 4: 4
The procedure of example 1 was repeated except that: erythritol is replaced by xylitol (one of the pentaols) of the same mass.
The reaction kinetics curves are shown in fig. 1 and fig. 2, and it can be seen from fig. 1 that the conversion rate of sodium borohydride reaches about 65% after 5 minutes of reaction, the conversion rate reaches about 75% after 15 minutes of reaction, and it can be seen from fig. 2 that the conversion rate reaches about 90% after 90 minutes of reaction.
Example 10 mass ratio of sodium borohydride, ethylene glycol and water is 1: 4: 4
100mg of sodium borohydride was added to a 20mL round-bottomed flask, and a rubber stopper was fitted to the flask. 400mg of water and 400mg of ethylene glycol were mixed to obtain a mixed solution, which was poured into a flask, and sodium borohydride was immersed therein. Meanwhile, a stainless steel pipeline is used for penetrating through the rubber plug to lead out the gas generated in the flask. The flask was heated in a water bath at 50 ℃ and the gas was collected by draining.
The reaction kinetics curve is shown in fig. 3, and it can be seen from fig. 3 that, within five minutes from the beginning of the reaction, hydrogen is rapidly discharged, the conversion rate of sodium borohydride reaches more than 60% after the reaction is performed for about 20 minutes, the conversion rate of sodium borohydride reaches more than 80% after the reaction is performed for 70 minutes, and the conversion rate of sodium borohydride reaches about 88% after the reaction is performed for 135 minutes.
Example 11 mass ratio of sodium borohydride, glycerol and water is 1: 4: 4
The procedure of example 10 was repeated except that: the ethylene glycol was replaced by an equivalent mass of glycerol.
The reaction kinetics curve is shown in fig. 3, and it can be seen from fig. 3 that, within five minutes from the beginning of the reaction, hydrogen is rapidly discharged, the conversion rate of sodium borohydride reaches more than 60% after the reaction is performed for about 20 minutes, the conversion rate of sodium borohydride reaches more than 80% after the reaction is performed for 70 minutes, and the conversion rate of sodium borohydride reaches about 90% after the reaction is performed for 135 minutes.
Example 12 mass ratio of sodium borohydride, erythritol, and tetrahydrofuran was 1: 3.4: 10
100mg of sodium borohydride (NaBH)4) 340mg erythritol (one of erythritol, molecular formula CH)2(OH)CH(OH)CH(OH)CH2(OH)), after grinding and mixing, the mixture was put into a 20mL round-bottomed flask, a rubber stopper was fitted to the flask, and 1000mg of tetrahydrofuran was further poured. The flask was heated in a water bath at 50 ℃ while passing a stainless steel pipe through the rubber stopper to conduct the gas generated in the flask, and the gas was collected by drainage and gas collection. Over 90 minutes, 22.5mL of gas was collected and the conversion of sodium borohydride was calculated to be 9%.
Example 13 mass ratio of sodium borohydride, erythritol and dimethylformamide was 1: 3.4: 10
The procedure of example 12 was repeated except that: tetrahydrofuran was replaced with an equivalent mass of dimethylformamide. Under the condition, the reaction rate is very slow, and the conversion rate of sodium borohydride is also low. Then gradually raising the temperature of the water bath slowly, and when the temperature is heated to about 65 ℃, the reactants are completely dissolved, and the reaction rate is accelerated. The final heating was to 120 ℃ and the conversion of sodium borohydride was 74%.
Comparative example
Comparative example 1 mass ratio of sodium borohydride, methanol and water was 1: 4.2: 4
The procedure of example 10 was repeated except that: the ethylene glycol was replaced with methanol, and the amount of methanol added was 420 mg.
The reaction kinetics curve is shown in fig. 4, and it can be seen from fig. 4 that after the reaction is performed for 20 minutes, the conversion rate of sodium borohydride reaches about 30%, the hydrogen release rate starts to decrease obviously and is slower and slower, and when the reaction is performed for 147 minutes, the conversion rate of sodium borohydride is about 43%, and at this time, the reaction rate is lower than 0.07% conversion rate/minute. The results show that the alcoholysis of sodium borohydride in aqueous methanol is incomplete in the absence of a catalyst and the conversion is low.
Examples of the experiments
Experimental example 1 Infrared Spectroscopy test
After reacting well to stop the hydrogen evolution in example 1, the products other than hydrogen were collected and all were in solution. The product after the reaction was completed was left in the flask, and vacuum dehydration was performed at room temperature by connecting to a vacuum pump until a dry solid remained in the flask. The solid was mixed with anhydrous potassium bromide (mass ratio about 100:1), ground and tableted with a tablet press, and then loaded into an infrared spectrometer for testing, the test results being shown in fig. 5.
As can be seen from FIG. 5, 3430cm-1Near and 1600cm-1The vibration absorption peak of O-H is nearby, 2900cm-1～3000cm-1Is the vibration absorption peak of C-H, 1100cm-11300-1500 cm around C-O vibration absorption-1The range of the B-O telescopic vibration absorption is 1100-1500 cm-1Vibration absorption in the range is typical of borate ester structures. The assumption of the invention is proved, and the boron atom in the product generated by the butanetetraol and the sodium borohydride is mainly connected with the alkoxy in the butanetetraol to form the structure of the butanetetraol borate.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (9)
1. A method for preparing hydrogen from borohydride is characterized by comprising the following steps:
step 1, mixing borohydride, hydroxyl compound and solvent;
step 2, heating the mixture obtained in the step 1 for reaction;
and 3, collecting hydrogen.
2. The method for producing hydrogen from borohydride according to claim 1, wherein, in step 1,
the borohydride is selected from M (BH)4)x、M(B3H8)xAnd M (B)10H10)xOne or more of the above;
m represents an alkali metal element, an alkaline earth metal element or an aluminum element, and x represents a positive real number;
the hydroxyl compound is a polyhydroxy compound.
3. The method for producing hydrogen from borohydride according to claim 2, wherein, in step 1,
the polyhydroxy compound is selected from one or more of ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, butanetetraol, pentaerythritol, pentanol, hexanehexol, heptanol, polyvinyl alcohol, starch, cellulose, triose, tetrose, pentose and hexose.
4. The method for producing hydrogen from borohydride according to claim 1, wherein, in step 1,
the solvent is one or more selected from tetrahydrofuran, dimethylformamide, water, ethylenediamine, benzene and chloroform.
5. The method for producing hydrogen from borohydride according to claim 1, wherein, in step 1,
if the polyhydroxy compound is a solid, the mixing mode is that the polyhydroxy compound and the borohydride are mixed firstly and then mixed with the solvent;
if the polyol is a liquid, the polyol is mixed with a solvent to form a mixed solution, which is then mixed with borohydride.
6. The method for producing hydrogen from borohydride according to claim 1, wherein, in step 1,
the mass ratio of the polyhydroxy compound to the borohydride is (0.1-20): 1.
7. The method for producing hydrogen from borohydride according to claim 1, wherein, in step 1,
the mass ratio of the solvent to the borohydride is (0.01-20): 1.
8. the method for producing hydrogen from borohydride according to claim 1, wherein, in step 2,
the reaction temperature is 20-100 ℃.
9. The method for producing hydrogen from borohydride according to claim 1, characterized in that,
the method for preparing hydrogen from borohydride is used for 100 minutes, and the conversion rate of the borohydride is 85-99%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011423835.XA CN112591708A (en) | 2020-12-08 | 2020-12-08 | Method for preparing hydrogen from borohydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011423835.XA CN112591708A (en) | 2020-12-08 | 2020-12-08 | Method for preparing hydrogen from borohydride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112591708A true CN112591708A (en) | 2021-04-02 |
Family
ID=75188862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011423835.XA Pending CN112591708A (en) | 2020-12-08 | 2020-12-08 | Method for preparing hydrogen from borohydride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112591708A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114534288A (en) * | 2022-02-22 | 2022-05-27 | 沧州华宇特种气体科技有限公司 | Separation and solvent recovery method for salt-containing mixed solution |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050255024A1 (en) * | 2004-05-14 | 2005-11-17 | Purdue Research Foundation | Method of controlled alcoholysis and regeneration of a borohydride |
| CN1980856A (en) * | 2004-04-14 | 2007-06-13 | 千年电池公司 | Systems and methods for hydrogen generation from solid hydrides |
| WO2009086541A1 (en) * | 2007-12-27 | 2009-07-09 | Enerfuel, Inc. | Hydrogen production system using dosed chemical hydrbdes |
| CN101884129A (en) * | 2007-05-18 | 2010-11-10 | 能源燃料公司 | Hydrogen production from borohydrides and glycerol |
| CN103240099A (en) * | 2013-05-11 | 2013-08-14 | 青岛科技大学 | Catalyst for alcoholysis hydrogen production through sodium borohydride and preparation method of catalyst |
-
2020
- 2020-12-08 CN CN202011423835.XA patent/CN112591708A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1980856A (en) * | 2004-04-14 | 2007-06-13 | 千年电池公司 | Systems and methods for hydrogen generation from solid hydrides |
| US20050255024A1 (en) * | 2004-05-14 | 2005-11-17 | Purdue Research Foundation | Method of controlled alcoholysis and regeneration of a borohydride |
| CN101884129A (en) * | 2007-05-18 | 2010-11-10 | 能源燃料公司 | Hydrogen production from borohydrides and glycerol |
| WO2009086541A1 (en) * | 2007-12-27 | 2009-07-09 | Enerfuel, Inc. | Hydrogen production system using dosed chemical hydrbdes |
| CN103240099A (en) * | 2013-05-11 | 2013-08-14 | 青岛科技大学 | Catalyst for alcoholysis hydrogen production through sodium borohydride and preparation method of catalyst |
Non-Patent Citations (1)
| Title |
|---|
| LILI FENG等: "Ionization inhibition in a polyol/water system for boosting H2 generation from NaBH4", 《RSC ADVANCES》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114534288A (en) * | 2022-02-22 | 2022-05-27 | 沧州华宇特种气体科技有限公司 | Separation and solvent recovery method for salt-containing mixed solution |
| CN114534288B (en) * | 2022-02-22 | 2023-08-04 | 沧州华宇特种气体科技有限公司 | Separation and solvent recovery method of salt-containing mixed solution |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wu et al. | Characterization of products from hydrothermal carbonization of pine | |
| Wang et al. | Comparison of the pyrolysis behavior of pyrolytic lignin and milled wood lignin by using TG–FTIR analysis | |
| Ji et al. | Pretreatment of sugarcane bagasse with deep eutectic solvents affect the structure and morphology of lignin | |
| Waldner et al. | Renewable production of methane from woody biomass by catalytic hydrothermal gasification | |
| Xu et al. | Alcohol-assisted hydrodeoxygenation as a sustainable and cost-effective pathway for biomass derivatives upgrading | |
| Long et al. | Hydrothermal depolymerization of lignin: Understanding the structural evolution | |
| OUYANG et al. | Oxidative degradation of lignin for producing monophenolic compounds | |
| Li et al. | Investigation of biomass slow pyrolysis mechanisms based on the generation trends in pyrolysis products | |
| Wei et al. | Thermal behavior analysis and reaction mechanism in the preparation of activated carbon by ZnCl2 activation of bamboo fibers | |
| CN112591708A (en) | Method for preparing hydrogen from borohydride | |
| Yang et al. | Hydrogen-rich gas production from the gasification of biomass and hydrothermal carbonization (HTC) aqueous phase | |
| Peng et al. | Hydrothermal conversion of lignin and black liquor for phenolics with the aids of alkali and hydrogen donor | |
| Lu et al. | Changes in active sites and reactivity induced by interactions among Ca, Si and Al during coal char gasification | |
| Wei et al. | Exploring the continuous cleavage-oxidation mechanism of the catalytic oxidation of cellulose to formic acid: A combined experimental and theoretical study | |
| CN112194766B (en) | Treatment method of phenol-based rectifying still residue | |
| Liu et al. | Preparation of carbonyl precursors for long-chain oxygenated fuels from cellulose ethanolysis catalyzed by metal oxides | |
| CN106565945A (en) | Preparation method of perfluoropolyether alcohol | |
| CN101941958A (en) | Method for preparing 5-hydroxymethyl furfural and 2,5-furandimethanol simultaneously | |
| Gao et al. | Insights into aromatic methyl groups in the hydrothermal aqueous phase to enhance the efficiency of sludge gasification for hydrogen production | |
| Dong et al. | Role of calcium ion in moso bamboo pyrolysis under microwave irradiation | |
| CN101126029B (en) | Technique for preparing biological diesel oil by microwave catalyzing and film separating method | |
| Meng et al. | Catalytic gasification of anthracene in supercritical water with Ni/TiO2 catalyst: Products distribution and kinetics | |
| Li et al. | Pyrolysis-reforming of cellulose to simultaneously produce hydrogen and heavy organics | |
| CN110947423B (en) | A kind of catalyst and preparation method for synthesizing propylene glycol ether | |
| Song et al. | Study on the catalytic degradation of sodium lignosulfonate to aromatic aldehydes over nano-CuO: Process optimization and reaction kinetics |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210402 |