CN105688982A - Bioactive catalyst enabling alcohol-water system to produce hydrogen through reforming - Google Patents

Bioactive catalyst enabling alcohol-water system to produce hydrogen through reforming Download PDF

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CN105688982A
CN105688982A CN201610026449.4A CN201610026449A CN105688982A CN 105688982 A CN105688982 A CN 105688982A CN 201610026449 A CN201610026449 A CN 201610026449A CN 105688982 A CN105688982 A CN 105688982A
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alcohol
extract
hydrogen
branch
water
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CN105688982B (en
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黄翔
黄丽莎
覃林
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Sanjou International New Energy Technology Co., Ltd
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Guangxi Sanjiu New Energy Technology Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/19Catalysts containing parts with different compositions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/003Catalysts comprising hydrides, coordination complexes or organic compounds containing enzymes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • C01B3/323Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C01B3/326Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041Composition of the catalyst
    • C01B2203/1088Non-supported catalysts
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205Composition of the feed
    • C01B2203/1211Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1217Alcohols
    • C01B2203/1223Methanol
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205Composition of the feed
    • C01B2203/1211Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1217Alcohols
    • C01B2203/1229Ethanol

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Abstract

The invention discloses a bioactive catalyst enabling an alcohol-water system to produce hydrogen through reforming. The bioactive catalyst is prepared from a mulberry branch extract, an apricot tree branch extract and a juncus effuses extract, the bioactive catalyst is placed in a gas generator, and a reforming reaction is conducted to generate high-purity hydrogen-rich gas to drive an engine to work; the bioactive catalyst can be applied to a vehicle-mounted device, or a generator device or a hydrogen-rich gas station device. The bioactive catalyst is made of the plant extracts, the raw materials are rich in source, and the extraction process is simple; by using the bioactive catalyst, the hydrogen purity is improved and closer to the theoretical value, the alcohol consumption is reduced substantially, and the hydrogen production method through reforming is an advanced hydrogen production method high in applicability.

Description

A kind of biological activity catalyst making alcohol water system reformation hydrogen production
Technical field
The present invention relates to the regenerative resource research and development technology field of environmental protection, be specially a kind of biological activity catalyst making alcohol water system reformation hydrogen production and preparation and application thereof。
Background technology
Facing mankind energy crisis and environmental pollution two hang-up。
Oil, natural gas, coal are that the Nature is presented to the high-grade energy of the mankind, are also the main bodys of current energy resource structure, are non-renewable resources。But it is estimated that whole world petroleum reserves is about 150,000,000,000 tons;Gas reserves is about 150 billion cubic meters;Increase according to Global Oil 2%/year of consumption;5%/year of gas consumption increases, and Global Oil will exhaust in 2032, and natural gas will exhaust in 2028, and the mankind exist energy crisis。Meanwhile, the serious threat of facing mankind environmental pollution, for obtaining economic and society sustainable development, it is necessary to research and develop alternative new forms of energy。
Hydrogen Energy has high inflammability, low ignition energy, homogenous combustion, high-octane rating, high-energy-density, adapts to higher compression ratio, and engine thermal efficiency is high, a kind of beyond doubt desirably cleaning, the energy efficient, reproducible。In nineteen seventies, the U.S., Germany and Japan all successively have developed the automobile using liquid hydrogen as fuel。Right Hydrogen Energy, because producing difficulty, stores, transports and hydrogenation stations danger coefficient height, add the problems such as hydrogen manufacturing high cost so that Hydrogen Energy fails to be generalizable。
Fortunately, the mankind being full of resource never stopped exploration, people have found a low price, cleaning, efficient, renewable, environmental protection, the substituting strong alcohol water system method for preparing hydrogen by reforming that can produce Hydrogen Energy moment, disposable solve Hydrogen Energy produce, store, the problem such as transport, make Hydrogen Energy popularization and application come true。
Existing alcohol water system method for preparing hydrogen by reforming is after being mixed by a certain percentage with water by methanol/ethanol, in reaction unit, by catalyst action under uniform temperature or pressure condition or magneticaction, methanol/ethanol aqueous solution generation reforming reaction is made to obtain with hydrogen (H2) it is main, simultaneously possibly together with carbon monoxide (CO), carbon dioxide (CO2), methane (CH4) and water (H2O) hydrogen-rich gas。The reforming reaction formula being directed to is as follows:
Methanol-water systems reform hydrogen production reaction formula:
1) primary response formula: CH3OH→→→→CO+2H2
CO+H2O→→→→CO2+H2
2) overall reaction: CH3OH+H2O→→→→CO2+3H2
3) side reaction CO+3H2→→→→CH4+H2O
Ethanol water system reformation hydrogen production reaction equation:
1) primary response formula: C2H5OH→→→→CO+3H2+C
CO+H2O→→→→CO2+H2
C+2H2O→→→→CO2+2H2
2) overall reaction: C2H5OH+3H2O→→→→2CO2+6H2
3) side reaction CO+3H2→→→→CH4+H2O
Reforming reaction is more abundant, and alcohol conversion is more high, and side reaction is more few, and hydrogen-rich gas hydrogen content is more high。The method of a publication 201210083938.5(hydrogen production from methanol-steam reforming), publication 201510055497.1(vehicle-mounted aquiferous ethanol low-temperature reformate hydrogen production process and device thereof and application system), publication 201510363608.5(methanol-water reformation hydrogen production machine and hydrogen production process thereof) and the mechanism of hydrogen generation of publication 201510553870.6 all such。The rare metal catalyst that the reforming reaction of the hydrogen preparation method disclosed in right above-mentioned patent adopts, reforming reaction process contacts insufficient because of alcohol water with catalyst, alcohol consumption is big, side reaction product is many, hydrogen purity is much lower compared with theoretical value, adopts rare metal as catalyst, promotes the use of and be restricted, in addition reaction temperature high (requiring reaction temperature more than 600 DEG C) so that Hydrogen Energy preparation cost remains high。
Summary of the invention
It is an object of the invention to: high for existing alcohol water system method for preparing hydrogen by reforming alcohol consumption, hydrogen purity is much lower compared with theoretical value, because of metallic catalyst restriction and reaction temperature high-leveled and difficult with the problem such as universal, the biological activity catalyst of a kind of alcohol water system reformation hydrogen production is provided, by adding biological activity catalyst in advance in alcohol water system and making its mix homogeneously, alcohol water is made to transform into cytokines alcohol。Cytokines alcohol is by certain device, and catalytic pyrolysis becomes hydrogen-rich gas at low temperatures。By using the biological activity catalyst of the present invention, hydrogen purity improves, and closer to theoretical value, alcohol consumption is significantly reduced, and is the hydrogen production process that more advanced, the suitability is higher at present。
The present invention realizes by the following technical solutions:
The active catalyst used by biological activity antigravity system biology making alcohol water system reformation hydrogen production of the present invention, is made up of the raw material of following parts by weight:
Mulberry branch extract 30-40 part;Apricot branch extract 20-30;Medulla Junci extract 10-25 part。
Described mulberry branch extract, apricot branch extract and Medulla Junci extract are by the second extract of mulberry branch, apricot branch and the water extract of Medulla Junci, water and organic solvent。
Described mulberry branch extract is to be shredded by mulberry branch, and the water boil of addition branch weight 5-10 weight 2-4 hour filters, filtering residue adds water boil 1-2 hour of 2-3 times of weight, merging twice filtrate, the relative density being concentrated into 6O DEG C of heat survey is 1.1, obtains mulberry branch extract。
Equally, apricot branch water extract is the chopping of apricot branch, the water boil of addition branch weight 5-10 weight 2-4 hour, filtering, filtering residue adds water boil 1-2 hour of 2-3 times of weight, merges twice filtrate, the relative density being concentrated into 6O DEG C of heat survey is 1.1, obtains apricot bar extract。
Medulla Junci water extract is Medulla Junci chopping, and the water boil of addition branch weight 5-10 weight 2-4 hour filters, filtering residue adds water boil 1-2 hour of 2-3 times of weight, merging twice filtrate, the relative density being concentrated into 6O DEG C of heat survey is 1.1, obtains Medulla Junci extract。
The second extract of mulberry branch organic solvent is to be shredded by mulberry branch, first with organic solvent extraction 1-2 hour, takes out liquid and mulberry branch slag respectively, and mulberry branch slag adds water boil 1-2 hour of 3-5 times, merging organic solvent extraction liquid and Aqueous extracts。
The second extract of apricot branch organic solvent is to be shredded by apricot branch, first with organic solvent extraction 1-2 hour, takes out liquid and apricot branch slag respectively, and apricot branch slag adds water boil 1-2 hour of 3-5 times, merging organic solvent extraction liquid and Aqueous extracts。
The second extract of Medulla Junci organic solvent is to be shredded by Medulla Junci, first with organic solvent extraction 1-2 hour, takes out liquid and Medulla Junci slag respectively, and Medulla Junci slag adds water boil 1-2 hour of 3-5 times, merging organic solvent extraction liquid and Aqueous extracts。
Described organic solvent is methanol, ethanol, ether, petroleum ether, benzene, toluene, chloroform, ethyl acetate and dichloroethanes;Or the mixture of methanol and ethanol;Or the mixture of benzene and toluene。
Above-mentioned mulberry branch extract, apricot bar extract and Medulla Junci extract need not be condensed into dry cream when concentration。
Above-described mulberry branch, for the dry twig of moraceae plants mulberry, latin name: MorusalbaL. originates in Central China, has the cultivation history of nearly 4,000 years, cultivates in extensive range, and northeast is on the south Harbin;Northwest from Southern Nei Mongol to Xinjiang, Qinghai, Gansu, Shaanxi;Reach Guangdong, Guangxi in the south, to the east of Taiwan;West to Sichuan, Yunnan;With the cultivation of various places, the middle and lower reach of Yangtze River at most。Vertical distribution is mostly at below height above sea level 1200m。Additionally, also there is cultivation Korea, Mongolia, Japan, Russia, Europe and North America。
The Chinese medicine of mulberry branch Ye Shi China, its herbal nature: twig part, taste is poor, is slightly cold, nontoxic。Ramulus Mori head: bitter in the mouth, cold in nature, nontoxic。
In the chemical analysis that mulberry branch extracts, (tannin) containing tannin [1], sucrose (sucrose), fructose (fructose), stachyose (stachyose), glucose (glucose), maltose (maltose), Raffinose (raffinose), arabinose (arabinose), xylose (xylose);Stem is containing flavones ingredient: Sang Su (mulberrin), mulberrochromene (mulbel-rochromene), cyclomulberrin (cyclomulberrin), cyclomulberrochromene (cyclomulbel-rochromene)。Timber containing morin (morin), three-bristle cudrania tree element (cudranin), 2,4,4 ', 6-tetrahydroxybenzophenone (2,4,4 ', 6-tetrahydroxybenzoph-none), 2,3 ', 4,4 ', 6-pentahydroxybenzophenone (2,3 ', 4,4 ', 6-pentahydrox-ybenzophenone, maclurin);Heartwood containing Dihydromorin. (dihydromo-rin), Dihydrokaempferol (dihydrokaempferol), 2,4, 3 ', 5 '-tetrahydroxystilbene (2,4,3 ', 5 '-tetrahydroxystilbene) [6], Morus alba eight alcohol (alboctalol), moracinC, D(moracinC, D), 2,4,4 ', 6-tetrahydroxybenzophenone (2,4,4 ', 6-tetrahydrox-ybenzophenone) and 2,3 ', 4,4 ', 6-pentahydroxybenzophenone (maclurin, 2,3 ', 4,4 ', 6-pentrahydrox-ybenzophenone), resvertrol (Rhizoma et radix veratri (Radix Rhizoma Veratri) phenol, resera-trol), Oxyresveratrol (oxyresveratrol), dihydro Oxyresveratrol (dihydrooxyresveratrol), Moracin A, B, E, F, G, H, (moracinA, B, E, F, G, H), Morusin (mulberrin), mulberrochromene (mulberrochromene), cyclomorusin (cyclomulberrin), cyclomulberrochromene (cyclomulberrochromene) and the acid of birch skin。
Mulberry has many kinds, and the mulberry branch selected by the present invention is able to raise the kind of Bombyxmori Linnaeus。
Apricot branch, is branch and the leaf of plant apricot, and apricot Latin literary fame: ArmeniacavulgarisLam. calls: Fructus Pruni, north prunus mume (sieb.) sieb.et zucc.。Section belongs to: Rosaceae, Prunus。The place of production is distributed: originate in Xinjiang, China, now widely distributed to various places, North China。Ecological habit: for heliophilous species, deep-rootedness, like light, drought-enduring, cold-resistant, wind resistance, last a long time, more than a century, for the Main Cultivation fruit tree in low mountains and hills area。Horticultural use: early spring blooms, first spends posterior lobe;Can plant in other lakeside, pond or before planting Yushan Hill Shi Ya limit, garden hall with green pine, Chinese incense cedar, great sight。
Apricot is deciduous tree, and all over China have cultivation more。High up to 5-8m, diameter of a cross-section of a tree trunk 1.3 meters above the ground 30cm。Dried bark taupe, without terminal bud, hibernaculum 2-3 piece is clustered。Single leaf alternate, leaf is avette to subcircular, long 5-9cm; wide 4-8cm, tip tool mucro, basal circular or closely heart-shaped; edge tool circle crenation, pinnate vein, lateral vein 4-6 pair; leaf mass color is sliding, and blade back has hairiness between seasonal pulse axil, and petiole is smooth; long 2-3cm; there are 1-6 body of gland, flower both sexes, Dan Huawu stalk or near without stalk in nearly phyllopodium place;The narrow cylindrical shape of calyx, opisthotonos during sepal flower;Floral white or micro-red, 25-45 piece of stamen, it is shorter than petal, fruit is spherical or avette, how shallow time ripe splits or yellowish red color, micro-hairiness。Plant core flattened round, many bitterness or sweet taste;March at florescence, the fruit ripe 6-7 month。
After apricot is gathered, it is necessary to prosperous branch is carried out branch pulling and angle opening, promote into colored relaxing tree vigo(u)r;Young sprout is performed twice at pinching, to inspire branch, cultivates branch group;Weak sagging fruitful branch notable after result suitably to be bounced back;The excessive growth branch of germinating in tree crown to be taked pinching, turned round the measures such as the tip, control it and nourish and grow;To the branch of excessive growth not having growing space, remove in time。So there is substantial amounts of apricot branch in annual orchard, being generally used in the past makes a fire cooks, now due to rural area also uses natural gas, so apricot branch can only be allowed to rot in orchard。
Apricot branch chemical analysis:
Cortex Pruni protease containing tool suppresses the tannin of the former cyanidin type with antiviral activity。
Folium Pruni is containing globulariacitrin (rutin), Quercetin-3-Fructus rhamni (Rhamnus davurica Pall.) glycoside (quercetin-3-rhamnoglucoside), prunase (prunase), chlorogenic acid (chlorogenicacid), neochlorogenic acid (neochlorogenicacid)。
Wild apricot leaf, containing quercitrin (quercitrin), rhamnetin-3-O-rhamnoside (rhamnetin-3-O-rhamnoside), rhamnocitrin-3-O-rhamnoside (rhamnocitrin-3-O-rhamnoside)。
Prunus armeniaca L.var.ansu Maxim. leaf is containing phlorhizin (phlorizin)。
In underdone fruit more containing flavonoid, flavonoid have prevention heart disease and reduce myocardial infarction effect;
Semen Armeniacae Amarum energy relieving cough and asthma, loosening bowel to relieve constipation, it is possible to treatment pneumonopathy, the disease such as cough;
Semen Armeniacae Amarum is possibly together with abundant vitamin C and polyphenol components, and this composition is not only able to reduce the content of cholesterol in human body, moreover it is possible to significantly reduce heart disease and the onset risk of a lot of chronic disease。
Semen Armeniacae Amarum chemical composition, containing amygdalin (amygdalin), fatty oil, emulsin (emulsin), cyaniding glycoside, amygdalase (amygdalase), prunase (prunase), estrone, alpha-estradiol, desmosterol etc.。
Medulla Junci, Chinese medicine name, for the dry stem pith of rush family plant Medulla Junci MedullaJunci。Another name: Medulla Junci, Lin's grass, Herba Poae Sphondylodis, wild seat grass, horse palm fibre root, wild horse palm fibre;Being perennial herb water plant, subterraneous stem is short, crawling property, stalk is grown thickly uprightly, and cylindrical shape is solid, basal part of stem tool is brown, degenerates in flakey first sheathing leaf, spike, top is raw, and in the raw shape in false side on stem, base portion bract extends in bulbous, spend 2 pieces of squamellas of lower tool, perianth sliver 6 pieces, 3 pieces of stamen, pistil stigma 3 difference。Isabelline capsule, avette or oval, seed yellow is obovate。Medulla Junci extracts stem to autumn late summer, dries, and takes out stem pith, and reason is straight, is bundled into wisp。This product is in thin cylindrical, up to 2250px, diameter 0.1~7.5px。Superficial white or yellowish white, have thin longitudinal grin。Body is light, and matter is soft, slightly elastic, easily breaks。
Medulla Junci is also traditional Chinese herbal medicine, and effect is classified: diuretic medicine;Antipyretic;Stranguria-relieving diuretic, meridian distribution of property and flavor is slightly cold;Sweet, light;GUIXIN;Lung;Small intestinal;Bladder warp, effect relieving stranguria by diuresis;Clearing heart fire。Cure mainly: gonorrhea;Edema;Dysuria, the puckery pain of oliguria;Jaundice due to damp-heat;Dysphoria and insomnia;The nocturnal fretfulness in infants;Sore throat;Aphtha of the mouth and tongue;Wound。
[pharmacological action]: relieving stranguria by diuresis;Clearing heart fire。Cure mainly: gonorrhea;Edema;Dysuria, the puckery pain of oliguria;Jaundice due to damp-heat;Dysphoria and insomnia;The nocturnal fretfulness in infants;Sore throat;Aphtha of the mouth and tongue;Wound。
[chemical composition]: containing arabinan (araban), xylan (xylan), methylpentosan (methylpentosan), tan acid anhydride (phlobaphene), luteolin (luteolin), luteolin-7-glucoside (luteolin-7-glucoside) etc.。
The extraction of Medulla Junci also had some bibliographical informations, such as, Medulla Junci phenanthrene effective kind part and its production and use Chinese Patent Application No.: 201410106877.9, applicant: Beijing University of Chinese Medicine: inventor: the yellow JIANMEI Li Gui cloud section gorgeous Wang Yang of Merak Zhan Xue;Medulla Junci phenanthrene effective kind part and preparation method thereof and its purposes in preparing anxiolytic drugs, described effective site comprises the effusol higher than 50%, dehydroeffusol, juncusol and dehydroujunation, described preparation method comprises the steps: to take Medulla Junci stem pith portion, uses ethanol water reflux, extract,;The extracting solution obtained merged and concentrates, using ethyl acetate ultrasonic extraction, united extraction liquid subsequently, the extracting solution after merging is concentrated, dry, obtain dry ethyl acetate extract;Take dry ethyl acetate extract, separate through silica gel column chromatography or high speed adverse current chromatogram, luxuriant and rich with fragrance effective kind part can be obtained。
Medulla Junci has a variety of, but as long as has medulla (i.e. lampwick) just can use。
The mechanism of the biological activity catalyst of the present invention is, owing to mulberry branch extract, apricot branch extract and Medulla Junci extract contain saccharide, ketone, phenols, olefines, leaf enzyme, peroxidase, chlorogenic acid, glucosides, after mixing with first/ethanol, the various hydroxyls of catalyst, phenolic group, ketone group, alkylene, phytoenzyme are by the hydroxy combining of hydrone group Yu first/ethanol so that also can accelerate cracking reaction when low temperature at first/ethanol water。The using method of the biological activity catalyst of the present invention is as follows:
(1) mulberry branch extract, apricot branch extract and Medulla Junci extract are mixed by weight, obtain biological activity catalyst;
(2) by the organic solvent of weight content 55-80%, for instance the above-mentioned biological activity catalyst of methanol or ethanol (water content 20-45%) and 2-5% is uniformly mixed acquisition cytokines alcohol。
(3) cytokines alcohol is in gas generator, treats that temperature is increased to more than 180 DEG C (180-400 DEG C) and reforming reaction can be occurred moment to produce highly purified hydrogen-rich gas。
(4) gas generator can be car-mounted device, rotor machine or hydrogen-rich gas station device, but is not limited to the device being previously mentioned。
Described car-mounted device is to dispose an alcohol to decompose generator A on automobile, alcohol is provided with feeder before decomposing generator A, alcohol-water solution and biological activity catalyst inject alcohol by feeder and decompose in generator A, described alcohol decomposes generator A and is provided with agitator and heating device, and alcohol-water solution catalytic reaction generates hydrogen, carbon dioxide and a small amount of carbon monoxide and methane;Alcohol decomposes generator A gas outlet and meets hydrogen-rich bottle A, by air relief valve and controller, from shower nozzle, hydrogen-rich gas is sprayed into the acting of electromotor A combusted cylinder;Weary gas after electromotor A burning connects the heat exchanger in feeder A, to alcohol-water solution and catalyzer temperature-elevating。The cytokines alcohol of the present invention is added to the automotive oil tank having installed said apparatus additional, utilizes engine valve waste heat, becomes hydrogen-rich gas at the outer cracking and catalyzing of cylinder, enters cylinder combustion under electromotor negative pressure state, replaces gasoline as motor vehicle fuel。
Described rotor machine is one the feeder B of arrangement at engine export, decompose generator B with alcohol to be connected, inject alcohol by feeder B after alcohol-water solution and catalyst heating and decompose in generator B, described alcohol decomposes generator B and is provided with agitator and heating device, and alcohol-water solution catalytic reaction generates hydrogen, carbon dioxide and a small amount of carbon monoxide and methane;Alcohol decomposes generator B gas outlet and connects hydrogen-rich bottle, by air relief valve and controller, from shower nozzle, hydrogen-rich gas is sprayed into engine cylinder work by combustion;Engine output shaft is connected with generator shaft。Alcohol-water solution can be catalytically conveted to hydrogen-rich gas by the engine exhaust heat of this device, provides the energy for electromotor, is converted into electric energy, can develop as small-sized electric station, and its cost of electricity-generating is lower than conventional fuel oil electromotor。
Described hydrogen-rich gas station device can utilize solar energy as heating source;The alcohol-water solution that alcohol thermally or electrically decomposes generator C of solar panels output and biological activity catalyst are heated decomposing, described alcohol decomposes generator C and is provided with agitator and heating device, and alcohol-water solution catalytic reaction generates hydrogen, carbon dioxide and a small amount of carbon monoxide and methane;Alcohol decomposes generator C gas outlet and connects low pressure gas cylinder and gas cylinder, is then passed to filling machine to the user needing hydrogen fuel, replace fossil energy for various Industrial Boilers, hotel, hotel, office, school lunch service catering industry。
The invention has the beneficial effects as follows:
1, catalyst is derived from plant extract, abundant raw material, extracts process simple。
2, being prepared by alcohol water Hydrogen Energy and progressively replace gasoline, tap a new source of energy, be an important task of current each countries and regions, promoting this technology before arriving in gasoline, natural gas exhaustion will be the direction developing the energy of the mankind。
3, with ethanol (methanol) for catalytic material cracking hydrogen production, there is Hydrogen Energy (alcohol hydrogen fuel, hydrogen-rich gas) production technology advantage (with producing with adding, can with car hydrogen manufacturing, use with car), solve Hydrogen Energy preparation difficulty, store the difficult problems such as transport difficult。
4, according to non-grain-production ethanol, for instance Ethanol Production by Biomass Fermentations such as sugar grass, corn stalk, rice hulls, Caulis Sacchari sinensis, molasses, its CO discharged that burns2The CO consumed is grown with the biogenic as raw material2, quantitatively remaining basically stable, this is to reducing atmospheric pollution and suppressing greenhouse effect significant。
5, the present invention can utilize the temperature that solar panel provides, more than 180 DEG C of heat energy, alcohol is made to decompose the instantaneous generation hydrogen-rich gas of cytokines alcohol of generator, can be pressed in hydrogen bottle, as hydrogen energy source, replace fossil energy and be used for the catering industry of various Industrial Boilers, hotel, hotel, office, school lunch service。
Accompanying drawing explanation
Fig. 1 is car-mounted device structural representation of the present invention。
Fig. 2 is rotor machine structural representation。
Tu3Shi hydrogen-rich gas station apparatus structure schematic diagram。
The component names that in figure, sequence number represents is:
1, feeder, 2, hydrogen-rich bottle, 3, alcohol decompose generator, 4, Pressure gauge, 5, air relief valve, 6, controller, 7, shower nozzle, 8, electromotor, 11, electromotor A, 12, hydrogen-rich air inlet pipe, 13, the exhaust pipe of engine, 14, feeder B, 15, alcohol decompose generator B, 16, hydrogen-rich bottle B, 17, engine shaft;18, electromotor, 19, storage battery;21, solar panels, 22, alcohol decompose generator C, 23, feeder, 24, low pressure gas cylinder, 25. gas cylinders, 26, filling machine。
As shown in Figure 1, described car-mounted device is to dispose an alcohol to decompose generator A2 on automobile, alcohol is provided with feeder 1 before decomposing generator A2, (cytokines alcohol) alcohol-water solution and biological activity catalyst inject alcohol by feeder 1 and decompose in generator A2, described alcohol decomposes generator A2 and is provided with agitator and heating device, and alcohol-water solution catalytic reaction generates hydrogen, carbon dioxide and a small amount of carbon monoxide and methane;Alcohol decomposes generator A2 gas outlet and meets hydrogen-rich bottle A3, by air relief valve 5 and controller 6, from shower nozzle 7, hydrogen-rich gas is sprayed into the acting of electromotor A11 combusted cylinder;Pressure gauge 4 is arranged on the pipeline of hydrogen-rich bottle A3 outlet;Weary gas after electromotor A11 burning connects the heat exchanger in feeder A1, to alcohol-water solution and catalyzer temperature-elevating。
As shown in Figure 2, described rotor machine is one the feeder B14 of arrangement in electromotor 11 outlet, decompose generator B15 with alcohol to be connected, inject alcohol by feeder B14 after (cytokines alcohol) alcohol-water solution and catalyst heating and decompose in generator B15, described alcohol decomposes generator B15 and is provided with agitator and heating device, and alcohol-water solution catalytic reaction generates hydrogen, carbon dioxide and a small amount of carbon monoxide and methane;Alcohol decomposes generator B15 gas outlet and connects hydrogen-rich bottle, by air relief valve and controller, from shower nozzle, hydrogen-rich gas is sprayed into engine cylinder work by combustion;Engine output shaft 17 is connected with electromotor 18 axle。Alcohol-water solution can be catalytically conveted to hydrogen-rich gas by the engine exhaust heat of this device, provides the energy for electromotor, is converted into electric energy, can develop as small-sized electric station, and its cost of electricity-generating is lower than conventional fuel oil electromotor。
As it is shown on figure 3, described hydrogen-rich gas station device can utilize solar energy as heating source;(cytokines alcohol) alcohol-water solution that alcohol thermally or electrically decomposes generator C22 of solar panels 21 output and biological activity catalyst are heated decomposing, described alcohol decomposes generator C22 and is provided with agitator and heating device, and alcohol-water solution catalytic reaction generates hydrogen, carbon dioxide and a small amount of carbon monoxide and methane;Alcohol decomposes generator C22 gas outlet and connects low pressure gas cylinder 24 and gas cylinder 25, is then passed to filling machine 26 to the user needing hydrogen fuel。
Detailed description of the invention
The following is the preparation embodiment of biological activity catalyst:
Embodiment 1:
(1) preparation of mulberry branch extract, apricot branch extract and Medulla Junci extract:
Being shredded by mulberry branch, add the water boil 2 hours of 5 times of weight of branch weight, filter, filtering residue adds the water boil 1 hour of 2 times of weight, merges twice filtrate, and being concentrated into the relative density that 6O DEG C of heat surveys is 1.1, obtains mulberry branch extract。
Apricot branch water extract is the chopping of apricot branch, and the water boil of addition 5 times of weight of branch weight 2 hours filters, filtering residue adds the water boil 1 hour of 2 times of weight, merging twice filtrate, the relative density being concentrated into 6O DEG C of heat survey is 1.1, obtains apricot branch extract。
Medulla Junci water extract is Medulla Junci chopping, adds the water boil 2 hours of 5 times of weight of branch weight, filters, and filtering residue adds the water boil 1 hour of 2 times of weight, merges twice filtrate, and being concentrated into the relative density that 6O DEG C of heat surveys is 1.1, obtains wick swath extract。
(2) using method of biological activity catalyst
1) mulberry branch extract, apricot branch extract and Medulla Junci extract are mixed by weight, obtain biological activity catalyst;
2) the biological activity catalyst mix stating (1st) step waterborne of weight content 55% ethanol (water content 45%) Yu 5% is stirred, it is thus achieved that cytokines alcohol;
3) by cytokines alcohol adding apparatus 1(car-mounted device) in, gasoline is the same to be run on highway with using can to make automobile。
4) by cytokines alcohol adding apparatus 2(rotor machine) in, electric energy can be produced。
5) by cytokines alcohol adding apparatus 3(hydrogen-rich gas station device) in, hydrogen-rich gas can be produced。
Embodiment 2:
(1) preparation of mulberry branch extract, apricot branch extract and Medulla Junci extract:
Being shredded by mulberry branch, add the water boil 3 hours of 10 times of weight of branch weight, filter, filtering residue adds the water boil 2 hours of 3 times of weight, merges twice filtrate, and being concentrated into the relative density that 6O DEG C of heat surveys is 1.1, obtains mulberry branch extract。
Apricot branch water extract is the chopping of apricot branch, and the water boil of addition 10 times of weight of branch weight 4 hours filters, filtering residue adds the water boil 2 hours of 2 times of weight, merging twice filtrate, the relative density being concentrated into 6O DEG C of heat survey is 1.1, obtains apricot branch extract。
Medulla Junci water extract is Medulla Junci chopping, adds the water boil 2 hours of 10 times of weight of branch weight, filters, and filtering residue adds the water boil 1 hour of 2 times of weight, merges twice filtrate, and being concentrated into the relative density that 6O DEG C of heat surveys is 1.1, obtains Medulla Junci extract。
(2) using method of biological activity catalyst
1) mulberry branch extract, apricot branch extract and Medulla Junci extract are mixed by weight, obtain biological activity catalyst;
2) the biological activity catalyst mix of weight content 80% ethanol (water content 20%) Yu above-mentioned (1st) step of 2% is stirred, it is thus achieved that cytokines alcohol;
3) by cytokines alcohol adding apparatus 1(car-mounted device) in, (decomposition temperature 180-400 DEG C) can make automobile with using the same operation on highway of gasoline。
4) by cytokines alcohol adding apparatus 2(rotor machine) in, (decomposition temperature 180-400 DEG C) can produce electric energy。
5) by cytokines alcohol adding apparatus 3(hydrogen-rich gas station device) in, (decomposition temperature 180-400 DEG C) can produce hydrogen-rich gas。
Embodiment 3:
(1) preparation of mulberry branch extract, apricot branch extract and Medulla Junci extract:
Being shredded by mulberry branch, first with the ethanol extraction 1.5 hours of weight content more than 70%, take out liquid and mulberry branch slag respectively, mulberry branch slag adds the water boil 1.5 hours of 3 times, merges organic solvent extraction liquid and Aqueous extracts, obtains mulberry branch extract。
The second extract of apricot branch organic solvent is to be shredded by apricot branch, first with the ethanol extraction 2 hours of weight content more than 70%, take out liquid and apricot branch slag respectively, apricot branch slag adds the water boil 1.5 hours of 3 times, merge organic solvent extraction liquid and Aqueous extracts, obtain apricot branch extract
Being shredded by Medulla Junci, first with the ethanol extraction 2 hours of weight content more than 70%, take out liquid and Medulla Junci slag respectively, Medulla Junci slag adds the water boil 1.5 hours of 3 times, merges organic solvent extraction liquid and Aqueous extracts。
(2) using method of biological activity catalyst
1) mulberry branch extract, apricot branch extract and Medulla Junci extract are mixed by weight, obtain biological activity catalyst;
2) the biological activity catalyst compounds of weight content 55% methanol (water content 45%) Yu above-mentioned (1st) step of 5% is uniformly mixed, it is thus achieved that cytokines alcohol;
3) adding in car-mounted device by cytokines alcohol, (decomposition temperature 180-400 DEG C) can make automobile with using the same operation on highway of gasoline。
4) being added in rotor machine by cytokines alcohol, (decomposition temperature 180-400 DEG C) can produce electric energy。
5) being added in hydrogen-rich gas station device by cytokines alcohol, (decomposition temperature 180-400 DEG C) can produce hydrogen-rich gas。
Embodiment 4,
(1) preparation of mulberry branch extract, apricot branch extract and Medulla Junci extract:
Being shredded by mulberry branch, first with the ether extraction 1 hour of weight content more than 70%, take out liquid and mulberry branch slag respectively, mulberry branch slag adds the water boil 1 hour of 3 times, merges organic solvent extraction liquid and Aqueous extracts, reclaims ether, obtain mulberry branch extract。
The second extract of apricot branch organic solvent is to be shredded by apricot branch, first with the ether extraction 1 hour of weight content more than 70%, take out liquid and apricot branch slag respectively, apricot branch slag adds the water boil 1 hour of 3 times, merge organic solvent extraction liquid and Aqueous extracts, reclaim ether, obtain apricot branch extract。
Being shredded by Medulla Junci, first with the ether extraction 1 hour of weight content more than 70%, take out liquid and Medulla Junci slag respectively, Medulla Junci slag adds the water boil 1 hour of 3 times, merges organic solvent extraction liquid and Aqueous extracts, reclaims ether, obtain Medulla Junci extract。
(2) using method of biological activity catalyst
1) mulberry branch extract, apricot branch extract and Medulla Junci extract are mixed by weight, obtain biological activity catalyst;
2) the biological activity catalyst mix of weight content 80% methanol (water content 20%) Yu above-mentioned (1st) step of 2% is stirred, it is thus achieved that cytokines alcohol;
3) being added in car-mounted device by cytokines alcohol, gasoline is the same to be run on highway with using can to make automobile。
4) cytokines alcohol is added in rotor machine, electric energy can be produced。
5) cytokines alcohol is added in hydrogen-rich gas station device, hydrogen-rich gas can be produced。
Embodiment 5:
(1) preparation of mulberry branch extract, apricot branch extract and Medulla Junci extract:
Mulberry branch is shredded, first extracts 2 hours by the ethyl acetate of weight content more than 70%, respectively taking-up liquid and mulberry branch slag, liquids recovery ethyl acetate, standby;Mulberry branch slag adds the water boil 1 hour of 4 times, merges organic solvent extraction liquid and Aqueous extracts, obtains mulberry branch extract。
The second extract of apricot branch organic solvent is to be shredded by apricot branch, first extracts 2 hours by the ethyl acetate of weight content more than 70%, respectively taking-up liquid and apricot branch slag, liquids recovery ethyl acetate, standby;Apricot branch slag adds the water boil 1 hour of 4 times, merges organic solvent extraction liquid and Aqueous extracts, obtains apricot branch extract。
Medulla Junci is shredded, first extracts 2 hours by the ethyl acetate of weight content more than 70%, respectively taking-up liquid and Medulla Junci slag, liquids recovery ethyl acetate, standby;Medulla Junci slag adds the water boil 1 hour of 3 times, merges organic solvent extraction liquid and Aqueous extracts。
(2) using method of biological activity catalyst
1) mulberry branch extract, apricot branch extract and Medulla Junci extract are mixed by weight, obtain biological activity catalyst;
2) the biological activity catalyst compounds with above-mentioned (1st) step of the ethanol (water content 30%) of weight content 70% Yu 4% is stirred, it is thus achieved that cytokines alcohol;
3) adding in car-mounted device by cytokines alcohol, (decomposition temperature 180-400 DEG C) can make automobile with using the same operation on highway of gasoline。
4) being added in rotor machine by cytokines alcohol, (decomposition temperature 180-400 DEG C) can produce electric energy。
5) being added in hydrogen-rich gas station device by cytokines alcohol, (decomposition temperature 180-400 DEG C) can produce hydrogen-rich gas。
In above-described embodiment, organic solvent extraction liquid can also use benzene, toluene or chloroform and dichloroethanes, and process and alcohol, ethyl acetate are similar。
Alcohol water system reformation hydrogen production hydrogen-rich gas theory composition (volume %) H2: 75%, CO2: 25%, the present invention (the cytokines alcohol of embodiment 2) value of calculation such as following table:
Experimental data shows: reaction temperature reaches 200 DEG C, and cmpletely, the hydrogen-rich gas that the present invention produces is not containing intermediate product (CO, CH for alcohol water system hydrogen manufacturing reforming reaction4), the use of this catalyst can make alcohol water system hydrogen manufacturing reforming reaction more completely, more abundant, product hydrogen-rich gas forms close to theoretical value, illustrate that the biological activity catalyst using the present invention can make alcohol water system catalytic pyrolysis at low temperatures become hydrogen-rich gas, hydrogen purity improves, closer to theoretical value, alcohol consumption is significantly reduced。
Cytokines alcohol methanol fuel is applied to car-mounted device by the present inventor, in in October, 2014 begin at Jining of Shandong Province, Wenzhou District of Zhejiang Province, Zhejiang Hangzhou carry out the taxi commerial vehicle test of little scope, power performance and gasoline are as good as, and traffic-operating period is good, and taxi driver is very satisfied。
In August, 2015, we transform a car, cytokines alcohol alcohol fuel on probation runs, achieve the data of automobile application, through cytokines alcohol sample presentation being given the detection department inspection of specialty, meeting car and use, every technical parameter is better than current 93# gasoline, what emit is steam, and environment is not polluted。Fuel cost is only the 50%--60% of gasoline, can replace 93# gasoline completely for automobile。Car uses cytokines alcohol as fuel, contrasts distance travelled: 4582 kilometers, in urban road distance travelled: 1367 kilometers, and average speed per hour 45 kilometers;At highway driving mileage: 3215 kilometers, average speed per hour 107 kilometers, climbing power foot。

Claims (8)

1. make a biological activity catalyst for alcohol water system reformation hydrogen production, be made up of the raw material of following parts by weight:
Mulberry branch extract 30-40 part;Apricot branch extract 20-30 part;Medulla Junci extract 10-25 part。
Described mulberry branch extract, apricot branch extract and Medulla Junci extract are by the water extract of mulberry branch, apricot branch and Medulla Junci, or the second extract of water and organic solvent。
2. the biological activity catalyst making alcohol water system reformation hydrogen production according to claim 1, it is characterized in that: the water extract of described mulberry branch is to be shredded by mulberry branch, water boil 2-4 hour of 5-10 times of weight is added by mulberry branch weight, filter, filtering residue adds water boil 1-2 hour of 2-3 times of weight, merging twice filtrate, the relative density being concentrated into 6O DEG C of heat survey is 1.1, obtains mulberry branch extract;
Described apricot branch water extract is the chopping of apricot branch, water boil 2-4 hour of 5-10 times of weight is added by apricot branch weight, filter, filtering residue adds water boil 1-2 hour of 2-3 times of weight, merge twice filtrate, the relative density being concentrated into 6O DEG C of heat survey is 1.1, obtains apricot branch extract;
Described Medulla Junci water extract is Medulla Junci chopping, adds water boil 2-4 hour of 5-10 times of weight by Medulla Junci weight, filters, filtering residue adds water boil 1-2 hour of 2-3 times of weight, merging twice filtrate, the relative density being concentrated into 6O DEG C of heat survey is 1.1, obtains Medulla Junci extract。
3. the biological activity catalyst making alcohol water system reformation hydrogen production according to claim 1, it is characterized in that: described mulberry branch water and the second extract of organic solvent are to be shredded by mulberry branch, first use organic solvent extraction 1-2 hour, take out liquid and mulberry branch slag respectively, mulberry branch slag adds water boil 1-2 hour of 3-5 times, merge organic solvent extraction liquid and Aqueous extracts, after reclaiming organic solvent, obtain second extract;
The second extract of apricot branch organic solvent is to be shredded by apricot branch, first use organic solvent extraction 1-2 hour, take out liquid and apricot branch slag respectively, apricot branch slag adds water boil 1-2 hour of 3-5 times, merge organic solvent extraction liquid and Aqueous extracts, after reclaiming organic solvent, obtain second extract;
The second extract of Medulla Junci organic solvent is to be shredded by Medulla Junci, first with organic solvent extraction 1-2 hour, taking out liquid and Medulla Junci slag respectively, Medulla Junci slag adds water boil 1-2 hour of 3-5 times, merge organic solvent extraction liquid and Aqueous extracts, after reclaiming organic solvent, obtain second extract。
4. the biological activity catalyst making alcohol water system reformation hydrogen production according to claim 1 or 3, it is characterised in that: described organic solvent is methanol, ethanol, ether, petroleum ether, benzene, toluene, chloroform, ethyl acetate and dichloroethanes;Or the mixture of methanol and ethanol;Or the mixture of benzene and toluene。
5. the using method of the biological activity catalyst making alcohol water system reformation hydrogen production described in claim 1, it is characterised in that:
(1) mulberry branch extract, apricot branch extract and Medulla Junci extract are mixed by weight, obtain biological activity catalyst;
(2) by the ethanol of weight content 55-80% or methanol, or the biological activity catalyst of any mixture of ethanol and methanol and 2-5% is uniformly mixed acquisition cytokines alcohol;
(3) alcohol that cytokines alcohol passes into car-mounted device, rotor machine or hydrogen-rich gas station device decomposes in generator, treats that temperature is increased to more than 180 DEG C, and moment occurs reforming reaction to produce highly purified hydrogen-rich gas。
6. the biological activity catalyst making alcohol water system reformation hydrogen production according to claim 1, it is characterized in that: described car-mounted device is to dispose an alcohol to decompose generator A on automobile, alcohol is provided with feeder before decomposing generator A, alcohol-water solution and biological activity catalyst inject alcohol by feeder and decompose in generator A, described alcohol decomposes generator A and is provided with agitator and heating device, and alcohol-water solution catalytic reaction generates hydrogen, carbon dioxide and a small amount of carbon monoxide and methane;Alcohol decomposes generator A gas outlet and meets hydrogen-rich bottle A, by air relief valve and controller, from shower nozzle, hydrogen-rich gas is sprayed into the acting of electromotor A combusted cylinder;Weary gas after electromotor A burning connects the heat exchanger in feeder A, to alcohol-water solution and catalyzer temperature-elevating。
7. the biological activity catalyst making alcohol water system reformation hydrogen production according to claim 1, it is characterized in that: described rotor machine is one the feeder B of arrangement at engine export, decompose generator B with alcohol to be connected, inject alcohol by feeder B after alcohol-water solution and catalyst heating and decompose in generator B, described alcohol decomposes generator B and is provided with agitator and heating device, and alcohol-water solution catalytic reaction generates hydrogen, carbon dioxide and a small amount of carbon monoxide and methane;Alcohol decomposes generator B gas outlet and connects hydrogen-rich bottle, by air relief valve and controller, from shower nozzle, hydrogen-rich gas is sprayed into engine cylinder work by combustion;Engine output shaft is connected with generator shaft。Alcohol-water solution can be catalytically conveted to hydrogen-rich gas by the engine exhaust heat of this device, provides the energy for electromotor, is converted into electric energy, can develop as small-sized electric station, and its cost of electricity-generating is lower than conventional fuel oil electromotor。
8. the biological activity catalyst making alcohol water system reformation hydrogen production according to claim 1, it is characterised in that: described hydrogen-rich gas station device can utilize solar energy as heating source;The alcohol-water solution that alcohol thermally or electrically decomposes generator C of solar panels output and biological activity catalyst are heated decomposing, described alcohol decomposes generator C and is provided with agitator and heating device, and alcohol-water solution catalytic reaction generates hydrogen, carbon dioxide and a small amount of carbon monoxide and methane;Alcohol decomposes generator C gas outlet and connects low pressure gas cylinder and gas cylinder, is then passed to filling machine to the user needing hydrogen fuel。
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1829821A1 (en) * 2006-03-01 2007-09-05 Enea-Ente Per Le Nuove Tecnologie, L'Energia e L'Ambiente Membrane process for hydrogen production from reforming of organic products, such as hydrocarbons or alcohols
CN104229734A (en) * 2014-09-03 2014-12-24 深圳北纯能源科技有限公司 Reforming hydrogen production reactor and hydrogen production method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1829821A1 (en) * 2006-03-01 2007-09-05 Enea-Ente Per Le Nuove Tecnologie, L'Energia e L'Ambiente Membrane process for hydrogen production from reforming of organic products, such as hydrocarbons or alcohols
CN104229734A (en) * 2014-09-03 2014-12-24 深圳北纯能源科技有限公司 Reforming hydrogen production reactor and hydrogen production method

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