CN109775662A - A kind of method for preparing hydrogen by reforming - Google Patents
A kind of method for preparing hydrogen by reforming Download PDFInfo
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- CN109775662A CN109775662A CN201910184935.2A CN201910184935A CN109775662A CN 109775662 A CN109775662 A CN 109775662A CN 201910184935 A CN201910184935 A CN 201910184935A CN 109775662 A CN109775662 A CN 109775662A
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Abstract
A kind of method for preparing hydrogen by reforming, the following steps are included: entering the first reactor for being built-in with the corresponding blade type electrode of at least a pair of positive and negative anodes after light hydrocarbon feedstocks gas and the water and air mixing rich in methane, plasma more reforming reactions occur under the action of excitation of plasma and oxygen carrier body catalyst, reaction temperature is 600-1100 DEG C, pressure is 0.05-3.5MPa, air speed 1500-10000h‑1, first reactor outlet streams are dehydrated, purify after export hydrogen.This method flexible operation, hydrogen manufacturing is at low cost, is especially suitable for small-scale hydrogen manufacturing.
Description
Technical field
The present invention relates to light hydrocarbon feedstocks hydrogen producing technology fields, are a kind of utilization plasma chemical chain technologies more specifically
Prepare the process of hydrogen.
Background technique
Hydrogen is widely used in the industrial production.Hydrogen is used to manufacture ammonium hydroxide and chemical fertilizer together with other materials, while
It is applied in gasoline refinery practice, glass polishing, gold welding, meteorological balloon detection and food industry.And liquified hydrogen can be made
For rocket fuel.
Hydrogen utilization form is more, both can generate thermal energy by burning, generate mechanical work in Thermal Motor, and can be with
It is used for fuel cell as energy and material, or is converted into solid state hydrogen as structural material.Coal and petroleum is replaced to make internal combustion engine with hydrogen
Fuel is not required to make existing technical equipment great transformation, and present internal combustion engine certain modification can be used.
The major advantage of Hydrogen Energy has: combustion heat value is high, and the calorific capacity of hydrogen is all fossil fuels, chemical industry combustion in addition to nuclear fuel
It is highest in material and bio-fuel, it is 142,351kJ/kg, the heat that the hydrogen for the equal quality that burns generates, about the 3 of gasoline times,
3.9 times of alcohol, 4.5 times of coke.Hydrogen burning performance is good, lights fastly, there is extensive flammable range when mixing with air, and
Burning point is high, and burning velocity is fast.Hydrogen itself is nontoxic, and the product of burning is water, is the energy most clean in the world.With other fuel phases
It is most cleaned when than hydrogen burning, such as carbon monoxide, carbon dioxide, nytron will not be generated in addition to generating water and a small amount of ammonia
The environmentally harmful polluters such as object, leaded object and dust particles, a small amount of ammonia will not pollute ring by proper treatment
Border, and the water generated that burns can also continue to hydrogen manufacturing, be repeatedly circulated.
Application of the Hydrogen Energy on car, truck, bus, taxi, motorcycle and business ship has become focus.
It replaces gasoline to make the fuel of automobile engine with hydrogen, has been subjected to the examination of many motor corporations such as Japan, the U.S., Germany, China
It tests, it was demonstrated that hydrogen is feasible as the technology of motor vehicle fuel.
The appearance of hydrogen energy automobile needs to build hydrogen filling station (or as hydrogenation stations).A kind of mode is built in strange land
If large-scale device for producing hydrogen, such as hydrogen production from coal gasification device, natural gas steam reforming hydrogen production device produce hydrogen, then by hydrogen
Fate is defeated to fill automobile to hydrogenation stations.But such mode is there are hydrogen transportation cost, hydrogen gas leakage etc. is pacified in transit
Full problem；Or hydrogen pipe network can be built, hydrogen is transported to hydrogenation stations by pipe network.But pipeline needs to occupy on the way largely
Soil, pipeline network construction and maintenance cost are expensive.It can also use and build water electrolysis hydrogen production furnished equipments hydrogen on the spot in hydrogenation stations,
But the hydrogen that such mode produces is compared to the at high cost of fossil feedstock hydrogen manufacturing, hydrogen price.
For a long time, natural gas steam reforming is always most economical hydrogen production process.The day obtained through underground mining
Right gas contains multicomponent, and main component is methane, and other ingredients have water, other hydrocarbons, hydrogen sulfide, nitrogen and carbon oxygen
Compound.Therefore, before natural gas enters pipe network, the impurity such as sulfide to be removed.Natural gas into pipe network generally contains methane
75%~85% and some low-carbon saturated hydrocarbons, carbon dioxide etc..The reaction of methane on nickel catalysts is as follows:
The carbon monoxide and steam reaction generated is reacted, realizes the further preparation of hydrogen, is reacted as follows:
Industrial methane steam reforming process uses Raney nickel, and 750~920 DEG C of operation temperature, operating pressure 2.17-
2.86MPa.The methane steam reforming process of early stage operates under normal pressure, but higher pressure can improve process efficiency.
Reaction is heat absorption, and heat is supplied by combustion chambers burn methane.Methane steam reforming synthesis gas obtained becomes by high/low temperature
Reaction general-carbon oxide conversion is changed into carbon dioxide and additional hydrogen.Methane steam reforming process analyses carbon, reaction in order to prevent
Excessive water vapour is used in charging, industrial process steam/hydrocarbons ratio is 3~5.
Natural gas hydrogen preparation technique is made of four big units, and mainly raw material gas disposal, steam conversion, CO transformation and hydrogen mention
Pure four units, these units play the role of in the hydrogen production process respectively it is different, constitute natural gas hydrogen preparation technology.
Unstripped gas processing unit: raw material gas disposal is first stage and initial stage for natural gas hydrogen preparation,
The quality of this phase process directly decides the quality of natural gas hydrogen preparation, this stage is mainly desulfurization, using some desulfurization
Agent carries out the desulfurization of Primordial Qi, because material gas quantity is bigger, this just needs to compress it, selects bigger centrifugal pressure
Contracting machine is proper, after distilling natural gas, needs to carry out sulfur removal technology before melting down.
Steam conversion unit: it is a more complicated stage that steam, which converts this unit, and vapor is oxidant, in nickel
Hydrocarbons are converted under the action of catalyst, obtain the conversion gas of hydrogen making.It is substantially in this stage using high temperature
The technological parameter of conversion and relatively low water charcoal ratio is arranged, and can preferably economize on resources, improve the economic benefit of enterprise.
CO converter unit: contain a certain amount of CO in the unstripped gas that second unit is sent, in the transformed of this unit
In journey under the effect of the catalyst, make CO and steam reaction and generate CO2And H2.In this unit mainly with high temperature (350
~400 DEG C) and middle low temperature (being lower than 300~350 DEG C) progress.With the development of science and technology, besides to the saving consideration side of resource
Face mainly takes two stages of pyrolytic conversion and low temperature conversion, can preferably economize on resources in this way, reduce cost.
Hydrogen purification unit: this is a critical stage of the last stage and natural gas hydrogen preparation.Current many systems
Hydrogen company all takes the pressure swing adsorption purge system of low power consuming, and decarburization of this hydrogen purification method compared to highly energy-consuming purifies system
Energy conservation and the simplification of process can be better achieved in more low consumption saving for system and methanation system.
Existing natural gas steam reforming hydrogen producing process there is also some problems that these problems are mainly manifested in following several at present
A aspect:
(1) process flow is long, and equipment number is more, and hydrogen manufacturing needs pyroreaction, this just needs more expensive material,
Otherwise it is not able to satisfy hydrogen manufacturing demand, causes equipment investment height.
(2) hydrogen production process needs a large amount of vapor, and a large amount of natural gas is needed to heat steam for fuel.And another party
Residual heat collection recycling in face is not high, and stack outlet temperature is excessively high in the hydrogen production process, leads to many heat wastes, and energy consumption is high, system
Hydrogen cost increases.
(3) whole process needs the catalyst of multiple types, such as selexol process catalyst, steam conversion unit Ni catalysis
Agent, synthesis gas high conversion catalyst, low change catalyzer, a variety of adsorbents of hydrogen purification unit.These catalyst are expensive, consume
Dosage is big, and technical management is complicated, increases administration fee.
(4) methane conversion is about 82%, and for CO conversion ratio less than 45%, process condition is harsh, right in conversion reaction
Equipment manufactures and designs more demanding with the technical ability of operator and theoretical level.
(5) SECTION TUBE FOR HYDROGEN MANNU-FACTURING FURNACE is bulky, and unit scale is big, takes up a large area.
(6) catalyst used in is required to carry out special process pretreatment before putting into production, and on-stream time is long, shut-down process
It is complicated.
Summary of the invention
In order to overcome the above-mentioned problems in the prior art, the invention proposes a kind of plasma chemical chain hydrogen manufacturing sides
Method.This method is suitable for small-scale hydrogen manufacturing, and skid-mounted design can be used, and is particluarly suitable for the scenes such as hydrogenation stations, gas station, utilizes
The gas in gas distributing system built well inexpensive hydrogen manufacturing on the spot, meets the construction demand of hydrogenation stations.
Basic inventive concept of the invention is as follows:
Since methane molecule structure is highly stable, so that methane molecule is difficult to be activated under the conditions of relatively mild.For
The drawback is solved, present invention employs low temperature plasmas for methane conversion.Plasma is electric current by gas, makes gas
The phenomenon that body carries sufficient charge, generates " electrical breakdown ", is a kind of very effective molecule activation means, has sufficiently high
Energy makes reactant molecule dissociation, excitation and ionization, to form the reaction species of overactivity state.It is each in plasma state
Kind particle and group have stronger chemical activity, reduce the supply of energy needed for reacting.
Plasma is mostly derived from bombardment of the high energy electron to methane molecule to the facilitation of methane reforming reaction, breaks
The c h bond of bad methane molecule, generates hydrogen ion group, and specific mechanism is following (Kado et al., 2003):
CH4+e→CH3+ H (E=9eV)
CH4+e→CH2+ 2H (E=10eV)
CH4+ e → CH+3H (E=11eV)
CH4+ e → C+4H (E=12eV)
In formula, e is indicated so that reaction carries out the energy of required bombardment electronics.
In methane, air (O2)、H2In the presence of while O, by CH4The CH generated by bombardmentX, on the one hand may be into one
Step is bombarded and dehydrogenation by high energy electron, may also can be chemically reacted between another aspect group, constantly be formed new activity
Group ultimately generates CO, H2, a small amount of CO of by-product2.It is main possibility process include:
CHX+e→CHX-1+H
CHX+CHX→C2H2X
CO2+e→CO+O
H2O+e→OH+O
O2+e→2O
O+H→OH
H+H→H2
H+CO2←→CO+OH
OH+H←→H2O
CHX+OH←→CHXO+H
CHX+O←→CHXO
CHXO←→CO+x/2H2
By above-mentioned reaction equation as it can be seen that in the present invention, double action of the reactant in plasma and oxygen carrier body catalyst
Under, apparently existing methane vapor reforming generates the reaction of synthesis gas, also has the reaction of carbon dioxide methane dry reforming, there are also first
Alkane partial oxidation and/or oxidation reaction are reforming process more than one (that is, the more reforming reactions of plasma of the present invention).By
In partial oxidation reaction heat release has occurred, which is used to compensate for heat absorption needed for reforming reaction, and reaction has reached heat certainly
Balance.
The product of the more reforming reactions of plasma is a kind of CO, H2、CO2And H2The gaseous mixture of O is preparing high purity hydrogen, and
It meets environmental requirements, according to the present invention preferred technical solution, uses the multiple whole, burning chemistry chains of plasma and pressure-variable adsorption
Hydrogen purification multiple-unit group technology.
Method for preparing hydrogen by reforming provided by the present invention the following steps are included:
It is corresponding at least a pair of of positive and negative anodes are built-in with after light hydrocarbon feedstocks gas and water and air mixing rich in methane
Plasma occurs under the action of excitation of plasma and oxygen carrier body catalyst for the first reactor of blade type electrode multiple whole anti-
It answers, reaction temperature is 600-1100 DEG C, pressure 0.05-3.5MPa, air speed 1500-10000h-1, first reactor outlet object
Hydrogen is exported after flowing through dehydration, purification.
Preferably, the first reactor outlet streams enter hydrogen purification unit after being dehydrated and are purified, and hydrogen mentions
The off-gas of pure unit is anti-into be built-in with the corresponding blade type electrode of at least a pair of of positive and negative anodes second after mixing with air
Device is answered, catalytic oxidation, water gas shift reaction occur under the action of excitation of plasma and oxygen carrier body catalyst, makes to discharge
H in gas2, the complete light hydrocarbon component of unreacted generates H in CO and first reactor2O and CO2, reaction temperature 600-1400
DEG C, pressure 0.05-3.5MPa, air speed 2000-13000h-1, the outlet streams of the second reactor be delivered to flue gas turbine expander hair
Electricity is simultaneously cooling, through overcooled fume-dehydrating, emptying.
In the present invention, the oxygen carrier body catalyst is Me-Fe/Al2O3Oxygen carrier, one of Me Ce, Zr, Ni or more
Kind, Me-Fe metal oxide content is substantially Al in 5-30 mass %, surplus in the oxygen carrier body catalyst2O3Oxygen carrier.
The preparation step of the oxygen carrier body catalyst is as follows: according to Me-Fe metal oxide content in catalyst in 5-30 mass %ization
It learns measurement Law and configures the Me-Fe solution that concentration is 1 mass %-30 mass %, pour at room temperature in advance by 900-1000
The oxidation aluminum strip of DEG C roasting temperature 2-6h is impregnated, and is impregnated 0.5-3h at room temperature, is then evaporated to nothing under 80 DEG C of water-baths
Liquid water dries moisture at 120 DEG C, then is warming up at 900-1200 DEG C with 10-100 DEG C/h speed and roasts 2-6h, obtains
Oxygen carrier body catalyst.
Preferably, it is corresponding to be built into few a pair of of positive and negative anodes respectively for the top of the first reactor and second reactor
Blade type electrode makes electric current gas breakdown logistics generate plasma, plasma arcs is along air-flow side under 2-25kV voltage
Extend to sliding, respectively enters the oxygen carrier catalyst bed inside first reactor and second reactor.
It is further preferred that the electrode is respectively provided with 2 pairs or 2 pairs or more in first reactor and second reactor, formed
One sliding arc blade type electrode group；Alternatively, multiple sliding arc blades are respectively set in first reactor and second reactor
Formula electrode group, to meet the requirement for improving treating capacity.
In the present invention, in the case where oxygen carrier body catalyst needs regenerated situation, by switching relevant pipeline and valve, make
The more reforming reactions of plasma of the light hydrocarbon feedstocks gas carry out in the second reactor, keep the catalysis oxidation of the off-gas anti-
It answers, water gas shift reaction carries out in the first reactor；Preferably, by switching relevant pipeline and valve, regularly into
Switching between the switching of row first reactor and second reactor or multiple reactors is (for example, three or more；Or
The reactor of the changeable operation of multiple groups is arranged in parallel), to maintain the reactivity worth of the oxygen carrier body catalyst.
Compared with the immediate prior art, method provided by the present invention is had the beneficial effect that:
(1) oxygen carrier body catalyst can come into operation without pretreatment, and device for producing hydrogen, which can be opened, to stop, and can also transport for a long time
Turn, is suitable for the live hydrogen manufacturing of the discontinuous stable gas consumption scene such as hydrogenation stations；
(2) plant area is small, can skid-mounted design, be suitable for the construction of distributed hydrogen energy system；
(3) the more reforming process of plasma are used, without the facilities such as additional heating furnace, safety and environmental protection；It is compared to tradition
Natural gas hydrogen preparation process energy consumption it is low, hydrogen manufacturing is at low cost；
(4) system integration fume afterheat generates electricity, power generation be used directly for the water pump of this system, compressor,
The electricity consumptions such as control system, electrical component, energy conversion efficiency are high；
(5) oxygen carrier body catalyst is fixed in reactor, without flowing, wears small, long service life.
Detailed description of the invention
Fig. 1 is a kind of flow diagram of embodiment of method provided by the present invention；
Fig. 2 is the structural schematic diagram of heretofore described reactor；
Fig. 3 is the schematic diagram of heretofore described sliding arc plasma blade plate electrode；
Fig. 4 is the schematic diagram of heretofore described sliding arc plasma blade plate electrode group；
Fig. 5 is multi-blade group scheme of installation in heretofore described reactor.
It should be noted that not providing heating, temperature measure and control, flow measurement and control in Fig. 1, cooling, changing
Heat, level gauging and control, pressure measurement and control, compressor, shutting down pay the ancillary equipments such as line, instrument, electrical, pipeline,
Valve and control loop and the gas-chromatography of necessary online analytical instrument such as gas composition analysis, but do not represent and be not required to
Want these facilities.
Specific embodiment
Plasma chemical chain hydrogen production process provided by the present invention is further illustrated below in conjunction with attached drawing, and the present invention is not
Therefore it is any way limited.
Present invention employs a kind of plasma chemical chain reforming hydrogen producing technologies from rich in methane gas hydrogen making.
Raw material of the invention is biogas, natural gas, shale gas, coal bed gas, oil refinery dry gas, oven gas, casing-head gas, coal mine
Road gas etc. is rich in the lighter hydrocarbons resource of methane, using plasma chemical chain burning technology, produces high-purity hydrogen (H2), it exports simultaneously
Electric energy.
The oxygen carrier body catalyst that the present invention uses is Me-Fe/Al2O3Oxygen carrier, one or more groups of Me Ce, Zr, Ni etc.
It closes.Following steps preparation can be used in the oxygen carrier body catalyst: according to Me-Fe metal oxide content in catalyst in 5-30%
(mass percent, similarly hereinafter) stoichiometric arrangement goes out the Me-Fe solution that concentration is 1%-30%, pours into prior warp at room temperature
The oxidation aluminum strip for crossing 900-1000 DEG C of roasting temperature 2-6h is impregnated, and impregnates 0.5-3h at room temperature, then in 80 DEG C of water-baths
Lower rotation is evaporated to no liquid water, then dries moisture at 120 DEG C in baking oven, then be warming up to 10-100 DEG C/h speed
2-6h is roasted at 900-1200 DEG C, obtains oxygen carrier body catalyst.Wherein Me metal oxide content accounts for Me-Fe metal oxide and contains
Amount is 0%-50%, preferably 0.5%-48%, further preferred 1%-45%.
As shown in Figure 1, unstripped gas is mixed with the recirculated water from the second water distributing can 4, (molal quantity of water rubs steam/hydrocarbons ratio with carbon
The ratio between your number) it can be 0.05-0.5, it is changed with 1 outlet streams of first reactor in heat exchanger 7 after the first valve 9
Then heat mixes with air, for example, carbon ratio (the ratio between oxygen atom molal quantity and carbon molal quantity) can be 0.7-2.0, it is acquired
Mixture flow enter first reactor 1.First reactor 1 serves as reforming reactor at this time, in first reactor by it is equal from
The more reforming reactions of plasma occur under the action of son and oxygen carrier body catalyst, will be reacted by adjusting the carbon ratio of incoming mixture
Temperature is controlled at 600-1100 DEG C, pressure 0.05-3.5MPa, air speed 1500-10000h-1；Preferably, reaction temperature controls
At 650-1050 DEG C, pressure 0.08-3.0MPa, air speed 1650-9500h-1；It is further preferred that reaction temperature control exists
700-1000 DEG C, pressure 0.1-2.8MPa, air speed 1800-9000h-1.First reactor outlet streams pass through third valve
11 flow to heat exchanger 7 and the mixture of unstripped gas and water exchanges heat and cools down, subsequently into the first water distributing can 3, in the first water distributing can 3
Bottom discharge, which is reformed, generates water (waste water).First water distributing can, 3 top gas phase logistics enters hydrogen purification unit 5, by pressure-variable adsorption
(PSA) technique obtains the hydrogen product of purity > 99.99%.The off-gas that PSA comes out passes through the 4th valve 12 and mixes with air
Enter second reactor 2 afterwards, second reactor 2 serves as combustion reactor at this time, in second reactor 2 by excitation of plasma and
Catalytic oxidation, water gas shift reaction occur under the action of oxygen carrier body catalyst, makes the H in PSA off-gas2, CO and
The complete light hydrocarbon component of unreacted generates H in one reactor2O and CO2, reaction temperature is 600-1400 DEG C, pressure 0.05-
3.5MPa, air speed 2000-13000h-1；Preferably, reaction temperature is 650-1350 DEG C, pressure 0.08-3.2MPa, air speed 2200-
12000h-1；It is further preferred that reaction temperature is 700-1300 DEG C, pressure 0.1-3.0MPa, air speed 2400-11000h-1.The
Two reactors, 2 outlet streams (oxygen deprivation flue gas) enter the power generation of flue gas turbine expander 6 and cooling after the second valve 10, through overcooled
Oxygen deprivation flue gas separating and dehydrating, CO in the second water distributing can 42It is emptied from top.
In order to improve the efficiency of process of the present invention and reduce the equipment volumes such as reactor, heat exchanger, water distributing can
And pipe diameter, it is preferable that air in the technique can be oxygen-enriched air, for example, with air separation plant by the oxygen content in air
It is increased to 90%-97% (volume).
In the case where oxygen carrier catalyst activity reduction needs regenerated situation, above-mentioned first valve 9, the second valve 10, third
Valve 11, the 4th valve 12 are switched to other direction, and first reactor 1 serves as combustion reactor at this time, in first reactor 1
Oxygen carrier body catalyst carry out coke burning regeneration.And second reactor 2 serves as reforming reactor hydrogen making.Such circulate operation,
Can the long periods of holding meanss do not stop work operation.
The reactor that the present invention uses is built-in sliding arc plasma reactor, and the structural schematic diagram of reactor is referring to fig. 2.
Feed gas stream enters from reactor head, the corresponding blade type electrode of at least a pair of of positive and negative anodes built in reactor head,
Feed gas stream passes through the blade type electrode, after electrode arc excitation, into oxygen carrier catalyst bed.
The schematic diagram of blade type electrode is referring to Fig. 3.Narrowest position distance is 0.5-10mm between two electrode blades, preferably
For 1-6mm.Blade lengths are 5-60mm, preferably 20-50mm.Under the high pressure of 2-25kV, it is preferable that in 5-20kV voltage
Under, it is further preferred that the voltage applied on two electrodes makes electric current gas breakdown generate plasma under 8-15kV voltage
Body, plasma arcs 15 is slided along airflow direction to extend.When requiring unstripped gas treating capacity larger, electrode is to can use 2
Pair or 2 pairs or more.Fig. 4 is the schematic diagram of sliding arc plasma blade plate electrode group.The alternate multipair electrode of positive and negative electrode surrounds air inlet
Pipe is installed to form a sliding arc blade electrode group, can form the sliding arc of a larger area, improve single feed inlet
Excitation of plasma treating capacity.The treating capacity of reactor is further increased if necessary, it can be using in reactor as shown in Figure 5
Multi-electrode group Installation Modes.Each 16 center of electrode group is feed inlet 17, and multiple feed improves the treating capacity of separate unit reactor.
Unit capacity can also be improved using more small reactor parallel way.
The present invention is reacted due to using oxygen carrier body catalyst and plasma exciatiaon, and reforming reaction is without carrying out catalyst
Pretreatment, and can realize to open and stop, device on-stream time is short, can reach reaction temperature, output hydrogen in 10-60min
Gas.
Further illustrate method for preparing hydrogen by reforming provided by the present invention below by embodiment, but the present invention not therefore and
It is any way limited.
Embodiment 1
This example demonstrates that: the preparation of oxygen carrier body catalyst.
Method for preparing catalyst are as follows: weigh the 980 of 13.84g Sinopec catalyst branch Chang Ling catalyst plant production
The cloverleaf pattern aluminium oxide extrusion roasted at DEG C is placed in 500ml round-bottomed flask for use.Separately weigh the prosperous beautiful peaking work in Taiyuan City
The nine water ferric nitrate (Fe (NO of industrial high-class product of factory's production3)3·9H2O) 20.23g, the production of group of the lanthanides Chemical Co., Ltd., Jining City
Cerium nitrate hexahydrate (Ce (NO3)36H2O) 5.44g is placed in 200ml beaker, and 112g distilled water is added into beaker, is stirred molten
Solution obtains Ce (NO3)3/Fe(NO3)3Solution.Configured Ce-Fe solution is slowly dropped to equipped with 13.84g aluminium oxide extrusion
500ml round-bottomed flask in, rotary evaporation 2h, revolving speed 35rpm/min, 80 DEG C of water-bath.The oxidation aluminium extruded of Ce-Fe will be impregnated with
Item moves in baking oven, and 120 DEG C of drying overnight obtain oxygen carrier catalyst precursor.Again by presoma in Muffle furnace, with 2 DEG C/
Min speed is warming up to 950 DEG C of constant temperature calcining 4h, and Temperature fall obtains oxygen carrier body catalyst A.
Weighing oxidation aluminum strip is 14.46g, the zirconium nitrate (Zr (NO produced with Shanghai Di Yang Chemical Co., Ltd.3)4·
5H2O) 5.38 grams of substitution cerium nitrate hexahydrates prepare oxygen carrier body catalyst B using preparation step same as oxygen carrier body catalyst A.
Weighing oxidation aluminum strip is 15.06g, the nickel nitrate (Ni (NO produced with Shandong De Sheng new material Co., Ltd3)2·
6H2O) 3.84 grams of substitution cerium nitrate hexahydrates prepare oxygen carrier body catalyst C using preparation step same as oxygen carrier body catalyst A.
16g aluminium oxide extrusion is weighed to be placed in 500ml round-bottomed flask for use.It is raw separately to weigh Xin Yu peaking factory, Taiyuan City
The nine water ferric nitrate (Fe (NO of industrial high-class product of production3)3·9H2O) 20.23g is placed in 200ml beaker, is added into beaker
52.5g distilled water, stirring and dissolving obtain Fe (NO3)3Solution.Configured iron nitrate solution is slowly dropped to equipped with 16g oxygen
In the round-bottomed flask for changing the 500ml of aluminium extruded item, rotary evaporation 2h, revolving speed 35rpm/min, 80 DEG C of water-bath.The oxygen of Fe will be impregnated with
Change aluminium extruded item to move in baking oven, 120 DEG C of drying overnight obtain oxygen carrier catalyst precursor.Again by presoma in Muffle furnace,
950 DEG C of constant temperature calcining 4h are warming up to 2 DEG C/min speed, Temperature fall obtains oxygen carrier body catalyst D.
Embodiment 2
This example demonstrates that: the implementation result of hydrogen production process provided by the present invention.
The test of plasma chemical chain reformation hydrogen production has been carried out on a set of experimental rig according to process flow shown in Fig. 1.
The internal diameter of first reactor and second reactor is 92mm, and reactor inlet is respectively mounted pair of sliding arc cutter plate electrode, and two
Narrowest position spacing is 2mm, the long 30mm of blade between electrode.Embodiment is respectively charged into first reactor and second reactor
The 1 oxygen carrier body catalyst 1.86L being prepared.Natural gas is used to carry out hydrogen manufacturing trial run as unstripped gas.Natural gas forms number
According to being shown in Table 1, the test result under different oxygen carrier body catalysts is shown in Table 2.
In addition, being transported for a long time using 500h has been carried out under the process conditions in embodiment 5 listed by oxygen carrier body catalyst A, table 2
Turn test, hydrocarbon conversion rate fall off rate is 0.06%/moon, it is seen that plasma catalytic part that is oxygen-containing in feed gas, having water
In oxidation reaction process, the carbon distribution that restrained effectively oxygen carrier body catalyst is inactivated, the deactivation rate very little of oxygen carrier body catalyst,
Running requirements steady in a long-term can be met.
Referring to attached drawing 1, when each on-test, air is first passed through to first reactor with 40NL/min flow, is then beaten
Plasma electrode power supply (220V/50Hz) is opened, 9.5kV voltage is applied to sliding arc blade electrode by transformer, is being observed
Plasma electric interpolar generates electric current (electric current meter reading fluctuates between 3.5-4.2 amperes in 220V electric power loop), oxygen carrier is urged
After agent bed head temperature changes, natural gas is passed through to first reactor with 4NL/min flow, on bed temperature is rapid
It rises.Since plasma electrode is powered " igniting " excitation plasma arc, reactor oxygen carrier catalyst bed top in about 20min
Temperature is warming up to 600 DEG C or more, and first reactor reaches multiple whole reacting initial temperature, start starting water filling, and increase air,
Natural gas feed flow adjusts carbon ratio and steam/hydrocarbons ratio, measures a large amount of hydrogen components in product gas flow after about 10min clock, show
There are more reforming reactions.
For second reactor, the program that goes into operation is similar to first reactor.Before this with 40NL/min flow be passed through air,
Plasma power supply is opened, natural gas is then passed through with the flow of 4NL/min, bed temperature rises rapidly, bed temperature in about 20min
Degree rises to 600 DEG C, natural gas is switched to the off-gas of hydrogen purification unit acquisition, into normal plasma catalytic oxygen
Change, water gas shift reaction.Air mass flow is adjusted to control the conversion ratio of CO, so that it is completely converted into CO2, without right in tail gas
The harmful CO gas of environment.
When shut-down, natural gas, plasma electrode power supply are directly cut off, is observing the decline of oxygen carrier reaction bed temperature
After cut off water filling, reduce Temperature fall after air mass flow to 10NL/min.
As seen from the data in Table 2, the minimum natural gas processing amount of the reactor assembly is 13NL/min, and maximum throughput is
125.5NL/min, the minimum 12.6NL/min of first reactor exporting hydrogen production quantity, maximum can reach 200.8NL/min, former
Material processing and hydrogen production quantity have very big flexibility.
By experimental result as it can be seen that the conversion ratio of methane can reach 98.1%, the hydrogen-carbon ratio for reforming gas be can reach
3.07, conversion efficiency is high.In addition, the steam/hydrocarbons ratio of first reactor is 0.14-0.23, insufficient conventional gas vapour reforming hydrogen producing
/ 10th of technique steam/hydrocarbons ratio, energy consumption needed for reforming reaction water filling vaporizes are greatly reduced.
As it can be seen that plasma chemical chain method for preparing hydrogen by reforming of the present invention, reactor volume is small, and treating capacity is flexible, shutting down speed
Degree is fast, can open and stop, and hydrogen yield is high, and operation energy consumption is low.The gas that plasma chemical chain reforming reaction generates is mentioned using PSA
Pure, hydrogen purity may be up to 99.99% or more.Live hydrogen manufacturing suitable for mobile, distributed hydrogenation stations.
1 natural gas of table composition
2 plasma chemical chain reformation hydrogen production test result of table
* note: use oxygen content for 95% oxygen-enriched air.
Claims (10)
1. a kind of method for preparing hydrogen by reforming, the following steps are included:
Enter after light hydrocarbon feedstocks gas rich in methane and water and air mixing and is built-in with the corresponding blade of at least a pair of of positive and negative anodes
The more reforming reactions of plasma occur under the action of excitation of plasma and oxygen carrier body catalyst for the first reactor of formula electrode, instead
Answering temperature is 600-1100 DEG C, pressure 0.05-3.5MPa, air speed 1500-10000h-1, first reactor outlet streams warp
Hydrogen is exported after dehydration, purification；Preferably, reaction temperature is 650-1050 DEG C, pressure 0.08-3.0MPa, air speed 1650-
9500h-1；It is further preferred that reaction temperature is 700-1000 DEG C, pressure 0.1-2.8MPa, air speed 1800-9000h-1。
2. method for preparing hydrogen by reforming according to claim 1, which is characterized in that the first reactor outlet streams are through being dehydrated
Enter hydrogen purification unit afterwards to be purified, the off-gas of hydrogen purification unit enters after mixing with air is built-in at least a pair
The second reactor of the corresponding blade type electrode of positive and negative anodes, is urged under the action of excitation of plasma and oxygen carrier body catalyst
Oxidation, water gas shift reaction make the H in off-gas2, the complete light hydrocarbon component of unreacted in CO and first reactor
Generate H2O and CO2, reaction temperature is 600-1400 DEG C, pressure 0.05-3.5MPa, air speed 2000-13000h-1, described second is anti-
It answers the outlet streams of device to be delivered to flue gas turbine expander to generate electricity and cool down, through overcooled fume-dehydrating, emptying；Wherein it is preferred to instead
Answering temperature is 650-1350 DEG C, pressure 0.08-3.2MPa, air speed 2200-12000h-1；It is further preferred that reaction temperature is
700-1300 DEG C, pressure 0.1-3.0MPa, air speed 2400-11000h-1。
3. method for preparing hydrogen by reforming according to claim 2, which is characterized in that the oxygen carrier body catalyst is Me-Fe/Al2O3
Oxygen carrier, one of Me Ce, Zr, Ni or a variety of, Me-Fe metal oxide content is 5-30 in the oxygen carrier body catalyst
Quality %, surplus Al2O3Oxygen carrier；Preferably, the content of Me metal oxide accounts for the ratio of Me-Fe metal oxide content
For 0-50%, preferably 0.5-48%, further preferred 1-45%.
4. method for preparing hydrogen by reforming according to claim 3, which is characterized in that the preparation step of the oxygen carrier body catalyst is such as
Under: going out concentration in 5-30 mass % stoichiometric arrangement according to Me-Fe metal oxide content in catalyst is 1 mass %-
The Me-Fe solution of 30 mass %, pour at room temperature in advance by 900-1000 DEG C of roasting temperature 2-6h oxidation aluminum strip into
Row dipping, impregnates 0.5-3h at room temperature, no liquid water is then evaporated under 80 DEG C of water-baths, dry moisture at 120 DEG C, then
It is warming up at 900-1200 DEG C with 10-100 DEG C/h speed and roasts 2-6h, obtain oxygen carrier body catalyst.
5. method for preparing hydrogen by reforming according to any one of claim 1 to 4, which is characterized in that the first reactor and
The top of second reactor is built into the corresponding blade type electrode of few a pair of of positive and negative anodes respectively, under 2-25kV voltage, preferably
Ground, under 5-20kV voltage, it is further preferred that so that electric current gas breakdown logistics is generated plasma under 8-15kV voltage,
Plasma arcs is slided along airflow direction to extend, and is formed by reaction stream and respectively enters positioned at first reactor and second instead
Answer the oxygen carrier catalyst bed inside device.
6. method for preparing hydrogen by reforming according to claim 5, which is characterized in that be set to first reactor and second reactor
Interior blade type electrode, the distance of narrowest position is 0.5-10mm, preferably 1-6mm between two corresponding electrode blade；
Blade lengths are 5-60mm, preferably 20-50mm.
7. method for preparing hydrogen by reforming according to claim 6, which is characterized in that in first reactor and second reactor, institute
It states blade type electrode and is respectively provided with 2 pairs or 2 pairs or more, the multipair electrode for keeping positive and negative electrode alternate is installed to form one around air inlet pipe
Sliding arc blade type electrode group；Alternatively, multiple sliding arc blade type electricity are respectively set in first reactor and second reactor
Pole group, to meet the requirement for improving unit capacity.
8. method for preparing hydrogen by reforming according to claim 1, which is characterized in that the light hydrocarbon feedstocks gas is selected from: biogas, natural
One of gas, shale gas, coal bed gas, oil refinery dry gas, oven gas, casing-head gas, coal mine gallery gas are a variety of.
9. the method for preparing hydrogen by reforming according to any one of 2,3 and 6-8 of claim, which is characterized in that be catalyzed in oxygen carrier
Agent needs in regenerated situation, by switching relevant pipeline and valve, keeps the plasma of the light hydrocarbon feedstocks gas multiple whole anti-
It should carry out in the second reactor, the catalytic oxidation that makes the off-gas, water gas shift reaction are in the first reactor
It carries out；Preferably, by switching relevant pipeline and valve, the switching of first reactor and second reactor is regularly carried out,
Or the switching between multiple reactors, to maintain the reactivity worth of the oxygen carrier body catalyst.
10. method for preparing hydrogen by reforming according to claim 9, which is characterized in that the air is oxygen-enriched air；Preferably,
Oxygen content in the oxygen-enriched air is 90-97 volume %.
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