CN104998654A - Nickel-based catalyst, preparation method thereof and method for catalyzing methane cracking to produce hydrogen - Google Patents
Nickel-based catalyst, preparation method thereof and method for catalyzing methane cracking to produce hydrogen Download PDFInfo
- Publication number
- CN104998654A CN104998654A CN201510358286.5A CN201510358286A CN104998654A CN 104998654 A CN104998654 A CN 104998654A CN 201510358286 A CN201510358286 A CN 201510358286A CN 104998654 A CN104998654 A CN 104998654A
- Authority
- CN
- China
- Prior art keywords
- methane
- hydrogen
- catalyst
- metal
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
Abstract
The invention provides a nickel-based catalyst, a preparation method thereof and a method for catalyzing methane cracking to produce hydrogen. The catalyst includes a nickel-based composite metal oxide with a general formula shown as xX.yA.zB.(100-x-y-z)M, wherein X is Ni and /or its oxide, A is an auxiliary metal component, B is an assistant metal component, and M is a carrier. The method for catalyzing methane cracking to produce hydrogen includes: contacting methane-containing feed gas with the catalyst in a high density circulating fluidized bed reactor, and carrying out catalytic cracking reaction to obtain hydrogen containing product-gas and a deactivated catalyst, performing separation in a settler, letting the catalyst carry carbon deposit to enter a regenerator for regeneration, thus obtaining regenerated flue gas containing CO or synthetic gas, and letting the regenerated catalyst enter the reactor again. The heat generated by regeneration supplies the energy need of the whole system to realize self-heating operation. The method provided by the invention can realize large-scale continuous production of hydrogen at low price, and can effectively reduce energy consumption and save the production cost.
Description
Technical field
The invention belongs to chemical preparation, petroleum gas chemical production technical field, particularly nickel-base catalyst of hydrogen and preparation method thereof is produced in a kind of catalytic methane cracking, and a kind of methane catalytic decomposition produces the method for hydrogen.
Background technology
Natural gas is the petrochemical industry fuel source enriched very much, and existing explored Natural Gas Reserve in World is 142.1 tcms, and prospective reserves is 250-350 tcm.The explored gas reserves of China is 3.1 tcms, and prospective reserves is 26-33 tcm, accounts for 1/10 of world's prospective reserves.Methane is the main component of natural gas, and its content is more than 90%, and thus many countries pay much attention to the processing and utilization of methane in the world in recent years.Hydrogen/the carbon atomic ratio of methane, up to 4 (naphtha is about 2, and liquefied petroleum gas is 2.5-2.7), is the fossil energy being rich in hydrogen most, is the ideal fossil feedstock of the cheap hydrogen of extensive preparation.
Be that waste hydrogen mainly contains two approach with methane: one is by preparing synthesis gas (H
2with the gaseous mixture of CO), then obtain hydrogen with physics or chemical method removing CO, comprise the techniques such as methane steam reforming (SRM), partial oxidation process (POM), self-heating recapitalization (ATR), CO 2 reformation and mixed reforming; Another is that direct for methane catalytic pyrolysis is obtained hydrogen and charcoal.
SRM is the industrial hydrogen production process be most widely used at present, technology is also ripe, but this technology transfer cost is high, technical process is owing to controlling by thermodynamical equilibrium, usually to carry out under high temperature (>800 DEG C), course of reaction needs to burn a large amount of natural gas to maintain the temperature needed for reaction, causes the waste of carbon resource.In order to obtain pure hydrogen, also need a series of conversion and purification process.Visible, it is higher that this technology has self single plant energy consumption, and equipment investment cost is high, CO
2discharge capacity is large waits deficiency.Although POM technique efficiently can produce relatively inexpensive hydrogen by highly selective, because this process uses pure oxygen, except increasing expensive air separation unit investment and oxygen cost, also there is huge hidden peril of explosion.Therefore there is potential safety hazard comparatively greatly in this technology, and technology maturity is not enough, and needs the shortcomings such as pure oxygen cost is higher, and single device capbility is lower.These technology create a large amount of CO and CO while generation hydrogen
2.From synthesis gas, remove CO not only makes reaction complicated, and also unfavorable to the economization of whole process.So the hydrogen production process generated without CO is the direction that current this area is being explored.
By contrast, the high temperature pyrolysis hydrogen producing technology that 20 middle of century just develop makes the direct catalytic pyrolysis of methane, and this reaction is the gentle endothermic reaction, and energy consumption is low, and course of reaction does not need aqueous vapor to replace and CO
2removing process, enormously simplify reaction process, and process is not to airborne release carbon dioxide, greenhouse effects can not be caused, simultaneously accessory substance more has economic worth, is easy to store and can be used for the solid carbon of following carbon resource, and can preparing high purity hydrogen, therefore this technique significantly can reduce investment and the hydrogen manufacturing cost of device for producing hydrogen, but because the carbon of this part is difficult to see economic benefit in a short time as functional materials such as CNTs, so key to resolve the continued operation of reactor, the recycling and the problems such as the utilization of carbon black of catalyst.
The method being directly used in hydrogen gas production by natural gas pyrolysis known in the art mainly comprises following several.Such as, in the patent CN100511802C of University Of Tianjin, disclose a kind of energy resource system based on methane cracking and fuel cell, the catalyst based catalytic cracking methane of the Ni of fluidized-bed process is adopted to generate hydrogen and carbon distribution, hydrogen is used for proton membrane fuel battery (PEMFC), and carbon distribution is as the raw material of carbon consuming cell.Its system thermal efficiency reaches 69%, simultaneously by utilizing heat-exchange network to achieve stable state autothermal operation.Although the method adopts fluidized-bed reactor, the object product of its methane catalytic decomposition process is hydrogen and Carbon fibe, cannot realize the reaction-regeneration cycle operation of catalyst.Secondly due to carbon consuming cell and the scale utilization of proton membrane fuel battery and the restriction of technology maturity; large-scale production cannot be realized; and proton membrane fuel battery to the ingredient requirement of methane catalytic decomposition and product hydrogen purity requirement higher, otherwise the CO be mixed with can cause the poisoning of battery material.
In the patent CN101193817B of Cabot Corporation, provide and a kind ofly adopt grading reactor can produce useful hydrogen or at least comprise the gas of hydrogen, simultaneously can with can the technical scheme of high-quality carbon black of receiving amount.Have employed grading reactor, the adaptive capacity for sulfur-bearing raw material strengthens, and can produce hydrogen and carbon black two kinds of products, but technique uses multiple reactor simultaneously simultaneously, causes operation too complicated; In the hydrogen of preparation, other components such as CO are more, and need to carry out purifying hydrogen of hydrogen by operations such as steam conversion, separation of products technique is loaded down with trivial details, and energy consumption is higher.
In the patent application CN101300191A of Electrovac AG, refer to and steam reformation is carried out to prepare hydrogen to the hydrocarbon gas carrying out reformer unit, produce the technology of nano-sized carbon simultaneously.This technology adopts granular ceramic body or granular vitreum to be the transition metal composite oxide catalytic agent of carrier, and optimize Mo, Co for its active component, the oxide of alkaline-earth metal and/or hydroxide are its inert component.The hydrogen-containing gas that hydrogen product/hydrogen alkane is used as gas station is sold, and is that the carbon nano-tube material produced provides some potential application.But the high energy consumption problem that steam reforming brings still does not solve, and the hydrogen purity of preparation is usually less than 80vol.%, therefore complicated last handling process still to be carried out in order to obtain pure hydrogen.
In the patent CN101164864B of Kunming University of Science and Technology, disclose a kind of method of methane catalytic decomposition hydrogen manufacturing and two-step method making synthesized gas, using cerium-based composite oxides as catalyst, the first catalytic pyrolysis of comparatively low discharge is adopted by methane to be hydrogen and charcoal, be carbon monoxide by char combustion again, realize catalyst regeneration simultaneously, collect respectively through hydrogen recovery system and carbon monoxide recovery system, be mixed into synthesis gas, described cerium-based composite oxides is cerium cobalt, cerium nickel or cerium iron complex oxides, and the mol ratio of cerium cobalt complex oxides is 2:1, the mol ratio of cerium ni compound oxide is 4:1, the mol ratio of cerium iron complex oxides is 7:30.This invention makes whole technological process short, and reaction temperature reduces than traditional hydrogen production process, simple to operate, can reduce production cost, can need the mixing carrying out different proportion, expanded application scope according to downstream chemical product or liquid hydrocarbon preparation technology.But because the method adopts fixed bed reactors and the time of catalyst regeneration carbon monoxide to be 60-90 minute, need intermittently operated, simultaneous reactions raw material only has 10-55Ncm
3min
-1, the treating capacity of unit interval is too little, cannot realize large-scale operation.
Tsing-Hua University provides a kind of method that low-temperature catalytic pyrolysis being applied to petroleum gas chemical field prepares hydrogen and nano-sized carbon in patent CN101337655B.The method adopts metallic catalyst catalytic cracking methane under the relative low temperature of 400-700 DEG C.Need before reaction to pass into hydrogen or carbon monoxide carries out reduction 0.5-2h to catalyst, need to consume the hydrogen of more amount or carbon monoxide, and due to the requirement of purity, cause running cost to raise, and according to hydrogen, directly cause the decline of hydrogen gross production rate; When needing during reaction together to pass into cracking with methane, the price such as ethene, acetylene, propylene of heat release is relatively expensive, produce the very large gas of power consumption, although these hydro carbons are conducive to collaborative methane cracking, effectively can reduce reaction temperature, but relatively current ethene, acetylene, propylene resource are shorter, therefore the extensive Cheap highly effective of the method prepares hydrogen, and the difficulty being applied to petrochemical industry is higher.
In the patent application CN101646488A of Eden Innovations Ltd. and University of Queensland, describing a kind of microwave that adopts provides energy warms cracking methane for hydrogen-rich fuel.This method adopts Ni or Ni alloy catalyst can obtain the hydrogen of about 20-30% by volume and the methane of about 70-80% by volume under room temperature.Need to use hydrogen pretreatment catalyst before heatable catalyst, after reaction, hydrogen pure is in fact obtained to generation gas treatment.The method effectively can reduce energy consumption, and realizes the needs of small-sized hydrogenation stations.
In the patent application CN101838480A of Qujin Zhongyi Finechemical Co., Ltd., describe a kind of methane under anaerobic hot conditions, realization response stove accumulation of heat in fixed bed reactors also gets rid of residual air-methane cracking alternation pattern, and multistage group by cracking reaction stove joins the amplification and continuous high-efficient production hydrogen and carbon black that can realize output.It is 1300-1500kcal/Nm that the method takes full advantage of calorific value
3low calorie fuels as combustion-supporting gas, reaction efficiency is higher.
In patent application CN102335609A and CN102335610A of East China Normal University, the Ni-based and nickel cobalt-base catalyst that to respectively describe with cerium modified aluminium oxide be carrier.First cerium salt solution incipient impregnation γ-Al is all adopted during this two kinds of catalyst preparing
2o
3on carrier, after drying and roasting, respectively incipient impregnation is in the mixed aqueous solution of nickel salt aqueous solution or nickel salt and cobalt salt, and final drying roasting obtains the presoma of catalyst, at 850-1050 DEG C, obtain two kinds of catalyst respectively after hydrogen reducing.The reaction of this Catalyst Design is methane-steam reformation, methane portion oxidation, methane-carbon dioxide or methane self-heating recapitalization prepare synthesis gas, and does not all relate to the application in methane catalytic decomposition reaction.The anti-carbon performance of catalyst, reactivity and selective higher, the stability of reaction is better.
In the patent application CN102583242A of Dalian University of Technology, describing a kind of active component adopting active carbon or carbon fiber to prepare is the catalyst of Fe, Co or Ni.This catalyst is at temperature 650-850 DEG C, 15L/ (hg
cat) total air speed under can be cracked into carbon distribution and hydrogen by catalytic methane.The carbon distribution that reaction generates can use as the catalyst of catalytic cracking methane again, and this carbon deposition catalyst has good catalytic activity and stability.But this catalyst hydrogen conversion is lower, the object preparing hydrogen on a large scale cannot be realized.
And it should be noted that, in the technology of current hydrogen manufacturing and synthesis gas, substantially fixed bed is all adopted to operate, process is comparatively loaded down with trivial details, production efficiency is low, is unfavorable for very much the efficient large-scale production of hydrogen, is unfavorable for the production cost reducing product, and carbon distribution can not get good utilization, reduce the economic benefit of whole technical process.
Between the pluses and minuses of above prior art, the method that novel methane catalytic decomposition produces hydrogen still needs to be developed further.
Summary of the invention
For solving the problems of the technologies described above, a kind of catalytic methane cracking is the object of the present invention is to provide to produce nickel-base catalyst of hydrogen and preparation method thereof.This nickel-base catalyst is a kind of Ni-based O composite metallic oxide catalyst, and it can produce hydrogen by efficient catalytic methane cracking at a lower temperature.
The present invention also aims to provide a kind of methane catalytic decomposition to produce the method for hydrogen.The method can reduce energy consumption and extensive cheapness prepares high-purity hydrogen.
For achieving the above object, the present invention provide firstly the nickel-base catalyst that hydrogen is produced in a kind of catalytic methane cracking, and this catalyst comprises the Ni-based composite metal oxide shown in general formula (I):
XXyAzB (100-x-y-z) M general formula (I),
Wherein, X is Ni and/or its oxide, and A is assistant metal component, and B is promoter metal component, and M is carrier, and x, y and z represent the mass percent of X, A and B respectively, and 0.1≤x≤40,0.1≤y≤30,0.1≤z≤10.
In above-mentioned nickel-base catalyst, preferably, described assistant metal component A comprises the oxide of one or more metals in Fe, Nb, Ta, Co, V, Cu, Zn, Ir, Ge, Sn, Mo, W, Ce and Sb etc. and/or metal; More preferably, described assistant metal component A comprises one or more metals in Fe, Nb, Mo, Ir, V, Ce, Co and Cu and/or metal oxide; Particularly preferably, described assistant metal component A comprises the oxide of one or more metals in Fe, Mo, Ce, Cu and Co and/or metal.
In above-mentioned nickel-base catalyst, preferably, described promoter metal B component comprises the oxide of one or more metals in Na, K and Mg etc. and/or metal; More preferably, described promoter metal B component comprises the oxide of K and/or Mg metal and/or metal; Particularly preferably, described promoter metal B comprises metal K and/or its oxide.
In above-mentioned nickel-base catalyst, preferably, described carrier M comprises Al
2o
3, SiO
2, TiO
2, the combination of one or more (can be several composite oxide carriers) in MgO and CaO etc.; More preferably, described carrier M comprises γ-Al
2o
3and/or SiO
2.
According to the specific embodiment of the present invention, preferably, the granularity of above-mentioned nickel-base catalyst is less than 200 μm.
Present invention also offers the preparation method that the nickel-base catalyst of hydrogen is produced in a kind of above-mentioned catalytic methane cracking, it comprises the following steps:
(1) at room temperature, make the metal nitrate of carrier M and assistant metal component A, metal phosphate, metal acetate salt, being combined in water of one or more in metal hydroxides and metal oxide mixes, be preferably the metal nitrate of assistant metal component A, add the metal carbonate of promoter metal B component again, the combination of one or more in alkali metal bicarbonate salt and metal hydroxide solutions, be preferably the metal carbonate (assistant metal component A is deposited on carrier M) of promoter metal B component, then dry at 80-200 DEG C, roasting at 400-800 DEG C again, obtain modified support,
(2) at room temperature, described modified support is mixed in water with the nitrate of nickel (nitrate solution that modified support floods nickel), then the combination of one or more in the metal carbonate of promoter metal B component, alkali metal bicarbonate salt and metal hydroxide solutions is added, be preferably the metal carbonate (nickel is deposited on modified support) of promoter metal B component, then dry at 80-200 DEG C, roasting at 600-1000 DEG C again, obtain Ni-based composite metal oxide, be the nickel-base catalyst that hydrogen is produced in described catalytic methane cracking.
In above-mentioned preparation method, carrier M the state of colloidal sol or gel can participate in reaction, and the colloidal sol of carrier M or the preparation method of gel all can be carried out the regulation and control of routine, as long as reaction can be made to carry out smoothly with concentration by those skilled in the art.
In above-mentioned preparation method, preferably, the concentration of the metal carbonate of the promoter metal B component in step (1) and step (2), alkali metal bicarbonate salt or metal hydroxide solutions is 0.1-1mol/L (gauge with slaine or hydroxide).
In above-mentioned preparation method, preferably, the combination of one or more in the metal carbonate of the promoter metal B component in step (1) and step (2), alkali metal bicarbonate salt and metal hydroxide solutions is that the mode dripped adds, and the speed of dropping can carry out conventional adjustment by those skilled in the art.
According to the specific embodiment of the present invention, preferably, above-mentioned preparation method is further comprising the steps of: step (2) is after adding the combination of one or more in the metal carbonate of promoter metal B component, alkali metal bicarbonate salt and metal hydroxide solutions, the washing of precipitate obtained is filtered, then dry at 80-200 DEG C.
In above-mentioned preparation method, preferably, dry at 80-200 DEG C in step (1) and step (2) time is 3-48 hour; More preferably, step (1) and the middle dry temperature of step (2) are 80-120 DEG C, and the time is 10-24 hour.
In above-mentioned preparation method, preferably, in step (1), the time of roasting at 400-800 DEG C is 1-56 hour; More preferably, in step (1), the temperature of roasting is 400-700 DEG C, and the time is 1-14 hour, is particularly preferably 1-4 hour; In step (2), the time of roasting at 600-1000 DEG C is 2-54 hour; More preferably, in step (2), the temperature of roasting is 600-800 DEG C, and the time is 2-4 hour.
In above-mentioned preparation method, preferably, the roasting in step (1) and step (2) is all carried out in air atmosphere.
According to the specific embodiment of the present invention, preferably, above-mentioned preparation method is further comprising the steps of: pulverize described modified support and sieve, and/or pulverizes described Ni-based composite metal oxide and sieve.
Nickel-base catalyst provided by the invention is a kind of Ni-based O composite metallic oxide catalyst, it can produce hydrogen by efficient catalytic methane cracking at a lower temperature, can realize maximum product hydrogen rate 90-100% (producing hydrogen rate by the getable actual hydrogen output of unit quality methane decomposition and the ratio of theoretical hydrogen amount).
In addition, present invention also offers a kind of method that methane catalytic decomposition produces hydrogen, the device that the method adopts comprises: High-density Circulating Fluidized Beds reactor, settler, regenerator, regenerator sloped tube and inclined tube to be generated; Wherein, described High-density Circulating Fluidized Beds reactor to comprise on one the cavity of thick lower narrow, secondary reducing, and the bottom of described cavity is provided with feeding pipe, and the top of cavity is provided with discharge nozzle; Described settler comprises the gas-solid separation equipment that a cavity and is arranged in cavity, and the bottom of described cavity is provided with material inlet, and the top of cavity is provided with and generates gas outlet, and in cavity or bottom is provided with catalyst outlet; The discharge nozzle of described High-density Circulating Fluidized Beds reactor is passed into by the material inlet bottom described settler in the cavity of described settler; The cavity and one that described regenerator to comprise on one thick lower narrow, secondary or three grades of reducings is arranged in the gas-solid separation equipment of cavity, the bottom of described cavity is provided with catalyst outlet pipe, the top of cavity is provided with regenerated flue gas outlet, in cavity or bottom is provided with catalyst inlet, and the bottom of cavity is provided with oxygen source entrance (can regulate the quantity of oxygen source entrance according to the species number of oxygen source); The catalyst outlet pipe of described regenerator is connected to the feeding pipe of described High-density Circulating Fluidized Beds reactor by described regenerator sloped tube; The catalyst inlet of described regenerator is connected to the catalyst outlet of described settler by described inclined tube to be generated;
The method comprises the following steps:
(1) unstripped gas comprising methane is made to enter reactor cavity by the feeding pipe of described High-density Circulating Fluidized Beds reactor bottom, produce the catalyst exposure of hydrogen with the catalytic methane cracking in reactor and catalytic cracking reaction occurs, obtaining comprising the generation gas of hydrogen and the catalyst of inactivation;
(2) make to comprise the generation gas of hydrogen and the catalyst of inactivation enters described settler by the discharge nozzle of described High-density Circulating Fluidized Beds reactor head, in settler, comprise the generation gas of hydrogen and the catalyst separation of inactivation, the generation gas comprising hydrogen exports out device by the generation gas at described settler top;
(3) catalyst of inactivation is made to enter described regenerator by described inclined tube to be generated, and oxygen source is passed in described regenerator, the catalyst of inactivation regenerates in described regenerator, obtain the catalyst after regenerating and regenerated flue gas, regenerated flue gas exports out device by the regenerated flue gas of described regenerator overhead;
(4) catalyst after regeneration is made to enter described High-density Circulating Fluidized Beds reactor by described regenerator sloped tube.
The heat that method of the present invention utilizes regenerated catalyst to carry is reactor heat supply, come for regenerator heat supply by the combustion heat release of coke on the catalyst of inactivation, by controlling the degree that regenerative process is made charcoal, regulate regenerator liberated heat, and then regulating system heat balance, thus realize autothermal operation.Therefore, when adopting the method, only when starting shooting to reactor heat supply, after catalyst circulation uses, then autothermal operation need can be realized.
Produce in the method for hydrogen at above-mentioned methane catalytic decomposition, preferably, the catalyst that hydrogen is produced in described catalytic methane cracking comprises the nickel-base catalyst that hydrogen is produced in above-mentioned catalytic methane cracking provided by the invention.
Produce at above-mentioned methane catalytic decomposition in the method for hydrogen, preferably, the upper diameter of the cavity of the secondary reducing of described High-density Circulating Fluidized Beds reactor and the ratio of lower diameter are (1.2-8.0): 1; More preferably, this ratio is (1.2-4.0): 1.
The present invention adopts the High-density Circulating Fluidized Beds of gas-solid high-efficient contact as reactor, and reducing is carried out to this reactor reproduce, the ratio that its expanding part and non-wide diameter portion are divided is (1.2-8.0): 1 (is more preferably (1.2-4.0): 1).The transformation of this reducing can overcome because methane molecule is less, adsorb the problem of relative difficulty on a catalyst, and utilize the High-density Circulating Fluidized Beds with the gas-solid high-efficient contact of interior backflow as reactor, make it can either provide the efficient gas-solid reaction environment of similar turbulent bed, fluidized bed circulation regeneration can be possessed again to maintain high activity of catalyst, time of contact and the contacting efficiency of catalyst and raw material can be improved simultaneously, thus improve the conversion ratio in whole reactor.
Produce in the method for hydrogen at above-mentioned methane catalytic decomposition, preferably, when the cavity of described regenerator is the cavity of secondary reducing, the ratio of its upper diameter and lower diameter is (1.2-8.0): 1, is more preferably (1.2-4.0): 1 (such as 2.0:1); When the cavity of described regenerator is the cavity of three grades of reducings, the ratio of its upper diameter, mid diameter and lower diameter is (1.2-8.0): (1.1-4.0): 1, be more preferably (1.2-4.0): (1.1-2.0): 1, and described upper diameter is greater than mid diameter, described mid diameter is greater than lower diameter.
Produce in the method for hydrogen at above-mentioned methane catalytic decomposition, preferably, described regenerator adopts dense bed or turbulent bed.
The regenerator that the present invention adopts has carried out reducing transformation on traditional catalytic cracking catalyst regenerator basis.The improved regenerator of this reducing, the climbing speed of the catalyst that can suitably slow down, increases time of contact, realizes highly efficient regeneration catalyst in the short time; And the carrying amount of catalyst carbon dust can be reduced, increase the service life, thus avoid the deposition of the carbon dust caused because regeneration is insufficient, block pipeline and cause shut-down.
According to this specific embodiment of the present invention, produce in the method for hydrogen at above-mentioned methane catalytic decomposition, preferably, described device also comprises two cover heat transmission equipments, wherein a set of heat transmission equipment is first order heat transmission equipment, another set of heat transmission equipment is second level heat transmission equipment, described first order heat transmission equipment and second level heat transmission equipment are the heat transmission equipment of heat exchange between two kinds of fluids, the first fluid intake of described first order heat transmission equipment is connected to the generation gas outlet at described settler top, the second fluid intake of described first order heat transmission equipment is connected to the unstripped gas source of the gas comprising methane, the second fluid issuing of described first order heat transmission equipment is connected to the second fluid intake of described second level heat transmission equipment, the first fluid intake of described second level heat transmission equipment is connected to the regenerated flue gas outlet of described regenerator overhead, the second fluid issuing of described second level heat transmission equipment is connected to the feeding pipe of described High-density Circulating Fluidized Beds reactor bottom.
In the apparatus of the present, described High-density Circulating Fluidized Beds reactor and regenerator are except carrying out reducing transformation, other structures can be all the High-density Circulating Fluidized Beds reactor of this area routine and the structure of catalytic cracking catalyst regenerator, and described settler can be the settler for gas solid separation of this area routine.Described gas-solid separation equipment also can be the gas-solid separation equipment of this area routine, such as cyclone separator etc.Described first order heat transmission equipment and second level heat transmission equipment all can comprise the heat exchanger of one or several this area routine, as long as the heat exchanger of heat exchange between two kinds of fluids.
Above-mentioned methane catalytic decomposition produce hydrogen method in, described in comprise methane unstripped gas can for the key component such as pure methane gas or natural gas be the gas of methane.
According to the specific embodiment of the present invention, preferably, the method that above-mentioned methane catalytic decomposition produces hydrogen is further comprising the steps of: before the unstripped gas comprising methane enters reactor cavity, the unstripped gas comprising methane is preheated to 100-700 DEG C, is more preferably 200-600 DEG C, particularly preferably, described preheating is two-stage preheating, the unstripped gas comprising methane is heated to 100-400 DEG C by first order preheating, more preferably, the unstripped gas comprising methane is heated to 200-400 DEG C by first order preheating, most preferably, first order preheating be adopt described in comprise the generation gas of hydrogen and the described unstripped gas (in first order heat transmission equipment) comprising methane and carry out heat exchange preheating is carried out to the described unstripped gas comprising methane, the unstripped gas comprising methane is heated to 100-700 DEG C by second level preheating, more preferably, the unstripped gas comprising methane is heated to 300-600 DEG C by second level preheating, most preferably, second level preheating is that the unstripped gas (in the heat transmission equipment of the second level) comprising methane after adopting described regenerated flue gas and first order preheating proceeds heat exchange and carries out preheating to the unstripped gas comprising methane after described first order preheating.
Method of the present invention preferably adopts two-stage preheating that methane is preheating to higher temperature, along with the rising of temperature, the increase of methane self specific heat is more obvious, and the high temperature heat source on device and low-temperature heat source can be utilized better, improve energy utilization efficiency, first order preheating preferably adopts and generates this low-temperature heat source of gas, and second level preheating preferably adopts this high temperature heat source of regenerated flue gas.
Produce at above-mentioned methane catalytic decomposition in the method for hydrogen, preferably, the charging rate that step (1) comprises the unstripped gas of methane is 10-1000L/ (hg
cat) (implication of this unit is the catalyst in liter/every gram of reactor per hour), be more preferably 10-900L/ (hg
cat), be particularly preferably 10-500L/ (hg
cat).Methane conversion is at 80-100% to adopt the charging rate of this methane to ensure, in the scope of even 95-100%.
Produce in the method for hydrogen at above-mentioned methane catalytic decomposition, preferably, the temperature of carrying out methane catalytic decomposition reaction in step (1) in described High-density Circulating Fluidized Beds reactor is 500-1000 DEG C, is more preferably 500-800 DEG C, is particularly preferably 650-700 DEG C; Pressure is 0.05-0.5MPa (absolute pressure).
Produce at above-mentioned methane catalytic decomposition in the method for hydrogen, preferably, the temperature of carrying out catalyst regeneration in step (3) in described regenerator is 600-1200 DEG C, is more preferably 600-900 DEG C, is particularly preferably 700-800 DEG C; Pressure is 0.05-0.5MPa (absolute pressure).
Produce in the method for hydrogen at above-mentioned methane catalytic decomposition, preferably, the temperature height 50-200 DEG C of the temperature of catalyst regeneration methane catalytic decomposition reaction middle than step (1) in step (3); The pressure that in step (3), the pressure of catalyst regeneration reacts lower than methane catalytic decomposition in step (1).
Produce in the method for hydrogen at above-mentioned methane catalytic decomposition, preferably, the oxygen source carrying out catalyst regeneration in step (3) in described regenerator comprises the combination of one or more in oxygen denuded air, oxygen-enriched air and steam etc.According to the needs of regenerated flue gas product composition, oxygen source can be selected to regenerate and selective oxidation catalyst, makes renewing catalyst activity and produce CO or synthesis gas (i.e. H
2with CO gaseous mixture).
Produce in the method for hydrogen at above-mentioned methane catalytic decomposition, preferably, the charging rate of oxygen source described in step (3) and step (1) comprise the ratio of the charging rate of the unstripped gas of methane for (1-10): 1.The flow velocity (i.e. charging rate) of oxygen source be according to energy balance (heat balance namely between reactor and regenerator) and desired by CO/CO in the regenerated flue gas that obtains
2ratio determine, as long as carry out according to actual needs regulating within the scope of this.
Produce at above-mentioned methane catalytic decomposition in the method for hydrogen, preferably, the one or more combination in the generation gas bag hydrogen comprising hydrogen, methane and CO in step (1), wherein hydrogen accounts for the 70-100% of described generation gas cumulative volume.
Produce at above-mentioned methane catalytic decomposition in the method for hydrogen, preferably, the regenerated flue gas in step (3) comprises CO, CO
2, H
2, N
2and H
2the combination of one or more in O.
According to the specific embodiment of the present invention, preferably, the method that above-mentioned methane catalytic decomposition produces hydrogen is further comprising the steps of: the generation gas comprising hydrogen obtained step (2) is separated to remove the CO of unreacted methane and/or generation, obtains technical pure hydrogen.
The method that methane catalytic decomposition provided by the invention produces hydrogen is under catalyst existent condition, the unstripped gas being preheating to uniform temperature is sent in High-density Circulating Fluidized Beds reactor, be hydrogen and carbon distribution by methane catalytic decomposition under certain operating conditions, then the catalyst carrying carbon distribution is sent into regenerator, by controlling the type of regeneration condition and regeneration gas, thus obtain CO or synthesis gas, then the catalyst regenerated is transported in reactor again and recycles, utilize the combustion heat release of coke on the catalyst of inactivation to come for regenerator heat supply simultaneously, the heat utilizing regenerated catalyst to carry is reactor heat supply.The method can co-producing high-purity hydrogen and CO or synthesis gas.And the method utilizes the heat of regeneration generation to provide the energy demand of whole system, by controlling the degree (CO/CO namely in regenerated flue gas that regenerative process is made charcoal
2ratio), regulate regenerator liberated heat, and then regulating system heat balance, thus realize autothermal operation.
With adopt natural gas hydrogen preparation to compare with the process of CO or synthesis gas at present, the present invention has following beneficial effect:
(1) methane catalytic decomposition being reacted hydrogen manufacturing and catalyst steam/air regenesis and selective oxidation process is placed in reactor and regenerator respectively, complete in two steps, not only can realize being separated of " reaction " and " regeneration ", eliminate huge hidden peril of explosion, and available air regenerates, the sky using pure oxygen to bring is avoided to divide cost;
(2) reactor adopts the High-density Circulating Fluidized Beds of gas-solid high-efficient contact, improve mass-and heat-transfer efficiency, be conducive to the impact that elimination external diffusion is reacted methane catalytic decomposition, improve the utilization rate of catalyst, thus improve the reaction rate of whole process; Regenerator adopts dense bed/turbulent bed, is conducive to the transmission of heat, avoids the problem of hot-spot in catalyst regeneration process; This reaction-regeneration system solves the problem such as course of reaction continued operation and catalyst circulation use, shortens the operation cycle, improves production efficiency;
(3) the multifunctional efficient catalyst being conducive to methane catalytic decomposition hydrogen manufacturing and coke selectivity conversion is adopted, facilitate the fast decoupled of methane and the selective conversion of coke, make methane conversion per pass bring up to 80-100%, improve the utilization ratio of raw material substantially, reduce CO
2discharge, for large-scale production hydrogen provides possibility;
(4) gaseous product that can control easily to generate is the hydrogen of high purity 70-100%; In the field not high to hydrogen purity requirement, methane and hydrogen do not need to be separated, and can directly use; In the field that hydrogen purity requirement is higher, can prepare High Purity Hydrogen by follow-up process for separating and purifying, due to not carbon oxide in gaseous product, therefore separation circuit is greatly simplified, thus reduces the production cost of High Purity Hydrogen;
(5) coke and the oxygen source such as air, steam that react generation carry out selective oxidation, the degree that carbon distribution is oxidized can be regulated and controled, regulate the amount generating CO or synthesis gas, while the effective product yield of raising, for whole system provides heat, the self-supporting heat of the system that achieves, not only reduces the energy consumption of whole process, cost-saving, and decrease CO
2discharge, improve environmental benefit;
(6) reaction temperature is relatively low, and without the need to injecting the excessive water steam preventing catalyst coking, reduces the energy consumption of whole process further.
In sum, nickel-base catalyst provided by the invention, methane catalytic decomposition produce the method for hydrogen and device can overcome in existing methane catalytic decomposition hydrogen producing technology that methane conversion is low, production capacity is little, carbon distribution utilizes and is difficult to balance the problems such as the contradiction between environment benefits and economic gains, and can efficient catalytic cracking methane, effectively can utilize the carbon distribution of generation simultaneously, reduce energy consumption and cost, reduce CO
2discharge, improves hydrogen gas production efficiency.
In addition, except as otherwise noted, the gas purity levels related in the present invention and percentage are percentages by volume.
In addition, applicant introduces the full content of the bibliography all mentioned in the disclosure particularly.In addition, when given amounts, concentration or other value or parameter are as the enumerating of scope, preferable range or preferred upper limit value and preferred lower limit value, this is understood to specifically disclose all scopes formed by any pairing of any upper limit boundary or preferred upper limit value and any upper limit boundary or preferred lower limit value, and no matter whether discloses separately these scopes.When enumerating number range herein, except as otherwise noted, this scope comprises its end points and whole integer and mark in this.When the range of definition, the scope of the invention is not limited to the occurrence enumerated.
Accompanying drawing explanation
Fig. 1 is the structural representation of the device of the methane catalytic decomposition production hydrogen of embodiment.
Fig. 2 is the variable-diameter structure schematic diagram of the High-density Circulating Fluidized Beds reactor of embodiment.
Fig. 3 is the variable-diameter structure schematic diagram of the regenerator of embodiment.
Primary clustering symbol description:
High-density Circulating Fluidized Beds reactor 1, settler 2, regenerator 3, regenerator sloped tube 4, inclined tube to be generated 5.
Detailed description of the invention
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
Embodiment 1
Present embodiments provide the nickel-base catalyst that hydrogen is produced in a kind of catalytic methane cracking, this nickel-base catalyst prepares by the following method:
In 78.25g boehmite, add 300.48g deionized water, stir evenly with 80 DEG C of water-baths, add salt acid for adjusting pH value and be about 3-4, obtain the gel of carrier; The cobalt nitrate of 15.6g, the phosphotungstic acid of 16.2g are mixed to join in the gel prepared, add the deionized water of 70g again, mechanical agitation is even, the speed of 1mL/min drips the solution of potassium carbonate of the 0.1mol/L of 100mL afterwards, dry 24 hours in 150 DEG C, then 400 DEG C of roastings 18 hours, pulverize and sieve after cooling, obtaining modified support; Taking 50g modified support adds in the aqueous solution of 39.8g nickel nitrate and 40g deionized water, the speed of 1mL/min drips the solution of potassium carbonate of the 0.1mol/L of 100mL, after washing of precipitate is filtered, then dry 12 hours at 140 DEG C, afterwards 600 DEG C of roastings 17 hours, cooling is pulverized and is sieved afterwards and obtains catalyst 24.2NiO15.0WO
36.2CoO2.3K
2o52.3Al
2o
3.
The present embodiment additionally provides the device that a kind of methane catalytic decomposition produces hydrogen, and as shown in Figure 1, this device comprises: High-density Circulating Fluidized Beds reactor 1, settler 2, regenerator 3, regenerator sloped tube 4 and inclined tube to be generated 5; Wherein, described High-density Circulating Fluidized Beds reactor 1 to comprise on one the cavity of thick lower narrow, secondary reducing, and the bottom of described cavity is provided with feeding pipe, and the top of cavity is provided with discharge nozzle; Described settler 2 comprises the gas-solid separation equipment that a cavity and is arranged in cavity, and the bottom of described cavity is provided with material inlet, and the top of cavity is provided with and generates gas outlet, and in cavity or bottom is provided with catalyst outlet; The discharge nozzle of described High-density Circulating Fluidized Beds reactor 1 is passed into by the material inlet bottom described settler 2 in the cavity of described settler 2; Described regenerator 3 comprises thick lower cavity and that is narrow, three grades of reducings on and is arranged in the gas-solid separation equipment of cavity, the bottom of described cavity is provided with catalyst outlet pipe, the top of cavity is provided with regenerated flue gas outlet, in cavity or bottom is provided with catalyst inlet, and the bottom of cavity is provided with oxygen source entrance; The catalyst outlet pipe of described regenerator 3 is connected to the feeding pipe of described High-density Circulating Fluidized Beds reactor 1 by described regenerator sloped tube 4; The catalyst inlet of described regenerator 3 is connected to the catalyst outlet of described settler 2 by described inclined tube 5 to be generated; The upper diameter of the cavity of the secondary reducing of described High-density Circulating Fluidized Beds reactor 1 and the ratio of lower diameter are (1.2-8.0): 1 (be preferably (1.2-4.0): 1, be specifically as follows 1.5:1), as shown in Figure 2; The ratio of the upper diameter of the cavity of three grades of reducings of described regenerator 3, mid diameter and lower diameter is (1.2-8.0): (1.1-4.0): 1 (is preferably (1.2-4.0): (1.1-2.0): 1, be specifically as follows 2.5:1.5:1), upper diameter is greater than mid diameter, mid diameter is greater than lower diameter, as shown in Figure 3; Described regenerator 3 adopts dense bed or turbulent bed.
This device can also comprise two cover heat transmission equipments, wherein a set of heat transmission equipment is first order heat transmission equipment, another set of heat transmission equipment is second level heat transmission equipment, described first order heat transmission equipment and second level heat transmission equipment are the heat transmission equipment of heat exchange between two kinds of fluids, the first fluid intake of described first order heat transmission equipment is connected to the generation gas outlet at described settler top, the second fluid intake of described first order heat transmission equipment is connected to the unstripped gas source of the gas comprising methane, the second fluid issuing of described first order heat transmission equipment is connected to the second fluid intake of described second level heat transmission equipment, the first fluid intake of described second level heat transmission equipment is connected to the regenerated flue gas outlet of described regenerator overhead, the second fluid issuing of described second level heat transmission equipment is connected to the feeding pipe of described High-density Circulating Fluidized Beds reactor bottom.
In above-mentioned device, described High-density Circulating Fluidized Beds reactor and regenerator are except carrying out reducing transformation, other structures can be all the High-density Circulating Fluidized Beds reactor of this area routine and the structure of catalytic cracking catalyst regenerator, and described settler can be the settler for gas solid separation of this area routine.Described gas-solid separation equipment also can be the gas-solid separation equipment of this area routine, such as cyclone separator etc.Described first order heat transmission equipment and second level heat transmission equipment all can comprise the heat exchanger of one or several this area routine, as long as the heat exchanger of heat exchange between two kinds of fluids.
The present embodiment additionally provides a kind of method that methane catalytic decomposition produces hydrogen, and the method adopts above-mentioned nickel-base catalyst and device, and it comprises the following steps:
(1) unstripped gas comprising methane is made to enter the feeding pipe of described High-density Circulating Fluidized Beds reactor bottom, and two-stage preheating is carried out to this unstripped gas, unstripped gas after preheating enters reactor cavity by feeding pipe, then contact with the described nickel-base catalyst in reactor and catalytic cracking reaction occurs, obtaining comprising the generation gas of hydrogen and the catalyst of inactivation;
(2) make to comprise the generation gas of hydrogen and the catalyst of inactivation enters described settler by the discharge nozzle of described High-density Circulating Fluidized Beds reactor head, in settler, comprise the generation gas of hydrogen and the catalyst separation of inactivation, the generation gas comprising hydrogen exports out device by the generation gas at described settler top;
(3) catalyst of inactivation is made to enter described regenerator by described inclined tube to be generated, and oxygen source is passed in described regenerator, the catalyst of inactivation regenerates in described regenerator, obtain the catalyst after regenerating and regenerated flue gas, regenerated flue gas exports out device by the regenerated flue gas of described regenerator overhead;
(4) catalyst after regeneration is made to enter described High-density Circulating Fluidized Beds reactor by described regenerator sloped tube.
The heat that the method utilizes regenerated catalyst to carry is reactor heat supply, utilizing the combustion heat release of coke on the catalyst of inactivation to come for regenerator heat supply, by controlling the degree that regenerative process is made charcoal, regulating regenerator liberated heat, and then adjusting device heat balance, thus realize autothermal operation.Therefore, when adopting the method, only when starting shooting to reactor heat supply, after catalyst circulation uses, then autothermal operation need can be realized.
In the above-mentioned methods, reaction condition is: unstripped gas is methane, the first order is preheated to 350 DEG C (adopt generation gas in first order heat transmission equipment, carry out heat exchange and carry out preheating), the second level is preheated to 540 DEG C (adopt regenerated flue gas in the heat transmission equipment of the second level, carry out heat exchange and carry out preheating), and methane feed speed is 400L/ (hg
cat); In reactor, pressure is 0.42MPa, and reaction temperature is 620 DEG C; In regenerator, pressure is 0.15MPa, and regeneration temperature is 750 DEG C, and regeneration oxygen source is air, and flow velocity is 1000L/ (hg
cat) (implication of this unit is the catalyst in liter/every gram of regenerator per hour).
Reaction result: methane conversion per pass is 88.4%; CO/CO in regenerated flue gas
2=2.9:1; The hydrogen selective of catalyst is (the theoretical hydrogen yield that the methane of selective=hydrogen actual recovery/conversion obtains) for 99.0%; The hydrogen purity generating gas is 85%.
Embodiment 2
Present embodiments provide the nickel-base catalyst that hydrogen is produced in a kind of catalytic methane cracking, this nickel-base catalyst prepares by the following method:
In 48.97g boehmite, add 300.48g deionized water and 127.64g Ludox, stir evenly with 80 DEG C of water-baths, add salt acid for adjusting pH value and be about 3-4, obtain the gel of carrier; The mixing of the phosphotungstic acid of the cobalt nitrate of 15.6g, 16.2g is added in the gel prepared, add the deionized water of 70g again, mechanical agitation is even, the speed of 1mL/min drips the solution of potassium carbonate of the 0.1mol/L of 100mL afterwards, dry 24 hours in 150 DEG C, then 400 DEG C of roastings 18 hours, pulverize and sieve after cooling, obtaining modified support; Taking 50g modified support adds in the aqueous solution of 39.8g nickel nitrate and 40g deionized water, the speed of 1mL/min drips the solution of potassium carbonate of the 0.1mol/L of 100mL, after washing of precipitate is filtered, dry 12 hours at 140 DEG C, then 800 DEG C of roastings 17 hours, pulverize and sieve after cooling and obtain catalyst 24.2NiO15.0WO
36.2CoO2.3K
2o24.7Al
2o
327.6SiO
2.
The present embodiment additionally provides a kind of method that methane catalytic decomposition produces hydrogen, the method adopts the device in above-mentioned nickel-base catalyst and embodiment 1, the concrete steps of the method are in the same manner as in Example 1, the reaction condition of the method: unstripped gas is methane, the first order is preheated to 400 DEG C, the second level is preheated to 580 DEG C, and methane feed speed is 200L/ (hg
cat); In reactor, pressure is 0.42MPa, and reaction temperature is 750 DEG C; In regenerator, pressure is 0.15MPa, and regeneration temperature is 880 DEG C, and regeneration oxygen source is air, and flow velocity is 800L/ (hg
cat).
Reaction result: methane conversion per pass is 95%; CO/CO in regenerated flue gas
2=2.7:1; The hydrogen selective of catalyst is 99.0%; Hydrogen purity is 90%.
Embodiment 3
Present embodiments provide the nickel-base catalyst that hydrogen is produced in a kind of catalytic methane cracking, this nickel-base catalyst prepares by the following method:
In 209.87g Ludox, add 90.47g deionized water, obtain the gel of carrier; The cerous nitrate of the copper nitrate of 16.8g, 7.7g, the mixing of 1.7g niobium hydroxide are added in the gel prepared, add the deionized water of 70g again, mechanical agitation is even, the speed of 1mL/min drips the solution of potassium carbonate of the 0.1mol/L of 100mL afterwards, dry 24 hours in 150 DEG C, then 400 DEG C of roastings 18 hours, pulverize and sieve after cooling, obtaining modified support; Taking 50g modified support adds in the aqueous solution of 39.8g nickel nitrate and 40g deionized water, the speed of 1mL/min drips the solution of potassium carbonate of the 0.1mol/L of 100mL, after washing of precipitate is filtered, dry 12 hours at 120 DEG C, then 700 DEG C of roastings 17 hours, pulverize and sieve after cooling and obtain catalyst 24.2NiO6.9CuO3.8Ce
2o
31.3Nb
2o
52.1K
2o61.7SiO
2.
The present embodiment additionally provides a kind of method that methane catalytic decomposition produces hydrogen, the method adopts the device in above-mentioned nickel-base catalyst and embodiment 1, the concrete steps of the method are in the same manner as in Example 1, the reaction condition of the method: unstripped gas is methane, the first order is preheated to 350 DEG C, the second level is preheated to 540 DEG C, and methane feed speed is 400L/ (hg
cat); In reactor, pressure is 0.42MPa, and reaction temperature is 620 DEG C; In regenerator, pressure is 0.15MPa, and regeneration temperature is 750 DEG C, and regeneration oxygen source is air, and flow velocity is 1000L/ (hg
cat).
Reaction result: methane conversion per pass is 92%; CO/CO in regenerated flue gas
2=2.9:1; The hydrogen selective of catalyst is 99.5%; Hydrogen purity is 95%.
Embodiment 4
Present embodiments provide the nickel-base catalyst that hydrogen is produced in a kind of catalytic methane cracking, this nickel-base catalyst prepares by the following method:
In 78.25g boehmite, add 300.48g deionized water, stir evenly with 80 DEG C of water-baths, add salt acid for adjusting pH value and be about 3-4, obtain the gel of carrier; The mixing of the vanadic anhydride of the cobalt nitrate of 15.6g, 16.2g is added in the gel prepared, add the deionized water of 70g again, mechanical agitation is even, the speed of 1mL/min drips the solution of potassium carbonate of the 0.1mol/L of 100mL afterwards, dry 18 hours in 800 DEG C, then 550 DEG C of roastings 10 hours, pulverize and sieve after cooling, obtaining modified support; Taking 50g modified support adds in the aqueous solution of 39.8g nickel nitrate and 40g deionized water, the speed of 1mL/min drips the solution of potassium carbonate of the 0.1mol/L of 100mL, after washing of precipitate is filtered, dry 12 hours at 140 DEG C, then 850 DEG C of roastings 19 hours, pulverize and sieve after cooling and obtain catalyst 24.2NiO15.4V
2o
56.1CoO2.2K
2o52.1Al
2o
3.
The present embodiment additionally provides a kind of method that methane catalytic decomposition produces hydrogen, the method adopts the device in above-mentioned nickel-base catalyst and embodiment 1, the concrete steps of the method are in the same manner as in Example 1, the reaction condition of the method: unstripped gas is methane, the first order is preheated to 400 DEG C, the second level is preheated to 600 DEG C, and methane feed speed is 200L/ (hg
cat); In reactor, pressure is 0.42MPa, and reaction temperature is 790 DEG C; In regenerator, pressure is 0.15MPa, and regeneration temperature is 950 DEG C, and regeneration oxygen source is air, and flow velocity is 800L/ (hg
cat).
Reaction result: methane conversion per pass 99%; CO/CO in regenerated flue gas
2=3.2:1; The hydrogen selective of catalyst is 99.9%; Hydrogen purity is 99%.
Claims (10)
1. a nickel-base catalyst for hydrogen is produced in catalytic methane cracking, and this catalyst comprises the Ni-based composite metal oxide shown in general formula (I):
XXyAzB (100-x-y-z) M general formula (I),
Wherein, X is Ni and/or its oxide, and A is assistant metal component, and B is promoter metal component, and M is carrier, and x, y and z represent the mass percent of X, A and B respectively, and 0.1≤x≤40,0.1≤y≤30,0.1≤z≤10.
2. nickel-base catalyst according to claim 1, wherein, described assistant metal component A comprises the oxide of one or more metals in Fe, Nb, Ta, Co, V, Cu, Zn, Ir, Ge, Sn, Mo, W, Ce and Sb and/or metal; Preferably, described assistant metal component A comprises one or more metals in Fe, Nb, Mo, Ir, V, Ce, Co and Cu and/or metal oxide;
Described promoter metal B component comprises the oxide of one or more metals in Na, K and Mg and/or metal; Preferably, described promoter metal B component comprises the oxide of K and/or Mg metal and/or metal;
Described carrier M comprises Al
2o
3, SiO
2, TiO
2, the combination of one or more in MgO and CaO; Preferably, described carrier M comprises γ-Al
2o
3and/or SiO
2;
The granularity of described nickel-base catalyst is less than 200 μm.
3. a preparation method for the nickel-base catalyst of hydrogen is produced in the catalytic methane cracking described in claim 1 or 2, and it comprises the following steps:
(1) at room temperature, being combined in water of one or more in the metal nitrate of carrier M and assistant metal component A, metal phosphate, metal acetate salt, metal hydroxides and metal oxide is mixed, be preferably the metal nitrate of assistant metal component A, add the combination of one or more in the metal carbonate of promoter metal B component, alkali metal bicarbonate salt and metal hydroxide solutions again, be preferably the metal carbonate of promoter metal B component, then dry at 80-200 DEG C, roasting at 400-800 DEG C, obtains modified support again;
(2) at room temperature, described modified support is mixed in water with the nitrate of nickel, then the combination of one or more in the metal carbonate of promoter metal B component, alkali metal bicarbonate salt and metal hydroxide solutions is added, be preferably the metal carbonate of promoter metal B component, then dry at 80-200 DEG C, roasting at 600-1000 DEG C again, obtains Ni-based composite metal oxide, is the nickel-base catalyst that hydrogen is produced in described catalytic methane cracking.
4. preparation method according to claim 3, wherein, the concentration of the metal carbonate of the promoter metal B component in step (1) and step (2), alkali metal bicarbonate salt or metal hydroxide solutions is 0.1-1mol/L; Time dry at 80-200 DEG C in step (1) and step (2) is 3-48 hour, and preferably, in step (1) and step (2), the temperature of drying is 80-120 DEG C, and the time is 10-24 hour; In step (1), the time of roasting at 400-800 DEG C is 1-56 hour, and preferably, in step (1), the temperature of roasting is 400-700 DEG C, and the time is 1-14 hour, is more preferably 1-4 hour; In step (2), the time of roasting at 600-1000 DEG C is 2-54 hour, and preferably, in step (2), the temperature of roasting is 600-800 DEG C, and the time is 2-4 hour; Roasting in step (1) and step (2) is all carried out in air atmosphere.
5. methane catalytic decomposition produces a method for hydrogen, and the device that the method adopts comprises: High-density Circulating Fluidized Beds reactor, settler, regenerator, regenerator sloped tube and inclined tube to be generated; Wherein, described High-density Circulating Fluidized Beds reactor to comprise on one the cavity of thick lower narrow, secondary reducing, and the bottom of described cavity is provided with feeding pipe, and the top of cavity is provided with discharge nozzle; Described settler comprises the gas-solid separation equipment that a cavity and is arranged in cavity, and the bottom of described cavity is provided with material inlet, and the top of cavity is provided with and generates gas outlet, and in cavity or bottom is provided with catalyst outlet; The discharge nozzle of described High-density Circulating Fluidized Beds reactor is passed into by the material inlet bottom described settler in the cavity of described settler; The cavity and one that described regenerator to comprise on one thick lower narrow, secondary or three grades of reducings is arranged in the gas-solid separation equipment of cavity, the bottom of described cavity is provided with catalyst outlet pipe, the top of cavity is provided with regenerated flue gas outlet, in cavity or bottom is provided with catalyst inlet, and the bottom of cavity is provided with oxygen source entrance; The catalyst outlet pipe of described regenerator is connected to the feeding pipe of described High-density Circulating Fluidized Beds reactor by described regenerator sloped tube; The catalyst inlet of described regenerator is connected to the catalyst outlet of described settler by described inclined tube to be generated;
The method comprises the following steps:
(1) unstripped gas comprising methane is made to enter reactor cavity by the feeding pipe of described High-density Circulating Fluidized Beds reactor bottom, produce the catalyst exposure of hydrogen with the catalytic methane cracking in reactor and catalytic cracking reaction occurs, obtaining comprising the generation gas of hydrogen and the catalyst of inactivation;
(2) make to comprise the generation gas of hydrogen and the catalyst of inactivation enters described settler by the discharge nozzle of described High-density Circulating Fluidized Beds reactor head, in settler, comprise the generation gas of hydrogen and the catalyst separation of inactivation, the generation gas comprising hydrogen exports out device by the generation gas at described settler top;
(3) catalyst of inactivation is made to enter described regenerator by described inclined tube to be generated, and oxygen source is passed in described regenerator, the catalyst of inactivation regenerates in described regenerator, obtain the catalyst after regenerating and regenerated flue gas, regenerated flue gas exports out device by the regenerated flue gas of described regenerator overhead;
(4) catalyst after regeneration is made to enter described High-density Circulating Fluidized Beds reactor by described regenerator sloped tube.
6. methane catalytic decomposition according to claim 5 produces the method for hydrogen, and wherein, the nickel-base catalyst of hydrogen is produced in the catalyst catalytic methane cracking comprised described in claim 1 or 2 of described catalytic methane cracking production hydrogen.
7. methane catalytic decomposition according to claim 5 produces the method for hydrogen, and wherein, the upper diameter of the cavity of the secondary reducing of described High-density Circulating Fluidized Beds reactor and the ratio of lower diameter are (1.2-8.0): 1; When the cavity of described regenerator is the cavity of secondary reducing, the ratio of its upper diameter and lower diameter is (1.2-8.0): 1; When the cavity of described regenerator is the cavity of three grades of reducings, the ratio of its upper diameter, mid diameter and lower diameter is (1.2-8.0): (1.1-4.0): 1, and described upper diameter is greater than mid diameter, described mid diameter is greater than lower diameter; Described regenerator adopts dense bed or turbulent bed.
8. methane catalytic decomposition according to claim 5 produces the method for hydrogen, and it is further comprising the steps of: before the unstripped gas comprising methane enters reactor cavity, and the unstripped gas comprising methane is preheated to 100-700 DEG C, is preferably 200-600 DEG C, more preferably, described preheating is two-stage preheating, the unstripped gas comprising methane is heated to 100-400 DEG C by first order preheating, particularly preferably, the unstripped gas comprising methane is heated to 200-400 DEG C by first order preheating, most preferably, first order preheating be adopt described in comprise the generation gas of hydrogen and the described unstripped gas comprising methane and carry out heat exchange preheating is carried out to the described unstripped gas comprising methane, the unstripped gas comprising methane is heated to 100-700 DEG C by second level preheating, particularly preferably, the unstripped gas comprising methane is heated to 300-600 DEG C by second level preheating, most preferably, second level preheating is that the unstripped gas comprising methane after adopting described regenerated flue gas and first order preheating proceeds heat exchange and carries out preheating to the unstripped gas comprising methane after described first order preheating.
9. methane catalytic decomposition according to claim 5 produces the method for hydrogen, and wherein, the charging rate that step (1) comprises the unstripped gas of methane is 10-1000L/ (hg
cat), be preferably 10-500L/ (hg
cat);
The temperature of carrying out methane catalytic decomposition reaction in step (1) in described High-density Circulating Fluidized Beds reactor is 500-1000 DEG C, is preferably 500-800 DEG C, is more preferably 650-700 DEG C; Pressure is 0.05-0.5MPa;
The temperature of carrying out catalyst regeneration in step (3) in described regenerator is 600-1200 DEG C, is preferably 600-900 DEG C, is more preferably 700-800 DEG C; Pressure is 0.05-0.5MPa;
The temperature height 50-200 DEG C of the temperature of catalyst regeneration methane catalytic decomposition reaction middle than step (1) in step (3); The pressure that in step (3), the pressure of catalyst regeneration reacts lower than methane catalytic decomposition in step (1);
The oxygen source carrying out catalyst regeneration in step (3) in described regenerator comprises the combination of one or more in oxygen denuded air, oxygen-enriched air, steam; The charging rate of described oxygen source and step (1) comprise the ratio of the charging rate of the unstripped gas of methane for (1-10): 1;
One or more combination in the generation gas bag hydrogen comprising hydrogen, methane and CO in step (1), wherein hydrogen accounts for the 70-100% of described generation gas cumulative volume;
Regenerated flue gas in step (3) comprises CO, CO
2, H
2, N
2and H
2the combination of one or more in O.
10. methane catalytic decomposition according to claim 5 produces the method for hydrogen, it is further comprising the steps of: the generation gas comprising hydrogen obtained step (2) is separated to remove the CO of unreacted methane and/or generation, obtains technical pure hydrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510358286.5A CN104998654B (en) | 2015-06-25 | 2015-06-25 | The method of nickel-base catalyst and preparation method thereof and methane catalytic decomposition production hydrogen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510358286.5A CN104998654B (en) | 2015-06-25 | 2015-06-25 | The method of nickel-base catalyst and preparation method thereof and methane catalytic decomposition production hydrogen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104998654A true CN104998654A (en) | 2015-10-28 |
| CN104998654B CN104998654B (en) | 2018-05-01 |
Family
ID=54371670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510358286.5A Active CN104998654B (en) | 2015-06-25 | 2015-06-25 | The method of nickel-base catalyst and preparation method thereof and methane catalytic decomposition production hydrogen |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104998654B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109999813A (en) * | 2019-03-15 | 2019-07-12 | 上海大学 | A kind of methane catalytic decomposition catalyst for preparing hydrogen and preparation method thereof |
| CN111097447A (en) * | 2018-10-29 | 2020-05-05 | 中国石油天然气股份有限公司 | Catalyst for low-temperature catalytic cracking of methane to produce hydrogen, preparation method thereof and low-temperature catalytic cracking method for methane to produce hydrogen |
| CN111689466A (en) * | 2020-05-27 | 2020-09-22 | 深圳市中科纳米科技有限公司 | Comprehensive treatment method and treatment system for organic waste |
| WO2020218917A1 (en) * | 2019-04-22 | 2020-10-29 | Universiti Kebangsaan Malaysia | A catalyst composition and method of making thereof for pure hydrogen production |
| CN111892019A (en) * | 2019-05-06 | 2020-11-06 | 中国石油化工股份有限公司 | Method for preparing high-purity hydrogen by adopting non-noble metal dehydrogenation catalyst |
| CN113213423A (en) * | 2021-06-17 | 2021-08-06 | 芶富均 | Device for preparing hydrogen by catalytic-assisted methane cracking |
| CN115043376A (en) * | 2022-06-01 | 2022-09-13 | 苏州道顺电子有限公司 | Method for preparing hydrogen and byproduct carbon material by catalytic cracking of methane |
| CN116322981A (en) * | 2020-04-03 | 2023-06-23 | 巴西石油公司 | Catalyst for producing hydrogen and/or synthesis gas, method for obtaining same and use in steam reforming process |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5368835A (en) * | 1992-08-14 | 1994-11-29 | Council Of Scientific & Industrial Research | Process for production of synthesis gas by oxidative conversion of methane or natural gas using composite catalysts |
| CN1168298A (en) * | 1996-06-19 | 1997-12-24 | 中国科学院大连化学物理研究所 | Catalyst for producing synthetic gas through the reaction between low-carbon alkane and carbon dioxide and its use |
| CN101337655A (en) * | 2008-08-29 | 2009-01-07 | 清华大学 | Process for preparing hydrogen gas and nanometer carbon by catalyzing and cracking methane at low temperature |
| CN101646488A (en) * | 2007-01-24 | 2010-02-10 | 艾登创新公司 | Use the method and system of methane decomposition manufacturing hydrogen-rich fuel on the auxiliary catalyst of microwave |
| CN102335609A (en) * | 2011-07-15 | 2012-02-01 | 华东师范大学 | Nickel-based catalyst as well as preparation method and application thereof |
| CN102489311A (en) * | 2011-11-23 | 2012-06-13 | 重庆大学 | Catalyst for hydrogen production through catalytic cracking of methane and its preparation method |
-
2015
- 2015-06-25 CN CN201510358286.5A patent/CN104998654B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5368835A (en) * | 1992-08-14 | 1994-11-29 | Council Of Scientific & Industrial Research | Process for production of synthesis gas by oxidative conversion of methane or natural gas using composite catalysts |
| CN1168298A (en) * | 1996-06-19 | 1997-12-24 | 中国科学院大连化学物理研究所 | Catalyst for producing synthetic gas through the reaction between low-carbon alkane and carbon dioxide and its use |
| CN101646488A (en) * | 2007-01-24 | 2010-02-10 | 艾登创新公司 | Use the method and system of methane decomposition manufacturing hydrogen-rich fuel on the auxiliary catalyst of microwave |
| CN101337655A (en) * | 2008-08-29 | 2009-01-07 | 清华大学 | Process for preparing hydrogen gas and nanometer carbon by catalyzing and cracking methane at low temperature |
| CN102335609A (en) * | 2011-07-15 | 2012-02-01 | 华东师范大学 | Nickel-based catalyst as well as preparation method and application thereof |
| CN102489311A (en) * | 2011-11-23 | 2012-06-13 | 重庆大学 | Catalyst for hydrogen production through catalytic cracking of methane and its preparation method |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111097447A (en) * | 2018-10-29 | 2020-05-05 | 中国石油天然气股份有限公司 | Catalyst for low-temperature catalytic cracking of methane to produce hydrogen, preparation method thereof and low-temperature catalytic cracking method for methane to produce hydrogen |
| CN109999813A (en) * | 2019-03-15 | 2019-07-12 | 上海大学 | A kind of methane catalytic decomposition catalyst for preparing hydrogen and preparation method thereof |
| CN113950370A (en) * | 2019-04-22 | 2022-01-18 | 马来西亚国立大学 | Catalyst composition for pure hydrogen production and method for preparing the same |
| WO2020218917A1 (en) * | 2019-04-22 | 2020-10-29 | Universiti Kebangsaan Malaysia | A catalyst composition and method of making thereof for pure hydrogen production |
| US20220119249A1 (en) * | 2019-04-22 | 2022-04-21 | Universiti Kebangsaan Malaysia | A catalyst composition and method of making thereof for pure hydrogen production |
| CN111892019A (en) * | 2019-05-06 | 2020-11-06 | 中国石油化工股份有限公司 | Method for preparing high-purity hydrogen by adopting non-noble metal dehydrogenation catalyst |
| CN111892019B (en) * | 2019-05-06 | 2022-09-27 | 中国石油化工股份有限公司 | Method for preparing high-purity hydrogen by adopting non-noble metal dehydrogenation catalyst |
| CN116322981A (en) * | 2020-04-03 | 2023-06-23 | 巴西石油公司 | Catalyst for producing hydrogen and/or synthesis gas, method for obtaining same and use in steam reforming process |
| CN111689466A (en) * | 2020-05-27 | 2020-09-22 | 深圳市中科纳米科技有限公司 | Comprehensive treatment method and treatment system for organic waste |
| CN113213423A (en) * | 2021-06-17 | 2021-08-06 | 芶富均 | Device for preparing hydrogen by catalytic-assisted methane cracking |
| CN113213423B (en) * | 2021-06-17 | 2024-01-30 | 成都达信成科技有限公司 | Catalytic auxiliary methane pyrolysis hydrogen production equipment |
| CN115043376A (en) * | 2022-06-01 | 2022-09-13 | 苏州道顺电子有限公司 | Method for preparing hydrogen and byproduct carbon material by catalytic cracking of methane |
| CN115043376B (en) * | 2022-06-01 | 2024-05-07 | 苏州道顺电子有限公司 | Method for preparing byproduct carbon material from hydrogen production by methane catalytic pyrolysis |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104998654B (en) | 2018-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104998654B (en) | The method of nickel-base catalyst and preparation method thereof and methane catalytic decomposition production hydrogen | |
| US10501318B2 (en) | Methods for fuel conversion | |
| CN105013506B (en) | Bifunctional catalyst and its preparation method and hydrogen production process for methane catalytic decomposition | |
| Vozniuk et al. | Spinel mixed oxides for chemical-loop reforming: from solid state to potential application | |
| CN105622305B (en) | A kind of method of the direct conversion for preparing arene co-production of methane of synthesis gas | |
| CN204848257U (en) | Device of methane catalytic cracking production hydrogen | |
| CN103288048B (en) | Process for preparing hydrogen by strengthening chemical chain reforming in continuous catalytic adsorption manner via moving bed | |
| CN101439844A (en) | Chemical link coupling catalytic reforming hydrogen making method and device | |
| CN110980644B (en) | Water-based chemical chain circulation hydrogen production system and method | |
| CN103373706A (en) | Methane reforming hydrogen production method and device | |
| CN102698817B (en) | Pure oxygen regeneration process for fluid catalytic cracking catalyst and hydrogen preparation method | |
| Gao et al. | Performance evaluation of rare earth (La, Ce and Y) modified CoFe2O4 oxygen carriers in chemical looping hydrogen generation from hydrogen-rich syngas | |
| Liu et al. | Inherently separated syngas production from plastic waste fast pyrolysis integrated with volatile chemical looping conversion with CO2 splitting | |
| CN103183319B (en) | A kind of method of lighter hydrocarbons producing hydrogen from steam conversion, device and reactive system | |
| CN209872347U (en) | Device for preparing hydrogen by double fluidized bed biomass pyrolysis gasification | |
| CN105197888A (en) | Method for preparing synthetic gas through methane-carbon dioxide chemical-looping catalytic reforming | |
| CN101376105A (en) | Catalyst for producing synthesis gas from atmospheric hydrogenation of arene and preparation method thereof | |
| CN110508304B (en) | Biological methanol catalyst NiCo for full-component conversion of biogas2O4/SiC-SiO2-Foam and preparation method | |
| CN103183318A (en) | Method for hydrogen production by light hydrocarbon steam reforming in moving bed and device | |
| CN112960645B (en) | Water-steam shift reactor for autothermal reforming hydrogen production reaction and method for improving CO conversion rate of water-steam shift reaction | |
| CN111377398B (en) | Method for preparing hydrogen and carbon monoxide by biomass pyrolysis and gasification | |
| WO2021134475A1 (en) | Water-based chemical chain cycle hydrogen production system and method | |
| KR101315676B1 (en) | Apparatus for simultaneous production of synthetic oil and electricity using Fischer-Tropsch synthesis reactor unit and Fuel Cell unit and method thereof | |
| CN211199134U (en) | Combined fluidized bed coal catalytic gasification hydrogen production device | |
| Yimin | SOLAR ENERGY-DRIVEN HYDROGEN PRODUCTION |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |