CN204848257U - Device of methane catalytic cracking production hydrogen - Google Patents
Device of methane catalytic cracking production hydrogen Download PDFInfo
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- CN204848257U CN204848257U CN201520443739.XU CN201520443739U CN204848257U CN 204848257 U CN204848257 U CN 204848257U CN 201520443739 U CN201520443739 U CN 201520443739U CN 204848257 U CN204848257 U CN 204848257U
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Abstract
The utility model provides a device of methane catalytic cracking production hydrogen. The device, its characterized in that includes: high density circulating fluidized bed reactor, settler, regenerator, regeneration inclined pipe and wait to give birth to the pipe chute, the cavity of high density circulating fluidized bed reactor is slightly descending cavity narrow, the second grade reducing on one, the matter entrance of discharging pipe bottom the settler of high density circulating fluidized bed reactor lets in in the cavity of settler, the cavity of regenerator is a cavity of going up thick narrow, second grade down or tertiary reducing, the catalyst outlet pipe of regenerator passes through regeneration inclined pipe and connects in the pan feeding pipe of high density circulating fluidized bed reactor, the catalyst entry of regenerator is through waiting that it connects in the catalyst export of settler to give birth to the pipe chute. Adopt the the device can high -efficient catalytic cracking methane, effective carbon deposit that generates that utilizes reduces energy consumption and cost simultaneously, reduces CO2 and discharges, improves hydrogen production efficiency, and then the extensive low -priced hydrogen of preparing.
Description
Technical field
The utility model belongs to chemical preparation, oil and gas chemical production technical field, and particularly a kind of methane catalytic decomposition produces the device of hydrogen.
Background technology
Sweet natural gas is the petrochemical complex 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 natural 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 Sweet 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 (petroleum naphtha is about 2, and liquefied petroleum gas (LPG) 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 synthetic gas (H
2with the gas mixture of CO), then obtain hydrogen with physics or chemical process 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 introduction cost is high, technological process is owing to controlling by thermodynamic(al)equilibrium, usually to carry out under high temperature (>800 DEG C), reaction process needs to burn a large amount of Sweet 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 scavenging process.Visible, it is higher that this technology has self single plant energy consumption, and equipment investment cost is high, CO
2quantity discharged 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 facility 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 synthetic 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 gentle thermo-negative reaction, and energy consumption is low, and reaction process does not need aqueous vapor to replace and CO
2removing process, enormously simplify reaction process, and process is not to airborne release carbonic acid gas, Greenhouse effect can not be caused, simultaneously by product 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 materialss such as carbon nanotubes, so key to resolve the operate continuously of reactor, the recycling and the problems such as the utilization of carbon black of catalyzer.
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 exchanger 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-reprocessing cycle operation of catalyzer.Secondly due to carbon consuming cell and the mass-producing utilization of proton membrane fuel battery and the restriction of technology maturity; scale operation 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 faculty 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 water vapour conversion, product separation 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 ingredient, the oxide compound of alkaline-earth metal and/or oxyhydroxide 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 catalyzer, 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 synthetic 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 technical process short, and temperature of reaction reduces than traditional hydrogen production process, simple to operate, can reduce production cost, can need the mixing carrying out different ratios, expanded application scope according to downstream chemical product or liquid hydrocarbon preparation technology.But because the method adopts fixed-bed reactor and the time of catalyst regeneration carbon monoxide to be 60-90 minute, need periodical operation, simultaneous reactions raw material only has 10-55Ncm
3min
-1, the treatment capacity of unit time is too little, cannot realize large-scale operation.
Tsing-Hua University provides a kind of method that low-temperature catalytic pyrolysis being applied to oil and 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 catalyzer, 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 overall yield; 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 temperature of reaction, 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 radiation 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 catalyzer before heatable catalyst, after reaction, hydrogen pure is in fact obtained to generation gas processing.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 reactor also gets rid of residual air-methane cracking alternation pattern, and multistage group by scission reaction stove joins the amplification and continuous high-efficient production hydrogen and carbon black that can realize turnout.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 aluminum 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 catalyzer, at 850-1050 DEG C, obtain two kinds of catalyzer respectively after hydrogen reducing.The reaction of this Catalyst Design is methane-steam reformation, methane portion oxidation, methane-carbonic acid gas or methane self-heating recapitalization prepare synthetic gas, and does not all relate to the application in methane catalytic decomposition reaction.The anti-carbon performance of catalyzer, reactive behavior and selectivity are higher, and the stability of reaction is better.
In the patent application CN102583242A of Dalian University of Technology, describing a kind of active ingredient adopting gac or carbon fiber to prepare is the catalyzer of Fe, Co or Ni.This catalyzer 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 catalyzer of catalytic cracking methane again, and this carbon deposition catalyst has good catalytic activity and stability.But this catalyzer 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 synthetic 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 scale operation of hydrogen, is unfavorable for the production cost reducing product, and carbon distribution can not get good utilization, reduce the economic benefit of whole technological process.
Between the relative merits of above prior art, the device that novel methane catalytic decomposition produces hydrogen still needs to be developed further.
Utility model content
For solving the problems of the technologies described above, the purpose of this utility model is to provide a kind of methane catalytic decomposition to produce the device of hydrogen.Adopt this device can reduce energy consumption and extensive cheapness prepares hydrogen.
For achieving the above object, the utility model provides the device that a kind of methane catalytic decomposition produces hydrogen, and this device comprises: High-density Circulating Fluidized Beds reactor, settling vessel, revivifier, 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 settling vessel 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 settling vessel in the cavity of described settling vessel; The cavity and one that described revivifier 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 revivifier is connected to the feeding pipe of described High-density Circulating Fluidized Beds reactor by described regenerator sloped tube; The catalyst inlet of described revivifier is connected to the catalyst outlet of described settling vessel by described inclined tube to be generated.
Produce at above-mentioned methane catalytic decomposition in the device of 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 utility model 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 internal reflux 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, duration of contact and the contact efficiency of catalyzer and raw material can be improved simultaneously, thus improve the transformation efficiency in whole reactor.
Produce in the device of hydrogen at above-mentioned methane catalytic decomposition, preferably, when the cavity of described revivifier 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; When the cavity of described revivifier 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 device of hydrogen at above-mentioned methane catalytic decomposition, preferably, described revivifier is the revivifier adopting dense bed or turbulent bed.
The revivifier that the utility model adopts has carried out reducing transformation on traditional catalytic cracking catalyst revivifier basis.The improved revivifier of this reducing, the climbing speed of the catalyzer that can suitably slow down, increases duration of contact, realizes highly efficient regeneration catalyzer in the short period of time; And the carrying amount of catalyzer 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 embodiment of the present utility model, preferably, the device that above-mentioned methane catalytic decomposition produces hydrogen also comprises two cover heat-exchange equipments, wherein a set of heat-exchange equipment is first step heat-exchange equipment, another set of heat-exchange equipment is second stage heat-exchange equipment, described first step heat-exchange equipment and second stage heat-exchange equipment are the heat-exchange equipment of heat exchange between two kinds of fluids, the first fluid intake of described first step heat-exchange equipment is connected to the generation gas outlet at described settling vessel top, the second fluid intake of described first step heat-exchange equipment is connected to the unstripped gas source of the gas comprising methane, the second fluid outlet of described first step heat-exchange equipment is connected to the second fluid intake of described second stage heat-exchange equipment, the first fluid intake of described second stage heat-exchange equipment is connected to the regenerated flue gas outlet of described regenerator overhead, the second fluid outlet of described second stage heat-exchange equipment is connected to the feeding pipe of described High-density Circulating Fluidized Beds reactor bottom.
In device of the present utility model, described High-density Circulating Fluidized Beds reactor and revivifier 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 revivifier, and described settling vessel can be the settling vessel 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 cyclonic separator etc.Described first step heat-exchange equipment and second stage heat-exchange equipment all can comprise the interchanger of one or several this area routine, as long as the interchanger of heat exchange between two kinds of fluids.
The device adopting methane catalytic decomposition of the present utility model to produce hydrogen carries out the method that methane catalytic decomposition produces hydrogen, can comprise 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 catalyzer of inactivation;
(2) make to comprise the generation gas of hydrogen and the catalyzer of inactivation enters described settling vessel by the discharge nozzle of described High-density Circulating Fluidized Beds reactor head, in settling vessel, comprise the generation gas of hydrogen and the catalyst separating of inactivation, the generation gas comprising hydrogen exports out device by the generation gas at described settling vessel top;
(3) catalyzer of inactivation is made to enter described revivifier by described inclined tube to be generated, and oxygen source is passed in described revivifier, the catalyzer of inactivation regenerates in described revivifier, obtain the catalyzer after regenerating and regenerated flue gas, regenerated flue gas exports out device by the regenerated flue gas of described regenerator overhead;
(4) catalyzer 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 utility model utilizes regenerated catalyst to carry is reactor heat supply, come for revivifier heat supply by the combustion heat release of coke on the catalyzer of inactivation, by controlling the degree that regenerative process is made charcoal, regulate revivifier liberated heat, and then regulation system heat balance, thus realize autothermal operation.Therefore, when adopting the method, only when starting shooting to reactor heat supply, after catalyst recirculation uses, then autothermal operation need can be realized.
Produce in the method for hydrogen at above-mentioned methane catalytic decomposition, the catalyzer of described catalytic methane cracking production hydrogen can be the catalyzer of the catalytic methane cracking production hydrogen of this area routine.
Above-mentioned methane catalytic decomposition produce hydrogen method in, described in comprise methane unstripped gas can for the main ingredient such as pure methane gas or Sweet natural gas be the gas of methane.
According to embodiment of the present utility model, 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 100-300 DEG C by first step preheating, more preferably, the unstripped gas comprising methane is heated to 200-300 DEG C by first step preheating, most preferably, first step preheating be adopt described in comprise the generation gas of hydrogen and the described unstripped gas comprising methane and in described first step heat-exchange equipment, 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 stage preheating, more preferably, the unstripped gas comprising methane is heated to 300-500 DEG C by second stage preheating, most preferably, second stage preheating is that the unstripped gas comprising methane after adopting described regenerated flue gas and first step preheating proceeds heat exchange and carries out preheating to the unstripped gas comprising methane after described first step preheating in the heat-exchange equipment of the described second stage.
Method of the present utility model preferably adopts two-stage preheating that methane is preheating to comparatively high temps, along with the rising of temperature, methane self is more obvious than heat gain, and the high temperature heat source on device and low-temperature heat source can be utilized better, improve energy utilization efficiency, first step preheating preferably adopts and generates this low-temperature heat source of gas, and second stage 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 input speed that step (1) comprises the unstripped gas of methane is 10-1000L/ (hg
cat) (implication of this unit is the catalyzer 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 input speed 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 revivifier 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 revivifier comprises the combination of one or more in oxygen-denuded air, oxygen-rich air and water vapour etc.According to the needs of regenerated flue gas product composition, oxygen source can be selected to regenerate and selective oxidation catalyzer, makes renewing catalyst activity and produce CO or synthetic gas (i.e. H
2with CO gas mixture).
Produce in the method for hydrogen at above-mentioned methane catalytic decomposition, preferably, the input speed of oxygen source described in step (3) and step (1) comprise the ratio of the input speed of the unstripped gas of methane for (1-10): 1.The flow velocity (i.e. input speed) of oxygen source be according to energy balance (heat balance namely between reactor and revivifier) 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 embodiment of the present utility model, 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 the methane catalytic decomposition that the utility model provides produces hydrogen is under catalyzer existent condition, the unstripped gas being preheating to certain 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 catalyzer carrying carbon distribution is sent into revivifier, by controlling the type of regeneration condition and regeneration gas, thus obtain CO or synthetic gas, then the catalyzer regenerated is transported in reactor again and recycles, utilize the combustion heat release of coke on the catalyzer of inactivation to come for revivifier 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 synthetic gas.And the method utilizes the heat of regeneration generation to provide the energy requirement of whole system, by controlling the degree (CO/CO namely in regenerated flue gas that regenerative process is made charcoal
2ratio), regulate revivifier liberated heat, and then regulation system heat balance, thus realize autothermal operation.
With adopt natural gas hydrogen preparation to compare with the process of CO or synthetic gas at present, the utility model has following beneficial effect:
(1) methane catalytic decomposition being reacted hydrogen manufacturing and catalyzer water vapour/air regenesis and selective oxidation process is placed in reactor and revivifier 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 ratio of catalyzer, thus improve the speed of reaction of whole process; Revivifier adopts dense bed/turbulent bed, is conducive to the transmission of heat, avoids the problem of local superheating in catalyst regeneration process; This reaction-regeneration system solves the problem such as reaction process operate continuously and catalyst recirculation use, shortens the operational cycle, improves production efficiency;
(3) the multifunctional efficient catalyzer 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 per pass conversion bring up to 80-100%, improve the utilising efficiency of raw material substantially, reduce CO
2discharge, for scale operation 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, water vapour 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 synthetic 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) temperature of reaction is relatively low, and without the need to injecting the excessive water steam preventing catalyzer coking, reduces the energy consumption of whole process further.
In sum, the device that methane catalytic decomposition that the utility model provides produces hydrogen 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 utility model and percentage are percentages by volume.
In addition, applicant introduces the full content of the reference 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 numerical 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 utility model scope 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 revivifier of embodiment.
Primary clustering nomenclature:
High-density Circulating Fluidized Beds reactor 1, settling vessel 2, revivifier 3, regenerator sloped tube 4, inclined tube to be generated 5.
Embodiment
In order to there be understanding clearly to technical characteristic of the present utility model, object and beneficial effect, existing following detailed description is carried out to the technical solution of the utility model, but can not be interpreted as to of the present utility model can the restriction of practical range.
Embodiment 1
Present embodiments provide the device that a kind of methane catalytic decomposition produces hydrogen, as shown in Figure 1, this device comprises: High-density Circulating Fluidized Beds reactor 1, settling vessel 2, revivifier 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 settling vessel 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 settling vessel 2 in the cavity of described settling vessel 2; Described revivifier 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 revivifier 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 revivifier 3 is connected to the catalyst outlet of described settling vessel 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 1.5:1, as shown in Figure 2; The ratio of the upper diameter of the cavity of three grades of reducings of described revivifier 3, mid diameter and lower diameter is 2.5:1.5:1, as shown in Figure 3; Described revivifier 3 is the revivifier adopting dense bed or turbulent bed.
This device can also comprise two cover heat-exchange equipments, wherein a set of heat-exchange equipment is first step heat-exchange equipment, another set of heat-exchange equipment is second stage heat-exchange equipment, described first step heat-exchange equipment and second stage heat-exchange equipment are the heat-exchange equipment of heat exchange between two kinds of fluids, the first fluid intake of described first step heat-exchange equipment is connected to the generation gas outlet at described settling vessel top, the second fluid intake of described first step heat-exchange equipment is connected to the unstripped gas source of the gas comprising methane, the second fluid outlet of described first step heat-exchange equipment is connected to the second fluid intake of described second stage heat-exchange equipment, the first fluid intake of described second stage heat-exchange equipment is connected to the regenerated flue gas outlet of described regenerator overhead, the second fluid outlet of described second stage heat-exchange 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 revivifier 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 revivifier, and described settling vessel can be the settling vessel 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 cyclonic separator etc.Described first step heat-exchange equipment and second stage heat-exchange equipment all can comprise the interchanger of one or several this area routine, as long as the interchanger of heat exchange between two kinds of fluids.
The present embodiment additionally provides the nickel-base catalyst that hydrogen is produced in a kind of catalytic methane cracking, and this nickel-base catalyst prepares by the following method:
In 78.25g pseudo-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 Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES of 15.6g, the phospho-wolframic acid of 16.2g are mixed to join in the gel prepared, add the deionized water of 70g again, mechanical stirring 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 nickelous 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 catalyzer 24.2NiO15.0WO
36.2CoO2.3K
2o52.3Al
2o
3.
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 catalyzer of inactivation;
(2) make to comprise the generation gas of hydrogen and the catalyzer of inactivation enters described settling vessel by the discharge nozzle of described High-density Circulating Fluidized Beds reactor head, in settling vessel, comprise the generation gas of hydrogen and the catalyst separating of inactivation, the generation gas comprising hydrogen exports out device by the generation gas at described settling vessel top;
(3) catalyzer of inactivation is made to enter described revivifier by described inclined tube to be generated, and oxygen source is passed in described revivifier, the catalyzer of inactivation regenerates in described revivifier, obtain the catalyzer after regenerating and regenerated flue gas, regenerated flue gas exports out device by the regenerated flue gas of described regenerator overhead;
(4) catalyzer 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 catalyzer of inactivation to come for revivifier heat supply, by controlling the degree that regenerative process is made charcoal, regulating revivifier liberated heat, and then setting device heat balance, thus realize autothermal operation.Therefore, when adopting the method, only when starting shooting to reactor heat supply, after catalyst recirculation uses, then autothermal operation need can be realized.
In the above-mentioned methods, reaction conditions is: unstripped gas is methane, the first step is preheated to 350 DEG C (adopt generation gas in first step heat-exchange equipment, carry out heat exchange and carry out preheating), the second stage is preheated to 540 DEG C (adopt regenerated flue gas in the heat-exchange equipment of the second stage, carry out heat exchange and carry out preheating), and methane feed speed is 400L/ (hg
cat); In reactor, pressure is 0.42MPa, and temperature of reaction is 620 DEG C; In revivifier, 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 catalyzer in liter/every gram of revivifier per hour).
Reaction result: methane per pass conversion is 88.4%; CO/CO in regenerated flue gas
2=2.9:1; The hydrogen selective of catalyzer is (the theoretical hydrogen yield that the methane of selectivity=hydrogen actual recovery/conversion obtains) for 99.0%; The hydrogen purity generating gas is 85%.
Embodiment 2
Present embodiments provide the device that a kind of methane catalytic decomposition produces hydrogen, as shown in Figure 1, this device comprises: High-density Circulating Fluidized Beds reactor 1, settling vessel 2, revivifier 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 settling vessel 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 settling vessel 2 in the cavity of described settling vessel 2; Described revivifier 3 comprises thick lower cavity and that is narrow, secondary reducing 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 revivifier 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 revivifier 3 is connected to the catalyst outlet of described settling vessel 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 1.5:1, as shown in Figure 2; The upper diameter of the cavity of the secondary reducing of described revivifier 3 and the ratio of lower diameter are 2.0:1; Described revivifier 3 is the revivifier adopting dense bed or turbulent bed.
This device can also comprise two cover heat-exchange equipments, wherein a set of heat-exchange equipment is first step heat-exchange equipment, another set of heat-exchange equipment is second stage heat-exchange equipment, described first step heat-exchange equipment and second stage heat-exchange equipment are the heat-exchange equipment of heat exchange between two kinds of fluids, the first fluid intake of described first step heat-exchange equipment is connected to the generation gas outlet at described settling vessel top, the second fluid intake of described first step heat-exchange equipment is connected to the unstripped gas source of the gas comprising methane, the second fluid outlet of described first step heat-exchange equipment is connected to the second fluid intake of described second stage heat-exchange equipment, the first fluid intake of described second stage heat-exchange equipment is connected to the regenerated flue gas outlet of described regenerator overhead, the second fluid outlet of described second stage heat-exchange 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 revivifier 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 revivifier, and described settling vessel can be the settling vessel 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 cyclonic separator etc.Described first step heat-exchange equipment and second stage heat-exchange equipment all can comprise the interchanger of one or several this area routine, as long as the interchanger of heat exchange between two kinds of fluids.
Claims (7)
1. methane catalytic decomposition produces a device for hydrogen, and it is characterized in that, this device comprises: High-density Circulating Fluidized Beds reactor, settling vessel, revivifier, 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 settling vessel 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 settling vessel in the cavity of described settling vessel; The cavity and one that described revivifier 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 revivifier is connected to the feeding pipe of described High-density Circulating Fluidized Beds reactor by described regenerator sloped tube; The catalyst inlet of described revivifier is connected to the catalyst outlet of described settling vessel by described inclined tube to be generated.
2. methane catalytic decomposition according to claim 1 produces the device of hydrogen, and it is characterized in that, 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.
3. methane catalytic decomposition according to claim 1 and 2 produces the device of hydrogen, and it is characterized in that, 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 (1.2-4.0): 1.
4. methane catalytic decomposition according to claim 1 produces the device of hydrogen, and it is characterized in that, when the cavity of described revivifier 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 revivifier 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.
5. the methane catalytic decomposition according to claim 1 or 4 produces the device of hydrogen, and it is characterized in that, when the cavity of described revivifier is the cavity of secondary reducing, the ratio of its upper diameter and lower diameter is (1.2-4.0): 1; When the cavity of described revivifier is the cavity of three grades of reducings, the ratio of its upper diameter, mid diameter and lower diameter is (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.
6. methane catalytic decomposition according to claim 1 produces the device of hydrogen, it is characterized in that, described revivifier is the revivifier adopting dense bed or turbulent bed.
7. methane catalytic decomposition according to claim 1 produces the device of hydrogen, it is characterized in that, the device that described methane catalytic decomposition produces hydrogen also comprises two cover heat-exchange equipments, wherein a set of heat-exchange equipment is first step heat-exchange equipment, another set of heat-exchange equipment is second stage heat-exchange equipment, described first step heat-exchange equipment and second stage heat-exchange equipment are the heat-exchange equipment of heat exchange between two kinds of fluids, the first fluid intake of described first step heat-exchange equipment is connected to the generation gas outlet at described settling vessel top, the second fluid intake of described first step heat-exchange equipment is connected to the unstripped gas source of the gas comprising methane, the second fluid outlet of described first step heat-exchange equipment is connected to the second fluid intake of described second stage heat-exchange equipment, the first fluid intake of described second stage heat-exchange equipment is connected to the regenerated flue gas outlet of described regenerator overhead, the second fluid outlet of described second stage heat-exchange equipment is connected to the feeding pipe of described High-density Circulating Fluidized Beds reactor bottom.
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