CN100497160C - Adsorption reinforced methane steam reforming hydrogen production process and apparatus using circulating fluidized bed - Google Patents
Adsorption reinforced methane steam reforming hydrogen production process and apparatus using circulating fluidized bed Download PDFInfo
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- CN100497160C CN100497160C CNB2006100535670A CN200610053567A CN100497160C CN 100497160 C CN100497160 C CN 100497160C CN B2006100535670 A CNB2006100535670 A CN B2006100535670A CN 200610053567 A CN200610053567 A CN 200610053567A CN 100497160 C CN100497160 C CN 100497160C
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Abstract
The invention discloses a hydrogen preparing process of strengthening methane steam reforming by cyclic fluidized bed adsorption, comprising: transporting 5-200 micron composite catalyst grains into a regenerator for pretreating; degasifying the pretreated composite catalyst and tranfering it to a fluidized bed reactor for reducing; charing methane and steam into the fluidized bed reactor in the water-carbon ratio of 2-10, and making the fluidized composite catalyst perform reforming hydrogen preparing reaction with methane and steam at the same time, and finally transferring the composite catalyst into regnerator to be regenerated and recycled, where the reacting time is 1s-5min, the reacting gas speed is 0.3-1.0m/s, and the ratio of composite catalyst to methane is 10 : 1-0.002 : 1 in g/ml. And it also discloses a device of implementing the above process. And the process can implement stable and continuous operation of fluidized bed reactor, and has advantages of high mass and heat transfer efficiencies.
Description
Technical field
The present invention relates to a kind of adsorption forced methane steam reforming hydrogen manufacturing process, especially relate to a kind of adsorption forced methane steam reforming hydrogen manufacturing process and device that adopts circulating fluidized bed.
Background technology
The reactor that is used for methane steam reforming hydrogen manufacturing in the at present domestic and international industrial production mostly is fixed-bed reactor.For reducing the reaction pressure drop, generally adopt particle diameter Φ 15-20 * 10-15mm, with the nickel oxide the cellular large granular catalyst of active ingredient.Two sections conversion reactions of the high temperature that fixed bed methane steam reforming hydrogen manufacturing reaction needed is 600-1000 ℃, the C0 of conversion reaction by-product need use transformation catalyst, carries out two sections conversion at 300-500 ℃ C0 is changed into CO
2, final equilibrated CO
2Gas phase content is 15-20%, and hydrogen content is less than 75%.
Though this process for making hydrogen was used till today from nineteen twenty-six always, because methane steam reforming hydrogen manufacturing is a strong endothermic reaction, still there are a lot of deficiencies in production technique.The problem that exists aspect catalyzer is that there is gradient in the internal heat transmission because granules of catalyst is big; Catalyst life is short, and reactor needs the big loading catalyst of diameter many, thereby influences reaction bed heat supply and reactivity worth, causes problems such as reactor throughput is low.Shortcomings such as have the temperature of reaction height at whole process aspect, density of hydrogen is low, and reaction process is long, facility investment is big exist process for making hydrogen reaction and the high problem of purification energy consumption all the time.
The improved patent in the relevant methane steam reforming hydrogen manufacturing fixed-bed reactor of Chinese patent aspect, Chinese invention patent application 200310114342.8 and 200310122344.1 are arranged, the board-like reforming hydrogen-preparation reactor of disclosed content for combining by a plurality of different cavity, by the filling structure of change fixed-bed reactor internals and catalyzer, thereby optimized the process that heat, matter are transmitted.
In the inventor's the Chinese patent application formerly numbers 200510060911.4, a kind of siliceous nano calcium oxide high temperature carbon dioxide sorbent material and this preparation of adsorbent method and the application in process for making hydrogen are disclosed.A kind of siliceous nano calcium oxide of main invention is used for the adsorption forced methane steam reformation catalyzing manufacturing of hydrogen technology of breaking molecular balance as the high temperature carbon dioxide sorbent material, can reduce temperature of reaction greatly, reduces the hydrogen manufacturing energy consumption.
In the inventor's the Chinese patent application formerly 200610052788.6, a kind of new adsorption forced methane steam reforming hydrogen manufacturing composite catalyst is disclosed, mainly by being the CaO of presoma with micron order and/or nano level lime carbonate and/or calcium hydroxide powder and being that the active nickel composition and the alumina supporter of presoma is composited that the each component mol ratio is: CaO:NiO:Al with nickelous carbonate, nickel oxide or nickelous nitrate
2O
3=1:(0.1-2.0): (0.1-3.0), catalysis in the methane steam reforming hydrogen manufacturing process and adsorption process are carried out on composite catalyst simultaneously.
For the new process for making hydrogen of adsorption forced methane steam reformation, because relating to catalyzer and sorbent material need constantly react with regenerated and circulate, therefore, use fixed-bed reactor can bring continuity production and the unhandy problem of catalyst regeneration, and circulating fluid bed reactor can be because of using the microsphere particle catalyzer, not only strengthened heat transfer, mass transfer, and can realize the regeneration of catalyzer and interpolation etc. flexibly, the continuous cyclical operation of can realization response regenerating.
It is closely similar that the circulating fluid bed reactor of widespread use carries out catalytic cracking reaction (being called for short FCC) in its pyroreaction of adsorption forced hydrogen production reaction and high temperature catalyst regenerated characteristics and the oil refining process.
At Chang Samuel Hsu, Paul R.Robinson, (Springer U.S.A.), has detailed description to catalytic cracking (FCC) technology in 2006 to Practical Advances inpetroleum processing.
In Chinese patent application 00818321.X, disclose a kind of circulating fluid bed reactor, introduced the structure of fluidized-bed reactor.Disclosing a kind of combined technical method of catalytic cracking in the Chinese patent 01144955.1, mainly is to utilize fluidized-bed reactor to carry out the catalytic cracking reaction of heavy crude component.
The method and apparatus that carries out the hydrocarbon conversion with fluidized-bed reactor is disclosed in the Chinese patent 97191523.7, a kind of in the method gas or liquid hydrocarbon raw material are passed into a circulating fluid bed reactor and react, and enumerated catalysis and uncatalyzed reaction system, but the undeclared methane steam reforming hydrogen manufacturing that is used for.
Summary of the invention
The invention provides a kind of adsorption forced methane steam reforming hydrogen manufacturing process that adopts circulating fluidized bed, have stable operation, continuous; Be convenient to catalyst regeneration; Characteristics such as mass transfer, heat transfer efficiency height.
The present invention also provides the device of above-mentioned process using, and this device is used for adsorption forced methane steam reforming hydrogen manufacturing, and the hydrogen production efficiency height is easy to operate.
The adsorption forced methane steam reforming hydrogen manufacturing reaction formula:
Sorbent material can be regenerated by thermolysis, and reaction formula is as follows:
The reaction formula of reduction reaction is:
A kind of adsorption forced methane steam reforming hydrogen manufacturing process that adopts circulating fluidized bed comprises the steps:
(1) be that the composite catalyst of the fresh calcic of 5-200 micron and nickel is delivered to and carries out the thermolysis pre-treatment in the fluid bed regenerator with particle diameter;
(2) the pretreated composite catalyst of thermolysis reduces after the degassing vessel degassing;
(3) composite catalyst is after reduction, in fluidized-bed reactor, feed methane and water vapor according to steam/hydrocarbons ratio 2-10, composite catalyst under fluidized state and methane, water vapor carry out the reformation hydrogen production reaction, reaction time is 1 second to 5 minutes, reaction gas speed 0.3-1.0 meter per second, the ratio of composite catalyst and reactants, methane is for to count with g/ml: 4:1-0.01:1, and the hydrogen that reaction produces carries out aftertreatment after collecting;
(4) composite catalyst is transferred to the fluid bed regenerator thermal regeneration after using, and returns fluidized-bed reactor and recycle after the degassing vessel degassing.
In described process for making hydrogen, pretreated composite catalyst is transferred to reducer after the degassing vessel degassing, feeds hydrogen and reduce in reducer, for the ease of operation, also can add inert gas dilution reduction down.Again composite catalyst is transferred to fluidized-bed reactor after the reduction.Also the composite catalyst after the degassing directly can be transferred to fluidized-bed reactor, in fluidized-bed reactor, reduce processing.
Pretreated temperature described in the described process for making hydrogen step (1) is 600-1000 ℃;
Reductive temperature described in the described process for making hydrogen step (2) is 50-600 ℃, and pressure is 0.1-2.OMPa;
The temperature of the reformation hydrogen production reaction described in the described process for making hydrogen step (3) is 400-800 ℃, and pressure is 0.1-2.OMPa.
The composite catalyst described in the described process for making hydrogen step (3) and the ratio of reactants, methane are counted with g/ml: 4:1-0.01:1.
Composite catalyst enters reducer and reduces after the degassing vessel degassing in the described process for making hydrogen step (4), and then returns fluidized-bed reactor and recycle.
After composite catalyst regeneration, the degassing, transferred in the fluidized-bed reactor after both can having reduced in reducer, and also can directly transfer in the fluidized-bed reactor without reduction and react, mainly the activity according to composite catalyst determines.
The present invention also provides the device of described process for making hydrogen, comprises fluid bed regenerator, fluidized-bed reactor, degassing vessel, reducer; Described revivifier bottom is the revivifier transportation section, and top is the revivifier fluidisation section of interior dress cyclonic separator, and revivifier transportation section and revivifier fluidisation section junction are provided with grid distributor; Described fluidized-bed reactor bottom is the reactor riser section, and top is the reactor fluidisation section of interior dress cyclonic separator and upflow tube, and reactor riser section and reactor fluidisation bed section junction are provided with grid distributor; Upflow tube in the fluidized-bed reactor links to each other with bottom, revivifier transportation section, the discharge port on fluid bed regenerator top links to each other with degassing vessel top, the degassing vessel bottom links to each other with fluidized-bed reactor riser tube pars infrasegmentalis through reducer, also can directly link to each other with the fluidized-bed riser tube.
Be provided with reducer between degassing vessel and fluidized-bed reactor, the degassing vessel bottom links to each other with reducer top, and the reducer bottom links to each other with the reactor riser section of fluidized-bed reactor bottom.
Described cyclonic separator is at least three grades a cyclonic separator, for guaranteeing that separating effect can adopt more progression.
Carry hydrogen secretly and enter revivifier for fear for the treatment of the regenerated composite catalyst, can between fluidized-bed reactor and fluid bed regenerator, be provided with the stripping jar, upflow tube in the fluidized-bed reactor links to each other with stripping jar top, and stripping jar bottom links to each other with bottom, revivifier transportation section.
Described revivifier transportation section has riser tube.
Technological process of the present invention:
When hydrogen production reaction, rise in the composite catalyst catalysis and adsorbing be respectively nickel and calcium oxide, but the nickel in the fresh composite catalyst is the form with nickel oxide to be existed, and partial oxidation calcium is that the form with lime carbonate exists, thereby need carry out pre-treatment and reduction to composite catalyst.
At first fresh composite catalyst is carried out pre-treatment, composite catalyst is packed in the fluid bed regenerator, geseous fuel such as bubbling air and methane are warming up to regeneration temperature, stop to carry out pre-treatment in 1-10 minutes.Pretreated composite catalyst enters fluidized-bed reactor bottom by discharge tube through tundish (comprising degassing vessel and reducer) from the top of fluid bed regenerator, has all changed into calcium oxide through original lime carbonate in the pretreated composite catalyst.
Composite catalyst in degassing vessel the water steam stripped further to remove the carbonic acid gas carried secretly and other combustion tail gas.Catalyzer needed to reduce with the hydrogen component before reaction, for ease of operation, also can add an amount of inert gas component.Reductive action by hydrogen makes that original nickel oxide is reduced into elemental nickel in the composite catalyst.Reduction can be directly to carry out in fluidized-bed reactor, also can carry out in reducer.
Finish after composite catalyst pre-treatment and the reduction, water vapor and methane carry out the reformation hydrogen production reaction through the composite catalyst that the gas jet that mixes the preheater preheating and be provided with bottom fluidized-bed reactor enters fluidized-bed reactor and fluidized.The hydrogen that reaction produces and the stripped vapor of unreacted a small amount of methane, carbon monoxide, carbon dioxide and feeding from the output of fluidized-bed reactor top, enter recovery of heat and scavenging process together.
Calcium oxide in the reacted composite catalyst has all changed into lime carbonate, needs regeneration.Composite catalyst to be generated is delivered to the fluid bed regenerator bottom by gravity through discharge tube from the top of fluidized-bed reactor, carry hydrogen for fear of spent agent and enter revivifier, can in discharge tube, feed the suitable quantity of water steam stripped, and make this strand gas reenter reactor.Fluid bed regenerator is by the air and the fuel heat supply that replenish, make temperature reach regeneration temperature, lime carbonate in the composite catalyst resolves into calcium oxide at 600-1000 ℃ and reaches the regeneration purpose, and the knot charcoal on the composite catalyst is removed by high-temp combustion and reached the regeneration purpose.Regeneration back composite catalyst returns fluidized-bed reactor after the fluid bed regenerator top process degassing (reducing in case of necessity), finish the circulation hydrogen production process.The carbonic acid gas that the fluid bed regenerator thermolysis produces and other waste gas are discharged from the fluid bed regenerator top, the removal process of reducing phlegm and internal heat.
For keeping hydrogen production reaction efficient, replenish an amount of fresh composite catalyst where necessary.
Supply the heat of fluid bed regenerator by the heat of gas fuel combustions such as air and additional methane generation, because the temperature of fluid bed regenerator is higher than fluidized-bed reactor, so amount and material rate that the temperature of fluidized-bed reactor is returned solid catalyst by adjusting are controlled.
Guarantee the carrying out that react and the mass transport and the discharge of fluidized-bed reactor by the ratio of regulating the gas-solid amount.
The purpose of degassing vessel is to remove the foreign gases such as oxygen, nitrogen and carbonic acid gas that the regeneration rear catalyst is carried secretly.The purpose of reducer be make after the regeneration may inactivation nickel oxide catalyst further under nitrogen atmosphere, be reduced to elemental nickel, to guarantee activity of such catalysts.
Beneficial effect of the present invention:
(1) composite catalyst and the circulating fluid bed reactor and the fluid bed regenerator of employing microsphere particle, as much as possible meet the characteristics and the requirement of strong heat absorption reformation hydrogen production reaction from aspects such as catalyzer, technology and equipment, realize the adsorption forced methane steam reformation reaction hydrogen manufacturing and the working cycle of adsorbent reactivation.
(2) reaction can directly produce the hydrogen that purity is higher than 90% content continuously.
(3) can realize the stability and the continuity of fluidized-bed reactor operation, have mass transfer, advantage that heat transfer efficiency is high.
(4) composite catalyst of Cai Yonging is 5-200 microns a small-particle, can effectively reduce the heat transfer loss, helps the carrying out of strong endothermic reaction.
(5) because the composite catalyst particle is little, can keeps the high dispersion of adsorption activity component, thereby help reducing decomposition temperature, effectively reduce the heat absorption loss, help the carrying out of regenerative response.
(6) reaction and regenerated waste heat energy obtain recycling, and the carbonic acid gas of by-product can focus utilization.
Description of drawings
Fig. 1 is the schematic flow sheet of technology of the present invention;
Fig. 2 is the structural representation of apparatus of the present invention, in Fig. 2
1, the riser tube 3 of fluid bed regenerator 2, revivifier, revivifier fluidisation section
4, grid distributor 5, three-stage cyclone separator 6, reactor discharge tube
7, revivifier discharge tube 8, degassing vessel 9, reducer
10, fluidized-bed reactor 11, reactor riser section 12, reactor fluidisation section
13, grid distributor 14, three-stage cyclone separator 15, reactor feed pipe
16, mix preheater 17, stripped vapor pipeline 18, air and fuel channel
19, superheat steam pipeline 20, methane and water vapor pipeline
21, reactant gases reclaiming clean pipeline 22, the regeneration gas recovery channel that reduces phlegm and internal heat that reduces phlegm and internal heat
23, reduce phlegm and internal heat recovery channel 24, hydrogen and nitrogen pipeline of degassing vessel gas
25, work off one's feeling vent one's spleen pipeline 26, stripping jar of reducer
Embodiment
Embodiment 1
Referring to Fig. 1, Fig. 2, at first composite catalyst is carried out thermolysis pre-treatment and catalyzer prereduction when using fresh composite catalyst.
Composite catalyst is carried out pre-treatment, with the microballoon composite catalyst fluid bed regenerator 1 of packing into, fluid bed regenerator 1 bottom is the revivifier transportation section, the revivifier transportation section of using in the present embodiment has riser tube 2, the revivifier fluidisation section 3 that three-stage cyclone separator 5 is established in being in fluid bed regenerator 1 top promotes between pipeline section 2 and the revivifier fluidisation section 3 and is provided with grid distributor 4.From the gas jet of riser tube 2 bottoms of revivifier by geseous fuel such as pipeline 18 bubbling airs and methane, be warming up to regeneration temperature, composite catalyst carries out pre-treatment (or regeneration) in revivifier fluidisation section 3, the composite catalyst particulate of gas entrainment is after three-stage cyclone separator 5 is collected, enter degassing vessel 8 from revivifier fluidisation section 3 by revivifier discharge tube 7, partial regeneration gas reduces phlegm and internal heat to reclaim and enters pipeline 22.
Import superheated vapour by pipeline 19 in the degassing vessel 8, remove the foreign gases such as oxygen, nitrogen and carbonic acid gas that pre-treatment (or regeneration) back composite catalyst is carried secretly.Composite catalyst after the degassing can directly enter fluidized-bed reactor 10; Also can enter reducer 9, reduce.The recovery of reducing phlegm and internal heat of degassing vessel gases is discharged by pipeline 23 in degassing vessel 8 tops.
Composite catalyst after the degassing is when entering reducer 9, in reducer 9, import nitrogen and hydrogen by pipeline 24, make after the regeneration may inactivation nickel oxide catalyst further under nitrogen atmosphere, be reduced to elemental nickel, to guarantee activity of such catalysts, composite catalyst after the reduction enters fluidized-bed reactor 10 by reactor feed pipe 15, and reducer 9 tops are discharged reducer by pipeline 25 and worked off one's feeling vent one's spleen.
Fluidized-bed reactor 10 bottoms are reactor riser section 11, and top is the reactor fluidisation section 12 of interior dress three-stage cyclone separator 14 and upflow tube, and reactor riser section 11 is provided with grid distributor 13 with reactor fluidisation section 12 junctions.Raw material methane and water vapor by pipeline 20 through mixing preheater 16 preheatings after the bottom of fluidized-bed reactor 10 sprays into fluidized-bed reactor 10 by gas jet, in fluidized-bed reactor 10, reach fluidized with composite catalyst, carry out steam reforming reaction.
The hydrogen that reaction produces and unreacted a small amount of methane, carbon monoxide, carbon dioxide with from the stripped vapor of pipeline 17 through three-stage cyclone separator 14, emit from fluidized-bed reactor 10 tops, by the pipeline 21 reactant gasess reclaiming clean that reduces phlegm and internal heat.Reacted composite catalyst is collected through three-stage cyclone separator 14, be transported to stripping jar 26 by gravity by reactor discharge tube 6, feed suitable quantity of water steam to stripping jar 26 and remove the hydrogen that composite catalyst is carried secretly as the stripping medium, the composite catalyst after stripping is handled enters fluid bed regenerator 1 and regenerates.Stripping jar 26 expellant gas return fluidized-bed reactor 10 by pipeline and apply mechanically.
Reacted composite catalyst by geseous fuel 18 heat supplies such as air that replenishes and methane, makes composite catalyst repeat thermolysis regeneration in fluid bed regenerator 1.
Wherein, composite catalyst CA-3 (preparation method: in beaker, add 5g nano-calcium carbonate calcium powder earlier, add 35ml solid content 10% alumina hydrosol then, after adding the less water stirring and evenly mixing, add saturated nickelous nitrate salts solution 10ml, mixing is after spray drying granulation, calcining, obtain composite catalyst powder CA-3, see Chinese invention patent application 200610052788.6 for details), median size is 60 microns, the hydrogen production reaction condition: steam/hydrocarbons ratio is 6,600 ℃ of temperature of reaction, reaction pressure 0.3MPa, methane flow are 0.5m/s, and the ratio of the amount of the composite catalyst of filling and the input of methane is 0.5:1 (g:ml), hydrogen content 93.1% in the reaction product gas, carbon monoxide content 0.4%, carbonic acid gas 2.3%, methane conversion 93.4%.800 ℃ of regeneration temperatures, gauge pressure 0.1MPa.
Carry out adsorption forced methane steam reforming hydrogen manufacturing according to the technical process among the embodiment 1.
Wherein, composite catalyst CA-3 catalyzer (preparation method is referring to embodiment 1), median size is 60 microns, the hydrogen production reaction condition: steam/hydrocarbons ratio is 4,600 ℃ of temperature of reaction, gauge pressure 0.2MPa, methane flow are 1m/s, the ratio of the amount of the composite catalyst of loading and the input of methane is 4:1 (g:ml), 20 seconds residence time, hydrogen content 92.7% in the reaction product gas, carbon monoxide content 0.5%, carbonic acid gas 2.9%, methane conversion 92.3%.750 ℃ of regeneration temperatures, gauge pressure 0.1MPa.
Carry out adsorption forced methane steam reforming hydrogen manufacturing according to the technical process among the embodiment 1.
Wherein, composite catalyst CA-3 catalyzer (preparation method is referring to embodiment 1), median size is 80 microns, the hydrogen production reaction condition: steam/hydrocarbons ratio is 4,600 ℃ of temperature of reaction, gauge pressure 0.2MPa, methane flow are 1m/s, the ratio of the amount of the composite catalyst of loading and the input of methane is 0.01:1 (g:ml), 30 seconds residence time, hydrogen content 91.6% in the reaction product gas, carbon monoxide content 0.9%, carbonic acid gas 3.8%, methane conversion 91.9%.800 ℃ of regeneration temperatures, gauge pressure 0.1MPa.
Embodiment 4
Carry out adsorption forced methane steam reforming hydrogen manufacturing according to the technical process among the embodiment 1.
Wherein, composite catalyst CA-3 catalyzer (preparation method is referring to embodiment 1), median size is 60 microns, the hydrogen production reaction condition: steam/hydrocarbons ratio is 6,650 ℃ of temperature of reaction, gauge pressure 0.15MPa, methane flow are 0.6m/s, the ratio of the amount of the composite catalyst of loading and the input of methane is 10:1 (g:ml), 1 minute residence time, hydrogen content 94.7% in the reaction product gas, carbon monoxide content 0.25%, carbonic acid gas 2.2%, methane conversion 94.2%.700 ℃ of regeneration temperatures, gauge pressure 0.1MPa.
Carry out adsorption forced methane steam reforming hydrogen manufacturing according to the technical process among the embodiment 1.Wherein, composite catalyst CAN-1 catalyzer (preparation method: in beaker, add 5g nano-calcium carbonate calcium powder earlier, the alumina hydrosol that adds 30g solid content 10% then, add 5g nickelous carbonate powder after adding the less water stirring and evenly mixing, add 1g rectorite leng powder, mixing, infrared drying is also made sphere, oven dry, the composite catalyst CAN-1 that calcining makes, see Chinese invention patent application 200610052788.6 for details), median size is 60 microns, the hydrogen production reaction condition: steam/hydrocarbons ratio is 4,600 ℃ of temperature of reaction, gauge pressure 0.5MPa, methane flow is 1m/s, and the ratio of the amount of the composite catalyst of filling and the input of methane is 0.002:1 (g:ml), 10 seconds residence time, hydrogen content 90.7% in the reaction product gas, carbon monoxide content 1.0%, carbonic acid gas 3.2%, methane conversion 90.5%.800 ℃ of regeneration temperatures, gauge pressure 0.1MPa.
Claims (10)
1, a kind of adsorption forced methane steam reforming hydrogen manufacturing process that adopts circulating fluidized bed comprises the steps:
(1) be that the composite catalyst of the calcic of 5-200 micron and nickel is delivered to and carries out the thermolysis pre-treatment in the fluid bed regenerator with particle diameter;
(2) the pretreated composite catalyst of thermolysis reduces after the degassing vessel degassing;
(3) composite catalyst is after reduction, in fluidized-bed reactor, feed methane and water vapor according to steam/hydrocarbons ratio 2-10, composite catalyst under fluidized state and methane, water vapor carry out the reformation hydrogen production reaction, reaction time is 1 second to 5 minutes, reaction gas speed 0.3-1.0 meter per second, the ratio of composite catalyst and reactants, methane is for to count with g/ml: 4:1-0.01:1, and the hydrogen that reaction produces carries out aftertreatment after collecting;
(4) composite catalyst is transferred to the fluid bed regenerator thermal regeneration after using, and returns fluidized-bed reactor and recycle after the degassing vessel degassing.
2, technology according to claim 1 is characterized in that: the reduction described in the step (2) is carried out in reducer, after reduction is finished composite catalyst is transferred to fluidized-bed reactor.
3, technology according to claim 1 is characterized in that: the reduction described in the step (2) is carried out in fluidized-bed reactor.
4, technology according to claim 1 is characterized in that: the pretreated temperature described in the step (1) is 600-1000 ℃; The temperature of the prereduction described in the step (2) is 50-600 ℃, and pressure is 0.1-2.0MPa; The temperature of the reformation hydrogen production reaction described in the step (3) is 400-800 ℃, and pressure is 0.1-2.0MPa.
5, technology according to claim 1 is characterized in that: composite catalyst enters reducer and reduces after the degassing vessel degassing in the step (4), and then returns fluidized-bed reactor and recycle.
6, a kind of device that adopts the adsorption forced methane steam reforming hydrogen manufacturing of circulating fluidized bed comprises fluid bed regenerator, fluidized-bed reactor, degassing vessel, reducer; Described fluid bed regenerator bottom is the revivifier transportation section, and top is the revivifier fluidisation section of interior dress cyclonic separator, and revivifier transportation section and revivifier fluidisation section junction are provided with grid distributor; Described fluidized-bed reactor bottom is the reactor riser section, and top is the reactor fluidisation section of interior dress cyclonic separator and upflow tube, and reactor riser section and reactor fluidisation bed section junction are provided with grid distributor; Upflow tube in the fluidized-bed reactor links to each other with bottom, revivifier transportation section, and the discharge port on fluid bed regenerator top links to each other with degassing vessel top, and the degassing vessel bottom links to each other with the reactor riser pars infrasegmentalis.
7, device according to claim 6 is characterized in that: be provided with reducer between degassing vessel and fluidized-bed reactor, the degassing vessel bottom links to each other with reducer top, and the reducer bottom links to each other with the reactor riser section of fluidized-bed reactor bottom.
8, device according to claim 6 is characterized in that: described cyclonic separator is at least three grades cyclonic separator.
9, device according to claim 6 is characterized in that: be provided with gas and carry jar between fluidized-bed reactor and fluid bed regenerator, the upflow tube in the fluidized-bed reactor is carried jar top with gas and is linked to each other, and gas is carried jar bottom and linked to each other with bottom, revivifier transportation section.
10, according to claim 6 or 9 described devices, it is characterized in that: described revivifier transportation section has riser tube.
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| CN101559924B (en) * | 2009-05-26 | 2011-03-30 | 清华大学 | Methane vapor reforming hydrogen production process and devices thereof |
| CN102464299B (en) * | 2010-10-28 | 2013-06-26 | 中国石油化工股份有限公司 | Method for producing hydrogen through fluidized-bed methane steam reforming |
| CN102795597A (en) * | 2011-05-23 | 2012-11-28 | 宝山钢铁股份有限公司 | Technology for increasing conversion efficiency of producing hydrogen from natural gas |
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| CN107188126A (en) * | 2017-06-01 | 2017-09-22 | 镇江严彦气体有限公司 | A kind of preparation method of high-purity hydrogen |
| CN110817801A (en) * | 2019-12-10 | 2020-02-21 | 太原理工大学 | Adsorption-enhanced methane steam reforming hydrogen production device and method |
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