CN103183318B - A kind of moving-bed lighter hydrocarbons producing hydrogen from steam conversion method and apparatus - Google Patents
A kind of moving-bed lighter hydrocarbons producing hydrogen from steam conversion method and apparatus Download PDFInfo
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- CN103183318B CN103183318B CN201110449278.3A CN201110449278A CN103183318B CN 103183318 B CN103183318 B CN 103183318B CN 201110449278 A CN201110449278 A CN 201110449278A CN 103183318 B CN103183318 B CN 103183318B
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- 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
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Abstract
A kind of moving-bed lighter hydrocarbons producing hydrogen from steam conversion method and apparatus, comprising: enter reactor by bottom after lighter hydrocarbons and water vapour preheating, the reforming catalyst different from particle diameter and adsorptive catalyst counter current contact, lighter hydrocarbons and water vapour react and generate H under steam reforming conditions
2, CO and CO
2, CO
2react with the CaO in adsorptive catalyst and be converted into CaCO
3; The product gas that reaction generates obtains high-purity hydrogen by entering subsequent purification tripping device after reactor head gas solid separation; Mixed catalyst enters screening separator by reactor bottom and is separated by size, and isolated reforming catalyst returns in moving-burden bed reactor and recycles, and isolated adsorptive catalyst returns moving-burden bed reactor and recycles after regeneration.It is in reducer, be reduced into W metal process after NiO that method and apparatus provided by the invention eliminates the frequent high temperature oxidation of reforming activity constituent element Ni, simplifies technological process, and life-span of extending catalyst also reduces system energy consumption.
Description
Technical field
The present invention relates to a kind of catalysis conversion method and device of petroleum hydrocarbon, more specifically, relate to a kind of methane vapor reforming hydrogen production process method and apparatus.
Background technology
The production of clean fuel must bring the increase to hydrogen demand, although hydrogen production process is a lot, but various mineral substance comprises with coal, oil and natural gas be raw material hydrogen producing technology or topmost method, the wherein the most ripe also the most frequently used steam reformation hydrogen production technique remaining hydro carbons, gas water steam reforming (SteamMethaneReforming, SME) be the method that in current hydrogen manufacturing, cost is minimum, hydrogen manufacturing amount is maximum, about have the hydrogen of 1/2 to be produced by natural gas steam reforming (SRM).Hydrogen production from methane vapor reforming many employings fixed-bed reactor are reduce reactor pressure decrease, and catalyzer generally adopts particle diameter to be the cellular solids catalyzer of Φ (15-20) × (10-15) mm, and active ingredient is nickel oxide.Hydrogen production process is included in one section or two sections of conversion reactions of 800-820 DEG C, and byproduct CO adopts 300-450 DEG C two sections and is transformed to CO
2, remove CO and CO further by solvent absorbing or methanol wash
2, the CO of final balance
2gas phase content is 15-20%, and hydrogen content is less than 75%.Highly purified industrial hydrogen is obtained subsequently through pressure-variable adsorption.Hydrogen production from methane vapor reforming has strong heat absorption reversible reaction feature, and it is high that process aspect exists temperature of reaction, and density of hydrogen is low, and reaction, purification process step are many, and throughput is low, invest the shortcomings such as large; In catalyzer, because granules of catalyst is large, the defects such as internal heat transmission exists gradient, and catalyst life is short.
CN1903431A discloses a kind of adsorption forced hydrogen production from methane vapor reforming composite catalyst, this catalyzer is primarily of with micron order and/or to be nano levelly composited with calcium carbonate and/or the calcium hydroxide powder CaO that is presoma with nickelous carbonate, nickel oxide or the nickelous nitrate active nickel composition that is presoma and alumina supporter, each component molar ratio is, CaO: NiO: Al
2o
3=1: (0.1-2.0): (0.1-3.0), described composite catalyst utilizes CaO by the method for chemical reaction by CO
2remove from reaction system in time, the steam reforming reaction of forced mathane.In addition, CaO and CO
2reaction liberated heat just in time makes up the strong endothermic heat demand of reformation hydrogen production.
CN1974375A discloses a kind of adsorption forced methane steam reforming hydrogen manufacturing method adopting fixed-bed reactor, and the regeneration of hydrogen production reaction and composite catalyst is carried out in different fixed-bed reactor simultaneously, is used alternatingly.Adopt the composite catalyst and fixed-bed reactor and regenerator system that contain catalyzer and sorbent material, realize stable, the continuous flow procedure of methane steam reformation reaction preparation high concentration hydrogen.Directly can produce the hydrogen of purity 90-98% content continuously.Due to sorbent material, to reach absorption saturated time very short, adopts this fixed bed alternately to switch fundamentally to be difficult to realize temporal coupling to carry out normal running.
CN1935634A proposes a kind of adsorption forced methane vapor reforming hydrogen production process adopting circulating fluidized bed.Adopt the composite catalyst particulate containing CaO and active nickel disclosed in CN1903431A, catalyst particle diameter is 5-200 micron, and the active component NiO on catalyzer is reduced into W metal; Catalyzer after reduction enters reactive system, and under fluidized state, methane and water vapour and catalyst exposure, reaction generates H
2and CO
2, the CO that reaction generates
2react with the CaO reactive chemistry on catalyzer, with CaCO
3form retain on the catalyst particles.React saturated rear catalyst through stripping, carry out high-temperature calcination in the revivifier entered, by CaCO
3pyrolytic decomposition is CaO and CO
2, make catalyzer recover chemisorption active, recycle.Concrete steps are, are delivered to by composite catalyst in revivifier and carry out pre-treatment; Pretreated composite catalyst reduces after degassed in the environment of hydrogen again; In fluidized-bed reactor, water vapor and methane is passed into according to steam/hydrocarbons ratio 2-10, composite catalyst under fluidized state and methane, water vapor carry out reformation hydrogen production reaction simultaneously, 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 10: 1 ~ 0.002: 1, composite catalyst transfers to revivifier thermal regeneration after using, recycle, stability and the continuity of fluidized-bed reactor operation can be realized, there is mass transfer, advantage that heat transfer efficiency is high.
Method disclosed in CN1935634A, by ciculation fluidized operate continuously, efficiently solve fixed-bed heat transfer, shortcoming that rate of mass transfer is low, but there is following shortcoming in the method:
1) owing to adopting composite catalyst, the sintering of Ni active component and inactivation is easily caused as the reactor of Ni in ciculation fluidized process of methane steam reforming active component, revivifier circulating reduction, oxidation, particularly high temperature regeneration process;
2) reforming activity constituent element Ni is after revivifier is oxidized to NiO, need to be reduced into W metal in reducer, its optimum regime is reduced at low temperatures, to avoid the gathering of Ni metallics and inactivation, such needs carry out reduction reaction after the catalyzer after regeneration is lowered the temperature, catalyzer after reduction carries out being warmed up to temperature of reaction again, causes a large amount of energy consumptions.
From hydrogen production from methane vapor reforming As-Is, because the catalyst development of hydrogen production from methane vapor reforming is relatively ripe, because hydrogen production from methane vapor reforming is a strong endothermic process, how to reduce the focus that process energy consumption becomes process exploitation and innovation.
But there is the defect of the frequent coke burning regeneration of catalyzer in these prior arts, catalyzer is easily caused to destroy its high degree of dispersion because of Ni grain growth, affect activity and the stability of catalyzer, make device be difficult to stably operate down, the sorbent material continuous adsorption regeneration how reasonably solved in adsorption forced steam reforming is the technical bottleneck problem that this field is generally acknowledged in the world.
Summary of the invention
One of the technical problem to be solved in the present invention is to provide a kind of light hydrocarbon steam and reforms and prepare the method for hydrogen, can meet continuous prodution requirement, prepares hydrogen simultaneously realizing steam reforming, catalyst activity is steady in a long-term, transmission and temperature plateau control in heat.
Two of the technical problem to be solved in the present invention is to provide a kind of structure simply prepares hydrogen production equipment for light hydrocarbon steam reformation.
The method of a kind of moving-bed lighter hydrocarbons producing hydrogen from steam conversion provided by the invention, comprising:
(1) enter reactor by bottom after lighter hydrocarbons and water vapour preheating, the reforming catalyst different from granules of catalyst particle diameter and adsorptive catalyst counter current contact, lighter hydrocarbons and water vapour react and generate H under steam reforming conditions
2, CO and CO
2, described CO
2react with the CaO in adsorptive catalyst and be converted into CaCO
3;
(2) product gas in step (1) and mixed catalytic are in reactor head gas solid separation, and isolated product gas enters subsequent purification tripping device and obtains high-purity hydrogen;
(3) mixed catalyst by reactor bottom enter screening separator be separated by particle diameter, recycle in isolated reforming catalyst Returning reactor, isolated adsorptive catalyst enter revivifier regeneration, then recycle in Returning reactor.
A kind of lighter hydrocarbons producing hydrogen from steam conversion moving bed reaction device, this device comprises moving-burden bed reactor, screening separator, catalyst riser and revivifier, moving-burden bed reactor bottom is communicated with screening separator, screening separator interior is divided into the catalyst outlet of two kinds of different-grain diameters through screen cloth, one of them catalyst outlet is communicated with bottom catalyst riser, another outlet is through expecting to be honored as a queen connection catalyst regenerator, be honored as a queen through material and be communicated with bottom catalyst riser in revivifier bottom, catalyst riser top is communicated with moving-burden bed reactor top; Described moving-burden bed reactor top arranges reacting product outlet through gas-solid separation equipment, and bottom arranges lighter hydrocarbons and water vapour feed(raw material)inlet.
Compared with prior art, the beneficial effect of moving-bed lighter hydrocarbons producing hydrogen from steam conversion method and apparatus provided by the invention is:
Method provided by the invention adopts the catalyzer of counter-flow moving bed reactor and two kinds of different-grain diameters, enhance methane vapor hydrogen production reaction on the one hand, on the other hand by screening by two kinds of catalyzer separately, do not make reforming catalyst enter revivifier, avoid the oxidation and sinter inactivation that high temperature regeneration process causes Ni active component.
Method and apparatus provided by the invention, lighter hydrocarbons hydrogen production conversion efficiency is high, temperature automatic control steadily and improve heat transfer efficiency, reasonably solve sorbent material continuous adsorption and regenerate this bottleneck problem, device and operation are simplified and safety more, and complete assembly structure is simple, compact.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of lighter hydrocarbons moving-bed producing hydrogen from steam conversion method and apparatus provided by the invention.
In figure: 3-moving-burden bed reactor; 5-sieves separator; 11-revivifier; 15-first particulate material envelope valve; 16-second particulate material envelope valve; 1,2,4,6,7,8,9,10,12,13,14,17 pipeline is.
Embodiment
Hydrogen production from methane vapor reforming method provided by the invention is so concrete enforcement:
(1) enter reactor by bottom after lighter hydrocarbons and water vapour preheating, the reforming catalyst different from granules of catalyst particle diameter and adsorptive catalyst counter current contact, lighter hydrocarbons and water vapour react and generate H under steam reforming conditions
2, CO and CO
2, described CO
2with adsorptive catalyst generation Chemisorption, the CaO in adsorptive catalyst is converted into CaCO
3;
(2) product gas in step (1) and mixed catalyst are in reactor head gas solid separation, and isolated product gas enters later separation purifying plant and obtains high-purity hydrogen;
(3) mixed catalyst by reactor bottom enter screening separator be separated by particle diameter, recycle in isolated reforming catalyst Returning reactor, isolated adsorptive catalyst enter revivifier regeneration, then recycle in Returning reactor.
In method provided by the invention, described lighter hydrocarbons are the petroleum hydrocarbon of C1 ~ C8, comprise dry gas, liquefied petroleum gas (LPG), virgin naphtha that the various oil refining apparatus of boiling range within the scope of < 220 DEG C produce.
In method provided by the invention, described lighter hydrocarbons and water vapour be preheated to 350 ~ 550 DEG C, preferably 400 ~ 450 DEG C introduce in reactors.
In method provided by the invention, described lighter hydrocarbons and the weight ratio of water vapour are 1: (1 ~ 5), preferably 1: (2 ~ 4).
In method provided by the invention, described steam reforming conditions is temperature is 650 ~ 860 DEG C, preferably 680 ~ 820 DEG C, and pressure is 0.1 ~ 3.0MPa, preferably 0.15 ~ 2.5MPa.
In method provided by the invention, described adsorptive catalyst high temperature regeneration is honored as a queen to be delivered in revivifier by air through material to regenerate, the temperature of revivifier is 690 ~ 1250 DEG C, preferably 720 ~ 920 DEG C, pressure is 0.1 ~ 0.2MPa, after having regenerated, regenerative adsorption catalyzer is reused through material Returning reactor of being honored as a queen, and controls the flow of the regenerative adsorption catalyzer of Returning reactor according to temperature of reaction.
In method provided by the invention, in described revivifier, preferably add fuel refreshment heat.Described heavy fuel oil (HFO) comprises atmospheric residue, decompressed wax oil, wax tailings, pitch, long residuum, vacuum residuum, coal water slurry, coal dust.
In method provided by the invention, preferably, described steam reforming catalyst is Large stone pellet catalyst, and described adsorptive catalyst is small particle size microspheric form catalyzer.Described small particle size refers to be compared with steam reforming catalyst grain diameter, and described adsorptive catalyst grain diameter is less.The grain diameter of more preferably described steam reforming catalyst is 2 ~ 3 millimeters, and described adsorptive catalyst mean particle size is 0.1 ~ 1 millimeter.
In method provided by the invention, described adsorptive catalyst is the heat-resistant inorganic oxide catalyzer containing calcium carbonate and/or calcium oxide active ingredient.Preferably, described adsorptive catalyst is calcium oxide and/or calcium carbonate, and the composite catalyst of aluminum oxide.More preferably, wherein, with catalyzer total amount for benchmark, with oxide basis, described adsorptive catalyst calcium oxide and/or the content of calcium carbonate are 5 ~ 30 heavy %, and the content of aluminum oxide is 70 ~ 95 heavy %.
In method provided by the invention, described steam reforming catalyst is the heat-resistant inorganic oxide catalyzer containing nickel oxide active ingredient.Described heat-resistant inorganic oxide is selected from the mixture of one or more in aluminum oxide, silicon-dioxide, zirconium white, titanium dioxide, weisspiessglanz, ferric oxide, cupric oxide, magnesium oxide, molybdenum oxide and Tungsten oxide 99.999.Preferably, described steam reforming catalyst is nickel oxide/alumina composite catalyst, more preferably, with catalyzer total amount for benchmark, with oxide basis, in described steam reforming catalyst, the content of nickel oxide is 12 ~ 16 heavy %, and the content of aluminum oxide is 84 ~ 88 heavy %.
In method provided by the invention, described moving-burden bed reactor refers to a kind of reactor in order to realize gas-solid phase reaction process or liquid and solid phase reaction process.Add particulate state or blocks of solid reactant or catalyzer continuously in reactor head, along with the carrying out of reaction, solid materials moves down gradually, finally draws off continuously from bottom.Fluid, or passes through solid bed then from bottom to top, to react.Owing to there is no relative movement between solid particulate, but there is the lower shifting movement of solid particle layer, therefore, also can be regarded as a kind of fixed-bed reactor of movement.
A kind of lighter hydrocarbons producing hydrogen from steam conversion moving bed reaction device, this device comprises moving-burden bed reactor, screening separator, catalyst riser and revivifier, moving-burden bed reactor bottom is communicated with screening separator, screening separator interior is divided into the catalyst outlet of two kinds of different-grain diameters through screen cloth, one of them catalyst outlet is communicated with bottom catalyst riser, another outlet is through expecting to be honored as a queen connection catalyst regenerator, be honored as a queen through material and be communicated with bottom catalyst riser in revivifier bottom, catalyst riser top is communicated with moving-burden bed reactor top; Described moving-burden bed reactor top arranges reacting product outlet through gas-solid separation equipment, and bottom arranges lighter hydrocarbons and water vapour feed(raw material)inlet.
Below in conjunction with accompanying drawing, method provided by the invention is described in detail.But the present invention is not therefore subject to any restriction.
Accompanying drawing is for being lighter hydrocarbons moving-bed producing hydrogen from steam conversion method flow diagram provided by the invention.As shown in drawings, moving-burden bed reactor 3 top arranges gas-solid separator, for separating of solid catalyst and product gas.Isolated product gas enters after follow-up Hydrogen Separation purifying plant is purified through pipeline 4 and enters pipe network; The solid catalyst that moving-burden bed reactor 3 bottom is flowed out contains the reforming catalyst of two kinds of different-grain diameters and adsorptive catalyst enters screening separator 5, by the catalyst separating of two kinds of variable grain particle diameters out, preferred steam reforming catalyst is the microspheric form catalyzer of Large stone, and adsorptive catalyst is small particle size microspheric form catalyzer.The bottom of catalyst riser line 10 is entered through catalyst transport pipeline 6, by the top returning moving-burden bed reactor 3 after the steam lifting of pipeline 8 through the isolated reforming catalyst of screening separator 5; The first material envelope granule valve 15 of isolated adsorptive catalyst through being used for locking gas lock pressure enters reclaimable catalyst line of pipes 9, deliver into bottom revivifier 11 by the air from pipeline 7, the heavy fuel oil (HFO) supplemented enters revivifier 11 bottom through pipeline 14, the adsorptive catalyst burning of having adsorbed carbonic acid gas removes the coke of attachment on it, and the carbonic acid gas in Removal of catalyst, improve temperature simultaneously.The high-temperature flue gas of regenerator overhead is discharged through pipeline 13, can be used to carry out heat exchange with water vapour; The second material envelope granule valve 16 and catalyst transport pipeline 12 of adsorptive catalyst after burning temperature raising through being used for locking gas lock pressure enter the bottom of catalyst riser line 10, by Returning reactor top after the steam lifting of pipeline 8, second material envelope granule valve 16 returns the flow of the adsorptive catalyst of moving-burden bed reactor 3 according to temperature of reactor regulating and controlling, the automatic steady of realization response actuator temperature controls; After the preheating of pipeline 1, light hydrocarbon feedstocks enters moving-burden bed reactor 3 by bottom together with the water vapour through pipeline 2, reacts with kind of the catalyst exposure of two in moving-burden bed reactor; Fresh adsorptive catalyst can supplement through pipeline 17 and enter catalyst transport pipeline 7, carries out interpolation at ambient pressure and supplements, and because supplementary interpolation speed is slow, can not control to impact to the temperature of reactor.
Below in conjunction with embodiment, the invention will be further described, but not thereby limiting the invention.
In embodiment, steam reforming catalyst is nickel oxide/alumina catalyzer, and preparation method is as follows:
Adopt commercially available particle diameter 2 ~ 3 millimeters of alumina globule (industrial goods, Shandong Aluminum Plant of China Aluminum Co., Ltd), in the ratio of nickel and aluminium, even if catalyzer contains the amount of the nickel oxide of 14 heavy %, nickel nitrate solution is adopted to flood 1 hour, 120 DEG C of dryings after 2 hours, 1000 DEG C of roastings obtain steam reforming catalyst in 2 hours.Nickel oxide containing 14 heavy % in steam reforming catalyst described by analysis, the aluminum oxide of 86 heavy %, particle diameter 2 ~ 3 millimeters, the apparent bulk density of catalyzer is 0.71 grams per milliliter.
Adsorptive catalyst is calcium oxide/aluminium oxide catalyst, and preparation method is as follows:
In the ratio of the calcium oxide containing 10 heavy %, by calcium oxide powder (industrial goods, Zibo Ethylene Plant in Qilu chemical company) and aluminum oxide powder (industrial goods, Shandong Aluminum Plant of China Aluminum Co., Ltd) mediate after, bowling machine is rolled onto the bead that particle diameter is 0.1 ~ 1 millimeter, at 120 DEG C after dry 4 hours, through 550 DEG C of roastings 2 hours, obtain adsorptive catalyst.The apparent bulk density of described catalyzer is 0.75 grams per milliliter, the calcium oxide containing 10 heavy %, the aluminum oxide of 90 heavy %.
Embodiment
Experiment process as shown in drawings, with the Sweet natural gas after desulfurization for light hydrocarbon feedstocks (methane content > 96v%, sulphur content < 0.5 microgram/gram) be preheated to 400 DEG C, water vapour enters moving-burden bed reactor by bottom after being preheated to 500 DEG C, with the steam reforming catalyst entered by moving-burden bed reactor top and adsorptive catalyst counter current contact, there is steam reforming reaction and generate hydrogen, the catalyzer flowed out from reactor bottom is isolated greatly through screening separator, the catalyzer of little two kinds of particle diameters, the steam reforming catalyst of Large stone enters after catalyst riser line is promoted by steam and directly returns to moving-burden bed reactor top, the adsorptive catalyst of small particle size enters catalyst transport line after the first material envelope granule valve, deliver in revivifier by air, spray into M100 oil fuel aid burning in revivifier, by the temperature of the regulating and controlling revivifier of oil mass, regenerated flue gas is discharged by top.Regenerative adsorption catalyst temperature is promoted to 850 DEG C-860 DEG C, enter after catalyst riser line is promoted by steam through the second material envelope granule valve and return moving-burden bed reactor, seal granule valve by the second material and regulate the flow of catalyzer to make the bed temperature of moving-burden bed reactor be maintained 780 DEG C.
The pressure of described moving-burden bed reactor is 0.5MPa, and bed temperature is 780 DEG C, and the pressure of revivifier is 0.1MPa, and temperature controls at 850 DEG C-860 DEG C.The volume space velocity of hydrogen product relative movement bed bioreactor is 1000h
-1the weight ratio of Sweet natural gas and water vapour is 1: 2.5, the transformation efficiency > 90% of methane in the rear Sweet natural gas of reaction, hydrogen containing 68 ~ 70v% in product gas, send into back segment membrane separation apparatus and be separated the medium purity hydrogen that can obtain 90 ~ 92v%, or send into the high-purity hydrogen that pressure-variable adsorption tripping device obtains more high purity 99.9999v%.
Claims (18)
1. a moving-bed lighter hydrocarbons producing hydrogen from steam conversion method, is characterized in that, comprising:
(1) enter reactor by bottom after lighter hydrocarbons and water vapour preheating, the steam reforming catalyst different from granules of catalyst particle diameter and adsorptive catalyst counter current contact, lighter hydrocarbons and water vapour react and generate H under steam reforming conditions
2, CO and CO
2, described CO
2react with the CaO in adsorptive catalyst and be converted into CaCO
3;
(2) product gas in step (1) and mixed catalyst are in reactor head gas solid separation, and isolated product gas enters later separation purifying plant and obtains high-purity hydrogen;
(3) mixed catalyst by reactor bottom enter screening separator be separated by particle diameter, recycle in isolated reforming catalyst Returning reactor, isolated adsorptive catalyst enter revivifier regeneration, then recycle in Returning reactor;
Steam reforming catalyst described in step (1) is Large stone pellet catalyst, and grain diameter is 2 ~ 3 millimeters; Described adsorptive catalyst is small particle size pellet catalyst, and grain diameter is 0.1 ~ 1 millimeter.
2. according to the method for claim 1, it is characterized in that, described lighter hydrocarbons are the petroleum hydrocarbon of C1 ~ C8.
3. according to the method for claim 1, it is characterized in that, described lighter hydrocarbons and the weight ratio of water vapour are 1: (1 ~ 5).
4. according to the method for claim 3, it is characterized in that, described lighter hydrocarbons and the weight ratio of water vapour are 1: (2 ~ 4).
5. according to the method for claim 1, it is characterized in that, described lighter hydrocarbons and water vapour are preheated to 350 ~ 550 DEG C and introduce in reactor.
6. according to the method for claim 5, it is characterized in that, described lighter hydrocarbons and water vapour are preheated to 400 ~ 450 DEG C and introduce in reactor.
7. according to the method for claim 1, it is characterized in that, described steam reforming conditions is: temperature is 650 ~ 860 DEG C, and pressure is 0.1 ~ 3.0MPa.
8. according to the method for claim 7, it is characterized in that, described steam reforming conditions is: temperature is 680 ~ 820 DEG C, and pressure is 0.15 ~ 2.5MPa.
9. according to the method for claim 1, it is characterized in that, described steam reforming catalyst is the heat-resistant inorganic oxide catalyzer containing nickel oxide active ingredient.
10. according to the method for claim 9, it is characterized in that, described steam reforming catalyst is nickel oxide/alumina composite catalyst.
11. according to the method for claim 10, and it is characterized in that, take total catalyst weight as benchmark, and with oxide basis, in described steam reforming catalyst, the content of nickel oxide is 12 ~ 16 heavy %, and the content of aluminum oxide is 84 ~ 88 heavy %.
12. according to the method for claim 1, and it is characterized in that, described adsorptive catalyst is the heat-resistant inorganic oxide catalyzer containing calcium carbonate and/or calcium oxide active ingredient.
13. according to the method for claim 12, and it is characterized in that, described adsorptive catalyst is the composite catalyst of calcium oxide and/or calcium carbonate and aluminum oxide.
14. according to the method for claim 13, and it is characterized in that, take total catalyst weight as benchmark, and with oxide basis, in described adsorptive catalyst, the content of calcium oxide and/or calcium carbonate is 5 ~ 30 heavy %, and the content of aluminum oxide is 70 ~ 95 heavy %.
15., according to the method for claim 1, is characterized in that, described adsorptive catalyst is honored as a queen to be delivered in revivifier by air through material and is regenerated at 690 ~ 1250 DEG C.
16. according to the method for claim 15, and it is characterized in that, in described revivifier, adsorptive catalyst regenerates under the condition of 720 ~ 920 DEG C.
17., according to the method for claim 15 or 16, is characterized in that, add fuel refreshment heat in described revivifier.
18. 1 kinds of moving-bed lighter hydrocarbons producing hydrogen from steam conversion reaction units, it is characterized in that, this device comprises moving-burden bed reactor, screening separator, catalyst riser and revivifier, moving-burden bed reactor bottom is communicated with screening separator, screening separator interior is divided into the catalyst outlet of two kinds of different-grain diameters through screen cloth, one of them catalyst outlet is communicated with bottom catalyst riser, another outlet is through expecting to be honored as a queen connection catalyst regenerator, be honored as a queen through material and be communicated with bottom catalyst riser in revivifier bottom, catalyst riser top is communicated with moving-burden bed reactor top, described moving-burden bed reactor top arranges reacting product outlet through gas-solid separation equipment, and bottom arranges lighter hydrocarbons and water vapour feed(raw material)inlet.
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| CN1903431A (en) * | 2006-08-01 | 2007-01-31 | 中国石油化工股份有限公司 | Composite catalyst used for reforming hydrogen prodn. using methane and water vapor as raw material, preparing process and use |
| CN1935634A (en) * | 2006-09-21 | 2007-03-28 | 中国石油化工股份有限公司 | Adsorption forced methane steam reforming hydrogen manufacturing process and apparatus using circulating fluidized bed |
| CN101439844A (en) * | 2008-12-16 | 2009-05-27 | 中国科学院广州能源研究所 | Chemical link coupling catalytic reforming hydrogen making method and device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1903431A (en) * | 2006-08-01 | 2007-01-31 | 中国石油化工股份有限公司 | Composite catalyst used for reforming hydrogen prodn. using methane and water vapor as raw material, preparing process and use |
| CN1935634A (en) * | 2006-09-21 | 2007-03-28 | 中国石油化工股份有限公司 | Adsorption forced methane steam reforming hydrogen manufacturing process and apparatus using circulating fluidized bed |
| CN101439844A (en) * | 2008-12-16 | 2009-05-27 | 中国科学院广州能源研究所 | Chemical link coupling catalytic reforming hydrogen making method and device |
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