CN101580228A - Natural gas auto-thermal reforming hydrogen production fluidized bed membrane reactor - Google Patents
Natural gas auto-thermal reforming hydrogen production fluidized bed membrane reactor Download PDFInfo
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- CN101580228A CN101580228A CNA2009103035020A CN200910303502A CN101580228A CN 101580228 A CN101580228 A CN 101580228A CN A2009103035020 A CNA2009103035020 A CN A2009103035020A CN 200910303502 A CN200910303502 A CN 200910303502A CN 101580228 A CN101580228 A CN 101580228A
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Abstract
The invention discloses a natural gas auto-thermal reforming hydrogen producing fluidized bed membrane reactor, relates to a hydrogen production reactor, and aims to solve the problem that small-scale distributed hydrogen production requirements of natural gas can not be met in the existing technology. The reactor comprises a reactor main body, a gas distribution component arranged in the reactor main body for fluidization reforming reaction, and a membrane component which is arranged in the reactor main body and used for membrane reaction in subsequent processes of the gas distribution component; wherein the gas distribution component comprises a sintered metal stainless steel plate fixed on the inner wall of the reactor main body; the membrane component is divided into an upper layer and a lower layer; a gas eduction tube at the lower end of the upper layer is connected with a gas eduction tube at the upper end of the lower layer; the gas eduction tube at the lower end of the lower layer is closed; the gas eduction tube at the upper end of the upper layer educes the reactor main body through a hydrogen eduction tube; and the reactor main body is further internally provided with a gas tube, one end of which leads to the gas distribution component.
Description
Technical field
The present invention relates to a kind of hydrogen-manufacturing reactor, especially a kind of integrated fluid bed reforming reaction of Sweet natural gas and film reaction of utilizing comes the reactor of hydrogen manufacturing.
Background technology
Hydrogen Energy as a kind of cleaning, efficient, safe, the continuable energy, is regarded as the most potential clean energy in this century, the effective substitute energy that also be regarded as solving Greenhouse effect, improves capacity usage ratio.
Gas water steam reformation (SMR) technology is the technology that hydrogen and synthetic gas are produced in industrial comparatively general being used to, and this reaction is a strong endothermic reaction, and almost can reach equilibrium state.Catalyzer commonly used is a nickel-base catalyst, and typical temperature of reaction is 800-900 ℃, pressure 2.5-3.5MPa.
Industrial tubular fixed-bed reactor commonly used carries out the gas water steam reforming, provides reaction required heat by indirect heating or partial oxidation.
Because steam reformation is a strong endothermic reaction, heat transfer is a bottleneck problem of this reaction of restriction.Traditional tubular fixed-bed reactor, reactor volume is huge, and heat-transfer effect is poor, is not suitable for the requirement of distributed hydrogen gas production on a small scale.
The unit equipment that membrane reactor is coupled and forms by specific mode as a kind of film separation unit and chemical reactor, target product is produced potential at separation efficiency, selectivity and productive rate strengthen the property, have a wide range of applications in fields such as chemical industry, biology, pharmacy.
And because gas renormalizing hydrogen manufacturing is a strong endothermic process, need at high temperature carry out, common organic membrane can not satisfy its requirement.
Summary of the invention
The objective of the invention is to solve prior art and can not satisfy Sweet natural gas distributed hydrogen manufacturing requirement problem on a small scale, a kind of auto-thermal reforming hydrogen production fluidized bed membrane reactor is provided, can save the natural gas hydrogen preparation operation, must not outer supplying heat source, reactor volume is littler, it is lower to help.
Purpose of the present invention realizes by following technical proposals:
A kind of natural gas auto-thermal reforming hydrogen production fluidized bed membrane reactor comprises
Reactor body;
Be arranged on the gas distribution assembly in the reactor body, be used for the fluid bed reforming reaction;
Be arranged on the membrane module in the reactor body, in the gas distribution assembly subsequent handling, be used for film reaction.
Described gas distribution assembly comprises the sintering metal stainless steel plate that is fixed on the reactor body inwall.
Described membrane module comprises hydrogen passage and the gas eduction tube that is communicated with it.
Described membrane module is divided into two-layer up and down, and the gas eduction tube of lower end, upper strata is connected with the gas eduction tube of lower floor upper end, the gas eduction tube sealing of lower floor lower end; The gas eduction tube of upper end, upper strata is drawn reactor body by the hydrogen delivery line.
Also be provided with tracheae in the described reactor body, the one end leads to gas distribution assembly place.
Be provided with by sintered stainless steel tube in the described reactor body and be fixed on the exhaust gas filter that constitutes on the stainless steel plate.
By the flange sealing, each flange inboard is provided with thermal insulation layer respectively at described reactor body two ends.
Described membrane module is installed on the described tracheae.
Described membrane module is a palladium membrane component, is fan-shaped distribution around described tracheae.
The present invention adopts said structure, the film reaction of Sweet natural gas fluidisation reforming reaction and hydrogen purification is integrated in the reactor body, and by tracheae bubbling air or oxygen in reactor, with with Sweet natural gas generation partial oxidation reaction, for reforming reaction provides heat, the hydrogen that reaction generates enters hydrogen passage, gas eduction tube, hydrogen delivery line by membrane module and draws reactor body under the effect of pressure reduction, tail gas is discharged with catalyst separating through filtering the back.
As seen, the present invention compared with prior art has following beneficial effect:
The present invention adopts advanced palladium membrane separating method, utilizes the device with said structure, can produce hydrogen in gas making, and the workshop section that has saved hydrogen purification makes original natural gas hydrogen preparation technology obtain simplifying.
The present invention adopts Sweet natural gas and air partly to be oxidized to reforming reaction heat is provided, and not needing provides external heat source to reactor, greatly the volume of the reactor of reduction.
Design temperature of the present invention is 650 ℃, lowers traditional gas renormalizing temperature greatly, makes the present invention can adopt common stainless material, does not need expensive steel consumptive material.
Description of drawings
The present invention will illustrate by example and with reference to the mode of accompanying drawing, wherein:
Fig. 1 is a natural gas auto-thermal reforming fluidized bed membrane reactor sectional view of the present invention.
Fig. 2 is a membrane module layout drawing of the present invention.
Number in the figure: the 1st, reactor body, the 2nd, feed distributing plate, the 3rd, membrane module, the 4th, film supports and the gas communication assembly, and the 5th, exhaust gas filter, the 6th, bottom blind flange, the 7th, top blind flange, the 8th, raw material inlet mouth, the 9th, air inlet and hydrogen air outlet, the 10th, tail gas air outlet, the 11st, instrumentation tap, the 12nd, gas eduction tube, the 13rd, hydrogen delivery line, the 14th, last gusset, the 15th, lower web plate, the 16th, air intake duct, the 17th, air nozzle.
Embodiment
As Fig. 1, a kind of natural gas auto-thermal reforming hydrogen production fluidized bed membrane reactor comprises the reactor body 1 of tubular and is arranged on reforming reaction district, film reaction district and free zone in the reactor body 1.
With top blind flange 7,6 sealings of bottom blind flange, the inboard of each flange is provided with thermal insulation layer respectively at the two ends of reactor body 1.Also being respectively arranged with four flange-interfaces on the sidewall of reactor body 1, is respectively instrumentation tap 11, tail gas air outlet 10, air inlet and hydrogen give vent to anger shared air outlet 9, raw material inlet mouth 8.The inboard of each flange all is provided with thermal insulation layer.It is to be applied to reactor to adapt to the pyritous requirement in order to satisfy existing flange that above-mentioned each flange is provided with thermal insulation layer.
Raw material inlet mouth 8 is arranged at the bottom of reactor body 1, reactor body 1 inside that is higher than raw material inlet mouth 8 is provided with feed distributing plate 2, feed distributing plate 2 is that circular sintered porous metal stainless steel plate constitutes, and can select material for use is that HastelloyX, thickness are that 5mm, filtering accuracy are that the stainless steel plate of 0.5um is made.The bearing rib that welds on feed distributing plate 2 and reactor body 1 inwall adopts bolt to be connected, as the supporter and the unstripped gas air inlet distribution apparatus of reforming reaction district fluid catalyst.
Film reaction district in reactor body 1, being provided with film supports and gas communication assembly 4, this assembly is for making for gapless stainless steel tube, constitute tracheae in the pipe as air passageways, the outer supporter as built-in membrane module 3 of pipe, gusset 14, lower web plate 15 are as the Holder Fasteners in reactor body 1 on the two ends up and down of built-in film support and gas communication assembly 4 have respectively.The lower end of air passageways extend into the reforming reaction district under the lower web plate 15, and its outer wall is provided with 8 stainless steel pipes that communicate with it and circularizes the air nozzle 17 (as shown in Figure 2) that fan is penetrated the formation that distributes, as the distribution mouth of bottom air; Gusset 14 is stretched out in the upper end of air passageways, and communicates with the external world by the tracheae that air intake duct 16 passes air inlet and hydrogen air outlet 9.
Be fixed on that film supports and the outer wall of gas communication assembly 4 on membrane module be palladium membrane component, its structure can be to be as described in the application for a patent for invention Publication Specification of CN101181975A as publication number, comprise film support frame, porous metal supporter and palladium alloy membrane, porous metal supporter and palladium alloy membrane are positioned at the both sides of film support frame respectively successively, adopt between film support frame and the sintering metal back up pad to be welded to connect.Palladium alloy membrane is that thickness is 10～50 microns palladium-silver alloy film.The film support frame includes the circulation passage that is cleaned hydrogen, and this passage is a rectangular toothed, and gas eduction tube 12 outlets are arranged on the support frame upper and lower ends, with the channel connection of purified hydrogen.Palladium membrane component becomes fan-shaped discharging in reactor body 1, two-layer up and down, the gas eduction tube welding of the gas eduction tube of lower end, upper strata and lower floor upper end, the gas eduction tube of lower floor lower end blocks, and upper end, upper strata gas eduction tube converges on an annular hydrogen delivery line 13 again draws reactor body 1 by the tracheae that passes air inlet and hydrogen air outlet 9.Membrane module 3 support with built-in palladium film and gas communication assembly 4 between adopt to live and be connected.
In the reactor body 1, be the free zone between last gusset 14 tops and the top blind flange 7, between air inlet and hydrogen air outlet 9 and tail gas air outlet 10, be provided with exhaust gas filter 5.Exhaust gas filter 5 is fixed on the stainless steel plate by four sintered stainless steel tubes and constitutes, and sintered stainless steel tube can be that material is that Hastelloy X, thickness are that 2mm, filtering accuracy are the tubing of 0.5um.
During work, natural hydrocarbon in gas and water vapor through preheating enter reactor body 1 by raw material inlet mouth 8, pass the reforming reaction district that feed distributing plate 2 enters reactor body 1, under the effect of nickel-base catalyst, carry out reforming reaction, air is by the air passageways of air intake duct 12, the support of built-in palladium film and gas communication assembly 4, by 17 ejections of annular air nozzle, with hydrocarbon polymer generation partial oxidation reaction, for reforming reaction provides heat.Synthetic gas (the H that series reaction produces
2, CO, CO
2, CH
4, H
2O etc.) the most of H in
2Be penetrated into the pure hydrogen passage of palladium membrane component 3 inside by palladium (alloy) membrane module, the high-purity hydrogen that each palladium membrane component produces by the manifold that confluxes to hydrogen delivery line 13, pass the flange of reactor body 1 upper air air inlet and hydrogen air outlet 9 and discharge reactor body, through becoming high purity product hydrogen after the cooling of downstream.Remaining gas in the synthetic gas is being crossed 5 times realizations of exhaust gas filter and catalyst separating, tail gas air outlet 10 from the reactor body 1 is drawn reactor and is entered unit operations such as downstream heat exchange, burning, and its granules of catalyst of carrying secretly is blocked in reactor body 1 inside by exhaust gas filter 5.
It is activeconstituents that catalyzer adopts with the metallic nickel, with?-Al
2O
3Be the pellet type catalyst of carrier, the particle diameter of catalyzer is normal distribution between 40 microns-300 microns, about 100 microns of median sizes.Gas discharge 12Nm
3/ H, water carbon mol ratio is controlled at 3.0, about 600 ℃ of temperature of reaction, pressure 1.5MPa, react required heat by 1000 ℃ of left and right sides high-temperature flue gas producing of reactor tail gas burning provide moving heat transfer of outer tube outflow, under this reaction conditions, the productive rate of hydrogen is about 20Nm
3/ H, purity is greater than 99.999%.
In the said process, reforming reaction reaches balance fast, react the hydrogen that generates and enter the inner hydrogen conduit output-response device that passes through on support of palladium film and the gas communication assembly of palladium membrane component at the palladium film that leads under the effect of pressure reduction on the palladium membrane component that places reaction zone, and the falling sharply of hydrogen, broken original balance, under the catalysis of catalyzer, reach new balance rapidly, thereby promoted the production of hydrogen.
Disclosed all features in this specification sheets, or the step in disclosed all methods or the process except mutually exclusive feature and/or step, all can make up by any way.
Disclosed arbitrary feature in this specification sheets (comprising any accessory claim, summary and accompanying drawing) is unless special narration all can be replaced by other equivalences or the alternative features with similar purpose.That is, unless special narration, each feature is an example in a series of equivalences or the similar characteristics.
The present invention is not limited to aforesaid embodiment.The present invention expands to any new feature or any new combination that discloses in this manual, and the arbitrary new method that discloses or step or any new combination of process.
Claims (9)
1. a natural gas auto-thermal reforming hydrogen production fluidized bed membrane reactor is characterized in that, comprises
Reactor body;
Be arranged on the gas distribution assembly in the reactor body, be used for the fluid bed reforming reaction;
Be arranged on the membrane module in the reactor body, in the gas distribution assembly subsequent handling, be used for film reaction.
2. a kind of according to claim 1 natural gas auto-thermal reforming hydrogen production fluidized bed membrane reactor is characterized in that described gas distribution assembly comprises the sintering metal stainless steel plate that is fixed on the reactor body inwall.
3. a kind of according to claim 1 natural gas auto-thermal reforming hydrogen production fluidized bed membrane reactor is characterized in that, described membrane module comprises hydrogen passage and the gas eduction tube that is communicated with it.
4. as a kind of natural gas auto-thermal reforming hydrogen production fluidized bed membrane reactor as described in the claim 3, it is characterized in that, described membrane module is divided into two-layer up and down, and the gas eduction tube of lower end, upper strata is connected with the gas eduction tube of lower floor upper end, the gas eduction tube sealing of lower floor lower end; The gas eduction tube of upper end, upper strata is drawn reactor body by the hydrogen delivery line.
5. as a kind of natural gas auto-thermal reforming hydrogen production fluidized bed membrane reactor as described in one of claim 1～4, it is characterized in that also be provided with tracheae in the described reactor body, the one end leads to gas distribution assembly place.
6. as a kind of natural gas auto-thermal reforming hydrogen production fluidized bed membrane reactor as described in the claim 5, it is characterized in that, be provided with by sintered stainless steel tube in the described reactor body and be fixed on the exhaust gas filter that constitutes on the stainless steel plate.
7. as a kind of natural gas auto-thermal reforming hydrogen production fluidized bed membrane reactor as described in the claim 6, it is characterized in that by the flange sealing, each flange inboard is provided with thermal insulation layer respectively at described reactor body two ends.
8. as a kind of natural gas auto-thermal reforming hydrogen production fluidized bed membrane reactor as described in the claim 7, it is characterized in that described membrane module is installed on the described tracheae.
9. as a kind of natural gas auto-thermal reforming hydrogen production fluidized bed membrane reactor as described in the claim 8, it is characterized in that described membrane module is a palladium membrane component, be fan-shaped distribution around described tracheae.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009103035020A CN101580228A (en) | 2009-06-22 | 2009-06-22 | Natural gas auto-thermal reforming hydrogen production fluidized bed membrane reactor |
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|---|---|---|---|
| CNA2009103035020A CN101580228A (en) | 2009-06-22 | 2009-06-22 | Natural gas auto-thermal reforming hydrogen production fluidized bed membrane reactor |
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| CN101580228A true CN101580228A (en) | 2009-11-18 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105174214A (en) * | 2015-09-18 | 2015-12-23 | 华南理工大学 | Method and device for manufacturing hydrogen through natural gas steam reforming by applying fluidized bed |
| CN114408864A (en) * | 2021-12-31 | 2022-04-29 | 江苏嘉宇特种装备股份有限公司 | Hydrogen production equipment with automatic control pressure regulation function |
-
2009
- 2009-06-22 CN CNA2009103035020A patent/CN101580228A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105174214A (en) * | 2015-09-18 | 2015-12-23 | 华南理工大学 | Method and device for manufacturing hydrogen through natural gas steam reforming by applying fluidized bed |
| CN114408864A (en) * | 2021-12-31 | 2022-04-29 | 江苏嘉宇特种装备股份有限公司 | Hydrogen production equipment with automatic control pressure regulation function |
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Open date: 20091118 |