CN101264860A - Oxygen-permeating film reactor used for coke oven crude gas mixing reforming hydrogen preparation technique - Google Patents
Oxygen-permeating film reactor used for coke oven crude gas mixing reforming hydrogen preparation technique Download PDFInfo
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- CN101264860A CN101264860A CNA2008100363673A CN200810036367A CN101264860A CN 101264860 A CN101264860 A CN 101264860A CN A2008100363673 A CNA2008100363673 A CN A2008100363673A CN 200810036367 A CN200810036367 A CN 200810036367A CN 101264860 A CN101264860 A CN 101264860A
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- oxygen
- coke oven
- crude gas
- oven crude
- permeable film
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Hydrogen, Water And Hydrids (AREA)
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Abstract
The invention relates to an oxygen-permeable membrane reactor used in coke oven crude gas mixed reforming hydrogen making technique, belonging to the technical field of coke oven gas reforming reaction device. The oxygen-permeable membrane reactor adopts nickel-based voelknerite type catalyst and perovskite-structured mixed conducting oxygen-permeable membrane; oxidizer comes from the water vapor carried by the coke oven crude gas and the oxygen provided by the oxygen-permeable membrane, the mixed reforming reaction of the coke oven crude gas is realized in the oxygen-permeable membrane reactor to completely convert the coke oven crude gas into H<SUB>2</SUB>, CO and CO<SUB>2</SUB> which are micro molecules. The invention has the advantages that the oxygen providing and the reforming process are coupled together, which improves the reaction efficiency; the applied catalyst has excellent activity, the operation is stable with high yield of hydrogen.
Description
Technical field
The present invention relates to a kind of oxygen-permeable membrane reactor that is used for coke oven crude gas mixing reforming hydrogen preparation technique, belong to coke-oven gas reforming reaction device technique field.
Background technology
For promoting the expanding economy of following cleaning Hydrogen Energy, efficient, economic, the large-scale Preparation of Hydrogen technology of exploitation is one of key issue that needs to be resolved hurrily.Existing hydrogen preparation method is a lot; though utilizing renewable energy source hydrogen manufacturing such as sun power, wind energy, underground heat is optimal pattern, utilize these renewable energy sources not possess mass-producing and economy now by the Hydrogen Energy of methods such as photodissociation, pyrolysis, electrolysis or microbiological degradation preparation.The maturation method that can be used at present scale hydrogen manufacturing in the world mainly is water electrolysis and fossil energy hydrogen manufacturing (coal, Sweet natural gas and liquid fossil energy).Utilize in the fossil energy hydrogen manufacturing, mainly comprise reformation and the separating of clean coke-oven gas etc. of steam reformation, the petroleum naphtha of methane.As the byproduct of coking, coke-oven gas is not only measured inexpensive greatly, and is rich in the hydrogen more than 50%, is a kind of fine hydrogen feedstock.Adsorb (PSA) technology to the original H in the clean coke-oven gas by transformation at present
2It has been the industrialization process of comparative maturity that component is separated with purifying hydrogen manufacturing, and separation efficiency can reach more than 70%.But this technology has only reclaimed the original H in the coke-oven gas
2Component.In present stage, clean coke-oven gas is to obtain after tar recovery, coal gas desulfurization, the coal gas by coke oven crude gas takes off purifying treatment operations such as naphthalene and crude benzol.In fact from the coke oven crude gas of coke oven discharge, body does not only have the high-temperature physics sensible heat more than 800 ℃, also contains H
2, H
2O, CH
4, CO and CO
2Etc. volatile high hydrocarbon components such as permanent gases composition and tar.Decontamination process at coke oven crude gas, condensation process has been lost the high physics sensible heat of coke oven crude gas, many coke-oven plants that do not have the gas purification operation have caused the direct emptying burning of a large amount of coke oven crude gas that coking produces the huge waste of the energy and serious environmental to pollute.Utilize the aspect from economy, environmental protection and resources effective, if high temperature coke oven crude gas integral body as a kind of resource, make full use of the high physics sensible heat of coke oven crude gas, directly the hydrocarbon components in the coke oven crude gas being carried out cracking reforms, rather than condensation cleaning, the high physics sensible heat of coke oven crude gas and high chemical energy component are transferred to cleaning hydrogen as much as possible.So not only make hydrogen output that the amount Billy that makes hydrogen from coke oven crude gas separates original hydrogen the clean coke-oven gas with pressure swing adsorption significantly even be multiplied, also for promoting the expanding economy of cleaning Hydrogen Energy to solve the problem of scale hydrogen manufacturing.
In addition, research and design goes out a kind of novel oxygen-permeable membrane reactor, just becomes the current technological core problem that presses for solution.
Summary of the invention
The purpose of this invention is to provide a kind of oxygen-permeable membrane reactor that is used for coke oven crude gas mixing reforming hydrogen preparation technique, this is critical, the most important device in the coal gas reforming reaction.
A kind of oxygen-permeable membrane reactor that is used for coke oven crude gas mixing reforming hydrogen preparation technique of the present invention, it includes coke oven crude gas inlet mouth, stainless steel containment member, reacting product outlet, catalyst bed, oxygen permeable film, electric heater, rich nitrogen outlet, metal o-ring, gas inlet, goes up sleeve pipe, running casing and center sleeve; It is characterized in that: whole oxygen-permeable membrane reactor is vertical vertical arrangement form, device is provided with catalyst bed in the center sleeve and is positioned at oxygen permeable film and the last sleeve pipe and the running casing that contact with the oxygen permeable film upper and lower surface under it, oxygen permeable film and sealing by metal o-ring between two sleeve pipes up and down; The center sleeve outer periphery is provided with an electric heater; Be provided with the coke oven crude gas inlet mouth at device center sleeve top; Its outside is communicated with reacting product outlet with the interior space of surveying of last sleeve pipe; The coke-oven gas inlet mouth inserts in the catalyst bed; Bottom at the device center sleeve is provided with gas inlet; Be provided with in its position of going up slightly and communicate with the running casing inboard and be positioned at lateral rich nitrogen outlet; This device main body upper and lower part is equipped with and prevents the stainless steel containment member that leaks gas; The catalyst bed in this device and the chemical substance of oxygen permeable film composed as follows:
(a) catalyzer in the catalyst bed is the hydrotalcite type catalyzer, and its molecular formula is Ni
0.5Mg
2.5AlO
δ
(b) oxygen permeable film is a kind of composite conductor oxygen-permeating film, and its molecular formula is: BaCo
0.4Fe
0.4Nb
0.2O
3-δ(0＜δ＜3).
Coke oven crude gas is directly introduced in the composite conductor oxygen-permeating film reactor of the present invention, and under catalyst action, the oxygen that oxygen permeable film provides is crossed in the water vapor and the air infiltration that utilize coke oven crude gas itself to carry, thereby reforming reaction takes place, and obtains H
2, CO and CO
2Deng micro-molecular gas.
Description of drawings
Fig. 1 is the structural representation of oxygen-permeable membrane reactor device of the present invention.
Fig. 2 is X-ray diffraction (XRD) figure of the used hydrotalcite type catalyzer of the present invention.
Fig. 3 is the variation diagram of micro-molecular gas flow before and after the reaction.
Embodiment
After now specific embodiments of the invention being described in.
Present embodiment is referring to Fig. 1, and the structure of oxygen-permeable membrane reactor device includes coke oven crude gas inlet mouth 1, stainless steel containment member 2, reacting product outlet 3, catalyst bed 4, oxygen permeable film 5, electric heater 6, rich nitrogen outlet 7, metal o-ring 8, gas inlet 9, goes up sleeve pipe 10, running casing 11 and center sleeve 12; It is characterized in that: whole oxygen-permeable membrane reactor is vertical vertical arrangement form, device is provided with catalyst bed 4 in the center sleeve 12 and is positioned at oxygen permeable film 5 and last sleeve pipe 10 that contact with the oxygen permeable film upper and lower surface and running casing 11 it under, oxygen permeable film and pass through metal o-ring 8 up and down between two sleeve pipes and seal; Center sleeve 12 outer periphery are provided with an electric heater 6; Be provided with coke oven crude gas inlet mouth 1 at device center sleeve 12 tops; Its outside is communicated with reacting product outlet 3 with the last sleeve pipe 10 interior spaces of surveying; Coke-oven gas inlet mouth 1 inserts in the catalyst bed 4; Bottom at device center sleeve 12 is provided with gas inlet 9; Be provided with in its position of going up slightly and communicate with running casing 11 inboards and be positioned at lateral rich nitrogen outlet 7; This device main body upper and lower part is equipped with and prevents the stainless steel containment member 2 that leaks gas; The catalyst bed 4 in this device and the chemical substance of oxygen permeable film 5 composed as follows: the catalyzer in (1) catalyst bed is the hydrotalcite type catalyzer, and its molecular formula is Ni
0.5Mg
2.5AlO
δ(2) oxygen permeable film is a kind of composite conductor oxygen-permeating film, and its molecular formula is: BaCo
0.4Fe
0.4Nb
0.2O
3-δ(0＜δ＜3).
Preparation hydrotalcite type Ni
0.5Mg
2.5AlO
δCatalyzer:
Under the room temperature, with 50mmol NI (NO
3)
26H
2O, 250mmol Mg (NO
3)
26H
2O, 100mmol Al (NO
3)
39H
2The urea of O and 2.7mol is dissolved in the there-necked flask that the 250mol deionized water is housed, and under vigorous stirring there-necked flask is immersed in 105 ℃ of oil baths, and dynamic crystallization is after 10 hours, and complete for guaranteeing urea decomposition, static-aging is 18 hours under 100 ℃ of temperature.Aging fully after, suction filtration immediately, with the deionization washing of heat 3 times, in 95 ℃ of dryings 20 hours, again that drying is good sample was 500 and 800 ℃ of roasting 16 and 3 hours respectively with the gained sample, fragmentation is sieved, 20～40 order scopes of getting are as catalyzer.The X-ray diffraction of this catalyzer (XRD) as shown in Figure 2, the BET method records this specific surface area of catalyst＞120m
2/ g.
Preparation BaCo
0.4Fe
0.4Nb
0.2O
3-δComposite conductor oxygen-permeating film:
According to BaCo
0.4Fe
0.4Nb
0.2O
3-δThe stoichiometric ratio of forming weighs analytical pure barium carbonate (BaCO respectively
3), cobalt oxide (Co
2O
3), ferric oxide (Fe
2O
3), niobium oxides (Nb
2O
5) powder, as dispersion medium mixing and ball milling after drying, 1100 ℃ of roastings 20 hours and secondary ball milling are pulverized drying and are obtained powder in retort furnace then with ethanol.The BCFN powder is pressed into the diaphragm that diameter is 20mm, the about 1.5mm of thickness, forming pressure 48MPa with universal hydraulic machine after adding an amount of PVA granulation.Prime ring 1150 ℃ of sintering in retort furnace obtained the oxygen permeable film material that needs in 5～20 hours.
The present invention adopts nickeliferous hydrotalcite type catalyzer, and temperature of reaction is the temperature of high temperature coke oven coal gas itself, and promptly between 750～850 ℃, volume space velocity is 0.5 * 10
4～2.0 * 10
5Between/the h, the oxygen that provides with entrained water vapor of coke oven crude gas itself and oxygen permeable film is oxygenant, carries out the coke oven crude gas mixing reforming reaction under the normal pressure, and reaction process can keep stable in the long period.
Film of the present invention is the composite conductor oxygen-permeating film of perovskite structure.Why be called the mixed conductor mould material and be meant that this material has the characteristics of electronics and oxygen conduction simultaneously, the power that oxygen transmits in film is that the oxygen partial pressure of film both sides is poor, as long as the film both sides exist oxygen partial pressure poor, airborne oxygen will be transferred to the reaction side of membrane reactor continually.
Reactant of the present invention is a high temperature coke oven coal gas, and the vapour content volume percent is 10～18%, and oxygen provides by oxygen permeable film, and the flow of control air just can be controlled the amount of oxygen supply.Hydrocarbon polymer carbon atom ratio (O/C) is between 0.5～1.0 in Sauerstoffatom that oxygen permeable film provides in the described reactant and the coke oven crude gas.
The oxygen that utilizes entrained water vapour of high temperature coke oven crude gas and oxygen permeable film to provide is oxygenant, reforms by steam reformation and partial oxidation, and the thick cyclostrophic of coke oven is turned to H
2, CO and CO
2Deng micro-molecular gas.Fig. 3 is seen in the variation of micro-molecular gas flow before and after the reaction.
Adopted the composite conductor oxygen-permeating film reactor technology, the supply of oxygen and reformation cracking process are coupled to together to carry out, the required water vapor of steam reformation is the entrained high-temperature water vapor of high temperature coke oven crude gas itself, need not provides any other heat by burner, provide oxygen by membrane reactor simultaneously, raw material is cheap air, does not need to produce specially the equipment of oxygen, greatly reduces investment and running cost; Owing to come air feed with composite conductor oxygen-permeating film, its cost might reduce nearly 50% than air separation legal system oxygen.
Claims (1)
1. oxygen-permeable membrane reactor that is used for coke oven crude gas mixing reforming hydrogen preparation technique, it includes coke oven crude gas inlet mouth (1), stainless steel containment member (2), reacting product outlet (3), catalyst bed (4), oxygen permeable film (5), electric heater (6), rich nitrogen outlet (7), metal o-ring (8), gas inlet (9), goes up sleeve pipe (10), running casing (11) and center sleeve (12); It is characterized in that: whole oxygen-permeable membrane reactor is vertical vertical arrangement form, be provided with catalyst bed (4) in device center sleeve (12) and be positioned at oxygen permeable film (5) and last sleeve pipe (10) that contact with the oxygen permeable film upper and lower surface and running casing (11) it under, oxygen permeable film and pass through metal o-ring (8) up and down between two sleeve pipes and seal; Center sleeve (12) outer periphery is provided with an electric heater (6); Be provided with coke oven crude gas inlet mouth (1) at device center sleeve (12) top; Its outside is communicated with reacting product outlet (3) with the interior space of surveying of last sleeve pipe (10); Coke-oven gas inlet mouth (1) inserts in the catalyst bed (4); Bottom at device center sleeve (12) is provided with gas inlet (9); Be provided with in its position of going up slightly and communicate with running casing (11) inboard and be positioned at lateral rich nitrogen outlet (7); This device main body upper and lower part is equipped with and prevents the stainless steel containment member (2) that leaks gas; The chemical substance of catalyst bed in this device (4) and oxygen permeable film (5) composed as follows:
(a) catalyzer in the catalyst bed is the hydrotalcite type catalyzer, and its molecular formula is Ni
0.5Mg
2.5AlO
δ
(b) oxygen permeable film is a kind of composite conductor oxygen-permeating film, and its molecular formula is: BaCo
0.4Fe
0.4Nb
0.2O
3-δ(0＜δ＜3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100363673A CN101264860B (en) | 2008-04-21 | 2008-04-21 | Oxygen-permeating film reactor used for coke oven crude gas mixing and reforming in hydrogen preparation technique |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100363673A CN101264860B (en) | 2008-04-21 | 2008-04-21 | Oxygen-permeating film reactor used for coke oven crude gas mixing and reforming in hydrogen preparation technique |
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| Publication Number | Publication Date |
|---|---|
| CN101264860A true CN101264860A (en) | 2008-09-17 |
| CN101264860B CN101264860B (en) | 2010-11-17 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060269A (en) * | 2010-10-29 | 2011-05-18 | 华南理工大学 | Fluidized bed oxygen permeable membrane reactor and method for producing synthesis gas containing hydrogen |
| CN102580478A (en) * | 2012-03-20 | 2012-07-18 | 南京工业大学 | Integrated tubular ceramic oxygen permeable membrane separation reactor |
| CN101767781B (en) * | 2009-01-04 | 2012-12-19 | 马叔骥 | Circulation process for treating tail gas pollution of heat-engine plant and preparing ammonium phosphate and sulphuric acid byproducts |
| CN102872727A (en) * | 2012-09-28 | 2013-01-16 | 中国科学院大连化学物理研究所 | Low-temperature stable mixed-conductor oxygen permeable membrane in perovskite type barium-containing iron series |
| CN103421924A (en) * | 2013-07-10 | 2013-12-04 | 中国恩菲工程技术有限公司 | Fluidization laterite ore reducing method |
| CN113214872A (en) * | 2021-03-21 | 2021-08-06 | 苏州铧泷磬能新能源科技有限公司 | Heat accumulating type coal gasification hydrogen production hydrogen permeation membrane reactor |
-
2008
- 2008-04-21 CN CN2008100363673A patent/CN101264860B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101767781B (en) * | 2009-01-04 | 2012-12-19 | 马叔骥 | Circulation process for treating tail gas pollution of heat-engine plant and preparing ammonium phosphate and sulphuric acid byproducts |
| CN102060269A (en) * | 2010-10-29 | 2011-05-18 | 华南理工大学 | Fluidized bed oxygen permeable membrane reactor and method for producing synthesis gas containing hydrogen |
| CN102060269B (en) * | 2010-10-29 | 2012-09-05 | 华南理工大学 | Fluidized bed oxygen permeable membrane reactor and method for producing synthesis gas containing hydrogen |
| CN102580478A (en) * | 2012-03-20 | 2012-07-18 | 南京工业大学 | Integrated tubular ceramic oxygen permeable membrane separation reactor |
| CN102872727A (en) * | 2012-09-28 | 2013-01-16 | 中国科学院大连化学物理研究所 | Low-temperature stable mixed-conductor oxygen permeable membrane in perovskite type barium-containing iron series |
| CN103421924A (en) * | 2013-07-10 | 2013-12-04 | 中国恩菲工程技术有限公司 | Fluidization laterite ore reducing method |
| CN113214872A (en) * | 2021-03-21 | 2021-08-06 | 苏州铧泷磬能新能源科技有限公司 | Heat accumulating type coal gasification hydrogen production hydrogen permeation membrane reactor |
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| Publication number | Publication date |
|---|---|
| CN101264860B (en) | 2010-11-17 |
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