CN201825722U - Oxygen permeation membrane reactor of fluidized bed - Google Patents

Oxygen permeation membrane reactor of fluidized bed Download PDF

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Publication number
CN201825722U
CN201825722U CN2010205902911U CN201020590291U CN201825722U CN 201825722 U CN201825722 U CN 201825722U CN 2010205902911 U CN2010205902911 U CN 2010205902911U CN 201020590291 U CN201020590291 U CN 201020590291U CN 201825722 U CN201825722 U CN 201825722U
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pipe
upper flange
oxygen
reaction tubes
fluidized
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Expired - Lifetime
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CN2010205902911U
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解东来
温明霞
叶健文
杨振华
曹志宇
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South China University of Technology SCUT
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South China University of Technology SCUT
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Abstract

The utility model discloses an oxygen permeation membrane reactor of a fluidized bed, which comprises a lower seal head, a distributor, a reaction pipe, an upper flange, an air inlet pipe, an air outlet pipe and an oxygen permeation membrane pipe, wherein the lower seal head is provided with a raw material gas inlet pipe, the lower seal head is arranged at the lower part of a reaction pipe, the distributor is arranged on the upper surface of the lower seal head, the upper flange is arranged at the upper part of the reaction pipe, a catalyst for hydrogen production in a self-heating reforming way is filled in the reaction pipe, the air inlet pipe penetrates the upper flange to be inserted into the reaction pipe and connected with the oxygen permeation membrane pipe, the oxygen permeation membrane pipe is connected with the air outlet pipe, the air outlet pipe penetrates the upper flange to be led to the outside of the reactor, the oxygen permeation membrane pipe is buried by the catalyst in the reaction pipe, the upper flange is provided with a synthetic gas leading-out pipe, and a tail gas filter is arranged at the lower end of the synthetic gas leading-out pipe. Air is introduced into a reactor, and nitrogen in the air does not participate in reaction.

Description

The fluidized-bed oxygen-permeable membrane reactor
Technical field
The utility model relates to the hydrogen generation technique, is specifically related to a kind of fluidized-bed oxygen-permeable membrane reactor.
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, also is regarded as solving the Greenhouse effect problem, improves effective substitute energy of energy utilization efficiency.Gas water steam reforming technology is the technology that is used to produce hydrogen and synthetic gas of industrial widespread usage.This reaction is a strong endothermic reaction, 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 the most frequently used reactor is a tubular fixed-bed reactor, provides reaction required heat by indirect heating or partial oxidation.When providing heat by indirect heating, because the fixed-bed heat transfer weak effect, so required heat-transfer surface is very big.When providing the heat that reacts required,, should adopt air for saving the cost of oxygen separation by partial oxidation, rather than pure oxygen is as oxygenant, but a large amount of nitrogen is brought in the introducing meeting of air in reactor, reduces the efficient of system, has also increased the load of follow-up Hydrogen Separation process.
The utility model content
The utility model provides a kind of air has been introduced reactor in order to overcome the deficiency that above prior art exists, and airborne nitrogen does not participate in the fluidized-bed oxygen-permeable membrane reactor that reacts.
The purpose of this utility model realizes by following technical scheme: this fluidized-bed oxygen-permeable membrane reactor, it is characterized in that: comprise lower cover, sparger, reaction tubes, upper flange, air intake duct, air escape pipe and oxygen permeable film pipe, described lower cover is provided with the unstripped gas inlet pipe, lower cover is installed in the bottom of reaction tubes, sparger is installed above the lower cover, upper flange is installed in the top of reaction tubes, be filled with the catalyzer that is used for self-heating reforming hydrogen manufacturing in the reaction tubes, air intake duct passes in the upper flange insertion reaction pipe and connects the oxygen permeable film pipe, oxygen permeable film pipe coupling air escape pipe, the air escape pipe passes upper flange and leads to outside the reactor, the oxygen permeable film pipe is buried (in case block gas is blasted in the reaction of the gas phase that does not have catalyzer and synthetic gas generation vigorous oxidation) by catalyzer in reaction tubes, upper flange is provided with the synthetic gas fairlead, and the lower end of synthetic gas fairlead is provided with exhaust gas filter.
For the stopping property that guarantees to connect, between described sparger and the lower cover one of pad is installed, one of pad adopts graphite, containing metal graphite material.
For the stopping property that guarantees to connect, two of pad is installed between described sparger and the reaction tubes, two of pad adopts graphite, containing metal graphite material.
For the stopping property that guarantees to connect, described reaction tubes top is connected with upper flange by three of pad, three employing graphite of pad, containing metal graphite material.
As a kind of preferred structure, described air intake duct, air escape pipe, synthetic gas fairlead are fixed on the upper flange by cutting ferrule respectively, and the upper end all is drawn out to the upper flange outside.
As a kind of preferred structure, described exhaust gas filter top and synthetic gas fairlead are welded to connect.
As a kind of preferred structure, be connected and fixed with bolt, nut between described lower cover and the reaction tubes, be connected and fixed with bolt, nut between upper flange and the reaction tubes.
Below, described reaction tubes side is equipped with discharge tube, is used for the catalyzer at device maintenance period unloading reaction tubes.Upper flange has the catalyst filling mouth.
As preferred scheme, described oxygen permeable film pipe is fine and close perovskite film pipe, and exhaust gas filter is the porous sintered metal pipe, and sparger is porous sintered metal or wire netting, and catalyzer is Ni-based natural gas auto-thermal reforming hydrogen production catalyzer, and carrier is α-Al 2O 3Powder, median size 40-100 micron; The material of air intake duct, air escape pipe, lower cover, reaction tubes, upper flange and exhaust gas filter is a stainless steel; Adopt cutting ferrule to be connected between oxygen permeable film pipe and air intake duct and the air escape pipe, cutting ferrule adopts 316 stainless steels two of Xiong Chuan company to lead to.
The method of the production hydrogen containing synthesis gas of above-mentioned fluidized-bed oxygen-permeable membrane reactor may further comprise the steps:
(1), keeping reactor pressure is normal pressure, Sweet natural gas and water vapor through preheating enter into lower cover inside by the unstripped gas inlet pipe, be evenly distributed in the reaction tubes through sparger then, make the interior catalyzer of reaction tubes reach the running status of bubbling fluidized bed;
(2), air enters into the oxygen permeable film pipe by air intake duct, most of oxygen wherein passes the oxygen permeable film pipe and enters into reaction tubes under the effect of pressure, the oxygen permeable film pipe at high temperature can and can only allow airborne oxygen from highly compressed one side thoroughly to the outer other side of pipe, airborne nitrogen and the remaining oxygen of oxygen permeable film pipe that do not pass are through air escape pipe discharge reactor;
(3), Sweet natural gas, water vapor, oxygen generation autothermal reforming reaction in the reactor, reaction process comprises:
Steam reformation CH 4+ H 2O=CO+3H 2Δ H=206.2kJ/mol,
Steam reformation CH 4+ 2H 2O=CO 2+ 4H 2Δ H=164.9kJ/mol,
Partial oxidation CH 4+ 0.5O 2=CO+2H 2Δ H=-35.7kJ/mol,
Complete oxidation CH 4+ 2O 2=CO 2+ 2H 2O Δ H=-802.7kJ/mol,
The main component of the hydrogen containing synthesis gas that produces is H 2, CO 2, CO, H 2O, CH 4
(4), hydrogen containing synthesis gas upwards flows, and leaves bed, enters the synthetic gas fairlead through exhaust gas filter and draws reactor, the granules of catalyst of carrying secretly in the hydrogen containing synthesis gas is blocked in inside reactor by exhaust gas filter.
The utility model has following advantage with respect to prior art:
(1) makes traditional fixed-bed reactor into fluidized-bed reactor, overcome the fixed-bed heat transfer weak effect, the uneven shortcoming of bed temperature.
(2) adopt the self-heating system not need the outside that thermal source is provided again, make the designs simplification of reactor can prevent the formation of carbon deposit in the reaction process simultaneously.
(3) the oxygen permeable film pipe is evenly distributed to airborne oxygen in the steam reforming reaction device, cooperates with fluidized-bed reactor, prevents that effectively local temperature is too high in the reactor.
(4) the oxygen permeable film pipe only imports reaction unit with airborne oxygen, can prevent that airborne nitrogen from reducing the molar fraction of hydrogen in the reactor.
(5) size of fluid catalyst particulate is far smaller than the fixed bed reforming catalyst, and catalyst efficient is improved greatly.
Description of drawings
Fig. 1 is the longitudinal sectional view of fluidized-bed oxygen-permeable membrane reactor of the present utility model.
Fig. 2 is the vertical view of upper flange.
Embodiment
The utility model is described in further detail below in conjunction with drawings and Examples.
Fluidized-bed oxygen-permeable membrane reactor as depicted in figs. 1 and 2, comprise lower cover 2, sparger 4, reaction tubes, upper flange 9, air intake duct 10, air escape pipe 12 and oxygen permeable film pipe 11, described lower cover is provided with unstripped gas inlet pipe 1, lower cover is installed in the bottom of reaction tubes 6, sparger is installed above the lower cover, upper flange is installed in the top of reaction tubes, be filled with the catalyzer 7 that is used for self-heating reforming hydrogen manufacturing in the reaction tubes, air intake duct passes in the upper flange insertion reaction pipe and connects the oxygen permeable film pipe, oxygen permeable film pipe coupling air escape pipe, the air escape pipe passes upper flange and leads to outside the reactor, the oxygen permeable film pipe is buried (in case block gas is blasted in the reaction of the gas phase that does not have catalyzer and synthetic gas generation vigorous oxidation) by catalyzer in reaction tubes, upper flange is provided with synthetic gas fairlead 13, and the lower end of synthetic gas fairlead is provided with exhaust gas filter 14.
For the stopping property that guarantees to connect, one of pad 3 is installed between described sparger and the lower cover, 25 of pad is installed between sparger and the reaction tubes, reaction tubes top is connected 8 by three of pad with upper flange.One of pad, two of pad, three of pad seals, and the temperature and pressure according to reaction can adopt materials such as graphite, containing metal graphite, and present embodiment employing thickness is 3 millimeters Graphite pad.
Air intake duct, air escape pipe, synthetic gas fairlead are fixed on the upper flange by cutting ferrule respectively, and the upper end all is drawn out to the upper flange outside.
Exhaust gas filter top and synthetic gas fairlead are welded to connect.
Be connected and fixed with bolt, nut between lower cover and the reaction tubes, be connected and fixed with bolt, nut between upper flange and the reaction tubes.
Below, described reaction tubes side is equipped with discharge tube 15, and 3 centimetres of discharge tube internal diameters are used for the catalyzer at device maintenance period unloading reaction tubes.
The oxygen permeable film pipe is fine and close perovskite film pipe, 6 millimeters of external diameters, 2 millimeters of wall thickness, 50 centimetres of length, this pipe at high temperature (500-800 ℃) can optionally allow airborne oxygen from highly compressed one side thoroughly to the pipe outside an other side.Exhaust gas filter is the porous sintered metal pipe, and sparger is a porous sintered metal, and material is a Hastelloy X stainless steel, and sintering metal hole rank is 0.5 micron.
Catalyzer is Ni-based natural gas auto-thermal reforming hydrogen production catalyzer, and carrier is α-Al 2O 3Powder, 65 microns of median sizes.During catalyst loading, the oxygen permeable film pipe is imbedded wherein, its surface exceeds 2 centimetres of oxygen permeable film pipes.
Air intake duct and air escape pipe can adopt 316 stainless steel tubes of 6 millimeters of external diameters.Can adopt cutting ferrule to be connected between oxygen permeable film pipe and air intake duct and the air escape pipe, cutting ferrule adopts 316 stainless steels two of Xiong Chuan company logical.
The lower cover material is generally selected 316 stainless steels for use, and 5 millimeters of wall thickness, concrete material category and wall thickness are selected and can be calculated definite by intensity according to the temperature and the pressure of real reaction.
The reaction tubes material is generally selected Hastelloy X stainless steel for use, and 20 centimetres of internal diameters, 5 millimeters of wall thickness, 100 centimetres of height, concrete material category and wall thickness are selected and can be calculated definite by intensity according to the temperature and the pressure of real reaction.
Upper flange material selection Hastelloy X stainless steel, 10 millimeters of wall thickness, concrete material category and wall thickness are selected and can be calculated definite by intensity according to the temperature and the pressure of real reaction.
Upper flange has blast main intake interface 21, the blast main interface 22 of giving vent to anger, and interface 21,22 adopts 0.25 inch NPT internal thread interface, is used to install air intake duct, air escape pipe after suitable cutting ferrule is installed.Upper flange also has synthetic gas fairlead interface 23, and interface 23 adopts 0.5 inch NPT internal thread interface, is used to install the synthetic gas fairlead after suitable cutting ferrule is installed.Upper flange also has catalyst filling mouth 24, and catalyst filling mouth 24 adopts 0.5 inch NPT internal thread interface, is used for loading catalyst after suitable cutting ferrule is installed, and 25 is bolt hole.
The strainer of 25 mm outer diameter that exhaust gas filter employing U.S. MOTT company is produced, material is a Hastelloy X stainless steel, sintering metal hole rank is 0.5 micron.316 stainless steel tubes of its opening one side and 25 millimeters are welded to connect, and are connected to 316 stainless steel synthetic gas fairleads of 10 millimeters of external diameters after degree, and the synthetic gas fairlead interface 23 by upper flange is connected to the reactor outside.
The method of the production hydrogen containing synthesis gas of above-mentioned fluidized-bed oxygen-permeable membrane reactor may further comprise the steps:
(1), keeping reactor pressure is normal pressure (relative pressure 0MPa), the Sweet natural gas of the 100kmol/h of process preheating and the water vapor of 200kmol/h enter into lower cover inside by the unstripped gas inlet pipe, be evenly distributed in the reaction tubes through sparger then, make catalyzer in the reaction tubes reach the running status of bubbling fluidized bed, in the reactor the superfacial velocity of gas be about 0.1m/s;
(2), the 270kmol/h air enters into the oxygen permeable film pipe by air intake duct, the relative pressure of air is controlled at 1MPa, 50kmol/h oxygen wherein passes the oxygen permeable film pipe and enters into reaction tubes under the effect of pressure, the oxygen permeable film pipe at high temperature can and can only allow airborne oxygen from highly compressed one side thoroughly to the outer other side of pipe, the airborne nitrogen of 220kmol/h and the remaining oxygen of oxygen permeable film pipe that do not pass are through air escape pipe discharge reactor;
(3), Sweet natural gas, water vapor, oxygen generation autothermal reforming reaction in the reactor, make temperature maintenance in the reactor at about 650 ℃, reaction process comprises:
Steam reformation CH 4+ H 2O=CO+3H 2Δ H=206.2kJ/mol
Steam reformation CH 4+ 2H 2O=CO 2+ 4H 2Δ H=164.9kJ/mol
Partial oxidation CH 4+ 0.5O 2=CO+2H 2Δ H=-35.7kJ/mol
Complete oxidation CH 4+ 2O 2=CO 2+ 2H 2O Δ H=-802.7kJ/mol
The main component of the hydrogen containing synthesis gas that produces is H 2, CO 2, CO, H 2O, CH 4, total flux is about 500kmol/h, and wherein about 40% is hydrogen;
(4), hydrogen containing synthesis gas upwards flows, and leaves bed, enters the synthetic gas fairlead through exhaust gas filter and draws reactor, the granules of catalyst of carrying secretly in the hydrogen containing synthesis gas is blocked in inside reactor by exhaust gas filter.
Above-mentioned embodiment is a preferred embodiment of the present utility model; can not limit the utility model; other any change that does not deviate from the technical solution of the utility model and made or other equivalent substitute mode are included within the protection domain of the present utility model.

Claims (9)

1. fluidized-bed oxygen-permeable membrane reactor, it is characterized in that: comprise lower cover, sparger, reaction tubes, upper flange, air intake duct, air escape pipe and oxygen permeable film pipe, described lower cover is provided with the unstripped gas inlet pipe, lower cover is installed in the bottom of reaction tubes, sparger is installed above the lower cover, upper flange is installed in the top of reaction tubes, be filled with the catalyzer that is used for self-heating reforming hydrogen manufacturing in the reaction tubes, air intake duct passes in the upper flange insertion reaction pipe and connects the oxygen permeable film pipe, oxygen permeable film pipe coupling air escape pipe, the air escape pipe passes upper flange and leads to outside the reactor, the oxygen permeable film pipe is buried by catalyzer in reaction tubes, upper flange is provided with the synthetic gas fairlead, and the lower end of synthetic gas fairlead is provided with exhaust gas filter.
2. fluidized-bed oxygen-permeable membrane reactor according to claim 1 is characterized in that: between described sparger and the lower cover one of pad is installed, one of pad adopts graphite, containing metal graphite material.
3. fluidized-bed oxygen-permeable membrane reactor according to claim 1 is characterized in that: two of pad is installed between described sparger and the reaction tubes, and two of pad adopts graphite, containing metal graphite material.
4. fluidized-bed oxygen-permeable membrane reactor according to claim 1 is characterized in that: described reaction tubes top is connected with upper flange by three of pad, three employing graphite of pad, containing metal graphite material.
5. fluidized-bed oxygen-permeable membrane reactor according to claim 1 is characterized in that: described air intake duct, air escape pipe, synthetic gas fairlead are fixed on the upper flange by cutting ferrule respectively, and the upper end all is drawn out to the upper flange outside.
6. fluidized-bed oxygen-permeable membrane reactor according to claim 1 is characterized in that: described exhaust gas filter top and synthetic gas fairlead are welded to connect.
7. fluidized-bed oxygen-permeable membrane reactor according to claim 1 is characterized in that: be connected and fixed with bolt, nut between described lower cover and the reaction tubes, be connected and fixed with bolt, nut between upper flange and the reaction tubes.
8. fluidized-bed oxygen-permeable membrane reactor according to claim 1 is characterized in that: below, described reaction tubes side is equipped with discharge tube, and upper flange has the catalyst filling mouth.
9. fluidized-bed oxygen-permeable membrane reactor according to claim 1, it is characterized in that: described oxygen permeable film pipe is fine and close perovskite film pipe, exhaust gas filter is the porous sintered metal pipe, sparger is porous sintered metal or wire netting, catalyzer is Ni-based natural gas auto-thermal reforming hydrogen production catalyzer, and carrier is α-Al 2O 3Powder, median size 40-100 micron; The material of air intake duct, air escape pipe, lower cover, reaction tubes, upper flange and exhaust gas filter is a stainless steel; Adopt cutting ferrule to be connected between oxygen permeable film pipe and air intake duct and the air escape pipe, cutting ferrule adopts 316 stainless steels two of Xiong Chuan company to lead to.
CN2010205902911U 2010-10-29 2010-10-29 Oxygen permeation membrane reactor of fluidized bed Expired - Lifetime CN201825722U (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
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
CN105692548A (en) * 2014-11-28 2016-06-22 中国科学院大连化学物理研究所 System and method for preparing synthetic ammonia raw gas
CN107311106A (en) * 2013-04-26 2017-11-03 普莱克斯技术有限公司 Use the method and system of the production synthesis gas for the oxygen transport membrane base reforming system reformed with secondary
CN111378513A (en) * 2018-12-28 2020-07-07 中国石油化工股份有限公司 Auxiliary agent for biomass treatment and biomass gasification treatment method

Cited By (6)

* Cited by examiner, † Cited by third party
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
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
CN107311106A (en) * 2013-04-26 2017-11-03 普莱克斯技术有限公司 Use the method and system of the production synthesis gas for the oxygen transport membrane base reforming system reformed with secondary
CN107311106B (en) * 2013-04-26 2019-09-20 普莱克斯技术有限公司 Use the method and system of the production synthesis gas with the secondary oxygen transport membrane base reforming system reformed
CN105692548A (en) * 2014-11-28 2016-06-22 中国科学院大连化学物理研究所 System and method for preparing synthetic ammonia raw gas
CN111378513A (en) * 2018-12-28 2020-07-07 中国石油化工股份有限公司 Auxiliary agent for biomass treatment and biomass gasification treatment method

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AV01 Patent right actively abandoned

Granted publication date: 20110511

Effective date of abandoning: 20120905