CN104944370B - Device for producing hydrogen from tail gas produced by MOCVD (metal-organic chemical vapor deposition) - Google Patents
Device for producing hydrogen from tail gas produced by MOCVD (metal-organic chemical vapor deposition) Download PDFInfo
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- CN104944370B CN104944370B CN201510337511.7A CN201510337511A CN104944370B CN 104944370 B CN104944370 B CN 104944370B CN 201510337511 A CN201510337511 A CN 201510337511A CN 104944370 B CN104944370 B CN 104944370B
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- 239000007789 gas Substances 0.000 title claims abstract description 203
- 239000001257 hydrogen Substances 0.000 title claims abstract description 139
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 139
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 238000005229 chemical vapour deposition Methods 0.000 title abstract 3
- 238000001179 sorption measurement Methods 0.000 claims abstract description 139
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 125
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 64
- 239000012535 impurity Substances 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 238000000746 purification Methods 0.000 claims abstract description 10
- 239000003463 adsorbent Substances 0.000 claims abstract description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 48
- 230000008929 regeneration Effects 0.000 claims description 40
- 238000011069 regeneration method Methods 0.000 claims description 40
- 238000004458 analytical method Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 239000002918 waste heat Substances 0.000 claims description 8
- 238000013022 venting Methods 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 230000007420 reactivation Effects 0.000 claims description 4
- 230000003139 buffering effect Effects 0.000 claims description 3
- 239000002594 sorbent Substances 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 35
- 229910021529 ammonia Inorganic materials 0.000 description 17
- 238000000034 method Methods 0.000 description 15
- 238000005868 electrolysis reaction Methods 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000005485 electric heating Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 108010022579 ATP dependent 26S protease Proteins 0.000 description 2
- 229910002601 GaN Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000012946 outsourcing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Separation Of Gases By Adsorption (AREA)
Abstract
The invention discloses a device for producing hydrogen from tail gas produced by MOCVD (metal-organic chemical vapor deposition). The device comprises a decomposing furnace used for decomposing tail gas containing hydrogen into mixture gas of hydrogen and nitrogen, temperature swing adsorption equipment used for removing impurities in the mixture gas of hydrogen and nitrogen while containing a reproducible adsorbent, pressure swing adsorption equipment used for performing concentration and purification on hydrogen in the mixture gas of hydrogen and nitrogen with impurities removed while producing high-pressure reverse-discharge gas and low-pressure reverse-discharge gas, and a hydrogen compressor used for pressurizing the mixture gas of hydrogen and nitrogen which is purified or not; the decomposing furnace, the temperature swing adsorption equipment and the pressure swing adsorption equipment are connected in sequence; the hydrogen compressor is arranged between the decomposing furnace and the temperature swing adsorption equipment or between the temperature swing adsorption equipment and the pressure swing adsorption equipment. According to the device for producing hydrogen from tail gas produced by MOCVD (metal-organic chemical vapor deposition), provided by the invention, not only is the problem of environmental pollution caused by emission of tail gas produced by MOCVD solved, but also the hydrogen raw material can be provided for MOCVD equipment, besides, the cost of obtained hydrogen is lower than that of hydrogen produced from electrolysed water in the prior, therefore, the device is suitable for being used by LED manufacture factories.
Description
Technical field
The present invention devises a device applying mechanically mocvd tail gas hydrogen manufacturing, and the method can be used for using metal organic-matter chemical gas
Mutually deposition (mocvd) produces in gallium nitride light-emitting diode (gan-led) producer, belongs to technical field of semiconductor preparation.
Background technology
A kind of important semi-conducting material is had become as with the iii group-III nitride as representative for the gallium nitride (gan), is done with gan
The light emitting diode (led) becoming has become as the main development direction of semiconductor lighting.
Mocvd is the unique method producing gallium nitride light-emitting diode (gan-led) at present.Produce gan-led in mocvd
During, one side mocvd equipment needs substantial amounts of high-purity hydrogen as carrier gas, and another aspect mocvd equipment can discharge again
A large amount of tail gas (waste gas), mainly have ammonia, hydrogen, nitrogen and other foreign gas in tail gas.
Although hydrogen is very abundant in the earth's crust, generally presented in " water ", there is not simple substance hydrogen in earth's crust surface to hydrogen
Gas.Current electrolysis water hydrogen manufacturing is commonly used method in gan-led manufacturing enterprise.But water electrolysis hydrogen production needs to consume in a large number
Electric energy, relatively costly.If using water gas hydrogen manufacturing or methane cracking hydrogen production method although cost is relatively low, but pollution is very big
And impurity is too many, led producer is general not in this way.
In addition, during mocvd produces led, also substantial amounts of tail gas can be discharged, in tail gas, contain ammonia, hydrogen, nitrogen
Deng.If directly by these waste gas discharges, environment certainly will be polluted.The processing method commonly used at present is: (i) water (or acid) absorbs
Method.Tail gas is passed through in water (or acid solution), the ammonia in tail gas is absorbed by water or acid.Although the method is simple, most of
Gan-led manufacturing enterprise adopts, but how to process ammonia (or ammonium salt) is also a pretty troublesome thing.One is simply asked by this
Topic transfers to another problem, but the not final solution of substantive issue；(ii) high-temperature decomposition.By tail gas pass through 600 DEG C～
In 900 DEG C of high temperature furnace, wherein ammonia resolves into hydrogen and nitrogen, is then discharged in air.The maximum shortcoming of the method is just
It is that energy consumption is very high, relatively costly, seldom adopted by gan-led enterprise；(iii) burning method.Tail gas is mixed with air, plus
Palladium catalyst, burns at a temperature of 300 DEG C～500 DEG C, ammonia is decomposed, is discharged in air.The method have one fatal
Shortcoming, it is simply that can produce the harmful substances such as nitrogen oxides and dioxin in burning process, pollutes environment, seldom by gan-led
Enterprise adopts.
Due to above reason, cause the concern of people in the recent period using mocvd tail gas hydrogen manufacturing.Chinese Patent Application No.
201410062339.4 proposing a kind of method of use mocvd tail gas hydrogen manufacturing.The basic thought of the method is: by mocvd tail gas
Become hydrogen nitrogen mixed gas through 300 DEG C～500 DEG C of reacting furnaces, then by palladium film purifier, impurity is gone with hydrogen nitrogen mixed gas
Remove and obtain highly purified hydrogen.The method has following critical defect: (i) reacting furnace temperature is relatively low, and ammonia decomposes insufficient；(ii)
Nitrogen content up to more than 55% in hydrogen nitrogen mixed gas, palladium film purifier is helpless to the nitrogen of such high concentration, Er Qieqing
Remaining ammonia in nitrogen mixed gas produces destruction to meeting palladium film purifier.Chinese Patent Application No. 20141022950.8 is then
Propose another method: first by mocvd tail gas pressurization freeze and separate ammonia (liquid phase), then gas phase is passed through pressure-variable adsorption
(psa) device separation hydrogen.The method has the disadvantage that: (i) reclaims ammonia and two products of hydrogen simultaneously, needs two sets of purifications to set
Standby, equipment investment is larger；(ii) this two products all cannot ensure led factory self-supporting in addition it is also necessary to outsourcing hydrogen and ammonia.
The invention provides a set of utilization mocvd tail gas device for producing hydrogen.This device both can solve mocvd exhaust emissions and cause
Problem of environmental pollution, can provide raw hydrogen for mocvd equipment again, and obtained hydrogen cost is less than conventional electrolysis water
The cost of hydrogen manufacturing.As in view of conventional mocvd vent gas treatment cost and electrolysis water cost, the cost of the hydrogen being manufactured with this device
Lower, only conventional mocvd vent gas treatment cost and 1/3rd of electrolysis water cost, suitable led manufacturer uses.
Content of the invention
It is an object of the present invention to provide one applies mechanically the device of mocvd tail gas hydrogen manufacturing.
One device applying mechanically mocvd tail gas hydrogen manufacturing, described device for producing hydrogen comprises:
For hydrogeneous tail gas being decomposed into the dore furnace of hydrogen nitrogen mixed gas,
For removing impurity in hydrogen nitrogen mixed gas, simultaneously the temp.-changing adsorption equipment containing regenerable sorbent,
Produce high-pressure reverse venting, low pressure inverse put gas for the hydrogen in the hydrogen nitrogen mixed gas after remove impurity is concentrated purification simultaneously
Variable-pressure adsorption equipment, and
For the hydrogen gas compressor that the hydrogen nitrogen mixed gas of non-remove impurity or remove impurity are pressurizeed；
Described dore furnace, temp.-changing adsorption equipment and variable-pressure adsorption equipment are sequentially connected；
Described hydrogen gas compressor between dore furnace and temp.-changing adsorption equipment or
Located between temp.-changing adsorption equipment and variable-pressure adsorption equipment.
Preferably, described device for producing hydrogen also comprises:
For the heat exchanger of heat exchange will be carried out between hydrogeneous tail gas and hydrogen nitrogen mixed gas；
For the first water cooler being cooled down the hydrogen nitrogen mixed gas through heat exchange；
For the second water cooler being cooled down the hydrogen nitrogen mixed gas of non-remove impurity or remove impurity；With
Flow and pressure for high-pressure reverse is exitted enter row buffering and stable inverse put gas surge tank.
Preferably, described dore furnace at least 1, the mode of heating of described dore furnace is electrical heating, heating temperature range
For 600 DEG C -900 DEG C.
Preferably, described hydrogen gas compressor be provided with for
It is passed through the air inlet of non-remove impurity or remove impurity hydrogen nitrogen mixed gas and for exporting non-remove impurity or remove impurity hydrogen nitrogen mixed gas
Gas outlet.
Preferably, the series of described hydrogen gas compressor is 1-3 level；The quantity of described hydrogen gas compressor at least one.
Preferably, described temp.-changing adsorption equipment is provided with
For being passed through the raw material gas inlet of the hydrogen nitrogen mixed gas of non-remove impurity,
Unstripped gas for exporting the hydrogen nitrogen mixed gas after remove impurity exports,
For being passed through the regeneration air inlet of the regeneration gas making adsorbent reactivation,
Make the regeneration gas outlet of the regeneration gas of adsorbent reactivation for output；
The regeneration gas outlet expellant gas ignition emptying of described temp.-changing adsorption equipment or directly emptying.
Preferably, described temp.-changing adsorption equipment comprises at least two adsorption towers；Described temp.-changing adsorption equipment can heat or not
Heating；The mode of heating of described temp.-changing adsorption equipment is electrical heating, or is heated with dore furnace waste heat, or uses hydrogen gas compressor
Waste heat heated.
Preferably, described variable-pressure adsorption equipment is provided with
For being passed through the raw material gas inlet of the hydrogen nitrogen mixed gas after remove impurity,
Concentrate the high-purity gas outlet of the high-purity hydrogen after purification for output,
It is deflated to the high-pressure reverse bleeder holes of inverse put gas surge tank and low pressure for exporting high-pressure reverse against bleeder holes.
Preferably, described variable-pressure adsorption equipment also includes vacuum analysis device, and is provided with vacuum analysis mouth；Described transformation is inhaled
The low pressure inverse put mouth of applying equipment and vacuum analysis mouth expellant gas ignition emptying or directly emptying.
Beneficial effects of the present invention are as follows:
The present invention can turn waste into wealth, and manufacture hydrogen with mocvd tail gas, both solved mocvd exhaust emissions and caused environment
Pollution problem, can do mocvd unstripped gas after passing through secondary purification with the high-purity hydrogen that this covering device is produced again and use,
And obtained hydrogen cost is less than the cost of routine water electrolysis hydrogen production, suitable led manufacturer uses.
Brief description
Below in conjunction with the accompanying drawings the specific embodiment of the present invention is described in further detail.
Fig. 1 is the main structure chart of the present invention and the agent structure schematic diagram of embodiment 1；
Fig. 2 is the agent structure schematic diagram of embodiments of the invention 2；
Fig. 3 is the structural representation of the variable-pressure adsorption equipment containing 2 adsorption towers；
Fig. 4 is the structural representation of the variable-pressure adsorption equipment containing 2 adsorption towers；
Fig. 5 is the structural representation of the variable-pressure adsorption equipment containing 6 adsorption towers；
Fig. 6 is the structural representation of the variable-pressure adsorption equipment containing 6 adsorption towers；
Fig. 7 is the structural representation of 2 adsorption tower temp.-changing adsorption equipment；
Fig. 8 is 3 kinds of regeneration heating arrangements of temp.-changing adsorption equipment；
Fig. 9 is the agent structure schematic diagram of embodiments of the invention 3.
Specific embodiment
In order to be illustrated more clearly that the present invention, with reference to preferred embodiments and drawings, the present invention is done further
Bright.In accompanying drawing, similar part is indicated with identical reference.It will be appreciated by those skilled in the art that institute is concrete below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
Embodiment 1
In conjunction with Fig. 1, Fig. 3, Fig. 4, Fig. 5, Fig. 6, Fig. 7, Fig. 8.Referring to Fig. 1, the device for producing hydrogen of the present invention includes: dore furnace 1,
Heat exchanger 2, hydrogen gas compressor 3, temp.-changing adsorption equipment 4, variable-pressure adsorption equipment 5, inverse put gas surge tank 6, the first water cooler 7 and
Second water cooler 8.
Heat exchanger 2 is connected with the air inlet 10 of dore furnace 1 and gas outlet 11, and heat exchanger 2 and the first water cooler 7 are even
Connect, the first water cooler 7 is connected with the air inlet 12 of hydrogen gas compressor 3, the gas outlet 13 of hydrogen gas compressor 3 and the second water cooler 8
Connect, the second water cooler 8 is connected with the raw material air inlet 14 of temp.-changing adsorption equipment 4, the raw material gas outlet 15 of temp.-changing adsorption equipment 4
It is connected with the raw material air inlet 18 of variable-pressure adsorption equipment 5, high-purity gas outlet 19 output high-purity hydrogen of variable-pressure adsorption equipment 5, defeated
The high-purity hydrogen going out is the use of mocvd equipment, the high pressure inverse put mouth 20 of variable-pressure adsorption equipment 5 and the air inlet of inverse put gas surge tank 6
Mouth connects, and the gas outlet of inverse put gas surge tank 6 is connected with the regeneration air inlet 16 of temp.-changing adsorption equipment 4, temp.-changing adsorption equipment 4
Regeneration gas outlet 17, the low pressure inverse put mouth 21 of variable-pressure adsorption equipment 5, vacuum analysis mouth 22, this 3 gas outlet expellant gas converge
Ignition emptying or directly emptying after conjunction.
Mocvd tail gas enters dore furnace 1 after over-heat-exchanger 2 and is decomposed, and the mocvd tail gas after decomposition is through dore furnace
Enter the air inlet 12 of hydrogen gas compressor 3 behind 1 gas outlet 11 and heat exchanger 2, the first water cooler 7, now enter hydrogen pressure
The decomposition gas of contracting machine is the hydrogen-nitrogen mixture gas containing impurity, and in hydrogen gas compressor 3, hydrogen nitrogen mixed gas are compressed and pressurize,
The impure hydrogen nitrogen mixed gas being compressed enter temp.-changing adsorption from raw material air inlet 14 behind gas outlet 13 and the second water cooler 8
Equipment 4, impurity in hydrogen nitrogen mixed gas (water, methane etc.) is removed by temp.-changing adsorption equipment 4, removes the hydrogen-nitrogen mixture gas after impurity
From unstripped gas outlet 15 discharge of temp.-changing adsorption equipment 4, then enter pressure-variable adsorption from the raw material air inlet 18 of variable-pressure adsorption equipment 5
Equipment 5, hydrogen in hydrogen nitrogen mixed gas and nitrogen are separated by variable-pressure adsorption equipment 5, and wherein hydrogen exports from high-purity gas outlet 19, nitrogen
Gas is discharged from high pressure inverse put mouth 20, low pressure inverse put mouth 21, vacuum analysis mouth 22, and high-purity gas outlet 19 exports high-purity hydrogen, is
Mocvd equipment uses, and in high-pressure reverse venting, main component is nitrogen (containing a little hydrogen), the high-pressure reverse through variable-pressure adsorption equipment 5
Put after mouth 20 enters inverse put gas surge tank 6 and keep in, subsequently into the regeneration air inlet 16 of temp.-changing adsorption equipment 4, purge alternating temperature and inhale
The foreign gas adsorbed in applying equipment 4, foreign gas is blown out temp.-changing adsorption equipment, then discharges from regeneration gas outlet 17,
The regeneration gas outlet 17 of temp.-changing adsorption equipment 4, the low pressure inverse put mouth 21 of variable-pressure adsorption equipment 5 and vacuum analysis mouth 22, this 3 go out
QI KOU expellant gas converge rear ignition emptying.
In this device, the effect of heat exchanger 2 is to carry out heat exchange by the air inlet of dore furnace 1 between giving vent to anger, and utilizes and divides
Air inlet is preheated, to reduce the energy consumption of dore furnace 1 by the heat that solution stove 1 is given vent to anger；
The effect of the first water cooler 7 is to carry out being cooled to room temperature by giving vent to anger of dore furnace 1；
The effect of the second water cooler 8 is to carry out being cooled to room temperature by the impure hydrogen nitrogen mixed gas being compressed；
In the device for producing hydrogen of the present invention, variable-pressure adsorption equipment is one of key device of the present invention, its adsorption tower containing
Quantity at least 2, and the quantity of adsorption tower determines to reclaim quantity, organic efficiency and the hydrogen purity of hydrogen.If reclaimed
The quantity of hydrogen less and also less demanding to organic efficiency in the case of it is only necessary to two adsorption towers.Fig. 3 is 2 suctions
The structure chart of the variable-pressure adsorption equipment of attached tower.This equipment has a, b totally 2 adsorption towers, and each adsorption tower needs to join 5 valves (volume
Number be respectively 1-4,6).Wherein: No. 1 valve (a1, b1) is raw material air intake valve；No. 2 valves (a2, b2) are high pressure inverse put valve
Door；No. 3 valves (a3, b3) are low pressure inverse put valve；No. 4 valves (a4, b4) are vacuum analysis valve, by vacuum machine assembly air-exhausting
Connect vacuum analysis mouth afterwards；No. 6 valves (a6, b6) are high-purity outlet valve.This equipment has 5 QI KOU, is respectively as follows: raw material air inlet
Mouth, high-purity gas outlet, high pressure inverse put mouth, low pressure inverse put mouth, vacuum analysis mouth.Raw material air inlet is only had to be defeated in this 5 QI KOU
Entrance, other is delivery outlet.Unstrpped gas inputs from raw material air inlet, and the gas after purification is discharged from high-purity gas outlet.
Inverse put gas is discharged from high pressure inverse put mouth and low pressure inverse put mouth respectively, and wherein the high-pressure reverse venting buffered tank of body is used as change after collecting
Blowback air during warm adsorption plant regeneration.
If the quantity reclaiming hydrogen is little, less demanding to organic efficiency and not high to hydrogen purity requirement situation
Under, vacuum analysis function can be saved, Fig. 4 is another kind of structure of the variable-pressure adsorption equipment of 2 adsorption towers, wherein eliminate true
Empty parsing part, including eliminating vacuum pump set, 2 No. 4 valves (a4, b4) and vacuum analysis mouth.
If the quantity reclaiming hydrogen is larger and higher situation is required to organic efficiency it is necessary to increase adsorption tower.
Fig. 5 show the structure chart of the variable-pressure adsorption equipment comprising 6 adsorption towers.Compared with Fig. 3: increased 4 absorption in (i) Fig. 5
Tower (c tower, d tower, e tower, f tower) and corresponding valve；(ii) increased in Fig. 56 No. 5 valves (a5, b5, c5, d5, e5,
f5).This 6 No. 5 valves are to use for all gas between each adsorption tower, to improve the organic efficiency of hydrogen.In addition, in Fig. 5
The function of each part identical with Fig. 3 it is not necessary to repeat.If by the vacuum pump set in Fig. 5 and 6 vacuum analysis valves (a4, b4,
C4, d4, e4, f4) remove, reform into the structure shown in Fig. 6.This structure just cannot be carried out vacuum analysis, is suitable in hydrogen
Use in the case that purity requirement is not high.Structure shown in Fig. 5 and Fig. 6 can expand to the situation of more than 6 adsorption towers, as long as
Increase adsorption tower quantity and corresponding valve；Adsorption tower quantity can also be reduced until 3 adsorption tower situations, as long as reducing
Adsorption tower number and corresponding valve.
In device for producing hydrogen of the present invention, temp.-changing adsorption equipment is also one key device of the present invention.Fig. 7 show and comprises 2
The temp.-changing adsorption equipment structure chart of adsorption tower.It has two adsorption towers of x, y, and each adsorption tower has 4 valves, wherein: No. 1 valve
(x1, y1) is raw material air intake valve；No. 2 valves (x2, y2) are regeneration outlet valve；No. 3 valves (x3, y3) are raw material air outlet valve
Door；No. 4 valves (x4, y4) are regeneration air intake valve.This equipment has 4 QI KOU, be respectively as follows: raw material air inlet, raw material gas outlet,
Regeneration air inlet, regeneration gas outlet.This equipment has two adsorption towers of x, y, alternating sorbent and regeneration between two towers, i.e. x tower absorption
When y tower regeneration, or y tower absorption when x tower regeneration.So-called " absorption " is it is simply that setting the foreign gas absorption in unstrpped gas
In standby, unstrpped gas is made to purify；So-called " regeneration " is it is simply that produced by boasting the impurity being adsorbed in equipment with regeneration gas, under being
Primary sorption provides condition.When certain tower is in adsorbed state, from the input of raw material air inlet, the gas after purification is from former
Material gas outlet is discharged.When certain tower is in reproduced state, regeneration gas inputs from regeneration air inlet, then from regeneration gas outlet
Discharge.X tower and y cone pulley change absorption and regenerate.
The adsorption tower that temp.-changing adsorption equipment shown in Fig. 7 comprises can expand to more than 2, as long as increasing adsorption tower quantity
And corresponding valve.During the regeneration of temp.-changing adsorption equipment, can be thermal regeneration it is also possible to not thermal regeneration.And the side of heating
Formula can be electrical heating it is also possible to be heated with the waste heat of dore furnace gas outlet it is also possible to be entered with the waste heat of compressor outlet
Row heating.
Fig. 8 is 3 kinds of regeneration heating arrangements of temp.-changing adsorption equipment: external electric heating arrangement, built-in electric heating device
And the waste-heat structure using dore furnace gas outlet steam/or the steam with compressor outlet.External electric heating arrangement
It is exactly the external electric heater 31 increasing a barrel shape outside adsorption tower, the heat being produced with external electric heater 31
Measure to adsorption tower heating；Built-in electric heating device is exactly to install at least one electric heating tube in drier rod 32 inside adsorption tower, uses
The heat of electric heating tube in drier rod 32 generation heats to adsorption tower；Using dore furnace gas outlet steam/or with compressor outlet
The waste-heat structure of steam is to install at least one heat pipe 33 inside adsorption tower, with dore furnace gas outlet steam or compression
The steam of machine outlet heats to adsorption tower after passing through heat pipe 33；A heat exchanger can also be utilized, by dore furnace gas outlet heat
In gas (or steam of compressor outlet), heat exchange, to regeneration gas, then regeneration gas heating is being heated temp.-changing adsorption
Molecular sieve in equipment.This 3 kinds of heating arrangements are all possible, depending on condition at that time.
Contain a heat exchanger in the present embodiment, carry out heat exchange between the gas of turnover dore furnace, using decomposition
Air inlet is preheated by the heat that stove is given vent to anger, with reducing energy consumption.Heat exchanger needs preferable heat-exchange capacity, and this is to reduction
Hydrogen manufacturing cost has larger contribution.
The effect of the inverse put gas surge tank 6 in Fig. 1 is pressure and the flow buffering with stable high voltage inverse put gas.If to height
The stability requirement of the pressure pressure of inverse put gas and flow is not high, can save inverse put gas surge tank, now variable-pressure adsorption equipment
High pressure inverse put mouth is joined directly together with the regeneration air inlet of temp.-changing adsorption equipment.
In mocvd tail gas, main component is nitrogen, hydrogen, ammonia, in addition contains a small amount of water, oxygen, methane, silicon
The impurity such as alkane, these impurity contents are generally less than 1%.This covering device can do raw material using mocvd tail gas and manufacture high-purity hydrogen,
Manufactured high-purity hydrogen uses for mocvd equipment.Its operation principle is as follows: referring to Fig. 1, the operating temperature of dore furnace is
500 DEG C -1000 DEG C, by mocvd tail gas after dore furnace, the ammonia in tail gas is just decomposed into hydrogen and nitrogen, therefore
Main component in gas after decomposing is hydrogen and nitrogen.Through calculating, the now ratio of hydrogen and nitrogen substantially 42:
58, the in addition foreign gas less than 1% also containing total amount.Gas after decomposing is used hydrogen gas compressor after first time water-cooled
Pressurization, is pressurized to the gases at high pressure of 5bar-30bar, then enters temp.-changing adsorption equipment after second water-cooled.Temp.-changing adsorption equipment
The foreign gases such as the residual ammonia gas and water vapour in gases at high pressure, methane are removed, obtains high-purity hydrogen nitrogen mixed gas.Then again will
High pure hydrogen nitrogen mixed gas pass through variable-pressure adsorption equipment, hydrogen is concentrated purification, obtains the hydrogen (nitrogen at concentrations up to more than 99%
Content is less than 1%), pure hydrogen is discharged from high-purity gas outlet.The high-pressure reverse venting body that variable-pressure adsorption equipment is discharged, delays through inverse put gas
Rush the regeneration air inlet that tank is followed by temp.-changing adsorption equipment, blowback air is provided when regenerating for temp.-changing adsorption equipment.Temp.-changing adsorption equipment
Regeneration gas outlet, the low pressure inverse put mouth of variable-pressure adsorption equipment, vacuum analysis mouth, after this 3 gas outlet expellant gas converge
Ignition emptying or directly emptying.
Embodiment 2
In conjunction with Fig. 2, Fig. 3, Fig. 4, Fig. 5, Fig. 6, Fig. 7, Fig. 8.Compared to Figure 1, hydrogen gas compressor 3 and temp.-changing adsorption set Fig. 2
Standby 4 order is exchanged.Referring to Fig. 2, in the present embodiment, mocvd tail gas is after over-heat-exchanger 2 from the air inlet of dore furnace 1
Mouth 10 entrance dore furnaces 1, become impure hydrogen nitrogen mixed gas after decomposing, discharge from the gas outlet 11 of dore furnace, Ran Houyi
Secondary enter temp.-changing adsorption equipment 4 from the raw material air inlet 14 of temp.-changing adsorption equipment 4 through over-heat-exchanger 2 with the first water cooler 7,
Now, enter temp.-changing adsorption equipment 4 is the hydrogen nitrogen mixed gas containing impurity, in temp.-changing adsorption equipment 4, hydrogen nitrogen mixed gas
Impurity is removed, and the hydrogen nitrogen mixed gas after remove impurity are discharged from temp.-changing adsorption equipment 4 raw material gas outlet 15, then by hydrogen gas compressor
3 air inlet 12 enters hydrogen gas compressor 3, and in hydrogen gas compressor, the hydrogen nitrogen mixed gas removing impurity are pressurized to 5bar-
30bar, the hydrogen nitrogen mixed gas after pressurization are discharged from the gas outlet 13 of hydrogen gas compressor 3, then by transformation after the second water cooler 8
The raw material air inlet 18 of adsorption plant 5 enters variable-pressure adsorption equipment 5, the hydrogen in variable-pressure adsorption equipment 5, in hydrogen nitrogen mixed gas
Separated with nitrogen, high-purity gas outlet 19 through variable-pressure adsorption equipment 5 for the hydrogen exports, the high-purity hydrogen of output is mocvd equipment
Use, nitrogen is discharged from the high pressure inverse put mouth 20 of variable-pressure adsorption equipment 5, low pressure inverse put mouth 21, vacuum analysis mouth 22, pressure-variable adsorption
High-pressure reverse venting body that the high pressure inverse put mouth 20 of equipment 5 is released (mainly nitrogen but have a little hydrogen) is through inverse put gas surge tank
Temp.-changing adsorption equipment 4, the regeneration gas outlet of temp.-changing adsorption equipment 4 is entered from the regeneration air inlet 16 of temp.-changing adsorption equipment 4 after 6
17th, the low pressure inverse put mouth 21 of variable-pressure adsorption equipment 5, vacuum analysis mouth 22, igniting after this 3 gas outlet expellant gas converge is fired
Burn emptying or directly empty.
In the present embodiment, except the order of hydrogen gas compressor 3 and temp.-changing adsorption equipment 4 is different from embodiment 1, Qi Tadou
Same as Example 1, the 26S Proteasome Structure and Function of each part all also same as Example 1 it is not necessary to repeat.
In the present embodiment, temp.-changing adsorption equipment is before hydrogen gas compressor, and gas enters before hydrogen gas compressor
Through there is no the ammonia of remnants.The present embodiment is expected to reduce the corrosivity requirement to ammonia for the hydrogen gas compressor, but temp.-changing adsorption
Equipment works under relatively low pressure (～1bar), under so low pressure, the absorption property of temp.-changing adsorption equipment is proposed more
High requirement.
Embodiment 3
Fig. 9 is the main structure chart of embodiments of the invention 3.Compared to Figure 1, two dore furnaces are contained in Fig. 9, respectively
First dore furnace 1 and the second dore furnace 1 ', two hydrogen gas compressors, are the first hydrogen gas compressor 3 and the compression of the second hydrogen respectively
Machine 3 ' and corresponding first heat exchanger 2 and second heat exchanger 2 ', water cooler etc..Two decomposition in the present embodiment
Stove connects side by side common decomposed tail gas, and every dore furnace undertakes the ammonia decomposition amount in a part of tail gas, in addition two hydrogen
Compressor connects common compression hydrogen side by side, and every hydrogen gas compressor undertakes the decrement of a part of hydrogen.
In the present embodiment, except the quantity of hydrogen gas compressor and dore furnace is different from embodiment 1, other all with embodiment
1 is identical, the 26S Proteasome Structure and Function of each part all also same as Example 1 it is not necessary to repeat.
In the present embodiment, the quantity of dore furnace and hydrogen gas compressor can arbitrarily increase.The present embodiment is suitable for tail gas gas
Measure very big situation.
The device for producing hydrogen of the present invention is highly suitable for gan-led manufacturer and uses.Produce the mistake of gan-led in mocvd
Cheng Zhong, one side mocvd equipment needs substantial amounts of high-purity hydrogen raw material, and another aspect mocvd can be discharged a large amount of tail gas again and (is mixed with
Hydrogen, nitrogen, ammonia and some foreign gases).By above example scheme, both can solve mocvd exhaust emissions and cause
Problem of environmental pollution, can provide raw hydrogen for mocvd equipment again, and obtained hydrogen cost is less than conventional electrolysis water
The cost of hydrogen manufacturing.As the summation in view of conventional mocvd vent gas treatment cost and electrolysis water cost, the hydrogen being manufactured with this device
Cost lower, 1/3rd of only conventional mocvd vent gas treatment cost and electrolysis water cost, can ensure that led factory completely
The hydrogen supply of family, is not required to outsourcing hydrogen, comprehensive benefit is considerable.In addition, variable-pressure adsorption equipment inverse put gas is discharged
Gas, hydrogen content can reach 20% about, can provide for factory living area with ignition or with this gas burning boiler
Domestic hot-water.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not right
The restriction of embodiments of the present invention, for those of ordinary skill in the field, also may be used on the basis of the above description
To make other changes in different forms, all of embodiment cannot be exhaustive here, every belong to this
Obvious change that bright technical scheme is extended out or change the row still in protection scope of the present invention.
Claims (9)
1. one apply mechanically mocvd tail gas hydrogen manufacturing device it is characterised in that: described device for producing hydrogen comprises:
For hydrogeneous tail gas being decomposed into the dore furnace (1) of hydrogen nitrogen mixed gas,
For removing impurity in hydrogen nitrogen mixed gas, simultaneously the temp.-changing adsorption equipment (4) containing regenerable sorbent,
For the hydrogen in the hydrogen nitrogen mixed gas after remove impurity is concentrated the change that purification produces high-pressure reverse venting, low pressure inverse put gas simultaneously
Pressure adsorption plant (5), and
For the hydrogen gas compressor (3) that the hydrogen nitrogen mixed gas of non-remove impurity or remove impurity are pressurizeed；
Described dore furnace (1), temp.-changing adsorption equipment (4) and variable-pressure adsorption equipment (5) are sequentially connected；
Described hydrogen gas compressor (3) between dore furnace (1) and temp.-changing adsorption equipment (4) or
Between temp.-changing adsorption equipment (4) and variable-pressure adsorption equipment (5).
2. device according to claim 1 it is characterised in that: described device for producing hydrogen also comprises:
For the heat exchanger (2) of heat exchange will be carried out between hydrogeneous tail gas and hydrogen nitrogen mixed gas,
For the first water cooler (7) being cooled down the hydrogen nitrogen mixed gas through heat exchange,
For the second water cooler (8) being cooled down the hydrogen nitrogen mixed gas of non-remove impurity or remove impurity, and
Flow and pressure for high-pressure reverse is exitted enter row buffering and stable inverse put gas surge tank (6).
3. device according to claim 2 it is characterised in that: described dore furnace (1) at least 1, described dore furnace
Mode of heating is electrical heating, and heating temperature range is 600 DEG C -900 DEG C.
4. device according to claim 2 it is characterised in that: described hydrogen gas compressor (3) is provided with for being passed through non-remove impurity
Or the air inlet of remove impurity hydrogen nitrogen mixed gas and the gas outlet for exporting non-remove impurity or remove impurity hydrogen nitrogen mixed gas.
5. device according to claim 4 it is characterised in that: the series of described hydrogen gas compressor (3) be 1-3 level；Described
The quantity of hydrogen gas compressor at least one.
6. device according to claim 2 it is characterised in that: described temp.-changing adsorption equipment (4) is provided with
For being passed through the raw material gas inlet of the hydrogen nitrogen mixed gas of non-remove impurity,
Unstripped gas for exporting the hydrogen nitrogen mixed gas after remove impurity exports,
For being passed through the regeneration air inlet of the regeneration gas making adsorbent reactivation,
Make the regeneration gas outlet of the regeneration gas of adsorbent reactivation for output；
The regeneration gas outlet expellant gas ignition emptying of described temp.-changing adsorption equipment (4) or directly emptying.
7. device according to claim 6 it is characterised in that: described temp.-changing adsorption equipment (4) comprises at least two absorption
Tower；Described temp.-changing adsorption equipment (4) can be heated or not heated；The mode of heating of described temp.-changing adsorption equipment (4) is electrical heating, or
Heated with dore furnace (1) waste heat, or heated with the waste heat of hydrogen gas compressor (3).
8. device according to claim 2 it is characterised in that: described variable-pressure adsorption equipment (5) is provided with
For being passed through the raw material gas inlet of the hydrogen nitrogen mixed gas after remove impurity,
Concentrate the high-purity gas outlet of the high-purity hydrogen after purification for output,
It is deflated to the high-pressure reverse bleeder holes of inverse put gas surge tank for exporting high-pressure reverse,
With low pressure against bleeder holes.
9. device according to claim 8 it is characterised in that: described variable-pressure adsorption equipment (5) also include vacuum analysis dress
Put, and be provided with vacuum analysis mouth；The low pressure inverse put mouth of described variable-pressure adsorption equipment (5) and the igniting of vacuum analysis mouth expellant gas
Burning emptying or directly emptying.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510337511.7A CN104944370B (en) | 2015-06-17 | 2015-06-17 | Device for producing hydrogen from tail gas produced by MOCVD (metal-organic chemical vapor deposition) |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510337511.7A CN104944370B (en) | 2015-06-17 | 2015-06-17 | Device for producing hydrogen from tail gas produced by MOCVD (metal-organic chemical vapor deposition) |
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| CN108100994A (en) * | 2018-02-02 | 2018-06-01 | 吴海雷 | A kind of hydrogen recycling purification system and its control method |
| CN109092010B (en) * | 2018-05-29 | 2021-01-15 | 浙江天采云集科技股份有限公司 | Method for recycling waste gas in LED-MOCVD process through full-temperature-range pressure swing adsorption hydrogen extraction |
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| CN103846001A (en) * | 2014-02-24 | 2014-06-11 | 苏州新纳晶光电有限公司 | MOCVD (Metal Organic Chemical Vapor Deposition) tail gas treatment system and method |
| CN204752196U (en) * | 2015-06-17 | 2015-11-11 | 湖南高安新材料有限公司 | A device of applying mechanically hydrogen manufacturing of MOCVD tail gas |
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