CN106145037A - The device of hydrogen and the method for High Purity Hydrogen processed is reclaimed from silicon epitaxial furnace emptying end gas - Google Patents
The device of hydrogen and the method for High Purity Hydrogen processed is reclaimed from silicon epitaxial furnace emptying end gas Download PDFInfo
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Abstract
The invention provides a kind of device of hydrogen and method of High Purity Hydrogen processed of reclaiming from silicon epitaxial furnace emptying end gas, the technology path of employing once washing, chemisorbed degree of depth dechlorination, hydrogen gas compressor supercharging, PSA gas separation system, catalytic deoxidation, water cooling, terminal purifying, backflow hydrogen control front-end pipelines pressure, regeneration gas return front end purification recovery and explosion precaution.Trace impurity remaining in hydrogen is removed to less than 99.99999% and obtains high-purity hydrogen；Product hydrogen purity obtained by the method can make reaches 99.9%～99.99999%, and the rate of recovery may be up to 95%.Chlorine in residual impurities, oxygen, silane etc. can distinguish as little as 1 × 10-8, and can be according to the purity requirement flexible modulation of product.The method is particularly well-suited in the emptying waste gas from silicon epitaxy production process separate and reclaims hydrogen, has very good economic benefit, environmental benefit.
Description
Technical field
The invention belongs to production and the application of electron trade silicon epitaxial wafer, be specifically related to one
The method that hydrogen prepares High Purity Hydrogen is reclaimed from electron trade silicon epitaxial furnace emptying end gas.
Background technology
Hydrogen is chemical raw material and novel clean energy resource, in the system of growth and the substrate of crystal
Standby, oxidation technology, epitaxy technique and chemical vapour deposition technique are intended to use hydrogen.High
In pure hydrogen, the volume ratio content of hydrogen is more than 99.9999%, and oxygen content is less than 1 × 10-6, one
Carbonoxide and carbon dioxide are containing again smaller than 1 × 10-6.High Purity Hydrogen is one of industrial gasses weights
Want kind, be widely used in chemical industry, petrochemical industry, oil, the energy, electronics, metallurgy, food,
The numerous areas such as machinery, Aero-Space, nuclear industry.In recent years, with Survey of Industrial Gases in Worldwide
Increasing rapidly of market, the demand of High Purity Hydrogen is also always in rising situation.In the electronics industry,
High Purity Hydrogen is as preparation SiH4/H2、PH3/H2、B2H6/H2Spirit in mixing and doping gas.Half
In conductor manufacture process high to spirit purity requirement, trace impurity mixes spirit will change half
Conductive surface characteristic, especially during electrovacuum material and device production, to hydrogen purity
Require very high.If tungsten, molybdenum are all the important materials of electrovacuum equipment, can be by oxide through hydrogen
Reduction obtains powder, is reprocessed into wire rod.Hydrogen purity is higher, and reducing degree is higher, institute
The granularity of tungsten powder is thinner, the metal device such as the anode of electron tube, negative electrode and grid,
Being required for through special annealing in hydrogen atmosphere process, the purity requirement to hydrogen is also very high.
The manufacture of extensive and super large-scale integration, and hydrogen brake pipe, ionic tube, laser
The filling of the various gas-filled electron tube such as pipe, is required for the very high hydrogen of purity.Electron trade is current
It is the maximum user of High Purity Hydrogen, only as a example by producing large scale integrated circuit, domestic annual production
1000000000 pieces of integrated circuits, about need to consume High Purity Hydrogen 10Mm3Left and right.
At present, China's silicon epitaxy enterprise is all energy consumption rich and influential family, and their hydrogen source is all based on water
Electrolysis, owing to water electrolysis hydrogen producing needs to consume substantial amounts of electric energy, and the electricity price of China is for enterprise
For heavy load, add country to the requirement of enterprise energy consumption and domestic energy-saving and emission-reduction overall situation,
All accelerate the development of energy-conserving and emission-cutting technology.The circulation of tail gas recycling reclaiming is alternatively enterprise's joint
Saving product cost, reducing enterprise energy consumption, these development being electronic enterprise provide stable
Development space.
Current silicon epitaxy enterprise produces contains hydrogen dense in a large number in the tail gas discharging, and one
In the case of as, H2＞ 95%, N2: 3%-5%, remaining for hydrogen chloride, hydrogen sulfide, phosphine and
Oxygen, carbon dioxide and water etc., but owing to not purifying recycling device, can only be discharged into
In air, slatterning in vain.
Owing to the production process of silicon epitaxy is complicated, main production parts epitaxial furnace therein is to gas
The condition such as pressure, purity requires very high, and particularly hydrogen purity to reach more than 99.99999%,
Current enterprise, after buying High Purity Hydrogen, to be typically further purified.This requires that recovery system needs
Reliable, stable with it with the use of tail gas is not only simply carried by recovering and purifying system
Pure, in control epitaxial furnace that also will be stable pressure, this allows at present both at home and abroad to the sector
Tail gas recycle utilize all not good solutions.And to the method for purification of High Purity Hydrogen according to former
The difference in material source has multiple method, and mainly having of wherein commonly using is following several.
1) low-temperature adsorption:
Condensation-low-temperature adsorption, purifies point 2 steps and carries out, and first, uses condensation at low temperature to enter
Row pretreatment.Need to carry out at different temperatures 2 times or multiple condensation separates, remove water impurity
With carbon dioxide etc..Recycling low-temperature adsorption refine, pre-cooled after hydrogen enter people's adsorption tower,
At liquid nitrogen vaporization temperature (-196 DEG C), remove minor amount of water, molecular sieve with activated alumina
Adsorbing deoxygenation, molecular sieve is denitrogenated, and silica gel removes carbon monoxide, ammonia, argon, and activated carbon removes first
Alkane etc..Adsorbent heating hydrogen regeneration, technique 2 adsorption tower blocked operations of many employings,
After purification, hydrogen volume fraction is up to 99.999%-99.9999%.
Low temperature absorption-absorption method, purifying also needs point 2 steps to carry out, first according to miscellaneous in feed hydrogen
The species of matter, selects suitable absorbent, such as methane, propane, ethene, propylene etc.,
Cyclic absorption and impurity in desorption hydrogen under low temperature.An oxygen is for example absorbed at low temperatures with liquid methane
Changing the impurity such as carbon, then absorbing, with propane, the methane wherein remaining, available volume fraction is
The hydrogen of 99.99%.Then again through low-temperature adsorption, wherein trace impurity is removed with adsorbent,
Obtain the High Purity Hydrogen that volume fraction is 99.999%%-99.9999%.
This is also the terminal purifying method that current most domestic silicon epitaxy enterprise uses, and it uses
Technology and equipment mostly from the big gas companies of external several families as than Europe, method liquid air, woods
Moral, Mei Saier etc. introduce.
2) pressure swing adsorption method (PSA):
Pressure-variable adsorption is difference and the absorption utilizing gas component characterization of adsorption on the sorbent
Measure pressure-dependent principle, realized the separation of gas by periodic pressure change procedure.
It is low that technology has energy consumption, and product purity is high, and technological process is relatively easy, and pre-processing requirements is low,
Convenient and reliable operation, automaticity advantages of higher, extensively made at gas separation field
With.
PSA method hydrogen manufacturing, can use various hydrogeneous sources of the gas to be raw material, according to feed hydrogen and process route
Difference, a preprocessed step can not obtain High Purity Hydrogen, or again through inhaling after simple pretreatment
Attached tower refines, and after purification, small product size fraction can be adjusted in the range of 99.0% 99.999% flexibly
Joint.The major defect of PSA technology is that gas purity is relatively low, the rate of recovery is relatively low in purification, about 86%
Left and right.
3) metal getter method:
With electrolysis hydrogen as raw material, drying is dehydrated, preliminary clearning to 99.995% purity, enters storage
In hydrogen alloy cylinder, utilizing hydrogen-storage alloy to inhale hydrogen at low temperatures, high temperature transfers the characteristic of hydrogen, can make
Take ultra-pure hydrogen.Hydrogen generally need to first pre-process before entering people's hydrogen alloy purifier, typically adopts
It is dried with palladium catalyst deoxidation and molecular sieve adsorption to remove major part oxygen, an oxygen in feed hydrogen
Change the impurity such as carbon, water.Purification devices is generally by more than 2 purifier joint operations, with even
Continuing and obtaining High Purity Hydrogen, volume fraction can reach more than 99.99999%.
4) palladium barrier diffusion method
Utilize palladium alloy membrane at uniform temperature (400-550 DEG C), hydrogen can only be made to pass through, and other
The impermeable characteristic of foreign gas, makes hydrogen be purified.Because oxygen can produce at palladium alloy membrane
Raw hydrogen-oxygen catalytic reaction causes palldium alloy hot-spot, and water can make palladium synthesis that oxidation poisoning occurs,
Therefore require low to oxygen in unstripped gas and water content, and purifier deoxygenation and water, then warp need to be first passed through
After filter dedusting, could send into palldium alloy diffuser casing and purify, available volume fraction is
The High Purity Hydrogen of 99.9999%.But this method is owing to requiring higher and subsequent maintenance cost very to unstripped gas
Height is progressively eliminated at present.
Above several method is only limited to the hydrogen more than purer (purity is more than 99.9%)
Purifying, and silicon epitaxy exhaust gas composition being complex, hydrogen purity is relatively low, and to need right simultaneously
Reclaiming gas and carrying out accurate Stress control, this requires that any of the above method all can not meet
Require.Such as: low-temperature adsorption consumes liquid nitrogen, and range is limited.Pretreatment of raw material is wanted
Asking high, production process energy consumption is high, and investment is big.Metal getter method purification effect is good but this work
Skill is consumption-type material, non-renewable, needs periodic replacement, requires that tail gas enters people's hydrogen alloy simultaneously
Generally need to first pre-process before purifier, general employing palladium catalyst deoxidation and molecular sieve are inhaled
Attached drying is to remove the impurity such as major part oxygen, carbon monoxide, water in feed hydrogen.In pretreatment
In deoxidation process, it is critical only that the removing degree of depth of chlorine, if entered in catalytic deoxidation reactor
Chlorinity in hydrogen more than 1ppm, then quickly can make catalyzing deoxidation agent poisoning (irreversible,
Actually active component is changed into chloride, thus lose deoxy activity).
For the deficiency of above-mentioned High Purity Hydrogen processing condition and method, former in conjunction with silicon epitaxy industrial tail gas
Material feature, develops a kind of new recovery hydrogen from silicon epitaxy industry emptying end gas and prepares high-purity
The method of hydrogen, has actively to the technical bottleneck breaking through the exploitation of silicon epitaxy industrial tail gas undoubtedly
Social effect and commercial value.
Content of the invention
It is an object of the invention to for silicon epitaxy industrial tail gas feature, in order to overcome prior art
Above-mentioned deficiency, provides a kind of new recovery hydrogen preparation height from silicon epitaxy industry emptying end gas
The method of pure hydrogen.
Concrete technical scheme is as follows:
A kind of method that recovery hydrogen prepares High Purity Hydrogen from silicon epitaxy industry emptying end gas, it is special
Levy and be: content according to the oxygen mainly containing in silicon epitaxy emptying end gas and hydrogen and
Index request in GB/T7445-1995 " pure hydrogen, High Purity Hydrogen and ultra-pure hydrogen ", the present invention adopts
With once washing, chemisorbed degree of depth dechlorination, hydrogen gas compressor supercharging, PSA gas segregative line
System, catalytic deoxidation, water cooling, terminal purifying, backflow hydrogen control front-end pipelines pressure, again
The angry technology path returning front end purification recovery and explosion precaution.
Silicon epitaxy hydrogen cleaning recovery system includes following components:
1) cleaning system: include water scrubber and essence dechlorinator, dedusting except water tower, hydrogen compression
Machine, water knockout drum, PSA separator, catalytic deoxidation device, water cooler and water knockout drum and drying
Adsorption tower, regeneration gas separator and terminal adsorption tower etc. form.
2) automatic control system: include centralized control unit, online oxygen analyzer, automatic gas
Dynamic regulation valve and correlate meter.
3) pressure stabilization control system: include PLC control unit, flowmeter, pressure sensing
Device, electric control valve and correlate meter.
Technological process is:
Raw material tail gas, first through water scrubber, removes wherein most hydrogen chloride, silane, phosphine,
Entering front buffer tank afterwards, front buffer tank can buffer the pressure wave that before and after's operation is brought
Dynamic, cause the device to more stable operation.Gas after buffered tank enter essence dechlorinator (2,
Alternately operating), make the chlorinity in hydrogen drop to below 0.1ppm, the working time of dechlorinator
100-300 days (depending on chlorine content), dechlorination effect is detected by chlorine analyzers timing sampling.
After dechlorinator was lost efficacy, drawing off the antichlor of inefficacy, changing new antichlor can use.Pass through
The gas of dechlorination tank enters preprocessor, and the solid particle in tail gas, aqueous water etc. are carried out
Prime removes, in order to avoid subsequent pipeline valve, compressor are impacted, and two preprocessors
One is working, and one standby in regeneration, and regeneration gas nitrogen, regeneration tail gas is discharged into emptying
House steward；Enter subsequently into removing silane, germane, phosphine, solid particle, the hydrogen of aqueous water
Enter piston type oilless (oil free) compressor supercharging, make gas pressure be raised to 1.0Mpa 1.3Mpa, with dimension
Hold the power required for process gas, and make subsequent handling preferably to run.Simultaneously in order to protect
Holding stablizing of pressure in epitaxial furnace prevents the pressure front buffer tank to be pumped into negative pressure and produce peace
Full hidden danger and damage epitaxial furnace, compressor outlet sets up regulation backflow bypass, automatic by PLC
Control and compressor variable frequency technology ensure the pressure stability of prime operation；Hydrogen after compression passes through
After moisture trap, enter into rearmounted air accumulator, the pressure sensor control compressor of air accumulator
Outlet regulating valve, when pressure is less than 1.0Mpa (can set), increases control valve opening, when
Pressure, more than (but can set the highest less than 1.3Mpa) during 1.3Mpa, reduces regulation valve
Aperture is until closing.Gas after supercharging enters in PSA separation circuit, and the degree of depth deviates from hydrogen
In a large amount of water, nitrogen, the impurity such as silane, make the content of nitrogen in gas drop to below 10ppm,
Dew point reaches less than-50 DEG C.
Enter catalytic deoxidation device through PSA purified gas, in the entrance peace of catalyzing deoxidation agent
Dress water seal explosion-proof apparatus, to prevent the destruction that prime is caused equipment by explosion time, de-in catalysis
Oxygen and hydrogen catalysis are generated water by oxygen column, react as follows:
1/2O2+H2→H2O+Q(129C)
Substantial amounts of heat is released in reaction simultaneously, and exporting hydrogen is water cooled but to be arrived after normal temperature, warp
Undue water sends into adsorption dry tower, micro amount of oxygen remaining in deep removal gas, water, titanium dioxide
The impurity such as carbon.Finally enter back into terminal adsorption tower, completely remove remaining in gas outside dehydrogenation
Impurity, the removing degree of depth is 10ppb.
Ultra-pure hydrogen is incorporated to epitaxial furnace front end Hydrogen Line after hydrogen pressure regulator valve, recycles.
In the present invention, raw material tail gas, first through water scrubber, removes major part hydrogen chloride, silane, phosphorus
The impurity such as alkane, subsequently into essence dechlorinator (2, alternately operating), make the chlorine in hydrogen contain
Amount drops to below 0.1ppm, to reach to remove the purpose of chlorine.Essence dechlorinator (draw ratio:
3～8:1) filling QT-C1 high performance dechloridizing agent (main component: ZnO/Al2O3/ CaO/ activated carbon/
Adding accelerator, Dalian Zhong Ding Chemical Co., Ltd. self-control mass ratio is the 20%th, the 40%th, the 15%th,
20%th, 5%) it, is provided with 2 essence dechlorinators, alternately operating.The working time 100-300 of tower
My god (depending on chlorine content), dechlorination effect is detected by chlorine analyzers timing sampling.
In the present invention, the catalyzing deoxidation agent of filling in described deoxidation tower uses noble metal catalyst.
As described noble metal catalyst, generally use platinum group catalyst, it is possible to use conventional catalyst
Prepared by preparation method, for example, support on carrier by methods such as dipping, sprayings by active component,
Make through roasting.Also the patent catalyzing deoxidation agent of ancient cooking vessel chemical technology in Dalian can be used
(active constituent is palladium to CTC-1 type noble metal catalyst, and carrier is aluminum oxide, and active constituent accounts for
The 0.2%～0.5% of vehicle weight).
When using noble metal catalyst, the oxygen in tail gas hydrogen and hydrogen are at noble metal catalyst
Effect under water generation reaction and heat, it is not necessary to consume additional energy.
Reaction temperature is not particularly limited, in the range of caning be controlled in 50～350 DEG C.But from
Save energy consumption and the angle of reduction high temperature secondary reaction is set out, preferably reaction temperature is controlled
In the range of 50～150 DEG C.
The mode preparing high-purity hydrogen combined by the present invention further preferably adsorption dry and terminal adsorption tower:
The water that catalytic deoxidation process produces, after water cooled point of water, enters terminal dehydrating tower adsorption dewatering.
Described adsorption dry tower (draw ratio: 3-10:1), interior filling molecular sieve (commercially available 3A, 4A,
5A), it is provided with 2 dehydrating towers of A/B, alternately operating.The regeneration of molecular sieve uses electricity to add
Heat, regeneration temperature 200-350 DEG C.
Terminal adsorption tower draw ratio: 3-10:1, the proprietary getter of ancient cooking vessel (XM-1) in interior filling Dalian,
Reaction temperature controls in the range of 400～550 DEG C, and in using, mode of heating is by O in gas2、
H2O、CO、CO 2、N2、CH4, the impurity such as TCH be purified to ppb level.
Regeneration gas reclaiming clean mode that the present invention is preferred: adsorbent equipment in PSA separation circuit
The regeneration gas of regeneration gas and adsorption dry tower uses the hydrogen after purifying, and regeneration tail gas returns by the road
Return deduster entrance, Recovery Purifying, improve the rate of recovery.
Product hydrogen purity obtained by the method can make reaches 99.999%～99.99999%,
The rate of recovery may be up to 95%.
The present invention further preferably reflux Hydrogen Vapor Pressure control mode: take the hydrogen after part is pressurizeed
Gas loops back with the pressure in stable epitaxial furnace, thus ensures epitaxial furnace safe operation.
The further preferably following explosion precaution of the present invention: at entrance and the catalytic deoxidation tower of hydrogen gas compressor
Entrance install water seal explosion-proof apparatus, to prevent the destruction that prime is caused equipment by explosion time；
The control system of equipment is equipped with anti-explosion electric regulation valve and temperature controller, can realize to return hydrogen
The Automatic Control of throughput, and there is operation, malfunction coefficient and overtemperature alarm function, entirely
Systemic-function is advanced, dependable performance；The oxygen content entered before deoxidation tower in hydrogen and product hydrogen by
Online oxygen analyzer device is analyzed continuously, and has excess warning function, ensuring equipment safe operation.
As concrete mode, carry out with the situation less than 100ppm for the chlorinity in tail gas hydrogen
Illustrate, for example, can be following manner:
Extension tail gas, after washing, is directly entered essence dechlorinator's dechlorination.
As concrete mode, carry out with the situation less than 0.5% for the oxygen content in tail gas hydrogen
Illustrate, for example, can be following manner:
Enter into the entrance of PSA separator after hydrogen gas compressor pressurization, separate further
Purify, pass through reflux line at compressor outlet simultaneously, accurately calculate through PLC unit, adjust
Whole recycle ratio (the entrance tolerance of entrance tolerance/return) makes the pressure of front end extension tail gas reach
Satisfaction (generally about 150mbar).
Brief description:
Fig. 1 is the technological process of the device reclaiming hydrogen in silicon epitaxial furnace emptying end gas；
In Fig. 1: 0 is water scrubber, and 1 is front buffer tank, and 2 is the first antiriot device, 3A/B
For essence chlorine purifier, 4A/B is deduster, and 5 is hydrogen gas compressor, and 6 is moisture trap, 7
For back buffer tank, 8 is PSA separator, and 9 is catalytic deoxidation tower, and 10 is water cooling
Device, 11A/B is adsorption dry tower, and 12A/B is water cooler, and 13 is terminal adsorption tower, 14
For terminal heat exchanger, 15 is terminal water cooler, and 16 is outlet filter, and 17 is regeneration gas
Water cooler, 18 is regeneration gas separator, and 19 is high-order evacuation port 201-20n extension tail
Gas entrance, 21 is displacement nitrogen inlet, and 22 is cooling water inlet, and 23 is coolant outlet,
24 is low level leakage fluid dram, and 25 is purified hydrogen outlet, and 26 is regeneration gas outlet, and 27 is second
Antiriot device, 28 is backflow hydrogen pipeline, and 29 is regeneration gas return pipeline.
Detailed description of the invention
Further describe the present invention below in conjunction with embodiment, but the scope of the present invention is not by embodiment
Impact.
Embodiment 1
(1) epitaxial furnace tail gas
Extension tail gas tolerance: 200m3/ h temperature: 25 DEG C of pressure: 0.15 atmospheric pressure
Mainly comprise: H297.5%th, O22%th, Cl2>=100ppm, remaining is a small amount of dioxy
Change carbon, silane, phosphine etc..
(2) antichlor
Filling QT-C1 high performance dechloridizing agent (main component: ZnO/Al2O3/ CaO/ activated carbon/add
Adding accelerator, Dalian Zhong Ding Chemical Co., Ltd. self-control mass ratio is the 20%th, the 40%th, the 15%th,
20%th, 5%), air speed: 1000h is used-1Filling total amount: 0.2m3
Essence dechlorinator's ratio of height to diameter: 5
(3) catalyst
Catalytic deoxidation CTC-1 type noble metal catalyst (active component is palladium, and carrier is aluminum oxide,
Active component accounts for the 0.2%～0.5% of carrier component weight)
Noble metal catalyst uses air speed: 5000h-1
Your Catalyst packing total amount: 0.04m3
Catalytic deoxidation tower ratio of height to diameter: 5
(4) step
By extension tail gas hydrogen (200m3/ h) (wherein chlorinity >=200ppm, oxygen content 2%)
It is passed through water scrubber, remove major part hydrogen chloride, control chlorinity≤80ppm.Then preposition slow
Rush tank and through essence chlorine purifier the hydrogen chloride of participation is removed to below 0.1ppm, dechlorination effect by
Chlorine analyzers timing sampling detects.Through hydrogen gas compressor, atmospheric hydrogen is pressurized to again
1.0Mpa～1.3Mpa, to provide the pressure of subsequent purification.Gas after supercharging enters PSA and divides
From purifier, the entrance at hydrogen gas compressor and PSA device installs water seal explosion-proof apparatus, with
Prevent explosion time and cause the destruction of equipment to prime.Entrance catalytic deoxidation tower, degree of depth deoxidation,
Catalytic deoxidation tower outlet oxygen content be less than 0.1%, reaction temperature rising about about 70 DEG C, cooled device
After being cooled to 30 DEG C and removing condensed water, the tail gas hydrogen after part deoxidation is returned to hydrogen pressure
Contracting machine entrance, recycle ratio (entrance tolerance/return tolerance) is 2:1, now deoxidation tower outlet
Oxygen content in gas can be gradually lowered, until the oxygen in extension tail gas hydrogen is taken off to being less than
0.1%.
Finally enter back into adsorption tower dry decontamination device and product hydrogen that terminal adsorbent equipment obtains
Gas purity reaches 99.999%～99.99999%, and the rate of recovery may be up to 95%.
High-purity hydrogen after purification uses before being recycled to epitaxial furnace through hydrogen pipeline.
Embodiment 2
(1) epitaxial furnace tail gas
Tail gas tolerance: 100m3/ h temperature: 25 DEG C of pressure: 0.13 atmospheric pressure
Mainly comprise: H299%th, O20.5%th, Cl2≤ 100ppm, remaining is a small amount of dioxy
Change carbon, silane, phosphine etc..
(2) antichlor
Filling QT-C1 high performance dechloridizing agent (main component: ZnO/Al2O3/ CaO/ activated carbon/add
Adding accelerator, Dalian Zhong Ding Chemical Co., Ltd. self-control mass ratio is the 20%th, the 40%th, the 15%th,
20%th, 5%), air speed: 2000h is used-1Filling total amount: 0.1m3
Essence dechlorinator's ratio of height to diameter: 7
(3) catalyst (ibid embodiment 1) noble metal catalyst uses air speed: 5000h-1
Your Catalyst packing total amount: 0.02m3
Catalytic deoxidation tower ratio of height to diameter: 6
(4) step
By extension tail gas hydrogen (100m3/ h) (wherein chlorinity≤100ppm, oxygen content 0.5%)
It is passed directly into essence dechlorinator (2, alternately operating), make the chlorinity in hydrogen drop to 0.1ppm
Hereinafter, dechlorination effect is detected by chlorine analyzers timing sampling.Remove by front buffer tank and dedusting
Entering hydrogen gas compressor after hydrophone, the gas pressure after supercharging is 1.0Mpa～1.3Mpa, at hydrogen
Air compressor and PSA separator entrance install water seal explosion-proof apparatus, to prevent explosion time
Cause the destruction of equipment to prime.Entering catalytic deoxidation tower, degree of depth deoxidation, catalytic deoxidation tower goes out
Mouth oxygen content is less than 0.01%, and reaction temperature rising about about 100 DEG C, cooled device is cooled to 30 DEG C
And enter adsorption dry tower, deep removal after removing condensed water.The product hydrogen purity obtaining reaches
99.999%～99.999999%, the rate of recovery may be up to 95%.
High-purity hydrogen after purification uses before being recycled to epitaxial furnace through hydrogen pipeline.
Claims (10)
1. from silicon epitaxial furnace emptying end gas, reclaim the device of hydrogen, it is characterized in that: include depending on
Secondary contacted by pipeline water scrubber, front buffer tank, essence dechlorinator, dedusting except water filter,
Hydrogen gas compressor, moisture trap, back buffer tank, PSA piece-rate system, catalytic deoxidation tower,
Water cooler, adsorption dry tower, terminal adsorption tower, terminal water cooler；Water scrubber is provided with
The entrance of silicon epitaxy emptying end gas；
Terminal water cooler is provided with purified hydrogen outlet；Hydrogen gas compressor export pipeline is provided with
The branch line being connected with front buffer tank export pipeline；
PSA piece-rate system is provided with regeneration gas outlet, between the entrance of regeneration gas outlet and deduster
It is provided with interconnective branch line, i.e. regeneration gas return pipeline；
Described adsorption dry tower replaces two adsorption dry towers of deoxidation dewatering operation for parallel connection；
Two essence dechlorinators that described essence dechlorinator is alternately dechlorination operation in parallel.
2. according to the device described in claim 1, it is characterized in that: flowed out by adsorption dry tower
Material first inflow terminal adsorption tower after terminal heat exchanger heat exchange, flowed out by adsorption dry tower
Material inflow terminal water cooler after terminal heat exchanger heat exchange again, by terminal water cooler stream
The material going out flows out purified hydrogen after outlet filter.
3. according to the device described in claim 1, it is characterized in that: branch line is provided with gas
Body regulation valve, pressure sensor；
Described dedusting removes water filter except water filter for two dedustings of alternately operating in parallel；
Connecting line between water scrubber and front buffer tank is provided with the first explosion-proof apparatus；Dedusting removes
Connecting line between water filter and hydrogen gas compressor is provided with the second explosion-proof apparatus；PSA separates
Connecting line between system and catalytic deoxidation tower is provided with the 3rd explosion-proof apparatus；
Water scrubber, essence dechlorinator, PSA piece-rate system, being respectively arranged below with of adsorption dry tower
Material inlet, top are respectively equipped with material outlet；
Catalytic deoxidation tower, terminal adsorption tower, the top of terminal water cooler are respectively equipped with material and enter
Mouthful, be respectively arranged below with material outlet.
4. according to the device described in claim 1, it is characterized in that: water scrubber, hydrogen compression
It is respectively equipped with the water inlet being connected with water source and water out on machine, water cooler；
It is equipped with electrical heating elements, electrical heating on terminal adsorption dry tower inside and/or outside wall surface
Element is one or two or more kinds in electrical heating wire, electrical heating silk ribbon or electric heating tube.
5. according to the device described in claim 1, it is characterized in that: filling in adsorption dry tower
Having adsorption desiccant, during adsorption desiccant regeneration, regeneration gas is entered above each adsorption dry tower
Enter and flow out below adsorption dry tower, through regeneration gas water cooling after the water cooled device of regeneration gas of outflow
The regeneration gas of recovery is obtained after device, regeneration gas separator,
Regeneration gas separator is provided with regeneration gas outlet, the entrance of regeneration gas outlet and deduster
Between be provided with interconnective branch line, i.e. regeneration gas return pipeline；The regeneration gas reclaiming is through pipe
Road is passed through to the gas access of deduster.
6. from silicon epitaxy emptying end gas, reclaim the method that hydrogen prepares High Purity Hydrogen, it is characterized in that:
From silicon epitaxial furnace emptying end gas as unstripped gas first via a water scrubber, remove in tail gas
Major part hydrogen chloride and the impurity such as silane, phosphine, then enter alternately operating through preposition surge tank
Two essence dechlorinator's unit, hydrogen chloride remaining in degree of depth abjection unstripped gas；Former after dechlorination
Two dedustings that material gas enters alternation remove water filter unit, then via hydrogen gas compressor
Supercharging, then after moisture trap and back buffer tank, enter PSA piece-rate system, by hydrogen
In oxygen, the impurity removal such as nitrogen, after subsequently entering catalytic deoxidation tower, more water cooled but device,
To the hydrogen purifying；Finally enter adsorption dry tower, terminal adsorption tower, terminal water cooler,
Obtain high-purity hydrogen；
Dedusting is provided with hydrogen except the connecting line between water filter unit and moisture trap
Compressor is to the gas boosting that will flow into PSA piece-rate system；
Hydrogen gas compressor outlet and front buffer tank outlet pipeline on be respectively equipped with regulation valve,
The pressure to prime for the pressure sensor controls in real time；
Connecting line between water scrubber and front buffer tank is provided with the first explosion-proof apparatus；Dedusting removes
Connecting line between water filter and hydrogen gas compressor is provided with the second explosion-proof apparatus；PSA separates
Connecting line between system and catalytic deoxidation tower is provided with the 3rd explosion-proof apparatus.
7. the method that recovery hydrogen as claimed in claim 6 prepares High Purity Hydrogen, its feature exists
In: two essence dechlorinators of a water scrubber and alternately operating are constituted dechlorination unit, unstripped gas
First through water scrubber drip washing, removing gas major part hydrogen chloride, chlorinity is laggard less than 80ppm
Entering essence dechlorinator, degree of depth dechlorination to chlorinity is less than 0.1ppm；
Essence dechlorinator (draw ratio: 3～8:1) filling QT-C1 high performance dechloridizing agent (main component:
ZnO/Al2O3/ CaO/ activated carbon/interpolation accelerator, Dalian Zhong Ding Chemical Co., Ltd. makes quality by oneself
Ratio the 20%th, the 40%th, the 15%th, the 20%th, 5%), it is provided with 2 essence dechlorinators, alternately operating.
8. the method that recovery hydrogen as claimed in claim 6 prepares High Purity Hydrogen, its feature exists
In: described hydrogen gas compressor supercharging refers to atmospheric hydrogen is pressurized to about 1.0-1.3Mpa,
To provide the pressure of follow-up purification.
9. the method that recovery hydrogen as claimed in claim 6 prepares High Purity Hydrogen, its feature
It is: the catalyzing deoxidation agent of filling in catalytic deoxidation tower uses noble metal catalyst；As described
Noble metal catalyst, generally uses platinum group catalyst, uses Dalian Zhong Ding chemical company technology
Catalyzing deoxidation agent CTC-1 type noble metal catalyst (active constituent is palladium, and carrier is aluminum oxide,
Active constituent accounts for the 0.2%～0.5% of vehicle weight)；Described catalytic deoxidation tower draw ratio 3～8:1,
Reaction temperature controls in the range of 50～150 DEG C；
Described adsorption dry tower draw ratio: 3-10:1, interior filling molecular sieve (commercially available 3A, 4A,
5A) and/or Dalian in ancient cooking vessel special deoxidizer (JDM-2), be provided with 2 adsorption towers of A/B,
Alternately operating；The regeneration of filler uses electrical heating, regeneration temperature 200-350 DEG C；
Described terminal adsorption tower draw ratio: 3-10:1, the proprietary getter of ancient cooking vessel in interior filling Dalian
(XM-1), reaction temperature controls in the range of 400～550 DEG C, and in using, mode of heating will
O in gas2、H2O、CO、CO2、N2、CH4, the impurity such as TCH be purified to ppb level.
10. the method that recovery hydrogen as claimed in claim 6 prepares High Purity Hydrogen, its feature
It is: utilize adsorbent at various pressures to the adsorption capacity of various gases, absorption affinity, suction
The different characteristic of attached speed, is easy to the component of absorption, thus reaches gas in pressurized adsorbent gas
The purpose purifying；PSA part in this device uses 6 tower absorption process, deep removal hydrogen
The impurity such as the oxygen in gas, water, nitrogen, silane, the removing degree of depth reaches below 1ppm；Absorption process
Regeneration gas use purify after hydrogen, regeneration tail gas returns deduster entrance by the road, purify
Reclaim；
Described backflow hydrogen (28, specifically refer to compressor outlet to the pipe after front buffer tank
Road) control front-end pipelines pressure refer to take the hydrogen gas by after Partial shrinkage to loop back,
Automatically controlled by PLC, thus stablize front buffer pressure tank, it is ensured that epitaxial furnace normal
Produce；Front buffer tank is provided with pressure sensor, at the outlet of front buffer tank and compressor
Backflow hydrogen pipeline between outlet is provided with motor regulated valve, the switch of electric control valve and opening
Pass size is aided with PLC automatic PID regulative mode by the pressure data of front-end detection and controls
System；The power adjusting utilizing frequency converter to pass through automatic control module regulation compressor regulates preposition slow simultaneously
Rush the pressure of tank；
The setting of explosion-proof apparatus, with prevent due in hydrogen too high oxygen level and there is explosion danger；Equipment
Control system has operation, malfunction coefficient and overtemperature alarm function；Enter hydrogen before catalytic deoxidation tower
Analyzed continuously by online oxygen analyzer device with the oxygen content in product hydrogen, and there is excess warning
Function, ensuring equipment safe operation；The product hydrogen purity finally giving reaches 99.9%～
99.999999%, the rate of recovery may be up to 95%.
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| CN107434243A (en) * | 2017-07-25 | 2017-12-05 | 大连中鼎化学有限公司 | A kind of superelevation pure hydrogen, argon gas, helium purification process |
| CN108444213A (en) * | 2018-05-28 | 2018-08-24 | 张家港富瑞氢能装备有限公司 | Purifier in liquefaction of hydrogen device |
| CN109592640A (en) * | 2019-01-22 | 2019-04-09 | 崇义章源钨业股份有限公司 | Hydrogen purification system and method |
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| CN107434243A (en) * | 2017-07-25 | 2017-12-05 | 大连中鼎化学有限公司 | A kind of superelevation pure hydrogen, argon gas, helium purification process |
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| CN110872527B (en) * | 2018-08-29 | 2022-03-11 | 中国石油化工股份有限公司 | C4～C6Light paraffin isomerization method |
| CN110872527A (en) * | 2018-08-29 | 2020-03-10 | 中国石油化工股份有限公司 | C4~C6Light paraffin isomerization method |
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| CN110302630A (en) * | 2019-07-18 | 2019-10-08 | 大连中鼎化学有限公司 | A purification device and process for preparing ultrapure gas from purified gas |
| CN110980647A (en) * | 2019-12-25 | 2020-04-10 | 厦门市乐立润安科技有限公司 | Hydrogen purification method suitable for liquefaction process |
| CN111996592A (en) * | 2020-09-03 | 2020-11-27 | 西安奕斯伟硅片技术有限公司 | Device, system and method for discharging reaction tail gas generated in epitaxial growth of silicon wafer |
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