CN204702506U - The device of recover hydrogen from silicon epitaxial furnace emptying end gas - Google Patents
The device of recover hydrogen from silicon epitaxial furnace emptying end gas Download PDFInfo
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- CN204702506U CN204702506U CN201520193971.2U CN201520193971U CN204702506U CN 204702506 U CN204702506 U CN 204702506U CN 201520193971 U CN201520193971 U CN 201520193971U CN 204702506 U CN204702506 U CN 204702506U
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Abstract
The utility model provides a kind of device of recover hydrogen from silicon epitaxial furnace emptying end gas, comprise contacted by pipeline successively water wash column, front buffer tank, smart dechlorinator, dedusting except water filter, hydrogen gas compressor, air water separator, back buffer tank, PSA separation system, catalytic deoxidation tower, watercooler, adsorption dry tower, terminal adsorption tower, terminal watercooler; Water wash column is provided with the entrance of silicon epitaxy emptying end gas.Use said apparatus trace impurity remaining in hydrogen can be removed to less than 99.99999% and obtain high-purity hydrogen, obtained product hydrogen purity can be made to reach 99.9% ~ 99.99999%, and the rate of recovery can up to 95%.Chlorine in residual impurities, oxygen, silane etc. can be low to moderate 1 × 10 respectively
-8, and can according to the purity requirement flexible of product.This utility model is specially adapted to be separated and recover hydrogen from the emptying waste gas silicon epitaxy production process, has very good economic benefit, environmental benefit.
Description
Technical field
The utility model belongs to production and the Application Areas of electron trade silicon epitaxial wafer, be specifically related to a kind of from electron trade silicon epitaxial furnace emptying end gas recover hydrogen prepare the method for High Purity Hydrogen.
Background technology
Hydrogen is chemical raw material and novel clean energy, in the preparation of the growth of crystal and substrate, oxidizing process, epitaxy technique and chemical vapour deposition technique, all will use hydrogen.In High Purity Hydrogen, the volume ratio content of hydrogen is more than 99.9999%, and oxygen level is less than 1 × 10
-6, carbon monoxide and carbonic acid gas are containing being also less than 1 × 10
-6.High Purity Hydrogen is an important kind in industrial gasses, is widely used in the numerous areas such as chemical industry, petrochemical industry, oil, the energy, electronics, metallurgy, food, machinery, aerospace, nuclear industry.In recent years, along with increasing rapidly of Survey of Industrial Gases in Worldwide market, the demand of High Purity Hydrogen is also always in rising situation.In the electronics industry, High Purity Hydrogen is as preparation SiH
4/ H
2, PH
3/ H
2, B
2h
6/ H
2deng the spirit of mixing and doping gas.High to spirit purity requirement in semiconductor fabrication, trace impurity mixes spirit will change semiconductor surface characteristic, especially in electrovacuum materials and devices production process, very high to hydrogen purity requirement.As the important materials that tungsten, molybdenum are all electrovacuum equipment, powder can be obtained by oxide compound through hydrogen reducing, be reprocessed into wire rod.Hydrogen purity is higher, and reducing degree is higher, and the granularity of gained tungsten powder is thinner, and the anode of electron tube, the metal device such as negative electrode and grid, all need through special annealing in hydrogen atmosphere process, also very high to the purity requirement of hydrogen.
The manufacture of extensive and super large-scale integration, and the filling of the various gas-filled electron tube such as hydrogen brake pipe, ionic valve, laser tube, all need the hydrogen that purity is very high.Electron trade is the maximum user of High Purity Hydrogen at present, and only to produce large-scale integrated circuit, domestic annual production 1,000,000,000 pieces of unicircuit, about need to consume High Purity Hydrogen 10Mm
3left and right.
At present, silicon epitaxy enterprise of China is all energy consumption rich anies influential family, their hydrogen source is all based on water electrolysis, because water electrolysis hydrogen producing needs to consume a large amount of electric energy, and the electricity price of China is heavier for burden enterprise, add that country is to the requirement of enterprise energy consumption and domestic energy-saving and emission-reduction overall situation, all accelerates the development of energy-conserving and emission-cutting technology.The circulation of tail gas recycling reclaimed also can be enterprise and saves product cost, and reduce enterprise energy consumption, these development being electronic enterprise provide stable development space.
Current silicon epitaxy enterprise produces containing hydrogen dense in a large number in the tail gas of discharge, generally, and H
2> 95%, N
2: 3%-5%, all the other are hydrogenchloride, hydrogen sulfide, phosphine and oxygen, carbonic acid gas and water etc., but due to recycling device of not purifying, can only be discharged in air, having slatterned in vain.
Because the production process of silicon epitaxy is complicated, main that manufactures parts epitaxial furnace is wherein very high to the conditional request such as gaseous tension, purity, and particularly hydrogen purity will reach more than 99.99999%, and current enterprise, after purchase High Purity Hydrogen, generally will be further purified.This just requires that recovery system needs reliable, stable to be mated use, recovering and purifying system is not only just purified to tail gas, pressure in control epitaxial furnace that also will be stable, this just makes the domestic and international tail gas recycle to the sector at present utilize all not good terms of settlement.And having multiple method to the method for purification of High Purity Hydrogen according to the difference of raw material sources, mainly containing of wherein commonly using is following several.
1) low-temperature adsorption:
Condensation-low-temperature adsorption, purifying divides 2 steps to carry out, and first, adopts condensation at low temperature to carry out pre-treatment.Need carry out at different temperatures 2 times or multiple condensation separation, removing water impurity and carbonic acid gas etc.Recycling low-temperature adsorption is refined, and the hydrogen after precooling enters people's adsorption tower, at liquid nitrogen vaporization temperature (-196 DEG C), remove minor amount of water with activated alumina, molecular sieve adsorption deoxygenation, molecular sieve is denitrogenated, silica gel is except carbon monoxide, ammonia, argon, and gac is except methane etc.Sorbent material is with adding hot hydrogen regeneration, the many employings of technique 2 adsorption tower alternate operations, and after purification, hydrogen volume mark can reach 99.999%-99.9999%.
Low temperature absorption-absorption method, purifying also needs point 2 steps to carry out, and first according to the kind of impurity in feed hydrogen, selects suitable absorption agent, as methane, propane, ethene, propylene etc., impurity in cyclic absorption and desorb hydrogen at low temperatures.Such as absorb the impurity such as carbon monoxide at low temperatures with liquid methane, then absorb wherein residual methane with propane, the hydrogen that volume fraction is 99.99% can be obtained.And then through low-temperature adsorption, remove wherein trace impurity with sorbent material, 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 adopts, its technology and equipment adopted mostly from the large gas companies of external a few family as than the introduction such as Europe, method liquid air, Lin De, Mei Saier.
2) pressure swing adsorption process (PSA):
Pressure-variable adsorption utilizes the gaseous fraction difference of characterization of adsorption and the pressure-dependent principle of adsorptive capacity on the sorbent, by the separation of periodic pressure change process implementation gas.It is low that technology has energy consumption, and product purity is high, and technical process is relatively simple, and pre-processing requirements is low, convenient and reliable operation, level of automation advantages of higher, is used widely in gas delivery field.
The hydrogen manufacturing of PSA method, available various hydrogeneous source of the gas is raw material, different with operational path according to feed hydrogen, can obtain High Purity Hydrogen without pre-treatment one step, or after simple pre-treatment again through adsorption tower refine, purification after small product size mark can in 99.0%-99.999% scope flexible.The main drawback of PSA technology is that purified gas purity is lower, the rate of recovery is lower, about about 86%.
3) metal getter method:
Take electrolysis hydrogen as raw material, drying is dewatered, and preliminary cleaning, to 99.995% purity, enters in hydrogen-storage alloy cylinder, utilizes hydrogen-storage alloy to inhale hydrogen at low temperatures, and high temperature transfers the characteristic of hydrogen, can produce ultra-pure hydrogen.Hydrogen first need carry out pre-treatment before entering people's hydrogen alloy purifier usually, general adopt palladium catalyst deoxidation and molecular sieve adsorption dry to remove in feed hydrogen the impurity such as most of oxygen, carbon monoxide, water.Purification devices is usually by more than 2 purifier combine operationss, and to obtain High Purity Hydrogen continuously, volume fraction can reach more than 99.99999%.
4) palladium barrier diffusion method
Utilize palladium alloy membrane at certain temperature (400-550 DEG C), can only make hydrogen through, and the impermeable characteristic of other foreign gas, makes hydrogen obtain purifying.Palldium alloy local superheating is caused because oxygen can produce hydrogen-oxygen catalyzed reaction at palladium alloy membrane, it is poisoning that water can make palladium synthesis that oxidation occurs, therefore require low to oxygen in unstripped gas and water-content, and need first through purifier deoxygenation and water, again after filter dedusting, palldium alloy diffuser casing purifying could be sent into, the High Purity Hydrogen that volume fraction is 99.9999% can be obtained.But this method is owing to requiring higher to unstripped gas and subsequent maintenance cost is very high is progressively eliminated at present.
The hydrogen that above several method is just limited to more than to purer (purity is greater than 99.9%) purifies, and silicon epitaxy exhaust gas composition is comparatively complicated, hydrogen purity is lower, need to carry out accurate pressure-controlling to recovery gas, this just requires that above any one method all can not meet the demands simultaneously.Such as: low-temperature adsorption consumes liquid nitrogen, and use range is limited.Require high to raw materials pretreatment, production process energy consumption is high, and investment is large.Good but this technique of metal getter method purification effect is consumption-type material, non-renewable, need periodic replacement, require that tail gas first need carry out pre-treatment before entering people's hydrogen alloy purifier usually simultaneously, general adopt palladium catalyst deoxidation and molecular sieve adsorption dry to remove in feed hydrogen the impurity such as most of oxygen, carbon monoxide, water.In pre-treatment deoxidation process, what key was chlorine removes the degree of depth, if the cl content entered in catalytic deoxidation reactor in hydrogen is more than 1ppm, catalyzing deoxidation agent then can be made very soon poisoning (irreversible, be actually and active ingredient is changed into muriate, thus lose deoxy activity).
For the deficiency of above-mentioned High Purity Hydrogen processing condition and method, in conjunction with silicon epitaxy industrial tail gas material characteristic, develop a kind of recover hydrogen from silicon epitaxy industry emptying end gas newly and prepare the method for High Purity Hydrogen, to the technical bottleneck breaking through the exploitation of silicon epitaxy industrial tail gas, there is positive social effect and commercial value undoubtedly.
Utility model content
The purpose of this utility model is for silicon epitaxy industrial tail gas feature, in order to overcome the above-mentioned deficiency of prior art, provides a kind of device of recover hydrogen from silicon epitaxial furnace emptying end gas newly.
Concrete technical scheme is as follows:
A kind of device of recover hydrogen from silicon epitaxial furnace emptying end gas, it is characterized in that: according to the index request in the content of the oxygen mainly contained in silicon epitaxy emptying end gas and hydrogen and GB/T7445-1995 " pure hydrogen, High Purity Hydrogen and ultra-pure hydrogen ", the utility model adopt once washing, the dechlorination of the chemisorption degree of depth, hydrogen gas compressor supercharging, PSA gas separation system, catalytic deoxidation, water cooling, terminal purifying, resurgent gases return that front end purification reclaims, the technological line of backflow hydrogen control front-end pipelines pressure and measures for the prevention of explosion.
From silicon epitaxial furnace emptying end gas, the apparatus system of recover hydrogen comprises following components:
The water wash column of being contacted by pipeline successively, front buffer tank, smart dechlorinator, dedusting except water filter, hydrogen gas compressor, air water separator, back buffer tank, PSA separation system, catalytic deoxidation tower, watercooler, adsorption dry tower, terminal adsorption tower, terminal watercooler; Water wash column is provided with the entrance of silicon epitaxy emptying end gas;
Terminal watercooler is provided with purified hydrogen outlet; Hydrogen gas compressor export pipeline is provided with the branch line be connected with front buffer tank export pipeline;
PSA separation system is provided with resurgent gases outlet, is provided with interconnective branch line, i.e. resurgent gases return pipeline between the entrance of resurgent gases outlet and fly-ash separator;
Described adsorption dry tower is two adsorption dry towers of alternately deoxidation dewatering operation in parallel;
Described smart dechlorinator is two smart dechlorinators of alternately dechlorination operation in parallel.
The material flowed out by adsorption dry tower is inflow terminal adsorption tower after the heat exchange of terminal interchanger first, the material flowed out by adsorption dry tower is inflow terminal watercooler after the heat exchange of terminal interchanger again, and the material flowed out by terminal watercooler flows out purified hydrogen after outlet filter.
Branch line is provided with the electronic or pneumatic adjusting valve of gas and pressure transmitter;
Two dedustings that described dedusting is alternately operating in parallel except water filter remove water filter;
Connecting pipeline between water wash column and front buffer tank is provided with the first explosion-proof apparatus; The connecting pipeline that dedusting removes between water filter and hydrogen gas compressor is provided with the second explosion-proof apparatus; Connecting pipeline between PSA separation system and catalytic deoxidation tower is provided with the 3rd explosion-proof apparatus;
Water wash column, smart dechlorinator, PSA separation system, adsorption dry tower below is respectively equipped with material inlet, top is respectively equipped with material outlet;
Catalytic deoxidation tower, terminal adsorption tower, terminal watercooler top is respectively equipped with material inlet, below is respectively equipped with material outlet.
Water wash column, hydrogen gas compressor, watercooler are respectively equipped with the water inlet be connected with water source and water out;
Terminal adsorption dry tower inside and/or outside wall surface are equipped with an electric heating element, and an electric heating element is one or two or more kinds in electrical heating wire, electrically heated silk ribbon or electric heating tube.
Adsorption desiccant is filled with in adsorption dry tower, during adsorption desiccant regeneration, resurgent gases enters and flows out below adsorption dry tower above each adsorption dry tower, the resurgent gases flowed out obtains the resurgent gases of recovery after water cooler after resurgent gases watercooler, resurgent gases water separator, resurgent gases water separator is provided with resurgent gases outlet, interconnective branch line is provided with, i.e. resurgent gases return pipeline between the entrance of resurgent gases outlet and fly-ash separator; The resurgent gases reclaimed passes into the gas inlet place to fly-ash separator by the road.
1) purification system: comprise water wash column and the composition such as smart dechlorinator, dedusting water eliminator, hydrogen gas compressor, water trap, PSA tripping device, catalytic deoxidation device, watercooler and water trap and drying adsorption tower, resurgent gases water separator and terminal adsorption tower.
2) automatic control system: comprise centralized control unit, online oxygen analyzer, automatic regulating valve and correlate meter.
3) pressure stabilization control system: comprise PLC control unit, under meter, pressure transmitter, motor-driven control valve and correlate meter.
Technical process is:
Raw material tail gas is first through water wash column, and removing wherein most of hydrogenchloride, silane, phosphine, enter front buffer tank afterwards, front buffer tank can cushion the pressure surge that front and back operation is brought, and makes equipment can steady running more.Gas after surge tank enters smart dechlorinator (2, alternately operating), make the cl content in hydrogen drop to below 0.1ppm, working hour 100-300 days (depending on the chlorine content) of dechlorinator, dechlorination effect is detected by chlorine analyzers time sampling.After dechlorinator was lost efficacy, drawn off by the dechlorinating agent of inefficacy, changing new dechlorinating agent can use.Gas through dechlorination tank enters preprocessor, solid particulate in tail gas, liquid water etc. are carried out prime remove, in order to avoid impact subsequent pipeline valve, compressor, two preprocessors one are working, one for subsequent use in regeneration, resurgent gases nitrogen, regeneration tail gas is discharged into emptying house steward; Then enter removing silane, germane, phosphine, solid particulate, liquid water hydrogen enter the supercharging of piston-type oil free compressor, make gaseous tension be raised to 1.0Mpa-1.3Mpa, to maintain the power required for process gas, and subsequent handling can better be run.Simultaneously stablely prevent the pressure of front buffer tank to be pumped into negative pressure in order to what keep pressure in epitaxial furnace and produce potential safety hazard and damage epitaxial furnace, compressor outlet is set up and is regulated backflow bypass, automatically controls the pressure-stabilisation with compressor variable frequency technical guarantee prime operation by PLC; Hydrogen after compression is after air water separator, enter into rearmounted gas-holder, the pressure transmitter of gas-holder controls compressor outlet variable valve, (can set) when pressure is less than 1.0Mpa, increase control valve opening, when pressure is greater than 1.3Mpa (but can set the highest be no more than 1.3Mpa), reduce control valve opening until close.Gas after supercharging enters into PSA separation circuit, and the degree of depth deviates from the impurity such as large water gaging, nitrogen, silane in hydrogen, and 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, at the entrance of catalyzing deoxidation agent, water seal explosion-proof apparatus be installed, during to prevent from blasting, prime caused to the destruction of equipment, in catalytic deoxidation tower, oxygen and hydrogen catalysis are generated water, react as follows:
1/2O
2+H
2→H
2O+Q(129C)
A large amount of heats is released in reaction simultaneously, and exporting hydrogen to close to after normal temperature, sends into adsorption dry tower through undue water through water cooling, the impurity such as micro amount of oxygen, water, carbonic acid gas remaining in deep removal gas.Finally enter terminal adsorption tower again, remove all the other impurity in gas outside dehydrogenation completely, removing the degree of depth is 10ppb.
Ultra-pure hydrogen is incorporated to epitaxial furnace front end Hydrogen Line after hydrogen relief valve, recycles.
In the utility model, raw material tail gas, first through water wash column, removes the impurity such as most of hydrogenchloride, silane, phosphine, then smart dechlorinator (2 is entered, alternately operating), make the cl content in hydrogen drop to below 0.1ppm, to reach the object removing chlorine.Essence dechlorinator (length-to-diameter ratio: 3 ~ 8:1) loads QT-C1 high performance dechloridizing agent (main component: ZnO/Al
2o
3/ CaO/ gac/interpolation promotor, Dalian Zhong Ding Chemical Co., Ltd. self-control mass ratio 20%, 40%, 15%, 20%, 5%), be provided with 2 smart dechlorinators, alternately operating.Working hour 100-300 days (depending on chlorine content) of tower, dechlorination effect is detected by chlorine analyzers time sampling.
In the utility model, the dedusting connecting pipeline dewatered between filter unit and air water separator is provided with hydrogen gas compressor to the gas boosting being about to flow into PSA separation system; Described hydrogen gas compressor supercharging refers to and atmospheric hydrogen is pressurized to about 1.0-1.3Mpa, to provide the pressure of follow-up purification.
The pipeline that hydrogen gas compressor outlet and front buffer tank export is respectively equipped with variable valve, the pressure of pressure transmitter to prime controls in real time;
In the utility model, the catalyzing deoxidation agent loaded in described deoxidation tower uses noble metal catalyst.As described noble metal catalyst, generally use platinum group catalyst, conventional catalyst preparation method can be used to prepare, such as, by methods such as dipping, sprayings, active ingredient is supported on carrier, make through roasting.Also the patent catalyzing deoxidation agent CTC-1 type noble metal catalyst (active constituent is palladium, and carrier is aluminum oxide, and active constituent accounts for 0.2% ~ 0.5% of vehicle weight) of ancient cooking vessel chemical technology in Dalian can be used.
When using noble metal catalyst, the oxygen in tail gas hydrogen and hydrogen water generation reaction and heat under the effect of noble metal catalyst, do not need to consume additional energy.
Temperature of reaction is not particularly limited, can be controlled in the scope of 50 ~ 350 DEG C.But from energy efficient and the angle reducing high temperature secondary reaction, preferably temperature of reaction is controlled in the scope of 50 ~ 150 DEG C.
PSA separation system described in the utility model, it is characterized in that: utilize the characteristic that sorbent material is different to the loading capacity of various gas, adsorptive power, rate of adsorption at various pressures, be easy to the component adsorbed in pressurized adsorbent gas, thus reach the object of gas purification; PSA part in this device adopts 6 tower absorption process, and the impurity such as the oxygen in deep removal hydrogen, water, nitrogen, silane, remove the degree of depth and reach below 1ppm.
The utility model also preferred adsorption dry and terminal adsorption tower combines the mode preparing high-purity hydrogen: the water that catalytic deoxidation process produces, and divides after water, enter terminal dehydration tower adsorption dewatering through water-cooled.Described adsorption dry tower (length-to-diameter ratio: 3-10:1), interior filling molecular sieve (commercially available 3A, 4A, 5A), is provided with A/B 2 dehydration towers, alternately operating.The regeneration of molecular sieve adopts electrically heated, regeneration temperature 200-350 DEG C.
Terminal adsorption tower length-to-diameter ratio: 3-10:1, the proprietary getter of ancient cooking vessel (XM-1) in interior filling Dalian, temperature of reaction controls in the scope of 400 ~ 550 DEG C, and in adopting, type of heating is by O in gas
2, H
2o, CO, CO
2, N
2, CH
4, the impurity such as TCH is purified to ppb level.
Resurgent gases reclaiming clean mode that the utility model is also preferred: in PSA separation circuit, the resurgent gases of adsorption unit and the resurgent gases of adsorption dry tower adopt the hydrogen after purifying, and regeneration tail gas returns fly-ash separator entrance by the road, and Recovery Purifying improves the rate of recovery.
The method can make obtained product hydrogen purity reach 99.999% ~ 99.99999%, and the rate of recovery can up to 95%.
The utility model is preferred reflux hydrogen pressure control mode also: take the hydrogen gas circulation after by part pressurization to go back with the pressure in stable epitaxial furnace, thus ensure epitaxial furnace safe operation.Described backflow hydrogen is (in figure 28, specifically refer to compressor export to front buffer tank after pipeline) control front-end pipelines pressure refer to take the hydrogen gas after by Partial shrinkage circulate go back, automatically controlled by PLC, thus stablize front buffer pressure tank, ensure the normal production of epitaxial furnace; Front buffer tank is provided with pressure transmitter, backflow hydrogen pipeline between the outlet of front buffer tank and compressor outlet is provided with motor regulated valve, and the switch of motor-driven control valve and switch size are aided with the automatic PID regulative mode of PLC by the pressure data of front-end detection and control; Utilize frequency transformer to regulate the power regulation of compressor to regulate the pressure of front buffer tank by automatic control module simultaneously.
The utility model is also preferably as follows measures for the prevention of explosion: the connecting pipeline between water wash column and front buffer tank is provided with the first explosion-proof apparatus; The connecting pipeline that dedusting removes between water filter and hydrogen gas compressor is provided with the second explosion-proof apparatus; Connecting pipeline between PSA separation system and catalytic deoxidation tower is provided with the 3rd explosion-proof apparatus.
At the entrance of hydrogen gas compressor and the entrance of catalytic deoxidation tower, water seal explosion-proof apparatus is installed, during to prevent from blasting, prime is caused to the destruction of equipment; The Controlling System of equipment is equipped with anti-explosion electric variable valve and temperature regulator, can realize the full automatic control to returning hydrogen flowing quantity, and has operation, malfunction coefficient and overtemperature alarm function, and whole system function is advanced, dependable performance; Oxygen level before entering deoxidation tower in hydrogen and product hydrogen is analyzed continuously by online oxygen analyzer device, and has excess warning function, ensuring equipment safe operation.
The setting of explosion-proof apparatus, to prevent the danger of blasting due to too high oxygen level in hydrogen; The Controlling System of equipment has operation, malfunction coefficient and overtemperature alarm function; Oxygen level before entering catalytic deoxidation tower in hydrogen and product hydrogen is analyzed continuously by online oxygen analyzer device, and has excess warning function, ensuring equipment safe operation; The product hydrogen purity finally obtained reaches 99.9% ~ 99.999999%, and the rate of recovery can up to 95%.
As concrete mode, the situation being less than 100ppm with the cl content in tail gas hydrogen is described, such as, can be as under type:
Extension tail gas, after washing, directly enters smart dechlorinator's dechlorination.
As concrete mode, the situation being less than 0.5% with the oxygen content in tail gas hydrogen is described, such as, can be as under type:
The entrance of PSA tripping device is entered into after hydrogen gas compressor pressurization, further separating-purifying, pass through reflux line at compressor outlet simultaneously, through PLC unit accurate calculation, adjustment recycle ratio (entrance tolerance/return entrance tolerance) makes the pressure of front end extension tail gas reach satisfaction (being generally about 150mbar).
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the device of recover hydrogen in silicon epitaxial furnace emptying end gas, wherein: 0 is water wash column, 1 is front buffer tank, 2 is the first antiriot device, 3A/B is smart chlorine purifier, 4A/B is fly-ash separator, 5 is hydrogen gas compressor, 6 is air water separator, 7 is back buffer tank, 8 is PSA tripping device, 9 is catalytic deoxidation tower, 10 is watercooler, 11A/B is adsorption dry tower, 12A/B is water cooler, 13 is terminal adsorption tower, 14 is terminal interchanger, 15 is terminal watercooler, 16 is outlet filter, 17 is resurgent gases watercooler, 18 is resurgent gases water separator, 19 is high-order evacuation port 201-20n extension gas inlet, 21 is displacement nitrogen inlet, 22 is cooling water inlet, 23 is cooling water outlet, 24 is low level leakage fluid dram, 25 is purified hydrogen outlet, 26 is resurgent gases outlet, 27 is the second antiriot device, 28 is backflow hydrogen pipeline, 29 is resurgent gases return pipeline.
Embodiment
Further describe the utility model below in conjunction with embodiment, but scope of the present utility model is not by the impact of embodiment.
Embodiment 1
(1) epitaxial furnace tail gas
Extension tail gas tolerance: 200m
3/ h temperature: 25 DEG C of pressure: 0.15 normal atmosphere
Main composition: H
297.5%, O
22%, Cl
2>=100ppm, all the other are a small amount of carbonic acid gas, silane, phosphine etc.
(2) dechlorinating agent
Filling QT-C1 high performance dechloridizing agent (main component: ZnO/Al
2o
3/ CaO/ gac/interpolation promotor, Dalian Zhong Ding Chemical Co., Ltd. self-control mass ratio 20%, 40%, 15%, 20%, 5%), use air speed: 1000h
-1filling total amount: 0.2m
3
Essence dechlorinator aspect ratio: 5
(3) catalyzer
Catalytic deoxidation CTC-1 type noble metal catalyst (active ingredient is palladium, and carrier is aluminum oxide, and active ingredient accounts for 0.2% ~ 0.5% of carrier component weight)
Noble metal catalyst uses air speed: 5000h
-1
Your catalyst loading total amount: 0.04m
3
Catalytic deoxidation tower aspect ratio: 5
(4) step
By extension tail gas hydrogen (200m
3/ h) (wherein cl content>=200ppm, oxygen level 2%) pass into water wash column, removes most of hydrogenchloride, controls cl content≤80ppm.Then front buffer tank and the hydrogenchloride of participation is removed to below 0.1ppm through smart chlorine purifier, dechlorination effect is detected by chlorine analyzers time sampling.Through hydrogen gas compressor, atmospheric hydrogen is pressurized to 1.0Mpa ~ 1.3Mpa again, to provide the pressure of subsequent purification.Gas after supercharging enters PSA separation purifier, installs water seal explosion-proof apparatus, during to prevent from blasting, prime is caused to the destruction of equipment at the entrance of hydrogen gas compressor and PSA device.Enter catalytic deoxidation tower, degree of depth deoxidation, catalytic deoxidation tower outlet oxygen level is less than 0.1%, reaction temperature rising about about 70 DEG C, be cooled to 30 DEG C through water cooler and after removing water of condensation, the tail gas hydrogen after part deoxidation turned back to hydrogen gas compressor entrance, recycle ratio (entrance tolerance/return tolerance) is 2:1, and the oxygen level now in deoxidation tower exit gas can reduce gradually, until the oxygen in extension tail gas hydrogen is taken off to being less than 0.1%.
Last enter the product hydrogen purity that adsorption tower dry decontamination device and terminal adsorption unit obtain again and reach 99.999% ~ 99.99999%, the rate of recovery can up to 95%.
High-purity hydrogen after purification is recycled to before epitaxial furnace through hydrogen pipeline and uses.
Embodiment 2
(1) epitaxial furnace tail gas
Tail gas tolerance: 100m
3/ h temperature: 25 DEG C of pressure: 0.13 normal atmosphere
Main composition: H
299%, O
20.5%, Cl
2≤ 100ppm, all the other are a small amount of carbonic acid gas, silane, phosphine etc.
(2) dechlorinating agent
Filling QT-C1 high performance dechloridizing agent (main component: ZnO/Al
2o
3/ CaO/ gac/interpolation promotor, Dalian Zhong Ding Chemical Co., Ltd. self-control mass ratio 20%, 40%, 15%, 20%, 5%), use air speed: 2000h
-1filling total amount: 0.1m
3
Essence dechlorinator aspect ratio: 7
(3) catalyzer (the same embodiment 1) noble metal catalyst uses air speed: 5000h
-1
Your catalyst loading total amount: 0.02m
3
Catalytic deoxidation tower aspect ratio: 6
(4) step
By extension tail gas hydrogen (100m
3/ h) (wherein cl content≤100ppm, oxygen level 0.5%) directly pass into smart dechlorinator (2, alternately operating), and make the cl content in hydrogen drop to below 0.1ppm, dechlorination effect is detected by chlorine analyzers time sampling.Enter hydrogen gas compressor by after front buffer tank and dedusting water eliminator, the gaseous tension after supercharging is 1.0Mpa ~ 1.3Mpa, installs water seal explosion-proof apparatus, during to prevent from blasting, prime is caused to the destruction of equipment at hydrogen gas compressor and PSA tripping device entrance.Enter catalytic deoxidation tower, degree of depth deoxidation, catalytic deoxidation tower outlet oxygen level is less than 0.01%, and reaction temperature rising about about 100 DEG C, is cooled to 30 DEG C through water cooler and enters adsorption dry tower after removing water of condensation, deep removal.The product hydrogen purity obtained reaches 99.999% ~ 99.999999%, and the rate of recovery can up to 95%.
High-purity hydrogen after purification is recycled to before epitaxial furnace through hydrogen pipeline and uses.
Claims (5)
1. the device of recover hydrogen from silicon epitaxial furnace emptying end gas, it is characterized in that: comprise contacted by pipeline successively water wash column, front buffer tank, smart dechlorinator, dedusting except water filter, hydrogen gas compressor, air water separator, back buffer tank, PSA separation system, catalytic deoxidation tower, watercooler, adsorption dry tower, terminal adsorption tower, terminal watercooler; Water wash column is provided with the entrance of silicon epitaxy emptying end gas;
Terminal watercooler is provided with purified hydrogen outlet; Hydrogen gas compressor export pipeline is provided with the branch line be connected with front buffer tank export pipeline;
PSA separation system is provided with resurgent gases outlet, is provided with interconnective branch line, i.e. resurgent gases return pipeline between the entrance of resurgent gases outlet and fly-ash separator;
Described adsorption dry tower is two adsorption dry towers of alternately deoxidation dewatering operation in parallel;
Described smart dechlorinator is two smart dechlorinators of alternately dechlorination operation in parallel.
2. according to device according to claim 1, it is characterized in that: the material flowed out by adsorption dry tower is inflow terminal adsorption tower after the heat exchange of terminal interchanger first, the material flowed out by adsorption dry tower is inflow terminal watercooler after the heat exchange of terminal interchanger again, and the material flowed out by terminal watercooler flows out purified hydrogen after outlet filter.
3. according to device according to claim 1, it is characterized in that: branch line is provided with the electronic or pneumatic adjusting valve of gas and pressure transmitter;
Two dedustings that described dedusting is alternately operating in parallel except water filter remove water filter;
Connecting pipeline between water wash column and front buffer tank is provided with the first explosion-proof apparatus; The connecting pipeline that dedusting removes between water filter and hydrogen gas compressor is provided with the second explosion-proof apparatus; Connecting pipeline between PSA separation system and catalytic deoxidation tower is provided with the 3rd explosion-proof apparatus;
Water wash column, smart dechlorinator, PSA separation system, adsorption dry tower below is respectively equipped with material inlet, top is respectively equipped with material outlet;
Catalytic deoxidation tower, terminal adsorption tower, terminal watercooler top is respectively equipped with material inlet, below is respectively equipped with material outlet.
4. according to device according to claim 1, it is characterized in that: water wash column, hydrogen gas compressor, watercooler are respectively equipped with the water inlet be connected with water source and water out;
Terminal adsorption dry tower inside and/or outside wall surface are equipped with an electric heating element, and an electric heating element is one or two or more kinds in electrical heating wire, electrically heated silk ribbon or electric heating tube.
5. according to device according to claim 1, it is characterized in that: in adsorption dry tower, be filled with adsorption desiccant, during adsorption desiccant regeneration, resurgent gases enters and flows out below adsorption dry tower above each adsorption dry tower, the resurgent gases flowed out obtains the resurgent gases of recovery after water cooler after resurgent gases watercooler, resurgent gases water separator, resurgent gases water separator is provided with resurgent gases outlet, interconnective branch line is provided with, i.e. resurgent gases return pipeline between the entrance of resurgent gases outlet and fly-ash separator; The resurgent gases reclaimed passes into the gas inlet place to fly-ash separator by the road.
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| CN201520193971.2U CN204702506U (en) | 2015-04-01 | 2015-04-01 | The device of recover hydrogen from silicon epitaxial furnace emptying end gas |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107297613A (en) * | 2016-04-15 | 2017-10-27 | 中国石油天然气股份有限公司 | Installation tool and compressor |
| CN115382390A (en) * | 2022-08-23 | 2022-11-25 | 浙江镇洋发展股份有限公司 | Purification system of chlor-alkali production hydrogen |
| CN107297613B (en) * | 2016-04-15 | 2024-04-30 | 中国石油天然气股份有限公司 | Mounting tool and compressor |
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2015
- 2015-04-01 CN CN201520193971.2U patent/CN204702506U/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107297613A (en) * | 2016-04-15 | 2017-10-27 | 中国石油天然气股份有限公司 | Installation tool and compressor |
| CN107297613B (en) * | 2016-04-15 | 2024-04-30 | 中国石油天然气股份有限公司 | Mounting tool and compressor |
| CN115382390A (en) * | 2022-08-23 | 2022-11-25 | 浙江镇洋发展股份有限公司 | Purification system of chlor-alkali production hydrogen |
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