CN102795608B - Method for purification and recovery of argon, nitrogen and hydrogen by rare earth alloy-sponge titanium mixture - Google Patents
Method for purification and recovery of argon, nitrogen and hydrogen by rare earth alloy-sponge titanium mixture Download PDFInfo
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Abstract
The invention relates to a method for purification and recovery of argon, nitrogen and hydrogen by a rare earth alloy-sponge titanium mixture. The rare earth alloy-sponge titanium mixture is a purification agent formed by mixing a rare earth lanthanide series based alloy getter and sponge titanium. The method consists of: putting the rare earth alloy-sponge titanium mixture into two temperature zones of a purification furnace tube to remove impurity gases from argon, nitrogen and hydrogen, finally conducting coarse filtration through a filling material in a coarse filtration zone to finish the purification process, then removing tiny dust through a filter and sending the gases to gas consumption spots. The invention not only expands the application scope, but also has higher purification efficiency. By adopting a purification agent, a most simple primary process, and a lowest cost, the invention replaces traditional methods employing a variety of purification agents and multi-stage integrated process for manufacturing high purity argon, nitrogen, and hydrogen, and realizes the design scheme of one machine with multiple purposes. And on the basis of purification, recovery of the gases is realized, and the gases can be recycled over and over again after repurification. Therefore, the method provided in the invention has great application value and economic benefits.
Description
Technical field
The present invention relates to purification and the recovery of argon gas, nitrogen, hydrogen, relate in particular to a kind of rare earth alloy and the method for titanium sponge mixture to argon, nitrogen, hydrogen purification and recovery of adopting.
Background technology
Rare gas element comprises (0 family's element) Home helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), radon (Rn).They not with any material generation chemical reaction.Because argon content in air is more, Chang Zuowei protection gas, carrier gas, carrier gas, Standard Gases etc. are widely used in many industries of national economy.Using argon gas below as discussing representative, and Technology is also applicable to other rare gas element.
The general purity rubric of current commercially available technical scale gas products is (argon, nitrogen, hydrogen are substantially close): technical purity >=99.9～99.99%, purity >=99.999～99.9999% of high-purity gas, the purity of high-purity gas is that factory detects data online, in fact owing to inevitably polluting in gas course of conveying, the purity of high-purity gas use gas point should be between 99.999～99.9995%.
Both at home and abroad the terminal method of purification of the gases such as argon, nitrogen, hydrogen is had a variety ofly, using often has following methods: select absorption method 1.; 2. pressure swing adsorption process; 3. catalyzed reaction method; 4. separation by deep refrigeration; 5. membrane separation process; 6. metal getter method etc.Same gas under different applicable cases to gas in foreign matter content require differently, the method for employing is also different, many purifying agents only remove effect to specific impurity.Removing impurities, usually adopts multiple purifying agent, multistage integrated method comprehensively.If process choice is improper, will greatly increase complex operation and cost.
200510136041.4 of patent No. ZL be called " silicon single crystal is prepared middle-weight rare earths lanthanide series radical alloy degasser purification argon gas and argon gas recovery process " patent of invention (with this patent be same applicant) in a kind of rare earth lanthanide series radical alloy degasser (hereinafter to be referred as CF01 agent) is disclosed; CF01 agent and technological design keys are to prepare for silicon single crystal; consider that nitrogen in silicon single crystal preparation, hydrogen are on not impact of silicon; even artificial nitrating in some technological process, and early stage study on floating zone silicon is to grow under hydrogen shield.Therefore to the nitrogen in argon, hydrogen without absorbing requirement, and in fact nitrogen, hydrogen richness are very little.Adopt single CF01 agent to purify to argon gas in silicon single crystal preparation, when normal press control temperature is generally 350-450 ℃, can meets and draw high quality monocrystalline silicon requirement, to eliminate affecting foreign gas prepared by silicon single crystal, adopting single CF01 agent and low temperature process main purpose is to simplify technique under the prerequisite of bonding crystal silicon quality, reduces costs.Adopt single CF01 agent not realize multiple gases is purified, as nitrogen and hydrogen.Therefore, how to adopt a kind of purifying agent, the simplest one-level technique, minimum cost produces equally and adopt multiple purifying agent, the identical even more highly purified high-purity argon of multistage integrated technique, nitrogen, hydrogen are in recent years always in the continuous problem of tackling key problem.
Summary of the invention
The object of the invention is to research and develop a kind of rare earth alloy and the method for titanium sponge mixture to argon, nitrogen, hydrogen purification and recovery of adopting.For realizing the method, another object of the present invention is that a kind of rare earth alloy and titanium sponge mixture of all adopting of research and development can be common to the clearing machine of argon, nitrogen, hydrogen purification and purifying-recovering machine.
The rare earth alloy that the present invention adopts is CF01 agent, the mixture forming with CF01 agent and titanium sponge is as purifying agent (hereinafter to be referred as rare titanium mixture), adopt rare titanium mixture in same many temperature provinces boiler tube to rare gas element, nitrogen, hydrogen purification and recovery, realized the design of a tractor serves several purposes.
Rare titanium mixture that the present invention adopts is to take CF01 agent as basis, to have increased pure titanium sponge, its objective is under different technology conditions from the further broadened application of purification of inert gases argon in purification nitrogen and hydrogen.The present invention is except the argon gas that still can be used for silicon single crystal and prepare is purified, and the multiple industry of be also widely used in purifying nitrogen, hydrogen, in many industries such as glove box, analytical instrument, high pure metal preparation and semi-conductor.
CF01 agent component and characteristic are existing in patent No. ZL 200510136041.4 patents of invention to be discussed in detail, does not repeat them here.Put into practice and experimental results show that: CF01 agent can produce the adsorption stronger compared with other metal or alloy under differing temps, thereby excites and accelerated reaction.Utilize CF01 agent to the more active strong adsorption effect of polar impurity gas of performance particularly of impurity in shielding gas, thereby reach purification shielding gas object, prepare high-purity gas.In CF01 agent, add titanium sponge can further improve purifying agent pumping property, and in dehydrogenation and hydrogen purification, bring into play unique effect in argon gas.
The titanium that hot reducing method is produced is spongy, is the intermediates of manufacturing metal titanium and titanium products, and high quality titanium sponge purity is generally 99.1～99.7%, and impurity element (quality) total amount is 0.3～0.9%.
Titanium and spongy its surface coverage at normal temperatures one deck oxide compound, are mainly titanium dioxide, and titanyl compound hinders gas with various and titanium generation chemical reaction.Therefore can long-term storage in air.Research shows, temperature raises and will cause film to occur breach, continuous rising along with temperature, gas except rare gas element and titanium speed of response and velocity of diffusion are accelerated, add titanium sponge the long-pending surface having of huge porous surface can, more accelerated speed of response and velocity of diffusion, the compound that generates titanium due to these gases and titanium combination reaction makes this amount of gas minimizing, often be referred to as so-called gettering effect, titanium or other ware (comprising CF01 agent) are called getter.Titanium and gas generate stable various titanium compounds, and temperature plays a major role to titanium and gas reaction.
Titanium sponge is not high as the usefulness of getter separately, and conventionally more than 800 ℃ could be efficiently air-breathing, but titanium be very important with reacting of hydrogen, has characteristic.React different from other gas, react for reversible reaction, in the time of 200-500 ℃, reaction is the solid compounds titanium hydride Ti+H of forward generation titanium
2→ TiH
2in the time of low temperature 200-500 ℃, being enough to make surface film to occur to produce so-called hydrogen with H-H reaction splits, very abundant 300 ℃ of above reactions, generate titanium hydride, titanium hydride is gap Solid solution, and unstable, and the hydrogen atom that atomic diameter is very little is easy to spread along titanium crystal boundary, in the Solid solution of titanium and hydrogen evolution, hydrogen atom number is concerning each titanium atom and non-integer, 500 ℃ when above after transition warm area reaction start to reversed reaction direction, to carry out gradually.Ti+H
2← TiH
2temperature raises more than 600 ℃, and reaction aggravates and forms backward reaction and emit hydrogen.
This characteristic of the reversible reaction of titanium and hydrogen is significant in the present invention, and low temperature dehydrogenation while can be used for purifying argon gas and nitrogen also can be used for high temperature in the reversible reaction process of titanium and hydrogen and puts hydrogen (titanium does not react with hydrogen) effect for purifying hydrogen of hydrogen.CF-01 agent is very high to the absorption usefulness of the gases such as nitrogen, oxygen, but high temperature the same as titanium not with H-H reaction.
Titanium does not directly react with rare earth alloys, and the metallic compound that titanium and gas reaction (comprising solid impurity) generate is very stable.Even there is not large structural changes with the resultant of the reversible reaction of hydrogen yet.Titanium sponge has porous spongy structure, except having huge surface, can increase its adsorption effect, and gas communication channel is unimpeded, and the amount (air speed) of unit volume purifying agent unit time purifying gas is more, has increased so-called air speed index.The not efflorescence of compound of titanium sponge is the desirable set filler of rare titanium mixture.With regard to gas purifying technique, the not efflorescence of resultant of reaction is extremely important, has not only alleviated follow-up filtration load, and has made air speed and getter can greatly not improve processing performance because of getter efflorescence performance linear decrease, has extended the getter life-span.This be also the present invention adopt CF-01 agent and titanium sponge mixture according to one of.
Rare titanium mixture is made according to a certain volume mechanical mixture and is used as purifying agent, take full advantage of CF01 agent efficient cryogenic and absorb the characteristics such as reversible reaction of polar gas and titanium sponge and hydrogen, utilize the stable feature (not efflorescence) of titanium sponge reaction materil structure simultaneously, greatly improved purification efficiency and improved composite technology performance.
In the working practice to long-term, in the analysis and research of record, experimental data and theory, find: high-quality titanium sponge mixes with CF-01 agent to use not only can efficiently absorb foreign gas, and in different process situation, there is the air-breathing feature of selection, can be used for multiple gases as the purification of argon gas, nitrogen, hydrogen.
In the dry technology of high-purity gas, metal and alloy dewatering are poor, most helpless, in Chinese nuclear power research institute putting institute glove box purification for argon recovery process, find when the online oxygen determination of flow process, water: in the 200-650 ℃ of purification for argon experiment that reduced water content 10PPm(Beijing oxygen installation can be done to system also in confirmation).In the silicon single crystal preparation of producing early stage, rare titanium mixture recycling machine also proves in Qinhuangdao magnificent power unit company is on probation, can be reduced to more than-76 ℃ reclaiming approximately-70 ℃ of argon water-content dew points.
The purity of unstripped gas of the present invention is more than 99.99%, and water-content is no more than 5PPm, and rare titanium mixture reduces water-content 10PPm significant during gas end is purified.Can reach high-purity grade of content of water in gas standard (being less than 1PPm).
The purification for argon that CF01 agent and rare titanium mixture were done respectively system in Beijing oxygen installation is tested: in the Italian 2700 type helium ionized gas phase chromatographic instruments of experiment employing, French AL-800 type argon, micro-groceries gas chromatograph, domestic 10-200 trace oxygen analyzer, 648A-5 trace oxygen analyzer, SH-81 type photoelectric dew-point hygrometer are tested.
Wherein nitrogenous up to 857-2000PPm, oxygen 965 PPm up to nearly 3000PPm(at tested argon gas impurity content) experiment while joining argon at 200-650 ℃, CF01 agent and rare titanium mixture all can drop to argon gas Semi-polarity gas total impurities amount in 0.1PPm (instrument lowest detectable limit).In experiment, also find that the hydrogen in argon gas cuts in and out, be actually the reversible reaction characteristic institute of hydrogen and titanium sponge extremely simultaneously.Inhale hydrogen for 200-500 ℃, 500 ℃ of above hydrogen usefulness of inhaling are successively decreased, when temperature when more than 600 ℃ rare titanium mixture inhale hardly hydrogen.Add rare titanium mixture of titanium sponge to be better than independent CF01 agent to dehydrogenation.
In this experiment, also find: CF01 agent and rare titanium mixture oxygen uptake usefulness are very high, in the time of 200-300 ℃, the oxygen of thousands of PPm does not almost detect (containing oxidizing gas, steam is in fact also oxygen-containing gas), oxygen level can be down in 0.1PPm, and temperature rising oxygen uptake usefulness is higher certainly.Therefore the temperature of oxygen uptake is applicable 200 ℃ of above very wide temperature provinces.And denitrogenation is ineffective in this temperature range, inhale hardly nitrogen, the temperature denitrogenation that raises is gradually accelerated, and inhales nitrogen usefulness and obviously aggravate in the time of 500 ℃, and during to 550 ℃, thousands of nitrogen contents has not measured.Although rare titanium mixture is higher 550 ℃ of above nitrogen usefulness of inhaling, but in this temperature range, be that hydrogen and rare titanium mixture are put hydrogen process (suction hydrogen is 200-500 ℃), therefore as prepared without nitrogen the ultrapure argon gas without hydrogen, must put rare titanium mixture in two temperature provinces, conventionally adopt two-step purification system, the present invention designs two temperature provinces in a boiler tube, has solved well this problem.
In sum, adopt single CF01 agent to purify to argon gas in silicon single crystal preparation and to have getter different in the present invention, purification usefulness is different, range of application is different, the not equal difference of Processes and apparatus, and the present invention is progress and the development on the former basis, wider compared with the former range of application, usefulness is higher, and equipment is simpler, and using value is higher.
The technical scheme that the present invention takes is: a kind of rare earth alloy and titanium sponge mixture are to argon, nitrogen, the method of hydrogen purification, it is characterized in that: rare earth alloy is the purifying agent being mixed with titanium sponge by rare earth lanthanide series radical alloy degasser with titanium sponge mixture, rare earth alloy and titanium sponge mixture and filler are put into purifying boiler tube, purifying boiler tube is divided into the first cold zone, the second high-temperature zone and coarse filtration district, two humidity provinces utilize the air-breathing characteristic of selection of the differing temps of rare earth alloy and titanium sponge mixture to remove argon, nitrogen, impurity gas in hydrogen, filler coarse filtration finally by coarse filtration district, complete purification process, after purification, by strainer, remove after micronic dust and send into and use gas point again, the operating temperature range of the first cold zone and the second high-temperature zone: 200～650 ℃.
The recovery method of rare titanium mixture of the present invention to argon, nitrogen, hydrogen purification, it is characterized in that: the high-purity gas after adopting rare titanium mixture to argon, nitrogen, hydrogen purification is through with after gas point use gas, the waste gas of discharging is through being pressed in surge tank without leaking high air-tight compressor, reenter purification system, and so forth circulation.
The beneficial effect that the present invention produces is: rare titanium mixture due to employing with gas characteristic beyond differing temps (200-650 ℃) interval selection is absorbed rare gas element is purified, not only expanded range of application, and the usefulness that argon, nitrogen, hydrogen are purified is higher, by adopting a kind of purifying agent, the simplest one-level technique, minimum cost to substitute the multiple purifying agent of original employing, multistage integrated technique is manufactured highly purified argon, nitrogen, hydrogen, has realized the design of a tractor serves several purposes.Reciprocal use capable of circulation after again purifying, energy-saving and emission-reduction, increase the benefit.
In the purification industry of above gas, there is very large using value and economic benefit.
Accompanying drawing explanation
Fig. 1 is clearing machine apparatus and process schema of the present invention.
Fig. 2 is purifying-recovering machine apparatus and process schema of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the invention will be further described.The mixture performance perameter that rare earth lanthanide series radical alloy degasser and titanium sponge form:
1) oxygen uptake capacity: 280 mls/g (CF01 agent meter);
2) air speed (amount of unit volume purifying agent unit time purifying gas): be greater than at 13000/ o'clock (CF01 agent meter);
3) operating pressure: normal pressure～0.03MPa;
4) working temperature: rare titanium mixture can be absorbed oxygen when temperature is 200-650 ℃, gas and steam are closed in oxidation; When being 200-500 ℃, temperature absorbs hydrogen, in temperature, be not inhale hydrogen when more than 600 ℃, (the transformation warm area that is reversible reaction between 500-600 ℃ can be considered equilibrium area), temperature is not inhaled nitrogen in time below 300 ℃, in temperature, be can remove nitrogen when more than 500 ℃ and raise and denitrification efficiency is strengthened with temperature, at any temperature, do not inhale rare gas element (argon, helium).
The temperature province that performance perameter sets is wider, and object is for to practice middle equipment alternative in wider temperature province larger, to adapt to for multiple gases purifying technique.Temperature is low, and to absorb impurity usefulness poor, and temperature height consumes energy high and reduces equipment life, therefore in setting effective temperature range, should to gas impurity content is different, require to select temperature according to user.
User can select the gas of required purification and grasp flexibly the gas of required absorption and reservation at the pumping property under differing temps according to rare titanium mixture.
5) purifying agent size: CF01 agent is diameter 2-3 millimeter, long 5-10 millimeter column form object.Titanium sponge is selected high quality kind as far as possible, and it is 3-6 millimeter that granularity is controlled at diameter.
6) stability: stable performance when CF01 agent and titanium sponge normal temperature, can in air, deposit for a long time.Rare earth alloy and titanium sponge mixture be disposable packs rear life-time service into, there is no complicated process for activating and regenerating.
7) unstripped gas: before purifying, unstripped gas purity is technical grade: 99.99%, with gas point, be in high-purity gas environment, as long as all Pipeline transport equipment and devices do not leak, reclaim gas purity and be not less than 99.99%
8) rare titanium mixture consumption: due to user's service condition and scale difference, can calculate CF01 agent weight according to the flow of the different material gas of CF01 agent oxygen uptake capacity, air speed index and required processing and the required foreign matter content of removing, then by CF01 agent and titanium sponge volume ratio 4:6, determine gross weight, can be decided to be 2 years duration of service.Rare titanium mixture and coarse filtration filler should be contained in blade diameter length ratio and be not less than in 12 purifying boiler tube.
Heatproof coarse filtration filler is equipped with in the coarse filtration district of the about 100mm length of purifying boiler tube outlet at bottom part, and filler can be selected internal diameter 1-2mm, the long porcelain tube that is less than 5mm.
The present invention adopts rare titanium mixture in argon gas is purified, and obtains the ultrapure argon gas without nitrogen hydrogen as wanted, must adopt temperature subregion clearing machine.The first cold zone temperature is controlled at 200-500 ℃ and removes hydrogen, oxygen, oxidation and close gas and steam, and the second high-temperature zone temperature is controlled at 500～650 ℃ and removes nitrogen, all impurity can be eliminated, and prepares ultrapure argon, helium.Take this technique, when unstripped gas purity (99.99%), raw material argon total impurities is less than 100PPm.Although rare titanium mixture removal of impurity total amount experimental data is very high, within should being limited to this standard from economic considerations.After purifying the purity inert gas such as argon gas can to reach 99.99995%(water single-row), foreign gas content (ppma) wherein: oxygen < 0.01, oxidizing gas < 0.01, nitrogen < 0.1, hydrogen < 0.1, hydro carbons < 0.1, below dew point-76 ℃.
The present invention adopts rare titanium mixture in nitrogen is purified, and the temperature of the first cold zone and the second high-temperature zone is all controlled at 200～300 ℃ and removes hydrogen, oxygen, oxidation and close gas and steam.Though it is not high that rare titanium mixture removes hydrogen usefulness in the time of 300 ℃, the hydrogen richness in Industrial Nitrogen seldom (is generally less than 10 ppma), and the hydrogen content after purifying is less than 5 ppma.Consider that nitrogen still has certain activity, to unstripped gas, require purity to be not less than 99.99%, after purifying, nitrogen gas purity reaches more than 99.999% (water is single-row).Foreign gas content (ppma) wherein: oxygen < 1, oxidizing gas < 1,, hydrogen < 5, hydro carbons < 1, below dew point-76 ℃.
If temperature over 300 ℃, will have part nitrogen to be removed and further affect rare titanium mixture life-span.
The present invention adopts rare titanium mixture in hydrogen is purified, and the temperature of the first cold zone and the second high-temperature zone is all controlled at 550～650 ℃ and removes nitrogen, oxygen, oxidation and close gas and steam.Unstripped gas requires purity to be not less than 99.99%, single-row in order to prepare 99.999%(water) hydrogen of above purity.Hydrogen must just can enter not containing in the vacuum purifying boiler tube of any gas (except rare gas element) when rising to 550 ℃～650 ℃.Foreign gas content (ppma) after purifying in hydrogen: oxygen < 0.1, gas < 1 is closed in oxidation, nitrogen < 5, hydro carbons < 2, below dew point-76 ℃.
At present many units purify to argon, nitrogen, hydrogen in different operations simultaneously, adopt temperature subregion clearing machine of the present invention can be flexibly with a kind of Device-General in to argon, nitrogen, hydrogen purification.Also can equally matched warm area if clearing machine is special nitrogen, hydrogen cleaning machine, now become a warm area, an a set of heating control system in He Er district, district, temperature is all controlled at the temperature range of requirement.
Rare gas element can be considered without content gas, in other gas purification, ignores.
Before rare earth lanthanide series radical alloy degasser and titanium sponge mixture are put into purifying boiler tube, carry out activation treatment, treatment process is: by titanium sponge concentration, be first that 10% following dilute hydrochloric acid liquid embathes a moment, then with deionized water, wash down oven dry; With the CF01 agent consumption that is about to calculate with process after titanium sponge by weight volume ratio mix at 4: 6, and by order shown in Fig. 1, pack in purifying boiler tube with coarse filtration filler simultaneously.After the purifying furnace seal of tube, rare earth lanthanide series radical alloy degasser and the titanium sponge mixture temperature two humidity provinces is 500-550 ℃ of following heating edge and vacuumizes more than 16 hours activation treatment, after once rare titanium mixture is processed, purifying boiler tube maintenance negative pressure disapproves any gas and enters, and it is motionless that the resistance to air loss of equipment should reach any duration pressure indicator.
The first cold zone and the second high-temperature zone all pack rare titanium mixture into, because rare titanium mixture pumping property raises and is level and smooth increase with temperature, there is no flex point and sudden change.Therefore junction, two humidity provinces temperature variation is less demanding, and without accurately controlling junction, two humidity provinces temperature value, the temperature range of two humidity provinces is the mean value of a relative length, and junction, humidity province temperature is a progressive formation.Two total boiler tube blade diameter length ratios of warm area, more than 12, have enough temperature to guarantee.Rare titanium mixture suction temperature scope of application is wider simultaneously, and temperature is controlled fluctuation and in 25 ℃, also do not had problem.Therefore when design alternative heating unit and temperature controlling system, adopt conventional heating and Controlling System.
Equipment that the present invention adopts is inexpensive, technique is simple, reliable.Certainly user is as needed computer high precision in control, and joins high precision detecting instrument instrument and also can.
Embodiment 1: with reference to Fig. 1, rare earth alloy and titanium sponge mixture are to argon, nitrogen, the clearing machine of hydrogen purification comprises and in purifying furnace 4, is provided with the purifying boiler tube 7 by heater element heat supply, the outer heat-preservation cylinder 10 that is provided with of purifying boiler tube 7, in purifying boiler tube 7, be provided with two humidity provinces, respectively the first cold zone 14 and the second high-temperature zone 15, and the heating system 16 by two humidity provinces is controlled respectively, rare earth alloy and titanium sponge mixture 8 are equipped with in the first normal temperature district 14 and the second cold zone 15, purifying boiler tube 7 bottoms are provided with coarse filtration district 17, filler 9 is equipped with in coarse filtration district 17, 7 imports of purifying boiler tube are connected with the first valve 1 by under meter 2, under meter 2 is connected with off-gas pump 6 by the second valve 5, the outlet of purifying boiler tube 7 is connected with strainer 12 by the 3rd valve 10, strainer 12 is connected and is used gas point by the 4th valve 13.
Rare earth alloy and titanium sponge mixture are to argon, nitrogen, the clearing machine apparatus and process process description of hydrogen purification: unstripped gas enters under meter 2 by the first valve 1, after controlling flow, under meter 2 enters in purifying furnace pipe 7, purifying agent-rare earth alloy and titanium sponge mixture (rare titanium mixture) 8 is housed in purifying boiler tube 7, at corresponding temperature, rare titanium mixture is absorbed the foreign gas in unstripped gas, the pure gas of product after purification is through coarse filtration filler 9 coarse filtrations of purifying boiler tube 7 exit portion, the dust that the rare titanium mixture of filler coarse filtration and gas reaction produce, then through the 3rd valve 11, enter accurate filter 12 and further remove by filter micronic dust, high-purity cleaning product gas through purification and dedusting is sent to and uses gas point through the 4th valve 13.
Tensimeter 3 is for detection of whole system pressure, and the second valve 5 is the switches that lead to off-gas pump gas, and the effect of off-gas pump 6 is resistance to air loss of detection system, and assurance system is in negative pressure state and rare titanium mixture activation treatment.The heating system 16 of two humidity provinces is comprised of the heating and the temperature control instrument that are positioned at outside purifying boiler tube.Temperature is produced by resistance-type heater strip, is controlled the power of heater strip by sensor thermopair and auto-controller instruments and meters, by user's requirement, automatically controls and produces different temperature.
Above technique is mainly used in the terminal purifying of unrenewable rare gas element (argon, helium), nitrogen, hydrogen industry.
Embodiment 2: with reference to Fig. 2, rare earth alloy and titanium sponge mixture are to argon, nitrogen, the purifying-recovering machine of hydrogen purification comprises without revealing high air-tight compressor 23 and surge tank 24, with gas point 19, be connected with tonifying Qi valve 20 and venting valve 21, the outlet of putting 19 combustion gas with gas is connected by the 5th valve 22 and the high air-tight compressor 23 of nothing leakage, without revealing high air-tight compressor 23, be connected with surge tank 24, without revealing between high air-tight compressor 23 imports and surge tank 24 outlets, be connected with regulated valve 25, surge tank 24 is connected with the first valve 1 by Decompression Controlling valve 26, between the first valve 1 and Decompression Controlling valve 26, be connected with air intake valve 18.
Rare earth alloy and the titanium sponge mixture purifying-recovering machine equipment work process description to argon, nitrogen, hydrogen purification: unstripped gas enters under meter 2 through intake valve 18 and the first valve 1 enters in purifying furnace 4 after under meter 2 is controlled flow.Rare titanium mixture purification in process purifying furnace 4 and the pure gas of coarse filtration filler coarse filtration dust enter the further essence of accurate filter 12 by the 3rd valve 11 and remove by filter micronic dust.High-purity cleaning product gas through purification and dedusting is sent to in gas point 19 through the 4th valve 13.With tonifying Qi valve 20 and venting valve 21 are housed on gas point 19, their effect is the pressure-stabilisation of microcall gas point 19.Tonifying Qi valve 20 is connected with external high-purity gas.The discarded gas of discharging with gas point 19 is collected through the 5th valve 22, and through being compressed in surge tank 24 without leaking high air-tight compressor 23, regulated valve 25 is controlled compressor 23 draughts, with regulation system flow in the required scope of user.Surge tank 24 gas is out stablized Decompression Controlling valve 26 by downstream the gas of the required steady pressure of user is sent to the first valve 1, by the first valve 1, again enters under meter 2, with this, moves in circles, and realizes and reclaiming.
Rare earth alloy and titanium sponge mixture are on the basis of clearing machine, to increase gas sampling, compression, purify to reach the object recycling again to the purifying-recovering machine of argon, nitrogen, hydrogen purification.The clearing machine of purification argon gas, nitrogen, hydrogen is identical with the furnace tube structure of purifying-recovering machine, and the purifying agent filling is identical, and adopt different temperature to can be used for above-mentioned gas and purify, be a kind of general purification recovery device.User can adopt the different temperature provinces different gas of purifying.The internal structure of purifying furnace 4 can be referring to Fig. 1 (shown in dotted line).
If continuously with gas, can adopt two cover purifying furnace 4 parallel connections, a set of work, a set of standby.Other flow process and equipment are constant.Under above processing condition, can make miniature, small-sized, medium-sized, large-scale purification and retrieving arrangement according to the process lot size of institute's purifying gas.
All circuit design and equipment are selected to meet high-purity gas standard.Clearing machine and recycling machine system all can not have any leakage, and when tensimeter detecting pressure is 0.5Mpa, each pipeline and equipment must not have any variation being no less than one week internal pressure table display data.
This technique and device can reclaim implementing reciprocation cycle purification for callable shielding gas such as glove box, high pure metal, semiconductor material preparations (argon gas of preparing as zone-melted silicon single crystal reclaims).Owing to protecting gas large usage quantity in above technique, high-purity gas cost is higher, so this technique greatly reduces cost, has very high usefulness and economic benefit.
Claims (3)
1. a rare earth alloy and titanium sponge mixture are to argon, nitrogen, the method of hydrogen purification, it is characterized in that: rare earth alloy is the purifying agent being mixed with titanium sponge by rare earth lanthanide series radical alloy degasser with titanium sponge mixture, rare earth alloy and titanium sponge mixture and filler are put into purifying boiler tube, purifying boiler tube is divided into the first cold zone, the second high-temperature zone and coarse filtration district, two warm areas utilize the air-breathing characteristic of selection of the differing temps of rare earth alloy and titanium sponge mixture to remove argon, nitrogen, impurity gas in hydrogen, filler coarse filtration finally by coarse filtration district, complete purification process, after purification, by strainer, remove after micronic dust and send into and use gas point again, the operating temperature range of the first cold zone and the second high-temperature zone: 200～650 ℃,
Described rare earth alloy and titanium sponge mixture are in purifying to argon gas, and the first cold zone temperature is controlled at 200-500 ℃ and removes hydrogen, oxygen, oxidation and close gas and steam, and the second high-temperature zone temperature is controlled at 500～650 ℃ and removes nitrogen;
Described rare earth alloy and titanium sponge mixture are in purifying to nitrogen, and the temperature of the first cold zone and the second high-temperature zone is all controlled at 200～300 ℃ and removes hydrogen, oxygen, oxidation and close gas and steam;
Described rare earth alloy and titanium sponge mixture are in purifying to hydrogen, and the temperature of the first cold zone and the second high-temperature zone is all controlled at 550～650 ℃ and removes nitrogen, oxygen, oxidation and close gas and steam;
Before rare earth lanthanide series radical alloy degasser and titanium sponge mixture are put into purifying boiler tube, carry out activation treatment, treatment process is: first by titanium sponge with embathing in dilute hydrochloric acid liquid, then with deionized water, wash down oven dry; Titanium sponge after processing is evenly mixed in proportion with rare earth lanthanide series radical alloy degasser, pack in purifying boiler tube with coarse filtration filler simultaneously, after the purifying furnace seal of tube, rare earth lanthanide series radical alloy degasser and the titanium sponge mixture temperature two humidity provinces is 500-550 ℃ of following heating edge and vacuumizes more than 16 hours activation treatment, after rare titanium mixture is processed, purifying boiler tube maintenance negative pressure disapproves any gas and enters.
2. rare earth alloy according to claim 1 and the method for titanium sponge mixture to argon, nitrogen, hydrogen purification, is characterized in that: the weightmeasurement ratio that described rare earth lanthanide series radical alloy degasser mixes with titanium sponge is 4: 6.
3. rare earth alloy according to claim 1 and the recovery method of titanium sponge mixture to argon, nitrogen, hydrogen purification, it is characterized in that: the high-purity gas after adopting rare earth alloy and titanium sponge mixture to argon, nitrogen, hydrogen purification is through with after gas point use gas, the waste gas of discharging is pressed in surge tank through compressor, reenter purification system, and so forth circulation.
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