CN101041425A

CN101041425A - Preparation and purification method of hydrogen selenide

Info

Publication number: CN101041425A
Application number: CN 200710011160
Authority: CN
Inventors: 王同文
Original assignee: DALIAN LIFANG CHEMICAL TECHNOLOGY Co Ltd
Current assignee: DALIAN LIFANG CHEMICAL TECHNOLOGY Co Ltd
Priority date: 2007-04-26
Filing date: 2007-04-26
Publication date: 2007-09-26
Anticipated expiration: 2027-04-26
Also published as: CN100567140C

Abstract

The invention discloses a purifying method to prepare hydrogen selenide, which comprises the following steps: reacting Al2Se3 and H2O; getting hydrogen selenide H2Se; removing water of H2Se gas through condensing; using Al2Se3 particle to adsorb remain water; entering into carboy to condense and liquefy; evacuating the carboy under the condition of cool bath; eliminating non-condensable gas impurity of solution in the liquid; closing the valve of carboy; getting purify hydrogen selenide; absorbing water; taking-up active solid of reacting with water as raw material; reacting Al2Se3 and H20; getting H2Se; reaching highly effective dewater effect.

Description

The preparation purification process of Selenium hydride

Technical field

The present invention relates to the preparation purifying, particularly aluminum selenide of chemical gas Selenium hydride and the Selenium hydride of water reaction generation and prepare purifying, be characterized in the water content height, its purifying emphasis is dehydration.

Background technology

Selenium hydride is a kind of liquable serious toxic gas, fills with steel cylinder.Hydrogen selenide gas is mainly used in synthesizing inorganic or organic selenium-containing compound, the preparation metallic selenium.High-purity Selenium hydride is semiconductor doping gas and copper indium diselenide solar cell precursor.

Several methods that prepare Selenium hydride are arranged, as: 1., can directly synthesize Selenium hydride more than 350 ℃ by hydrogen and simple substance selenium; 2., metal selenide and water or diluted acid effect; 3., selenium reacts with carbon monoxide and water in the presence of triethylamine.Usually adopt preceding two kinds of methods.

Metal selenide is easier to control with the method reaction process ratio that Selenium hydride is produced in water or diluted acid effect, and cost is lower, also compares safety.Particularly, the scope that this method is fit to use is wider, can prepare voluntarily in common laboratory.Metal selenide adopts aluminum selenide usually.

But the gas of this prepared in laboratory can only instant generating and using, and both purifying not can not store and forward, has influenced its applicability.The hydrogen selenide gas that this aluminum selenide hydrolysis takes place fills steel cylinder as through appropriate purifying, just may store, transport and use as product.

So far, also not about this aluminum selenide hydrolysis hydrogen selenide gas purifying that takes place and the public technology that fills.EP 0 470936 A1, WO 00/20330 are the patents of binomial hydrogen-containing gas purifying, and SiH mainly is discussed ₄, GeH ₄, NH ₃, AsH ₃, PH ₃, B ₂H ₆High-purity purification technique of electron gas, and do not relate to H ₂Se does not relate to the general purifying of status nascendi gas yet.

For the dehydration of special gas purifying, generally adopt dew point condensation method, absorption process, absorption method, rectification method, membrane separation process etc.Dew point condensation method, absorption method are more convenient.When adopting absorption method, when shallow degree dehydration and dehydrating amount are big, adopt calcium chloride more; When middle deep dehydration and dehydrating amount are little, adopt silica gel more; Deep dehydration and when taking off trace water adopts molecular sieve.

Summary of the invention

The present invention will solve the issues of purification that Selenium hydride is produced, and a kind of preparation purification process of Selenium hydride of aluminum selenide hydrolysis generation is provided.

The preparation purification process of Selenium hydride of the present invention is raw material aluminum selenide Al ₂Se ₃With water H ₂Selenium hydride H takes place in the O reaction ₂Behind the Se, H ₂Water in the Se gas is removed through condensation; It is characterized in that: continue to adsorb residual H with containing aluminum selenide particulate adsorber ₂Moisture content in the Se gas makes H ₂Behind the Se gas depth drying, H ₂Se gas enters the steel cylinder inner condensat liquidization; Liquid H is housed ₂The steel cylinder of Se vacuumizes under cryostat, gets rid of the noncondensable gas impurity that is dissolved in the liquid; Close cylinder valve and directly be contained in the interior purifying Selenium hydride of steel cylinder.Purifying to hydrogen selenide gas with the technological method that fills employing is: aluminum selenide Al ₂Se ₃With water H ₂Selenium hydride H takes place in the O reaction ₂Behind the Se, H ₂Se gas anhydrates in the following condensation of the dew-point temperature of water; Continue to make the gas depth drying with aluminum selenide particle absorption residual moisture; Subsequently, H ₂Se is low-temperature liquefaction in steel cylinder; Finish one batch fill after, liquid H is housed ₂The gas bomb of Se is light and slow vacuumizing under the low temperature cryostat, gets rid of the noncondensable gas that is dissolved in the liquid; At last, close cylinder valve, finish the whole purifying of this batch and fill operation.Absorption moisture content also takes out with the sorbent material of water reaction and to be re-used as raw material aluminum selenide Al ₂Se ₃With water H ₂Selenium hydride H takes place in the O reaction ₂Se.

The present invention's adsorption method that dewaters is directly to adopt aluminum selenide as sorbent material.The present invention preferably directly gets the fresh Al of high reaction activity ₂Se ₃, be broken into small-particle, as H ₂The dehydrated adsorbent of Se purifying can not produce new impurity, obtains efficient adsorption effect.The present invention makes H ₂The Se liquefaction of gases charges into to vacuumize behind the steel cylinder to be got rid of non-condensable gas and is equivalent to flash distillation.Put it briefly, the present invention finishes simultaneously in purge process and fills, and purge process comprises the dew point condensation-Al of water ₂Se ₃Absorption-liquid H ₂The Se flash distillation.The characteristics of aluminum selenide are strong with the water reactive behavior.Adopt the aluminum selenide particle of high reaction activity to do the sorbent material dehydration, reach the high-efficiency dehydration effect.After the aluminum selenide particle absorption moisture content reduction as sorbent material, also be directly used in the raw material of preparation Selenium hydride, make full use of resource, and reduced of the pollution of discarded sorbent material environment.Through handling like this, make Selenium hydride become a kind of liquefied gas product of packing with steel cylinder that 99.95% above purity is arranged.

Description of drawings

Fig. 1 is adsorber and Al ₂Se ₃The granule adsorbent structural representation; Wherein, 1-Al ₂Se ₃Granular filler, 2-adsorber, 3-man-made fiber filtering layer, 4-H ₂The Se gas inlet, 5-H ₂The Se pneumatic outlet.Al ₂Se ₃The size 3-8mm of granular filler 1.

Fig. 2 is H ₂Se purification for gas and fill schematic flow sheet; Wherein, the nascent H of 6- ₂The Se gas introduction port, 7-ice bath thermometer, 8-ice bath groove, 9-saturation vapour condenser, 1-Al ₂Se ₃Granular filler, 2-adsorber, 3-man-made fiber filtering layer, 4-H ₂Se gas is at the inlet of adsorber, 5-H ₂Se gas is in the outlet of adsorber, 10-liquid H ₂The Se steel cylinder, 11-low-reading thermometer, 12-low temperature bath, 13-cascade refrigeration machine, 14-tail gas absorber, 15-solid KOH particle, 16-man-made fiber filtering layer, 17-gas buffer jar, 18-tail gas blow-down pipe, 19-vacuum pump, 20～24-stopping valve.

Embodiment

A kind of example of preparation purification process of Selenium hydride of the present invention, the flow process of its process is as follows:

(Al ₂Se ₃+ H ₂O) → wet H ₂Se gas → (0 ℃) removes H ₂O → use Al ₂Se ₃Absorption H ₂H in O → (50 ℃) steel cylinder ₂Se liquefaction → (50 ℃) liquid H ₂The Se steel cylinder is light and slow to vacuumize → closes steel cylinder valve complete operation

Contrast Fig. 2:

Nascent H ₂Se gas 6 feeds saturation vapour condensers 9, a part of saturation water ice bath groove 8 in below 0 ℃ under the cooling condensation remove, then entering the mouth by adsorber 4 enters adsorber 2, residual moisture content wherein and adsorbent A l ₂Se ₃ Granular filler 1 contact reacts is fallen H ₂After the man-made fiber filtering layer 3 that Se gas finish-drying, the particulate of gas entrainment are adsorbed device filters out, enter H by steel cylinder valve 21 by the outlet 5 of adsorber 2 ₂ Se steel cylinder 10, H ₂ Se steel cylinder 10 is positioned at-55 ℃ of low temperature baths 12, and low-temperature receiver provides H by superposition type small-sized refrigerating unit 13 ₂The Se boiling point is-42 ℃, H ₂Se is condensed, and non-condensable gases is via steel cylinder valve 22, through tail gas absorber 14, gas buffer jar 17, by 18 emptying of tail gas blow-down pipe.Finish one batch fill after, close steel cylinder valve 21, liquid H is housed ₂The gas bomb 10 of Se by vacuum pump 19 light and slow vacuumizing, by steel cylinder valve 22, is got rid of the noncondensable gas that is dissolved in the liquid low temperature cryostat 12 times.At last, close steel cylinder valve 22, take off steel cylinder 10.

The following describes the concrete grammar of each operation steps.

The present invention is the unstripped gas access port with the outlet that the producer gas generator of hydrogen selenide gas takes place for aluminum selenide and water reaction.No matter the hydrogen selenide gas that the hydrogen selenide gas producer takes place has or not stream of nitrogen gas to follow, all be applicable to technology provided by the present invention.

H ₂Major impurity is H among the Se ₂O, H ₂S, N ₂, O ₂, and THC (total hydrocarbon).

Al ₂Se ₃With H ₂The H that the O reaction takes place ₂Be full of H among the Se ₂O steam is wet H ₂Se in order to obtain dry gas, must thoroughly take off contained humidity.The present invention adopts the cryosel water-bath with saturated H earlier ₂The condensation of O vapour.Then, use chemiadsorption, with Al ₂Se ₃As sorbent material, compare Al with other drying means ₂Se ₃Has the most convenient advantage efficiently.H ₂O steam runs into the Al as sorbent material ₂Se ₃, upright both with its reaction, be converted into H ₂Se.Can make adsorbent A l forever ₂Se ₃Keep fresh,, just can take off it and go to use as into H takes place because do not wait it to die down ₂The raw material A l of Se ₂Se ₃And use, again with fresher Al ₂Se ₃It is substituted.Make Al ₂Se ₃The method of sorbent material is exactly with Al ₂Se ₃Piece is broken into pieces, and the particle of screening diameter 3-8mm scope is loaded in the adsorber.For the gas that treating lab takes place, gas volume is little, adsorber diameter 20-30mm, and the long 300-500mm of gas path just can produce a desired effect.Such treating processes, H ₂Contain H among the Se ₂The O amount can drop to below the 100ppm.

H ₂The cryogenic condensation process of Se is that the 2L twoport gas bomb in the low temperature cryostat carries out.Low-temperature receiver is provided by a superposition type small-sized refrigerating unit, and the unit refrigeration temperature is controlled at-56 ℃.Raw spirit will be delivered to the low temperature cryostat as cold carrier by the alcohol of refrigeration with pump.

H ₂The boiling point of Se is-42 ℃, under-50 °～56 ℃ envrionment temperature, and H ₂Se is condensed, and foreign gas H ₂S, N ₂, O ₂, and THC (THC is with CH ₄Be representative) then be non-condensable gas, with H ₂Se separates.

Finish one batch fill after, also need to concentrate and deviate to be dissolved in liquid H ₂The non-condensable gas of Se.Be dissolved in liquid H ₂The non-condensable gas of Se removes under negative pressure.Because the dissolved non-condensable gas is to shift out liquid phase by diffusion way, process is slower, vacuumize with under the low temperature, low pressure reduction, little free air delivery is advisable, the pumpdown time is lasting a little longer, 20～40 minutes, light and slow operation, more appropriate.Foreign gas content can drop to below the 50ppm.2L gas bomb H ₂The filling weight of Se must not surpass 2800g.

Claims

1, a kind of preparation purification process of Selenium hydride, raw material aluminum selenide Al ₂Se ₃With water H ₂Selenium hydride H takes place in the O reaction ₂Behind the Se, H ₂Water in the Se gas is removed through condensation; It is characterized in that: continue to adsorb residual H with containing aluminum selenide particulate adsorber ₂Moisture content in the Se gas makes H ₂Behind the Se gas depth drying, H ₂Se gas enters the steel cylinder inner condensat liquidization; Liquid H is housed ₂The steel cylinder of Se vacuumizes under cryostat, gets rid of to be dissolved in and does not coagulate foreign gas in the liquid; Close cylinder valve and directly be contained in the interior purifying Selenium hydride of steel cylinder.

2, as the preparation purification process of the said Selenium hydride of claim 1, it is characterized in that: absorption moisture content also takes out with the sorbent material of water reaction and to be re-used as raw material aluminum selenide Al ₂Se ₃With water H ₂Selenium hydride H takes place in the O reaction ₂Se.