CN109368593A - A method of preparing the electronic grade hydrogen chloride gas of ppbv grades of moisture impurities - Google Patents
A method of preparing the electronic grade hydrogen chloride gas of ppbv grades of moisture impurities Download PDFInfo
- Publication number
- CN109368593A CN109368593A CN201811415776.4A CN201811415776A CN109368593A CN 109368593 A CN109368593 A CN 109368593A CN 201811415776 A CN201811415776 A CN 201811415776A CN 109368593 A CN109368593 A CN 109368593A
- Authority
- CN
- China
- Prior art keywords
- gas
- hydrogen chloride
- parts
- grades
- tower
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/30—Loose or shaped packing elements, e.g. Raschig rings or Berl saddles, for pouring into the apparatus for mass or heat transfer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Of Gases By Adsorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to high-purity gas preparation fields, particularly with regard to a kind of method of electronic grade hydrogen chloride gas for preparing ppbv grades of moisture impurities；A kind of method for the electronic grade hydrogen chloride gas preparing ppbv grades of moisture impurities disclosed in the method for the present invention, for this method using a kind of reaction gas come the water in remaining in absorbing hydrogen chloride, the reaction gas in this method reacts the component that production silica, boric acid and hydrogen etc. are easy to remove with micro water.Not only the moisture in hydrogen chloride can be down to ppbv grades by ppmv grades by this method, but also also solve the problem of aqueous chlorination hydrogen feedstock cannot remove weight impurity by way of rectifying；This method provides a kind of Synergistic filler of yttrium containing erbium, this kind of filler can after reaction gas is effectively adsorbed, effectively broken off relations the problem of reaction gas remains.Present invention process is continuous operation, not only economic and reliable, and hydrogen chloride gas weight is stablized, and moisture content is extremely low.
Description
Technical field
The present invention relates to high-purity gas preparation fields, particularly with regard to a kind of electron level chlorination for preparing ppbv grades of moisture impurities
The method of hydrogen.
Background technique
High-purity hydrogen chloride gas use is extensive, can be used for system dye, fragrance, drug etc., and is integrated circuit production process
The important materials of the techniques such as middle silicon chip etching, passivation and extension, it can also be used to the fields such as synthetic catalyst, metal smelt.With
The demand of the development of every profession and trade, high-purity hydrogen chloride is increasing.
CN101948094A discloses a kind of synthetic technology of high-purity hydrogen chloride, mainly by mixing gas purifier, cooler,
Synthetic furnace, hydrogen chloride purifying device, vacuum pump, tail gas absorption treating column are linked in sequence by connecting pipeline, are consisted of one assembly.
Rational technology, preparation is simple, and the hydrogen chloride purity is high produced, and solves problem of environmental pollution, is ideal hydrogen chloride
Technology of preparing.
CN106276796A provides a kind of method for preparing high-purity hydrogen chloride, is prepared for high-efficiency adsorbent first.Electronics
The hydrogen of grade, the chlorine of electron level, which enters, is collectively referred to as furnace synthesising hydrogen, enters back into the adsorption tower purification equipped with this high-efficiency adsorbent
Dechlorination, the hydrogen chloride gas after absorption remove hydrogen and fixed gas, obtain high-purity hydrogen chloride product using cooling liquid.
CN103387211A discloses a kind of method for preparing electronic grade high-purity chlorine as raw material using industrial liquid chlorine, by industry
Nitrogen, oxygen, hydrogen, one are removed through multistage physical dryness, adsorbing and removing carbon dioxide, compression condensation, rectifying after liquid chlorine vaporizing
99.999% or more electronic grade high-purity chlorine is made in the low-boiling point gas such as carbonoxide, methane.The preparation method is at low cost, income
Height, product purity obtained is high, and product can be widely applied to the preparation of fiber optic communication, microelectronics, high temperature superconducting materia.
The above patent and the prior art are generally miscellaneous in hydrogen chloride gas to remove using the method for absorption or rectifying
Matter, these methods, since affinity of the chlorine to water is extremely strong, can generally by the moisture removal in hydrogen chloride to ppmv rank
Water content is relatively difficult in further separating hydrogen chloride.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of electronic grade hydrogen chloride gases for preparing ppbv grades of moisture impurities
Method.
A method of the electronic grade hydrogen chloride gas of ppbv grades of moisture impurities being prepared, its technical solution is as follows:
The thick drying of step 1, gas, by hydrogen chloride gas crude product after compression filtering, with the pressure and 0.5- of 0.1-1MP
5m3The flow velocity of/h is dry by drying tower, adsorbing and removing most of moisture；
The hydrogen chloride gas of preliminarily dried is heated to 50-80 DEG C, then with 1- by the removal of traces of moisture in step 2, gas
5m3The flow velocity of/h enters in reaction tower, simultaneously with 0.001-0.005m in reaction tower3The flow velocity of/h is passed through reaction gas and nitrogen
The mixed gas of gas, the volume parts of reaction gas are 5%-10% in the mixed gas；
Step 3, compression condensation, gas enter in compression condensation tower, extremely by gas compression after reaction tower after filtering
1.5-3.5MP is cooled to subzero 10 DEG C -30 DEG C；
Step 4, rectifying separation, the hydrogen chloride gas after compression condensation are passed into rectifying column, the rectifying column point
For lightness-removing column and weight-removing column；Nitrogen, oxygen, hydrogen, the low-boiling point gas such as methane go out from lightness-removing column top row, and hydrogen chloride gas is from de-
Light tower bottom is discharged into weight-removing column；In weight-removing column, hydrogen chloride vaporization removing than hydrogen chloride weight high boiling component, and from de-
Heavy distillation column tower top comes out；It is characterized in that can effectively remove duplicate removal using a kind of Synergistic filler of yttrium containing erbium in the weight-removing column
Remaining reaction gas in component；
Step 5, gas filling, the high-purity hydrogen chloride come out from de- heavy distillation column tower top are bottled through compressed filling system.
The Synergistic filler of yttrium containing erbium is prepared according to following scheme:
According to mass fraction, by 14.6-23.4 parts of zirconium oxychloride, 1.32-5.78 parts of yttrium chloride, 0.5-5 parts of poly- second two
Alcohol 400 and 200-300 parts of deionized water are added in reaction kettle, 50-70 DEG C of temperature control, are stirring evenly and then adding into ammonium hydroxide, will be molten
Liquid pH value is adjusted to 6.5-10, stands overnight after stirring 20-30min, then filters, by residue washing after clean and 5-10 parts
Iron powder, 1-5 parts of copper powder, 0.1-1 parts of neopelex and 60-100 parts of deionized water is added in reaction kettle,
Temperature is increased to 65-85 DEG C, stirs 30-60min；Then material is put into and the coarse grain that diameter is 1 millimeter is made in granulator, and
In Muffle kiln roasting, maturing temperature is 400-600 DEG C, when it is 1-5 hours a length of, then with 6-10 parts of perlites, 1-5 parts of micas
Stone, 0.5-3 parts of stearic acid and 0.5-1 parts of isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, 0.01-1 part three [N,
Bis- (trimethyl silane) amine of N-] erbium, 0.05-1 parts of hydrogenated styrene/methyl styrene/indene copolymer, 0.01-1 parts of poly- hydroxyl
Base terephthalic acid (TPA) zinc, the water of 0.02-0.1 parts of S- carboxyethyl isothiourea salt and 20-30 part is in 2000-3000r/min
Mixing shakes up under revolving speed, when a length of 5-10min, be then pressed into blank filler in the extruding force of 150-300KN, it is dry after
30-60min is heated at 200-300 DEG C, is then broken into 0.5-3mm particulate material, and the Synergistic filler of yttrium containing erbium can be obtained.
Desiccant used in the drying tower is zeolite molecular sieve or phosphorus pentoxide or calcium chloride.
The reaction gas is silicon tetrachloride vapor or trichlorosilane steam or dichlorosilane or three hydrogen silicon of a chlorine or three
Boron chloride.
It is 0.1-0.8MPa that pressure is kept in the reaction tower, and temperature is 60-90 DEG C.
A kind of method for the electronic grade hydrogen chloride gas preparing ppbv grades of moisture impurities, this method disclosed in the method for the present invention
Using a kind of reaction gas come the water in remaining in absorbing hydrogen chloride, the reaction gas in this method reacts production with micro water
Silica, boric acid and hydrogen etc. are easy to the component removed.The moisture in HCl can not only be dropped by ppmv grades by this method
To ppbv grades, and also solve the problem of aqueous chlorination hydrogen feedstock cannot remove weight impurity by way of rectifying；
This method provides a kind of Synergistic filler of yttrium containing erbium, this kind of filler can after reaction gas is effectively adsorbed, effectively broken off relations reaction gas
The problem of body remains.Present invention process is continuous operation, not only economic and reliable, and hydrogen chloride gas weight is stablized, moisture content pole
It is low.
Specific embodiment
The invention is described further below by specific embodiment:
Embodiment 1
A method of the electronic grade hydrogen chloride gas of ppbv grades of moisture impurities being prepared, its technical solution is as follows:
The thick drying of step 1, gas, by hydrogen chloride gas crude product after compression filtering, with the pressure and 2.5m of 0.5MP3/h
Flow velocity it is dry by drying tower, adsorbing and removing most of moisture；
The hydrogen chloride gas of preliminarily dried is heated to 60 DEG C, then with 3m by the removal of traces of moisture in step 2, gas3/ h's
Flow velocity enters in reaction tower, simultaneously with 0.003m in reaction tower3The flow velocity of/h is passed through the mixed gas of reaction gas and nitrogen,
The volume parts of reaction gas are 8% in the mixed gas；
Step 3, compression condensation, gas enter in compression condensation tower, extremely by gas compression after reaction tower after filtering
2.5MP is cooled to subzero 20 DEG C；
Step 4, rectifying separation, the hydrogen chloride gas after compression condensation are passed into rectifying column, the rectifying column point
For lightness-removing column and weight-removing column；Nitrogen, oxygen, hydrogen, the low-boiling point gas such as methane go out from lightness-removing column top row, and hydrogen chloride gas is from de-
Light tower bottom is discharged into weight-removing column；In weight-removing column, hydrogen chloride vaporization removing than hydrogen chloride weight high boiling component, and from de-
Heavy distillation column tower top comes out；It is characterized in that can effectively remove duplicate removal using a kind of Synergistic filler of yttrium containing erbium in the weight-removing column
Remaining reaction gas in component；
Step 5, gas filling, the high-purity hydrogen chloride come out from de- heavy distillation column tower top are bottled through compressed filling system.
The Synergistic filler of yttrium containing erbium is prepared according to following scheme:
According to mass fraction, by 18.6 parts of zirconium oxychloride, 3.51 parts of yttrium chloride, 2.5 parts of polyethylene glycol 400 and 260 parts
Deionized water be added in reaction kettle, 60 DEG C of temperature control, be stirring evenly and then adding into ammonium hydroxide, solution ph be adjusted to 8, stirring
It stands overnight after 25min, then filters, by residue washing clean rear and 8 parts of iron powder, 3 parts of copper powder, 0.5 part of dodecane
Base benzene sulfonic acid sodium salt and 80 parts of deionized water are added in reaction kettle, and temperature is increased to 75 DEG C, stir 45min；Then by material
Being put into and diameter is made in granulator is 1 millimeter of coarse grain, and in Muffle kiln roasting, maturing temperature is 500 DEG C, when it is a length of 3 small
When, then with 8 parts of perlites, 3 parts of micarexes, 1.5 parts of stearic acid and 0.8 part of (the dioctylphyrophosphoric acid acyl-oxygen of isopropyl three
Base) titanate esters, 0.02 part of three [bis- (trimethyl silane) amine of N, N-] erbium, 0.08 part of hydrogenated styrene/methyl styrene/indenes is total
Polymers, 0.4 part of poly- hydroxyterephthalic acid's zinc, 0.1 part of S- carboxyethyl isothiourea salt and 25 parts of water are in 2500r/
Mixing shakes up under min revolving speed, when a length of 8min, be then pressed into blank filler in the extruding force of 240KN, it is dry after at 250 DEG C
Lower heating 45min, is then broken into 1.5mm particulate material, and the Synergistic filler of yttrium containing erbium can be obtained.
Desiccant used in the drying tower is zeolite molecular sieve.
The reaction gas is silicon tetrachloride vapor.
It is 0.4MPa that pressure is kept in the reaction tower, and temperature is 70 DEG C.
This experiment preparation hydrogen chloride gas moisture content be 135ppb, the used Synergistic filler of yttrium containing erbium at 100 DEG C,
Under conditions of one chlorine, three hydrogen silicon partial pressure is 0.4bar, equilibrium adsorption capacity 28.7wt%.
Embodiment 2
A method of the electronic grade hydrogen chloride gas of ppbv grades of moisture impurities being prepared, its technical solution is as follows:
The thick drying of step 1, gas, by hydrogen chloride gas crude product after compression filtering, with the pressure and 0.5m of 0.1MP3/h
Flow velocity it is dry by drying tower, adsorbing and removing most of moisture；
The hydrogen chloride gas of preliminarily dried is heated to 50 DEG C, then with 1m by the removal of traces of moisture in step 2, gas3/ h's
Flow velocity enters in reaction tower, simultaneously with 0.001m in reaction tower3The flow velocity of/h is passed through the mixed gas of reaction gas and nitrogen,
The volume parts of reaction gas are 5% in the mixed gas；
Step 3, compression condensation, gas enter in compression condensation tower, extremely by gas compression after reaction tower after filtering
1.5MP is cooled to subzero 10 DEG C；
Step 4, rectifying separation, the hydrogen chloride gas after compression condensation are passed into rectifying column, the rectifying column point
For lightness-removing column and weight-removing column；Nitrogen, oxygen, hydrogen, the low-boiling point gas such as methane go out from lightness-removing column top row, and hydrogen chloride gas is from de-
Light tower bottom is discharged into weight-removing column；In weight-removing column, hydrogen chloride vaporization removing than hydrogen chloride weight high boiling component, and from de-
Heavy distillation column tower top comes out；It is characterized in that can effectively remove duplicate removal using a kind of Synergistic filler of yttrium containing erbium in the weight-removing column
Remaining reaction gas in component；
Step 5, gas filling, the high-purity hydrogen chloride come out from de- heavy distillation column tower top are bottled through compressed filling system.
The Synergistic filler of yttrium containing erbium is prepared according to following scheme:
According to mass fraction, by 14.6 parts of zirconium oxychloride, 1.32 parts of yttrium chloride, 0.5 part of polyethylene glycol 400 and 200 parts
Deionized water be added in reaction kettle, 50 DEG C of temperature control, be stirring evenly and then adding into ammonium hydroxide, solution ph be adjusted to 6.5, stirring
It stands overnight after 20min, then filters, by residue washing clean rear and 5 parts of iron powder, 1 part of copper powder, 0.1 part of dodecane
Base benzene sulfonic acid sodium salt and 60 parts of deionized water are added in reaction kettle, and temperature is increased to 65 DEG C, stir 30min；Then by material
Being put into and diameter is made in granulator is 1 millimeter of coarse grain, and in Muffle kiln roasting, maturing temperature is 400 DEG C, when it is a length of 1 small
When, then with 6 parts of perlites, 1 part of micarex, 0.5 part of stearic acid and 0.5-1 parts of (the dioctylphyrophosphoric acid acyl of isopropyl three
Oxygroup) titanate esters, 0.01 part of three [bis- (trimethyl silane) amine of N, N-] erbium, 0.05 part of hydrogenated styrene/methyl styrene/indenes
Copolymer, 0.01 part of poly- hydroxyterephthalic acid's zinc, 0.02 part of S- carboxyethyl isothiourea salt and 20 parts of water exist
Mixing shakes up under 2000r/min revolving speed, when a length of 5min, be then pressed into blank filler in the extruding force of 150KN, it is dry after
30min is heated at 200 DEG C, is then broken into 0.5mm particulate material, and the Synergistic filler of yttrium containing erbium can be obtained.
Desiccant used in the drying tower is phosphorus pentoxide.
The reaction gas is trichlorosilane steam.
It is 0.1MPa that pressure is kept in the reaction tower, and temperature is 60 DEG C.
This experiment preparation hydrogen chloride gas moisture content be 147ppb, the used Synergistic filler of yttrium containing erbium at 100 DEG C,
Under conditions of one chlorine, three hydrogen silicon partial pressure is 0.4bar, equilibrium adsorption capacity 24.1wt%.
Embodiment 3
A method of the electronic grade hydrogen chloride gas of ppbv grades of moisture impurities being prepared, its technical solution is as follows:
The thick drying of step 1, gas, by hydrogen chloride gas crude product after compression filtering, with the pressure and 5m of 1MP3The stream of/h
Speed is dry by drying tower, adsorbing and removing most of moisture；
The hydrogen chloride gas of preliminarily dried is heated to 80 DEG C, then with 5m by the removal of traces of moisture in step 2, gas3/ h's
Flow velocity enters in reaction tower, simultaneously with 0.005m in reaction tower3The flow velocity of/h is passed through the mixed gas of reaction gas and nitrogen,
The volume parts of reaction gas are 10% in the mixed gas；
Step 3, compression condensation, gas enter in compression condensation tower, extremely by gas compression after reaction tower after filtering
3.5MP is cooled to subzero 30 DEG C；
Step 4, rectifying separation, the hydrogen chloride gas after compression condensation are passed into rectifying column, the rectifying column point
For lightness-removing column and weight-removing column；Nitrogen, oxygen, hydrogen, the low-boiling point gas such as methane go out from lightness-removing column top row, and hydrogen chloride gas is from de-
Light tower bottom is discharged into weight-removing column；In weight-removing column, hydrogen chloride vaporization removing than hydrogen chloride weight high boiling component, and from de-
Heavy distillation column tower top comes out；It is characterized in that can effectively remove duplicate removal using a kind of Synergistic filler of yttrium containing erbium in the weight-removing column
Remaining reaction gas in component；
Step 5, gas filling, the high-purity hydrogen chloride come out from de- heavy distillation column tower top are bottled through compressed filling system.
The Synergistic filler of yttrium containing erbium is prepared according to following scheme:
According to mass fraction, by 23.4 parts of zirconium oxychloride, 5.78 parts of yttrium chloride, 5 parts of polyethylene glycol 400 and 300 parts
Deionized water is added in reaction kettle, 70 DEG C of temperature control, is stirring evenly and then adding into ammonium hydroxide, solution ph is adjusted to 10, stirring
It stands overnight after 30min, then filters, by residue washing clean rear and 10 parts of iron powder, 5 parts of copper powder, 1 part of dodecyl
Benzene sulfonic acid sodium salt and 100 parts of deionized water are added in reaction kettle, and temperature is increased to 85 DEG C, stir 60min；Then material is put
Entering to be made diameter in granulator is 1 millimeter of coarse grain, and in Muffle kiln roasting, maturing temperature is 600 DEG C, when it is 5 hours a length of,
Then with 10 parts of perlites, 5 parts of micarexes, 3 parts of stearic acid and 1 part of isopropyl three (dioctylphyrophosphoric acid acyloxy) metatitanic acid
Ester, 1 part of three [bis- (trimethyl silane) amine of N, N-] erbium, 1 part of hydrogenated styrene/methyl styrene/indene copolymer, 1 part
Poly- hydroxyterephthalic acid's zinc, 0.1 part of S- carboxyethyl isothiourea salt and 30 parts of water mix under 3000r/min revolving speed
Conjunction shakes up, when a length of 10min, be then pressed into blank filler in the extruding force of 300KN, heated at 300 DEG C after dry
Then 60min is broken into 0.5-3mm particulate material, the Synergistic filler of yttrium containing erbium can be obtained.
Desiccant used in the drying tower is calcium chloride.
The reaction gas is dichlorosilane.
It is 0.8MPa that pressure is kept in the reaction tower, and temperature is 90 DEG C.
This experiment preparation hydrogen chloride gas moisture content be 94ppb, the used Synergistic filler of yttrium containing erbium at 100 DEG C,
Under conditions of one chlorine, three hydrogen silicon partial pressure is 0.4bar, equilibrium adsorption capacity 31.6wt%.
Embodiment 4
A method of the electronic grade hydrogen chloride gas of ppbv grades of moisture impurities being prepared, its technical solution is as follows:
The thick drying of step 1, gas, by hydrogen chloride gas crude product after compression filtering, with the pressure and 5m of 1MP3The stream of/h
Speed is dry by drying tower, adsorbing and removing most of moisture；
The hydrogen chloride gas of preliminarily dried is heated to 80 DEG C, then with 5m by the removal of traces of moisture in step 2, gas3/ h's
Flow velocity enters in reaction tower, simultaneously with 0.005m in reaction tower3The flow velocity of/h is passed through the mixed gas of reaction gas and nitrogen,
The volume parts of reaction gas are 10% in the mixed gas；
Step 3, compression condensation, gas enter in compression condensation tower, extremely by gas compression after reaction tower after filtering
3.5MP is cooled to subzero 30 DEG C；
Step 4, rectifying separation, the hydrogen chloride gas after compression condensation are passed into rectifying column, the rectifying column point
For lightness-removing column and weight-removing column；Nitrogen, oxygen, hydrogen, the low-boiling point gas such as methane go out from lightness-removing column top row, and hydrogen chloride gas is from de-
Light tower bottom is discharged into weight-removing column；In weight-removing column, hydrogen chloride vaporization removing than hydrogen chloride weight high boiling component, and from de-
Heavy distillation column tower top comes out；It is characterized in that can effectively remove duplicate removal using a kind of Synergistic filler of yttrium containing erbium in the weight-removing column
Remaining reaction gas in component；
Step 5, gas filling, the high-purity hydrogen chloride come out from de- heavy distillation column tower top are bottled through compressed filling system.
The Synergistic filler of yttrium containing erbium is prepared according to following scheme:
According to mass fraction, by 14.6 parts of zirconium oxychloride, 1.32 parts of yttrium chloride, 0.5 part of polyethylene glycol 400 and 200 parts
Deionized water be added in reaction kettle, 50 DEG C of temperature control, be stirring evenly and then adding into ammonium hydroxide, solution ph be adjusted to 6.5, stirring
It stands overnight after 20min, then filters, by residue washing clean rear and 5 parts of iron powder, 1 part of copper powder, 0.1 part of dodecane
Base benzene sulfonic acid sodium salt and 60 parts of deionized water are added in reaction kettle, and temperature is increased to 65 DEG C, stir 30min；Then by material
Being put into and diameter is made in granulator is 1 millimeter of coarse grain, and in Muffle kiln roasting, maturing temperature is 400 DEG C, when it is a length of 1 small
When, then with 6 parts of perlites, 1 part of micarex, 0.5 part of stearic acid and 0.5-1 parts of (the dioctylphyrophosphoric acid acyl of isopropyl three
Oxygroup) titanate esters, 0.01 part of three [bis- (trimethyl silane) amine of N, N-] erbium, 1 part of hydrogenated styrene/methyl styrene/indenes is total
Polymers, 0.01 part of poly- hydroxyterephthalic acid's zinc, 0.1 part of S- carboxyethyl isothiourea salt and 20 parts of water exist
Mixing shakes up under 2000r/min revolving speed, when a length of 5min, be then pressed into blank filler in the extruding force of 150KN, it is dry after
30min is heated at 200 DEG C, is then broken into 0.5mm particulate material, and the Synergistic filler of yttrium containing erbium can be obtained.
Desiccant used in the drying tower is calcium chloride.
The reaction gas is boron chloride.
It is 0.3MPa that pressure is kept in the reaction tower, and temperature is 70 DEG C.
This experiment preparation hydrogen chloride gas moisture content be 129ppb, the used Synergistic filler of yttrium containing erbium at 100 DEG C,
Under conditions of one chlorine, three hydrogen silicon partial pressure is 0.4bar, equilibrium adsorption capacity 128.7wt%.
Embodiment 5
A method of the electronic grade hydrogen chloride gas of ppbv grades of moisture impurities being prepared, its technical solution is as follows:
The thick drying of step 1, gas, by hydrogen chloride gas crude product after compression filtering, with the pressure and 0.5m of 0.1MP3/h
Flow velocity it is dry by drying tower, adsorbing and removing most of moisture；
The hydrogen chloride gas of preliminarily dried is heated to 50 DEG C, then with 1m by the removal of traces of moisture in step 2, gas3/ h's
Flow velocity enters in reaction tower, simultaneously with 0.001m in reaction tower3The flow velocity of/h is passed through the mixed gas of reaction gas and nitrogen,
The volume parts of reaction gas are 5% in the mixed gas；
Step 3, compression condensation, gas enter in compression condensation tower, extremely by gas compression after reaction tower after filtering
1.5MP is cooled to subzero 10 DEG C；
Step 4, rectifying separation, the hydrogen chloride gas after compression condensation are passed into rectifying column, the rectifying column point
For lightness-removing column and weight-removing column；Nitrogen, oxygen, hydrogen, the low-boiling point gas such as methane go out from lightness-removing column top row, and hydrogen chloride gas is from de-
Light tower bottom is discharged into weight-removing column；In weight-removing column, hydrogen chloride vaporization removing than hydrogen chloride weight high boiling component, and from de-
Heavy distillation column tower top comes out；It is characterized in that can effectively remove duplicate removal using a kind of Synergistic filler of yttrium containing erbium in the weight-removing column
Remaining reaction gas in component；
Step 5, gas filling, the high-purity hydrogen chloride come out from de- heavy distillation column tower top are bottled through compressed filling system.
The Synergistic filler of yttrium containing erbium is prepared according to following scheme:
According to mass fraction, by 23.4 parts of zirconium oxychloride, 5.78 parts of yttrium chloride, 5 parts of polyethylene glycol 400 and 300 parts
Deionized water is added in reaction kettle, 70 DEG C of temperature control, is stirring evenly and then adding into ammonium hydroxide, solution ph is adjusted to 10, stirring
It stands overnight after 30min, then filters, by residue washing clean rear and 10 parts of iron powder, 5 parts of copper powder, 1 part of dodecyl
Benzene sulfonic acid sodium salt and 100 parts of deionized water are added in reaction kettle, and temperature is increased to 85 DEG C, stir 60min；Then material is put
Entering to be made diameter in granulator is 1 millimeter of coarse grain, and in Muffle kiln roasting, maturing temperature is 600 DEG C, when it is 5 hours a length of,
Then with 10 parts of perlites, 5 parts of micarexes, 3 parts of stearic acid and 1 part of isopropyl three (dioctylphyrophosphoric acid acyloxy) metatitanic acid
Ester, 0.01 part of three [bis- (trimethyl silane) amine of N, N-] erbium, 0.05 part of hydrogenated styrene/methyl styrene/indene copolymer, 1
Poly- hydroxyterephthalic acid's zinc of part, 0.09 part of S- carboxyethyl isothiourea salt and 30 parts of water are in 3000r/min revolving speed
Lower mixing shakes up, when a length of 10min, be then pressed into blank filler in the extruding force of 300KN, heated at 300 DEG C after dry
Then 60min is broken into 0.5-3mm particulate material, the Synergistic filler of yttrium containing erbium can be obtained.
Desiccant used in the drying tower is zeolite molecular sieve.
The reaction gas is three hydrogen silicon of a chlorine.
It is 0.7MPa that pressure is kept in the reaction tower, and temperature is 75 DEG C.
This experiment preparation hydrogen chloride gas moisture content be 116ppb, the used Synergistic filler of yttrium containing erbium at 100 DEG C,
Under conditions of one chlorine, three hydrogen silicon partial pressure is 0.4bar, equilibrium adsorption capacity 25.6wt%.
Comparative example 1
Zirconium oxychloride, the other the same as in Example 1 is not added in preparation component.
The used Synergistic filler of yttrium containing erbium is at 100 DEG C, under conditions of three hydrogen silicon of chlorine partial pressure is 0.4bar, equilibrium adsorption
Amount is 10.8wt%.
Comparative example 2
Yttrium chloride, the other the same as in Example 1 is not added in preparation component.
The used Synergistic filler of yttrium containing erbium is at 100 DEG C, under conditions of three hydrogen silicon of chlorine partial pressure is 0.4bar, equilibrium adsorption
Amount is 16.7wt%.
Comparative example 3
Three [bis- (trimethyl silane) amine of N, N-] erbiums, the other the same as in Example 1 is not added in preparation component.
The used Synergistic filler of yttrium containing erbium is at 100 DEG C, under conditions of three hydrogen silicon of chlorine partial pressure is 0.4bar, equilibrium adsorption
Amount is 20.9wt%.
Comparative example 4
Hydrogenated styrene/methyl styrene/indene copolymer, the other the same as in Example 1 is not added in preparation component.
The used Synergistic filler of yttrium containing erbium is at 100 DEG C, under conditions of three hydrogen silicon of chlorine partial pressure is 0.4bar, equilibrium adsorption
Amount is 21.5wt%.
Comparative example 5
Prepare not addition polymerization hydroxyterephthalic acid zinc in component, the other the same as in Example 1.
The used Synergistic filler of yttrium containing erbium is at 100 DEG C, under conditions of three hydrogen silicon of chlorine partial pressure is 0.4bar, equilibrium adsorption
Amount is 22.1wt%.
Comparative example 6
S- carboxyethyl isothiourea salt, the other the same as in Example 1 is not added in preparation component.
The used Synergistic filler of yttrium containing erbium is at 100 DEG C, under conditions of three hydrogen silicon of chlorine partial pressure is 0.4bar, equilibrium adsorption
Amount is 25.2wt%.
Claims (5)
1. a kind of method for the electronic grade hydrogen chloride gas for preparing ppbv grades of moisture impurities, its technical solution is as follows:
The thick drying of step 1, gas, by hydrogen chloride gas crude product after compression filtering, with the pressure and 0.5- of 0.1-1MP
5m3The flow velocity of/h is dry by drying tower, adsorbing and removing most of moisture；
The hydrogen chloride gas of preliminarily dried is heated to 50-80 DEG C, then with 1- by the removal of traces of moisture in step 2, gas
5m3The flow velocity of/h enters in reaction tower, simultaneously with 0.001-0.005m in reaction tower3The flow velocity of/h is passed through reaction gas and nitrogen
The mixed gas of gas, the volume parts of reaction gas are 5%-10% in the mixed gas；
Step 3, compression condensation, gas enter in compression condensation tower, extremely by gas compression after reaction tower after filtering
1.5-3.5MP is cooled to subzero 10 DEG C -30 DEG C；
It is characterized by:
Step 4, rectifying separation, the hydrogen chloride gas after compression condensation are passed into rectifying column, the rectifying column point
For lightness-removing column and weight-removing column；Nitrogen, oxygen, hydrogen, the low-boiling point gas such as methane go out from lightness-removing column top row, and hydrogen chloride gas is from de-
Light tower bottom is discharged into weight-removing column；In weight-removing column, hydrogen chloride vaporization removing than hydrogen chloride weight high boiling component, and from de-
Heavy distillation column tower top comes out；Using a kind of Synergistic filler of yttrium containing erbium in the weight-removing column, it can effectively remove in heavy constituent and remain
Reaction gas；
Step 5, gas filling, the high-purity hydrogen chloride come out from de- heavy distillation column tower top are bottled through compressed filling system.
2. a kind of method of electronic grade hydrogen chloride gas for preparing ppbv grades of moisture impurities according to claim 1, special
Sign is: the Synergistic filler of yttrium containing erbium is prepared according to following scheme:
According to mass fraction, by 14.6-23.4 parts of zirconium oxychloride, 1.32-5.78 parts of yttrium chloride, 0.5-5 parts of poly- second two
Alcohol 400 and 200-300 parts of deionized water are added in reaction kettle, 50-70 DEG C of temperature control, are stirring evenly and then adding into ammonium hydroxide, will be molten
Liquid pH value is adjusted to 6.5-10, stands overnight after stirring 20-30min, then filters, by residue washing after clean and 5-10 parts
Iron powder, 1-5 parts of copper powder, 0.1-1 parts of neopelex and 60-100 parts of deionized water is added in reaction kettle,
Temperature is increased to 65-85 DEG C, stirs 30-60min；Then material is put into and the coarse grain that diameter is 1 millimeter is made in granulator, and
In Muffle kiln roasting, maturing temperature is 400-600 DEG C, when it is 1-5 hours a length of, then with 6-10 parts of perlites, 1-5 parts of micas
Stone, 0.5-3 parts of stearic acid and 0.5-1 parts of isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, 0.01-1 part three [N,
Bis- (trimethyl silane) amine of N-] erbium, 0.05-1 parts of hydrogenated styrene/methyl styrene/indene copolymer, 0.01-1 parts of poly- hydroxyl
Base terephthalic acid (TPA) zinc, the water of 0.001-0.1 parts of polyaminopropyl biguanide and 20-30 part is in 2000-3000r/min revolving speed
Lower mixing shakes up, when a length of 5-10min, be then pressed into blank filler in the extruding force of 150-300KN, it is dry after in 200-
30-60min is heated at 300 DEG C, is then broken into 0.5-3mm particulate material, and the Synergistic filler of yttrium containing erbium can be obtained.
3. a kind of method of electronic grade hydrogen chloride gas for preparing ppbv grades of moisture impurities according to claim 1, special
Sign is: desiccant used in the drying tower is zeolite molecular sieve or phosphorus pentoxide or calcium chloride.
4. a kind of method of electronic grade hydrogen chloride gas for preparing ppbv grades of moisture impurities according to claim 1, special
Sign is: the reaction gas is silicon tetrachloride vapor or trichlorosilane steam or dichlorosilane or three hydrogen silicon of a chlorine or trichlorine
Change boron.
5. a kind of method of electronic grade hydrogen chloride gas for preparing ppbv grades of moisture impurities according to claim 1, special
Sign is: it is 0.1-0.8MPa that pressure is kept in the reaction tower, and temperature is 60-90 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811415776.4A CN109368593B (en) | 2018-11-26 | 2018-11-26 | Method for preparing electronic grade hydrogen chloride gas containing ppbv grade moisture impurities |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811415776.4A CN109368593B (en) | 2018-11-26 | 2018-11-26 | Method for preparing electronic grade hydrogen chloride gas containing ppbv grade moisture impurities |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109368593A true CN109368593A (en) | 2019-02-22 |
| CN109368593B CN109368593B (en) | 2020-04-10 |
Family
ID=65383707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811415776.4A Active CN109368593B (en) | 2018-11-26 | 2018-11-26 | Method for preparing electronic grade hydrogen chloride gas containing ppbv grade moisture impurities |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109368593B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110697656A (en) * | 2019-11-12 | 2020-01-17 | 浙江博瑞电子科技有限公司 | Preparation method of high-purity hydrogen chloride |
| CN111422870A (en) * | 2020-04-15 | 2020-07-17 | 浙江博瑞电子科技有限公司 | Preparation and application method of HF electronic gas deep purification material |
| CN112777568A (en) * | 2021-02-22 | 2021-05-11 | 张吉瑞 | System and method for jointly producing electronic chlorine and electronic hydrogen chloride |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4867960A (en) * | 1987-01-29 | 1989-09-19 | Hercules Incorporated | Water scavengers for hydrochloric acid streams |
| EP0199854B1 (en) * | 1985-05-01 | 1990-01-31 | European Atomic Energy Community (Euratom) | Process for ultra-drying of a gas |
| CN1826167A (en) * | 2003-07-21 | 2006-08-30 | 安格斯公司 | Hydride gas purification for the semiconductor industry |
| CN102153051A (en) * | 2011-05-19 | 2011-08-17 | 河北邢矿硅业科技有限公司 | Method for removing moisture in hydrogen chloride gas |
| CN103387211A (en) * | 2013-08-09 | 2013-11-13 | 杭州电化集团有限公司 | Method for preparing electronic grade high-purity hydrogen chloride from industrially synthesized hydrogen chloride |
| CN103482573A (en) * | 2013-09-26 | 2014-01-01 | 新特能源股份有限公司 | Method and device for drying hydrogen chloride gas in polysilicon production |
| CN206108892U (en) * | 2016-07-26 | 2017-04-19 | 天津中科拓新科技有限公司 | Prepare device of high -purity hydrogen chloride |
-
2018
- 2018-11-26 CN CN201811415776.4A patent/CN109368593B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0199854B1 (en) * | 1985-05-01 | 1990-01-31 | European Atomic Energy Community (Euratom) | Process for ultra-drying of a gas |
| US4867960A (en) * | 1987-01-29 | 1989-09-19 | Hercules Incorporated | Water scavengers for hydrochloric acid streams |
| CN1826167A (en) * | 2003-07-21 | 2006-08-30 | 安格斯公司 | Hydride gas purification for the semiconductor industry |
| CN102153051A (en) * | 2011-05-19 | 2011-08-17 | 河北邢矿硅业科技有限公司 | Method for removing moisture in hydrogen chloride gas |
| CN103387211A (en) * | 2013-08-09 | 2013-11-13 | 杭州电化集团有限公司 | Method for preparing electronic grade high-purity hydrogen chloride from industrially synthesized hydrogen chloride |
| CN103482573A (en) * | 2013-09-26 | 2014-01-01 | 新特能源股份有限公司 | Method and device for drying hydrogen chloride gas in polysilicon production |
| CN206108892U (en) * | 2016-07-26 | 2017-04-19 | 天津中科拓新科技有限公司 | Prepare device of high -purity hydrogen chloride |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110697656A (en) * | 2019-11-12 | 2020-01-17 | 浙江博瑞电子科技有限公司 | Preparation method of high-purity hydrogen chloride |
| CN110697656B (en) * | 2019-11-12 | 2021-03-16 | 浙江博瑞电子科技有限公司 | Preparation method of high-purity hydrogen chloride |
| CN111422870A (en) * | 2020-04-15 | 2020-07-17 | 浙江博瑞电子科技有限公司 | Preparation and application method of HF electronic gas deep purification material |
| CN111422870B (en) * | 2020-04-15 | 2021-04-09 | 浙江博瑞电子科技有限公司 | Preparation and application method of HF electronic gas deep purification material |
| CN112777568A (en) * | 2021-02-22 | 2021-05-11 | 张吉瑞 | System and method for jointly producing electronic chlorine and electronic hydrogen chloride |
| CN112777568B (en) * | 2021-02-22 | 2022-10-14 | 北京华宇同方化工科技开发有限公司 | System and method for jointly producing electronic chlorine and electronic hydrogen chloride |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109368593B (en) | 2020-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109368593A (en) | A method of preparing the electronic grade hydrogen chloride gas of ppbv grades of moisture impurities | |
| CN104828827B (en) | The method of purification trichlorosilane | |
| CN112250073A (en) | Method and device of chlorosilane purification system | |
| CN215101986U (en) | High-purity electronic grade chlorine purification apparatus for producing | |
| CN113321184B (en) | High-purity electronic-grade chlorine purification production device and technology thereof | |
| CN213623299U (en) | Device of chlorosilane purification system | |
| CN113247862A (en) | High-purity electronic-grade hydrogen chloride production device and process | |
| CN211847167U (en) | Device for preparing high-purity boron trichloride | |
| CN100465094C (en) | Method of synthesizing ammonia by hydrogen gas purified by tail gas of sodium cyanide and alkali-chloride production | |
| CN102863023B (en) | Synthesis and purification method of electronic grade arsines | |
| CN116925123A (en) | Preparation method of electronic-grade hexamethyldisilazane | |
| CN102030335B (en) | Method and device for removing boron impurity in chlorosilane system by rectification through double-tower thermocouple reaction | |
| CN201543362U (en) | Treatment device for treating hydrogen in polysilicon tail gas through temperature and pressure variation method | |
| CN217051660U (en) | Ultra-pure polycrystalline silicon and silicon derivative production system | |
| CN115259165A (en) | Trichlorosilane purification process in polycrystalline silicon production process | |
| CN104923026B (en) | Polysilicon tail gas recovering method and device thereof | |
| CN1559001A (en) | A process and apparatus for purifying hydrogen bromide | |
| CN113401907B (en) | Method and device for purifying and separating silicon tetrachloride in polycrystalline silicon synthesis | |
| CN114229849A (en) | Chlorosilane purification system and method | |
| CN100345753C (en) | Recovery and purifying method for silicon tetrachloride produced in zircon sand fluidizing chlorination reaction | |
| US3041144A (en) | Process for production of hyperpure silicon by heat decomposition of a chloro-silane | |
| CN216711608U (en) | Chlorosilane purification system | |
| CN112645976A (en) | Method for preparing methyl chlorosilane organic silicon by using tail gas FTrPSA (fluorine-doped polysilicon-fluoride) in growth process of chlorine-based CVD (chemical vapor deposition) crystal film | |
| CN104860973A (en) | High-efficient purifying method for trimethyl gallium | |
| CN218945032U (en) | Preparation facilities of electron level trimethyl silane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |