CN103708420A - Method of producing hydrogen chloride - Google Patents
Method of producing hydrogen chloride Download PDFInfo
- Publication number
- CN103708420A CN103708420A CN201310452021.2A CN201310452021A CN103708420A CN 103708420 A CN103708420 A CN 103708420A CN 201310452021 A CN201310452021 A CN 201310452021A CN 103708420 A CN103708420 A CN 103708420A
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- chlorine
- reaction
- hydrogen chloride
- chloride gas
- 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.)
- Pending
Links
Images
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
-
- 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
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
-
- 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
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/081—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing particle radiation or gamma-radiation
-
- 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
- C01B7/012—Preparation of hydrogen chloride from the elements
-
- 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
- C01B7/015—Chlorine hydrates; Obtaining chlorine therefrom
-
- 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
- C01B7/017—Preparation of hydrogen chloride by reacting together chlorine, water and carbon or carbon monoxide (the carbon not acting only as catalyst)
-
- 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
- C01B7/03—Preparation from chlorides
- C01B7/04—Preparation of chlorine from hydrogen chloride
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method of producing hydrogen chloride. The purpose of the invention is to provide a method of producing hydrogen chloride that can inhibit temperature rising of a reaction system through more simple steps. According to the producing method, hydrogen and chlorine are irritated in the existence of hydrogen chloride gas, and the hydrogen chloride gas is generated because of reaction between hydrogen and chlorine.
Description
Technical field
The present invention relates to make hydrogen and chlorine reaction to manufacture the chlorination method for preparing hydrogen of hydrogenchloride.
Background technology
Hydrogenchloride is used in the clean purposes of the growth furnace of etching gas, silicon wafer for dry etching of silicon semiconductor.And, be also used in recent years in silicon carbide purposes, particularly the utilization in semiconductor applications is widened to some extent.Therefore in semiconductor applications, because sneaking into of impurity can be reduced qualification rate greatly, in each technique, need most and avoid sneaking into of impurity, to the whole compounds that use in technique exigent purity all.And then also requirement can be manufactured at an easy rate.
As the method that hydrogen and chlorine is reacted obtain hydrogenchloride, just like following formula, be shown in the method for burning chlorine in hydrogen and directly generating hydrogenchloride.
H
2＋Cl
2→2HCl＋184.7kJ
Therefore owing to only only mixing hydrogen and chlorine, be can not react, in order to promote this reaction, need to utilize burner etc. to heat, temperature of reaction becomes the high temperature of approximately 2500 ℃.In addition, under this high temperature, in chemical equilibrium, instead would not finish, to wait while mole making hydrogen and chlorine reaction, the chlorine adding approximately 2% residual with unreacted state.
The synthesizer of the hydrochloric acid that Japanese kokai publication hei 5-105408 communique is recorded possesses before reaction at least one party in hydrogen and chlorine is carried out to cooling cooling end.In addition, in the synthetic method that Japanese kokai publication hei 5-105408 communique is recorded, the feed rate that makes hydrogen is required in theory feed rate 1.2～1.5 times.
Utilize condenser to carry out when cooling the reaction product gas of high temperature, needing to improve the thermotolerance of the material that forms condenser or the formation of improvement condenser.
Comprise that the improvement of the condenser that material improves is due to very difficult, therefore adopt water directly to absorb the reaction product gas of high temperature, the temporary transient method reclaiming with the form of hydrochloric acid.For hydrogenchloride is separated from this hydrochloric acid, for example, as recorded in TOHKEMY 2001-192202 communique, make the salt with the effect of saltouing exist to distill.
When hydrogenchloride is separated from hydrochloric acid by distillation, because azeotropic can occur for hydrogenchloride and water, therefore need to use the dewatering agents such as calcium chloride, magnesium chloride or sulfuric acid to dewater from the azeotropic mixture obtaining by distillation.Therefore, in existing manufacture method, thus the only practical poor manufacture method of this energy efficiency of distilling, dewater acquisition hydrogen chloride gas by hydrochloric acid after the hydrogen chloride gas of reaction product is reclaimed with the form of hydrochloric acid.
Summary of the invention
The chlorination method for preparing hydrogen that the temperature that the object of the present invention is to provide the simpler step of utilization to suppress reaction system rises.
The present invention is a kind of chlorination method for preparing hydrogen, it is characterized in that, under the existence of hydrogen chloride gas, hydrogen and chlorine is irradiated to light, makes hydrogen and chlorine reaction, thereby generates hydrogen chloride gas.
In addition, the present invention is a kind of chlorination method for preparing hydrogen, it is characterized in that, has following operation: mix hydrogen, chlorine and hydrogen chloride gas and obtain the mixed processes of mixed gas; With mixed gas is irradiated to light so that contained hydrogen and chlorine reaction and generate the rayed operation of hydrogen chloride gas in mixed gas.
In addition, the present invention is a kind of chlorination method for preparing hydrogen, it is characterized in that, has following operation: the supply operation that hydrogen, chlorine and hydrogen chloride gas is supplied to respectively continuously to reactor; With under the existence of hydrogen chloride gas to being supplied to that the hydrogen of reactor and chlorine irradiate light so that hydrogen and chlorine reaction and generate the rayed operation of hydrogen chloride gas.
As mentioned above, according to the present invention, the reaction heat being produced by the reaction of hydrogen and chlorine is chlorinated hydrogen and absorbs, and temperature rises and suppressed.Hydrogen chloride gas, owing to being reaction product, therefore does not need to carry out separation after reaction.
By making like this hydrogen chloride gas coexist, can come the temperature of inhibited reaction system to rise by more simple step.
In addition, preferably to make to start the mole number of the hydrogen chloride gas of light-struck time point be the more than 5 times of mole number of less person in hydrogen mole number and chlorine mole number in the present invention.
According to the present invention, by making to start the mole number of the hydrogen chloride gas of light-struck time point, be the more than 5 times of mole number of less person in hydrogen mole number and chlorine mole number, the temperature in the reaction system that reaction heat can be brought is suppressed at below 800 ℃.
In addition, the mole number that the present invention preferably makes to start the hydrogen of light-struck time point is less than the mole number of chlorine.
According to the present invention, can obtain afterwards at the hydrogen chloride gas as reaction product and in as the hydrogen chloride gas of raw material supplying, further contain the mixture of unreacted hydrogen in reaction, when making hydrogenchloride liquefaction, can easily hydrogen be removed as gas phase, and then the hydrogen of having removed can be recycled as unstripped gas.
In addition, the present invention is preferably 250～450nm to the light wavelength of hydrogen and chlorine irradiation.
According to the present invention, by the light that is 250～450nm to hydrogen and chlorine illumination wavelength, can by chlorine molecule, generate chlorine radical efficiently.
Accompanying drawing explanation
Object of the present invention, characteristic and advantage can become more clear and definite by following detailed description and accompanying drawing.
Figure 1A and Figure 1B are the process picture sheet of the example of the manufacture method of expression hydrogen chloride gas.
Fig. 2 is for representing for implementing the sketch chart of the formation of hydrogenchloride manufacturing installation of the present invention.
Embodiment
Referring to accompanying drawing, explain the preferred embodiment of the present invention.
The mixed gas of hydrogen and chlorine is in the dark stable under room temperature, but by the rayed of heating or ultraviolet ray etc., reacts explosively and carry out.If utilize this reaction, by using highly purified hydrogen and highly purified chlorine as raw material, can disposablely obtain in large quantities highly purified hydrogen chloride gas.
Initiation reaction
Cl
2+ luminous energy → 2Cl(free radical)
Chain reaction
H
2+ Cl(free radical) → HCl+H(free radical)
Cl
2+ H(free radical) → HCl+Cl(free radical)
In initiation reaction, chlorine molecule is accepted luminous energy, ftractures into chlorine radical.Chlorine radical reacts with hydrogen molecule and generates hydrogenchloride, generates hydroperoxyl radical simultaneously.This hydroperoxyl radical and chlorine molecular reaction generate hydrogenchloride, chlorine radical are regenerated simultaneously.Like this, by the chlorine radical generating at first, started, react the chain type that becomes and carry out.
Above-mentioned, by hydrogen and chlorine, directly generated in the reaction of hydrogenchloride, because temperature of reaction is the high temperature of 2500 ℃, so need cooling.Therefore, adopted the hydrogen chloride gas dissolving making as reaction product, the temporary transient manufacture method reclaiming with the form of hydrochloric acid in the past always.As long as ultimate aim thing is that hydrochloric acid is no problem, but in order to reclaim hydrogen chloride gas, need to be from hydrochloric acid separating hydrogen chloride gas, energy efficiency extreme difference.
In any case, for the temperature of inhibited reaction system rises, except water, the material of absorption reaction heat must be made an addition in reaction system.But the material being added in reaction system becomes impurity after reaction finishes, thus the lock out operation of reaction product and hydrogenchloride become essential.
In view of this situation, what the present application people furtherd investigate found that, as finishing the formation reaction of hydrogenchloride and the substance can inhibited reaction temperature rising in reaction system by being added into, as the hydrogen chloride gas of reaction product, be preferred.
While making hydrogen and chlorine reaction under the existence at hydrogen chloride gas, reaction heat is chlorinated hydrogen and absorbs, and the temperature of reaction system can be suppressed to for example 800 ℃ of following temperature.Because hydrogen chloride gas is reaction product, even if be therefore added in reaction system and can not become impurity yet, and do not need the hydrogen chloride gas to generating by reaction to carry out separated with the hydrogen chloride gas as additive.
The invention is characterized in, under the existence of hydrogen chloride gas, the hydrogen of raw material and chlorine are irradiated to light, make hydrogen and chlorine reaction, thereby generate hydrogen chloride gas.
When the irradiation by light causes the reaction of hydrogen and chlorine, because temperature of reaction can rise immediately, therefore hydrogen and chlorine are irradiated to light carry out initiation reaction being pre-existing under the state of hydrogen chloride gas.Therefore, in manufacture method of the present invention, so long as carry out rayed under the existence of hydrogen chloride gas, can be, any order.For example, can be to be pre-mixed hydrogen, chlorine and hydrogen chloride gas to generate mixed gas, generated mixed gas is irradiated to light; Also can be to supply with hydrogen and chlorine under the state that hydrogen chloride gas is irradiated to light; Can also be that hydrogen, chlorine and hydrogen chloride gas are supplied to reactor continuously irradiates light on one side on one side.
Can make the mixture ratio of hydrogen, chlorine and hydrogen chloride gas suitably change.In order temperature of reaction to be suppressed at when reaction finishes 800 ℃ below, preferably below 500 ℃, preferably according to the mole number starting light-struck time point, hydrogen chloride gas with respect to hydrogen and chlorine in less person's mole number be more than 5 times, the preferred mixed chlorinated hydrogen of more than 8 times modes.
When the mole number of hydrogen chloride gas is less than 5 times, the effect of inhibited reaction temperature reduces.In addition, when to make the mole number of hydrogen chloride gas be more than decades of times and widely superfluous, the hydrogenchloride generating due to unit reaction volume and unit reaction times reduces, therefore not preferred.
For the mixture ratio of the hydrogen in unstripped gas and chlorine, the mole number of hydrogen can be 1 with the ratio (mole number of the mole number/chlorine of hydrogen) of the mole number of chlorine, and the mole number of mole number/chlorine that also can hydrogen is less than 1 or be greater than 1.
When the mole number of the mole number/chlorine of hydrogen is less than 1, in the irradiation of light, obtain afterwards as the hydrogen chloride gas of reaction product and the mixture of unreacted chlorine.And when the mole number of the mole number/chlorine of hydrogen is greater than 1, after rayed, obtain as the hydrogen chloride gas of reaction product and the mixture of unreacted hydrogen.Under any circumstance, as long as gained mixture is liquefied, distilled, can obtain highly purified hydrogen chloride gas.
When the mole number of the mole number/chlorine of hydrogen is greater than 1, by gained mixture being compressed after reaction, hydrogenchloride liquefies, but residual as hydrogen because hydrogen can not liquefy, therefore can be by they separation.This separated hydrogen contains micro-hydrogenchloride, can be used as unstripped gas and recycles.By the recycling to this unstripped gas, can be by the hydrogen of raw material and chlorine, with 100% yield in fact, obtain hydrogen chloride gas.
In addition, if the mole number of the mole number/chlorine of hydrogen is greater than at 1 o'clock is preferably below 5 (5 times moles following), more preferably (3 times moles following) 3 below, can be after reaction from gained mixture by hydrogenchloride liquefaction and taking-up effectively.
As mentioned above, the present invention be due to so long as can make hydrogen and chlorine reaction under the existence of hydrogen chloride gas, so processing mode can be batch mode, can be also continuous mode.Fig. 1 means the process picture sheet of example of the manufacture method of hydrogen chloride gas.
As shown in Figure 1A, when being batch mode, in the light for irradiating for initiation reaction is at least part of transparent reaction vessel, enclosing to be pre-mixed becomes the mixed gas of the hydrogen of raw material and chlorine and hydrogen chloride gas (steps A 1 mixed processes).Afterwards, by being arranged at light source outside reaction vessel to reaction vessel internal radiation light, make the unstripped gas reaction (steps A 2 rayed operations) in reaction vessel.After reaction finishes, using hydrogen chloride gas contained in the mixed gas of the hydrogen chloride gas as reaction product and raw material and unreacting material, the mixture of unreacting material when residual takes out from reaction vessel, obtains hydrogen chloride gas.When being batch mode, when reaction starts, the temperature in reaction vessel rises, the pressure rise of the gas of enclosing, so reaction vessel preferably uses pressure vessel.
As shown in Figure 1B, when being continuous mode, hydrogen, chlorine and hydrogen chloride gas are supplied to reaction vessel (step B1 supplies with operation) continuously from supplying tubing.Pass through rayed, in reaction vessel, under hydrogen chloride gas exists, make hydrogen and chlorine reaction (step B2 rayed operation), the mixture of the hydrogen chloride gas as reaction product and the hydrogen chloride gas of supplying with and the unreacting material when having unreacted raw material is taken out continuously from reaction vessel.
Preferably suitably adjust position to the supplying opening of each gas of supplying with in reaction vessel, be supplied to the inflow direction of each gas in reaction vessel etc., according to each gas in reaction vessel, can exist equably and the mode that becomes same admixture is supplied with each gas.For example, preferably according to flowing, can not become the mode of sinuous flow state in reactor each supplied with gas is supplied with, preferably the inflow direction of each gas is set as to the direction of eddy generation in reaction vessel.
Fig. 2 is for representing for implementing the sketch chart of the formation of hydrogenchloride manufacturing installation 1 of the present invention.Hydrogenchloride manufacturing installation 1 has photoreactor 2, water cooler 3, compressor 4 and pump 5.The hydrogen, chlorine and the hydrogen chloride gas that become raw material are supplied to photoreactor 2, in photoreactor 2, under the existence of hydrogen chloride gas, irradiate light, hydrogen and chlorine react, and the hydrogen chloride gas as reaction product and the hydrogen chloride gas of supplying with and the mixture of the unreacting material when having unreacting material are directed in water cooler 3.Utilize water cooler 3 that mixture is cooled to behind 100～200 ℃ of left and right, by a part, again for unstripped gas, compressor 4 compressions for remainder, obtain liquefaction hydrogenchloride.As the composition of raw material, when the mole number of the mole number/chlorine of hydrogen is greater than 1, when utilizing compressor 4 to compress, by by hydrogenchloride liquefaction, make hydrogen contained in mixture keep the former state of gas, can obtain not hydrogeneous hydrogenchloride.
In the reaction of photoreactor 2, owing to can not producing byproduct of reaction etc., in the mixture therefore obtaining afterwards in reaction, do not contain and become the material that raw material forms impurity in addition.Therefore, a part of again utilizing mixture during as unstripped gas, does not need, for removing the lock out operation of impurity, only to use pump 5 part for the mixture of being derived by water cooler 3 to be back to the supply source of raw material.
In addition, utilize 3 pairs of mixtures of deriving from photoreactor 2 of water cooler to carry out cooling until liquefy, also can obtain liquefaction hydrogenchloride.Now do not need compressor 4.In addition, also the hydrogenchloride of temporarily liquefaction can be recycled as raw material.
As mentioned above, the formation reaction of the hydrogenchloride in the present invention is because the formation reaction of the chlorine radical that utilizes the irradiation of light to carry out is the stage that determines speed of response, so the speed of response of the formation reaction integral body large left and right that can not be under pressure.Thereby the necessity that improves the pressure in photoreactor 2 is few, as pressure, although also depend on the supplying temperature of raw material chlorine, is preferably below 1MPa.In addition, pressure in photoreactor 2 is that 0.67MPa is when above, because chlorine at 20 ℃ can liquefy, the chlorine that is therefore supplied to photoreactor 2 proceeds to generating gasification in photoreactor 2 needs the time, thereby need to extend the residence time in photoreactor 2.When utilizing liquefied chlorine, by heating in advance liquefied chlorine, being supplied to photoreactor 2 as chlorine, do not need to extend the residence time, so the pressure in photoreactor 2 can be according to suitably selections such as the specifications of photoreactor 2.
Pressure in photoreactor 2 is during lower than 0.03MPa, and the hydrogen in photoreactor 2 and the dividing potential drop of chlorine reduce, and the collision frequency of each molecule and free radical reduces, and speed of response reduces, so unit photoreactor 2 volumes, the reduction of the productivity in unit reaction times.
For causing light wavelength that hydrogen irradiates with reacting of chlorine so long as the light irradiating can be by chlorine molecular absorption, there is the wavelength of the energy that can shear the key between chlorine atom-chlorine atom that breaks, the preferably wavelength region may of 250～450nm.The light of this wavelength region may is owing to being also contained in sunlight, therefore by by solar light irradiation in unstripped gas, also can initiation reaction.
As for irradiating the light source of the light of this wavelength region may, use high voltage mercury lamp more.As other light source, such as also using XeF(xenon fluoride) excimer laser (irradiation light wavelength is 351nm), XeCl(chlorination xenon) LASER Light Source such as excimer laser (irradiation light wavelength is 308nm).
Carrying out along with reaction, hydrogen in photoreactor 2 and the concentration of chlorine reduce, but as long as the energy of the light that irradiated by light source is roughly 1/1000000th～more than 1/10000th, can generates fully chlorine radical with respect to the chlorine mole number in photoreactor 2 in its photon (photon) number.
Light source is configurable in photoreactor 2, also configurable outside photoreactor 2.Be disposed at photoreactor 2 when outer, adopting the light with respect to above-mentioned wavelength region may is that transparent window member is arranged in the wall portion of photoreactor 2, light is taken in to forming in photoreactor 2 by this window member; Or the conduit that uses the light such as optical fiber imports light into the formation in photoreactor 2.If light source is configured in photoreactor 2, need not use thisly for light-struck formation, be therefore preferred.In addition, if light source is configured in photoreactor 2, do not need to use window member etc., therefore can form with the material of resistance to pressure excellence photoreactor 2.
The speed of response of the hydrogenchloride in the present invention, due to higher, therefore can reduce the volume of photoreactor 2.Preferably being set as supplied with unstripped gas residence time in photoreactor 2 reaches several seconds～tens of seconds such volumes.When the residence time is shorter than this scope, the possibility that a part that has hydrogen or chlorine flows out from photoreactor 2 with unreacted state.When the residence time is longer than this scope, owing to finishing in fact in the interior formation reaction of photoreactor 2, therefore do not need to extend the residence time.
As the material that forms photoreactor 2, as to until the temperature of 500 ℃ of left and right has the material of tolerance, can use general metal material, can preferably make cylinder iron, SUS304, SUS310, SUS316, SUS316L, nickel, titanium, tantalum, high heat-and corrosion-resistant specific alloy etc.In addition, also can preferably use the glass materials such as glass, thermal glass, silica glass, also can utilize these materials to be coated on the material on metallic surface, for example enamel material.And then, as to until the temperature of 250 ℃ of left and right has the material of tolerance, also can use and be coated with the material that ethylene fluoride is the poly-fluorinated hydrocarbons such as resin, polyvinylidene difluoride (PVDF), tetrafluoroethylene.
As water cooler 3, can use tube exchanger, double hose interchanger, enamel heat exchanger made, coil tube type enamel heat exchanger made, submerged coil heat exchanger, spiral heat exchanger, plate-fin heat exchanger, shower serpentine formula interchanger, impervious graphite heat exchanger made etc.
Material as forming water cooler 3, can preferably make cylinder iron, SUS304, SUS310, SUS316, SUS316L, nickel, titanium, tantalum, high heat-and corrosion-resistant specific alloy etc.In addition, also can preferably use the glass materials such as glass, thermal glass, silica glass, also can utilize these materials to be coated on the material on metallic surface, for example enamel material.In addition, also can utilize fluoro-resin impregnation impervious graphite.
As compressor 4, can use reciprocation compressor, screw compressor, membrane compressor, radial compressor etc.In addition, also can replace compressor and use fan.As fan, can utilize reciprocating pump, rotary pump, turboblower, displacement blower, centrifugal fan, mixed flow fan, tubeaxial fan etc.
[embodiment]
(embodiment 1)
The diameter that the introducing port, the bottom that are provided with 2 place's unstripped gases on top is provided with to the outlet of 1 place's reaction product is that 20cm, the high thermal glass rounding cylinder flask for 50cm are used as photoreactor 2.The mode eddying in a circumferential direction on the top of photoreactor 2 according to the unstripped gas being imported by unstripped gas introducing port is blown into unstripped gas in photoreactor 2.Unstripped gas is supplied with from bomb continuously with following feed rate respectively.With the flow of 6NL/ minute, raw hydrogen is supplied with from 1 introducing port.The mixed gas of chlorine and hydrogen chloride gas be take to the flow that chlorine is 120NL/ minute as 5NL/ minute, hydrogen chloride gas to be supplied with from another 1 introducing port.Unit " NL/ minute " is the flux unit with the every volume flowing through for 1 minute of gas (liter) expression of standard state.
In the central authorities of this photoreactor 2, the high voltage mercury lamp (Ushio motor M-102 processed) of configuration 100W, as light source, carries out rayed.The temperature of unstripped gas is 30 ℃, and the temperature of the mixture that contains hydrogen chloride gas of being derived by photoreactor 2 after reaction is 198 ℃.Forming of the mixture of being derived by photoreactor 2 is that hydrogen is that 0.8vol%, hydrogenchloride are 99.2vol%, have no chlorine.
(embodiment 2)
Replacement, in the high voltage mercury lamp as light source is configured in photoreactor 2, but is configured in outside photoreactor 2, by outside, carries out rayed, in addition carries out similarly to Example 1.100W high voltage mercury lamp (Ushio Electric Co., Ltd system, M-102) is configured in to the distance that the center apart from photoreactor 2 is 1m.The temperature of unstripped gas is 30 ℃, and the temperature of the mixture that contains hydrogen chloride gas of being derived by photoreactor 2 after reaction is 190 ℃.Forming of the mixture of being derived by photoreactor 2 is that hydrogen is that 0.7vol%, hydrogenchloride are that 99.3vol%, chlorine are 50ppm.
(embodiment 3)
Except the flow of the hydrogen that makes to import is that 16.5NL/ minute, the flow of chlorine are that 15NL/ minute, the flow of hydrogen chloride gas are 120NL/ minute, carry out similarly to Example 2.The temperature of unstripped gas is 30 ℃, and the temperature of the mixture that contains hydrogen chloride gas of being derived by photoreactor 2 after reaction is 480 ℃.Forming of the mixture of being derived by photoreactor 2 is that hydrogen is that 1.0vol%, hydrogenchloride are 99.0vol%, have no chlorine.
(embodiment 4)
Using frozen water as refrigerant, and the condenser that use SUS316L system, heat transfer area are 0.3m2, as water cooler 3, carries out cooling to the mixture that contains hydrogen chloride gas of being derived by photoreactor 2 of embodiment 1.By water cooler 3, the temperature of mixture is cooled to 30 ℃.Utilize pump 5 to collaborate with the 120NL/ minute chlorine by this mixture and raw material, mixture is recycled as unstripped gas.The temperature of unstripped gas is 30 ℃, and the temperature of the mixture that contains hydrogen chloride gas of being derived by photoreactor 2 after reaction is 190 ℃.Forming of the mixture of being derived by photoreactor 2 is that hydrogen is that 0.6vol%, hydrogenchloride are 99.4vol%, have no chlorine.
(embodiment 5)
Use compressor 4 that the mixture of being derived by water cooler 3 of embodiment 4 is compressed to 0.9MPaG, cooling by utilizing dry ice-propanone refrigeration agent (78 ℃) to carry out the container with sleeve pipe (volume is 2L), make hydrogenchloride liquefaction.Now, by other pipeline gas phase cleaned on one side, reaction 1 hour continued on one side.The liquefaction hydrogenchloride of gained is 958kg, and yield is 98%.Hydrogen as impurities in liquefaction hydrogenchloride is below 1ppm.
(embodiment 6)
Except the flow of the hydrogen that makes to import is that 4NL/ minute, the flow of chlorine are that 5NL/ minute, the flow of hydrogen chloride gas are 120NL/ minute, carry out similarly to Example 1.The temperature of unstripped gas is 30 ℃, and the temperature of the mixture that contains hydrogen chloride gas of being derived by photoreactor 2 after reaction is 160 ℃.Forming of the mixture of being derived by photoreactor 2 is that hydrogen is that 0.8vol%, hydrogenchloride are 99.2vol%, have no chlorine.
(embodiment 7)
Except the flow of the hydrogen that makes to import is that 6NL/ minute, the flow of chlorine are that 5NL/ minute, the flow of hydrogen chloride gas are 120NL/ minute and make they are pre-mixed the mixed gas forming is directed in photoreactor 2, carry out similarly to Example 1.The temperature of unstripped gas is 30 ℃, and the temperature of the mixture that contains hydrogen chloride gas of being derived by photoreactor 2 after reaction is 198 ℃.Forming of the mixture of being derived by photoreactor 2 is that hydrogen is that 0.8vol%, hydrogenchloride are 99.2vol%, have no chlorine.
The present invention can implement with other various forms in the situation that not departing from its spirit or principal character.Therefore, aforesaid embodiment is only simple example in all respects, and scope of the present invention is shown in claims, is not subject to specification sheets any constraint herein.And then, belong to the distortion of claims or change all within the scope of the invention.
Claims (6)
1. a chlorination method for preparing hydrogen, is characterized in that, under the existence of hydrogen chloride gas, hydrogen and chlorine is irradiated to light, makes hydrogen and chlorine reaction, thereby generates hydrogen chloride gas.
2. a chlorination method for preparing hydrogen, is characterized in that, has following operation:
Mix hydrogen, chlorine and hydrogen chloride gas to obtain the mixed processes of mixed gas; With
Mixed gas is irradiated to light so that contained hydrogen and chlorine reaction and generate the rayed operation of hydrogen chloride gas in mixed gas.
3. a chlorination method for preparing hydrogen, is characterized in that, has following operation:
Hydrogen, chlorine and hydrogen chloride gas are supplied to respectively continuously to the supply operation of reactor; With
Under the existence of hydrogen chloride gas to being supplied to that the hydrogen of reactor and chlorine irradiate light so that hydrogen and chlorine reaction and generate the rayed operation of hydrogen chloride gas.
4. according to the chlorination method for preparing hydrogen described in claim 1～3 any one, it is characterized in that, the mole number that makes to start the hydrogen chloride gas of light-struck time point is the more than 5 times of mole number of less person in hydrogen mole number and chlorine mole number.
5. according to the chlorination method for preparing hydrogen described in claim 1～3 any one, it is characterized in that, make to start the mole number of hydrogen of light-struck time point more than the mole number of chlorine.
6. according to the chlorination method for preparing hydrogen described in claim 1～3 any one, it is characterized in that, is 250～450nm to the light wavelength of hydrogen and chlorine irradiation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-219238 | 2012-10-01 | ||
| JP2012219238A JP5955187B2 (en) | 2012-10-01 | 2012-10-01 | Method for producing hydrogen chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103708420A true CN103708420A (en) | 2014-04-09 |
Family
ID=50401823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310452021.2A Pending CN103708420A (en) | 2012-10-01 | 2013-09-27 | Method of producing hydrogen chloride |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5955187B2 (en) |
| KR (1) | KR101812081B1 (en) |
| CN (1) | CN103708420A (en) |
| TW (1) | TWI510435B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107311184A (en) * | 2016-04-26 | 2017-11-03 | 内蒙古盾安光伏科技有限公司 | A kind of production technology for improving producing trichlorosilane by coldly hydrogenating conversion ratio |
| CN107848799A (en) * | 2015-08-10 | 2018-03-27 | 昭和电工株式会社 | Chlorination method for preparing hydrogen |
| CN108079747A (en) * | 2017-12-14 | 2018-05-29 | 邱苏英 | A kind of chemical industry experiment hydrochloric acid device for making |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05105408A (en) * | 1991-10-17 | 1993-04-27 | Tsurumi Soda Kk | Device for synthesis of hydrochloric acid and production method therefor |
| CN1890174A (en) * | 2003-12-11 | 2007-01-03 | 旭硝子株式会社 | Method and apparatus for producing carbonyl fluoride |
| CN101248006A (en) * | 2005-08-26 | 2008-08-20 | 昭和电工株式会社 | Method and apparatus for producing nitrogen trifluoride |
| US20110081561A1 (en) * | 2009-05-29 | 2011-04-07 | Majid Keshavarz | Methods of producing hydrochloric acid from hydrogen gas and chlorine gas |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5120092A (en) * | 1974-08-12 | 1976-02-17 | Asahi Denka Kogyo Kk | GASUNOSEISEIHO |
| JPS5120094A (en) * | 1974-08-12 | 1976-02-17 | Asahi Denka Kogyo Kk | ENKASUISOGASUNOSEIHO |
| JPS5121596A (en) * | 1974-08-19 | 1976-02-20 | Showa Denko Kk | Ensogasuno seiseiho |
| FR2560067B1 (en) * | 1984-02-24 | 1989-04-07 | Vicarb Sa | METHOD AND DEVICE FOR UNIFYING, OR MAINTAINING, A CHEMICAL REACTION BY PHOTON EXCITATION |
| JPS61276325A (en) * | 1985-05-31 | 1986-12-06 | Fujitsu Ltd | Etching method for silicon substrate |
| JP5037022B2 (en) * | 2006-02-24 | 2012-09-26 | 公立大学法人大阪府立大学 | Method for producing dry hydrogen halide |
-
2012
- 2012-10-01 JP JP2012219238A patent/JP5955187B2/en active Active
-
2013
- 2013-09-11 KR KR1020130109155A patent/KR101812081B1/en active IP Right Grant
- 2013-09-13 TW TW102133256A patent/TWI510435B/en active
- 2013-09-27 CN CN201310452021.2A patent/CN103708420A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05105408A (en) * | 1991-10-17 | 1993-04-27 | Tsurumi Soda Kk | Device for synthesis of hydrochloric acid and production method therefor |
| CN1890174A (en) * | 2003-12-11 | 2007-01-03 | 旭硝子株式会社 | Method and apparatus for producing carbonyl fluoride |
| CN101248006A (en) * | 2005-08-26 | 2008-08-20 | 昭和电工株式会社 | Method and apparatus for producing nitrogen trifluoride |
| US20110081561A1 (en) * | 2009-05-29 | 2011-04-07 | Majid Keshavarz | Methods of producing hydrochloric acid from hydrogen gas and chlorine gas |
Non-Patent Citations (2)
| Title |
|---|
| 《中学化学教师手册》编写组: "《中学化学教师手册》", 31 December 1985 * |
| 郑石子等: "《聚氯乙烯生产与操作》", 31 January 2008 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107848799A (en) * | 2015-08-10 | 2018-03-27 | 昭和电工株式会社 | Chlorination method for preparing hydrogen |
| CN107848799B (en) * | 2015-08-10 | 2020-07-17 | 昭和电工株式会社 | Method for producing hydrogen chloride |
| CN107311184A (en) * | 2016-04-26 | 2017-11-03 | 内蒙古盾安光伏科技有限公司 | A kind of production technology for improving producing trichlorosilane by coldly hydrogenating conversion ratio |
| CN108079747A (en) * | 2017-12-14 | 2018-05-29 | 邱苏英 | A kind of chemical industry experiment hydrochloric acid device for making |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014070006A (en) | 2014-04-21 |
| KR20140043274A (en) | 2014-04-09 |
| TW201418162A (en) | 2014-05-16 |
| JP5955187B2 (en) | 2016-07-20 |
| TWI510435B (en) | 2015-12-01 |
| KR101812081B1 (en) | 2017-12-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6812988B2 (en) | Method for producing 1-chloro-2,3,3,3-tetrafluoropropene | |
| TWI429587B (en) | Production process for high purity silicon | |
| CN103708420A (en) | Method of producing hydrogen chloride | |
| US4117250A (en) | Continuous process for producing alkylene glycols from alkylene carbonates | |
| CN107108409A (en) | Method for preparing high-purity chloralkane | |
| JP3967376B2 (en) | Production of carbonyl fluoride | |
| CN101747176A (en) | Method for preparation of trifluoro acetyl chloride with trifluoroethane chlorinated mixture | |
| TW201348136A (en) | Method and apparatus for producing fluorine gas | |
| WO2010055769A1 (en) | Inter-halogen compound synthesis method | |
| CN107686443A (en) | A kind of production method of chlorine pinacoline | |
| CN203816452U (en) | System for treating by-product exhaust generated in chloromethane production | |
| CN103879977B (en) | A kind of continuous production method of high pure nitric acid and production equipment | |
| JP2010116282A (en) | Method for producing germanium tetrafluoride | |
| US7413722B2 (en) | Method and apparatus for manufacturing nitrogen trifluoride | |
| JPS58162536A (en) | Production of carbon tetrafluoride | |
| JPH11322703A (en) | Photochemical sulfochlorination of gaseous alkanes | |
| CN106744685A (en) | The deep-purifying method of circulating hydrogen in electronic-grade polycrystalline silicon production | |
| TW201335112A (en) | Process and apparatus for heat recovery in vinyl chloride monomer plants or in integrated vinyl chloride monomer/polyvinyl chloride plants | |
| WO2019168115A1 (en) | Production method for 1,2-dichloro-2,3,3,3-tetrafluoropropane and production method for 1-chloro-2,3,3,3-tetrafluoropropene | |
| JP6730605B2 (en) | Method for producing iodine pentafluoride oxide | |
| JP5288026B2 (en) | Method for producing carbonyl fluoride | |
| JP2010116281A (en) | Method for producing interhalogen compound | |
| KR100876290B1 (en) | A apparatus for preparing electrolyte solvent | |
| CN203741044U (en) | Continuous production device of high-purity nitric acid | |
| JP2010116280A (en) | Method for synthesizing interhalogen compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140409 |