CN103476705A - Use of liquid hydrogen chloride as a refrigerant in methods for producing chlorine - Google Patents
Use of liquid hydrogen chloride as a refrigerant in methods for producing chlorine Download PDFInfo
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- CN103476705A CN103476705A CN2012800189953A CN201280018995A CN103476705A CN 103476705 A CN103476705 A CN 103476705A CN 2012800189953 A CN2012800189953 A CN 2012800189953A CN 201280018995 A CN201280018995 A CN 201280018995A CN 103476705 A CN103476705 A CN 103476705A
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- 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
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- 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
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- 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
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- 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
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- 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
- C01B7/0712—Purification ; Separation of hydrogen chloride by distillation
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- 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
- C01B7/0743—Purification ; Separation of gaseous or dissolved chlorine
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Abstract
The invention relates to a method for producing chlorine from hydrogen chloride, comprising the following steps: a) making a liquid hydrogen chloride flow a available as a refrigerant flow; b) feeding at least one flow b1 that contains hydrogen chloride and a flow b2 that contains oxygen to a hydrogen chloride oxidation zone and catalytically oxidizing hydrogen chloride to chlorine, a product gas flow b3 being obtained that contains chlorine, water, oxygen, carbon dioxide and inert gases; c) contacting the product gas flow b3 with aqueous hydrochloric acid I in a phase contact unit and partially removing water and hydrogen chloride from flow b3, a gas flow c being obtained that contains hydrogen chloride, chlorine, water, oxygen, carbon dioxide and optionally inert gases; d) drying the gas flow c, a substantially water-free gas flow d remaining that contains hydrogen chloride, chlorine, oxygen, carbon dioxide and optionally inert gases; e) partially liquefying the gas flow d by compression and cooling, an at least partially liquefied flow e being obtained; f) performing a gas-liquid separation of flow e to give a gas flow f1 that contains chlorine, oxygen, carbon dioxide, hydrogen chloride and optionally inert gases and a liquid flow f2 that contains hydrogen chloride, chlorine, oxygen and carbon dioxide, and optionally returning at least part of gas flow f1 to step b); g) separating liquid flow f2 by distillation in a column to give a chlorine flow g1 and a flow g2 that substantially consists of hydrogen chloride, oxygen and carbon dioxide; the cooling and partial liquefaction of gas flow d in step e) being the result of indirect heat exchange with the liquid hydrogen chloride flow a, at least a part of the liquid hydrogen chloride flow a being evaporated and this part being obtained as gaseous hydrogen chloride flow a'.
Description
The present invention relates to a kind of method by preparation of hydrogen chloride chlorine, wherein liquid hydrogenchloride is used as refrigeration agent, and relates to liquid hydrogenchloride purposes as refrigeration agent in preparing the method for chlorine.
For example, in the chemical process of much use chlorine or chlorine derived product (phosgene), hydrogenchloride obtains as by product.The preparation that example is isocyanic ester, polycarbonate and the chlorination of aromatic substance.The hydrogenchloride obtained as by product can be by electrolysis or by with dioxygen oxidation, transforming back chlorine.In this way the chlorine of preparation can then be repeated to utilize.
By Deacon in the method for catalyzed oxidation hydrogenchloride of exploitation in 1868, hydrogenchloride becomes chlorine by dioxygen oxidation in the exothermic equilibrium reaction.Hydrogenchloride makes the preparation of chlorine to separate with the preparation of the sodium hydroxide undertaken by chloric alkali electrolysis to the conversion of chlorine.This separation is attracting, and this is because the needs that for the world of chlorine, need to be compared to sodium hydroxide increase rapidlyer.
In the currently known methods of useful hydrogen chloride oxidation with oxygen, reaction obtains not only comprising the gaseous mixture that target product chlorine also comprises water, unreacted hydrogenchloride and oxygen and possible other submembers (for example carbonic acid gas and rare gas element).For obtaining pure chlorine, this product gas mixture is cooled to the degree that the water of reaction and hydrogenchloride condense with the form of concentrated hydrochloric acid after reaction.Isolate formed hydrochloric acid and by with vitriol oil washing or by remove the residuary water in residual gas mixture with Zeolite dehydration.Compression cooling this anhydrous gas mixture so that chlorine condense and oxygen and other low-boiling point gas compositions are still stayed in gas phase subsequently.Separate and optionally be further purified the chlorine of described liquefaction.
EP-A 0 765 838 discloses a kind of method of this reactant gases of aftertreatment, described reactant gases is by the chlorine obtained in oxidation of hydrogen chloride, hydrogenchloride, oxygen and water vapor form, the reactant gases that wherein leaves oxidation reactor is cooled to the degree that the water of reaction and hydrogenchloride condense with the form of concentrated hydrochloric acid, this concentrated hydrochloric acid is isolated and discharged from reactant gases and the residue reactant gases that has basically removed moisture and partial oxidation hydrogen is carried out to drying, will be by chlorine, the reactant gases of the drying that oxygen and hydrogenchloride form is compressed to 1 to 30 bar and cooling and therefore most of liquefaction by the reactant gases of this compression, the reactive gas species that can not be condensed out is recycled in reactor at least partly.
In order to separate chlorine, extremely approximately 10 to 20% remaining proportion liquefies the reaction gas mixtures of drying compression in being configured to the chlorine recuperator of flash cooler.Subsequently will be in the chlorine recuperator in distillation tower the main cl gas flow of isolated liquid state carry out after purifying, in described distillation tower, chlorine has removed hydrogenchloride, oxygen and the rare gas element of residual dissolving.The main gas re-circulation be comprised of hydrogenchloride, chlorine, oxygen and rare gas element shifted out at the top of distillation tower is to compression stage.The gaseous fraction do not condensed in the chlorine recuperator (comprising residual chlorine) in rear cooling stages at significantly lower temperature partial liquefaction.The residual exhaust that contains unreacted hydrogenchloride, oxygen and rare gas element is recycled in oxidation reactor.Make the subflow of recycle gas isolate as gaseous purge stream and discharge to avoid the accumulation of impurity from this process.
WO 2007/134716 has put down in writing with WO 2007/085476 advantageous effects that has HCl in chlorine separates.In method in being recorded in WO 2007/085476, carry out condensation phase to water and HCl so that the hydrogenchloride of favourable amount enters compressor by drying stage together with process gas and chlorine subsequently separates.In method in being recorded in WO 2007/134716, the part gaseous hydrogen chloride takes out and is fed directly in the separation of chlorine by other the treatment stage from the feedstream of the process of entering.
Put down in writing a kind of method by preparation of hydrogen chloride chlorine in WO 2007/085476.The method comprises the following steps:
A) the material stream a2 that introduces the material stream a1 that comprises hydrogenchloride and comprise oxygen to oxidation zone, and the catalytic oxidation of hydrogen chloride is become to chlorine, obtain the product gas flow a3 that comprises chlorine, water, oxygen, carbonic acid gas and rare gas element;
B) then product gas flow a3 is contacted in the device that contacts with hydrochloric acid soln I and partly isolate water and hydrogenchloride from material stream a3, obtain comprising the air-flow b of hydrogenchloride, chlorine, water, oxygen, carbonic acid gas and possible rare gas element, and at least 5% the hydrogenchloride be contained in material stream a3 is still stayed in air-flow b;
C) drying air stream b, obtain the substantially anhydrous air-flow c that comprises hydrogenchloride, chlorine, oxygen, carbonic acid gas and possible rare gas element;
D), by compressing and the cooling partial liquefaction air-flow c of coming, obtain the material stream d of liquefaction at least partly;
E) will expect that stream d gas/liquid is separated into air-flow e1 and the liquid stream e2 that comprises hydrogenchloride, chlorine, oxygen and carbonic acid gas that comprises chlorine, oxygen, carbonic acid gas, hydrogenchloride and possible rare gas element and optionally at least part of air-flow e1 is recycled in step a);
F) by distillation in tower, liquid is flowed to the material stream f2 that e2 is separated into cl gas flow f1 and mainly is comprised of hydrogenchloride, oxygen and carbonic acid gas, during simultaneously partial oxidation hydrogen is back to tower in the condensation of the top of tower and as anti-stream (runback), the material stream f2 that to obtain thus chlorine content be<1 % by weight.
In step d), the air-flow c that will mainly by chlorine and oxygen, be formed and be contained in addition the drying of hydrogenchloride and rare gas element (carbonic acid gas, nitrogen) is compressed to approximately 10 to 40 bar in a plurality of stages.This pressurized gas is cooled to the temperature of approximately-10 to-40 ℃.
Finally by this compression and two-phase mixture partial liquefaction fractionation in mass transfer rig.Now, not the air-flow of liquefaction with adverse current or and stream mode with the main liquid formed by carbonic acid gas, hydrogenchloride and the oxygen of chlorine and dissolving, contact.What therefore, the gas of liquefaction was not assembled until reach thermodynamic(al)equilibrium in liquid chlorine, thereby can realize rare gas element by the tail gas from chlorine distills subsequently---particularly carbonic acid gas---removes.
The liquefied chlorine gas of common chlorine content>85 % by weight is approximately being distilled under 10 to 40 bar.Bottom temp is approximately 30 to 110 ℃, and head temperature---depends on the hydrogen chloride content in liquefied chlorine gas---for approximately-5 to-8 ℃ of peace treaty-25 to-30 ℃.Hydrogenchloride is in the condensation of the top of tower being back to tower.Because HCl refluxes, therefore almost realized the separation fully of chlorine and therefore made the chlorine minimization of loss.The purity of have>99.5 % by weight of the chlorine shifted out from the bottom of tower.
In order to form low temperature, usually use refrigerator.Suitable refrigeration agent for as be recorded in US 5,490, the full halogenated hydrocarbon in 390.Full halogenated hydrocarbon utmost point torpescence.It is not with chlorine with in the situation that other materials that leak in being present in chlorine production equipment carry out any chemical reaction, and this angle from safety is considered highly beneficial.But these materials have the excessive risk of Latent destruction ozonosphere when discharging into the atmosphere, so its application is extremely restricted or forbids in a large number.
More active and therefore in the situation that the chlorine equipment leakage causes the risk of undesired chemical reaction as the hydrocarbon of the only part halo that replaces refrigeration agent.
Ammonia is similarly the fit closely refrigeration agent for refrigerator.But, directly ammonia not being had to practical significance for the chlorine condensation, this is because in the situation that NCl can occur in leakage
3formation, its even also explosibility decomposition under lower concentration.
A kind of for avoiding chlorine with refrigeration agent in the situation that to leak the possibility directly contact be the safe interchanger that sleeve pipe and Gap monitoring are equipped with in use.Another kind of possibility is to provide a kind of intermediate enclosed secondary coolant circuit that uses the inert cryogen operation, as is recorded in US 5,490, in 390.In the situation that chlorine is as material to be cooled, CO
2be suitable as inert cryogen.
An object of the present invention is to provide a kind ofly by the improving one's methods of preparation of hydrogen chloride chlorine, described method considers it is favourable from economy and security standpoint.Another object of the present invention is to provide a kind of for separate alternative refrigeration agent of chlorine from the process air-flow of chlorine production equipment by condensation.
This purpose is by the realization of the method by preparation of hydrogen chloride chlorine, and it comprises the following steps:
A) provide liquid hydrogenchloride material stream a as refrigerant stream;
B) the material stream b2 that introduces at least one material stream b1 that comprises hydrogenchloride and comprise oxygen to oxidation zone, and the catalytic oxidation of hydrogen chloride is become to chlorine, obtain the product gas flow b3 that comprises chlorine, water, oxygen, carbonic acid gas and rare gas element;
C) product gas flow b3 is contacted in the device that contacts with hydrochloric acid soln and from material stream b3 part isolate water and hydrogenchloride, obtain comprising the air-flow c of hydrogenchloride, chlorine, water, oxygen, carbonic acid gas and possible rare gas element;
D) drying air stream c, obtain the substantially anhydrous air-flow d that comprises hydrogenchloride, chlorine, oxygen, carbonic acid gas and possible rare gas element;
E), by compressing and the cooling partial liquefaction air-flow d of coming, obtain the material stream e of liquefaction at least partly;
F) will expect that stream e gas/liquid is separated into air-flow f1 and the liquid stream f2 that comprises hydrogenchloride, chlorine, oxygen and carbonic acid gas that comprises chlorine, oxygen, carbonic acid gas, hydrogenchloride and possible rare gas element and optionally at least part of air-flow f1 is recycled in step b);
G) by distillation in tower, liquid is flowed to the material stream g2 that f2 is separated into cl gas flow g1 and mainly is comprised of hydrogenchloride, oxygen and carbonic acid gas,
Wherein in step e), the cooling and partial liquefaction of air-flow d, by carrying out with liquid hydrogenchloride material stream a indirect heat exchange, causes at least part of liquid hydrogenchloride material stream a evaporation and this part to form gaseous hydrogen chloride material stream a '.
By in indirect heat exchange cooling, hydrogenchloride material stream a does not directly contact each other with air-flow d, and directly contact will cause the mixing of material stream.But heat exchange is carried out in interchanger.Described interchanger can have any structure.Suitable interchanger is for example tube and shell heat exchanger, U-shaped tube heat-exchanger, spiral-plate exchanger or plate-type heat exchanger.
Have been found that HCl be particularly suitable as chlorine is to inertia material as the refrigeration agent in chlorine production equipment.
HCl can be by carrying out relatively easily condensation by condensation with conventional refrigeration equipment under 10 to 25 bar under the condensing temperature of-10 to-40 ℃.
The easy means that the use of hydrogenchloride of liquefaction be take by evaporation by this way as chlorine in low temperature range the condensation of (temperature<20 ℃) required " refrigeration " is provided.The HCl---running status that depends on the HCl oxidation furnaces---of evaporation needn't all circulate (i.e. cooling, optionally compression and condensation again), but can be used as gaseous feed, is delivered in the HCl-oxidation furnaces.
HCl is in the situation that interchanger may leak HCl and chlorine does not carry out any chemical reaction as an advantage of operative.
Another advantage is, consistent with the vapor-pressure curve of HCl, when HCl evaporates, can realize low temperature.For example, set up respectively the vaporization temperature-32 ℃ ,-42 ℃ and-51 ℃ of HCl under the pressure of 10,7 and 5 bar.Therefore, under low pressure or for example, under the existence of gas (nitrogen, carbonic acid gas, oxygen, argon gas and hydrogen) chlorine can be by total condensation.The dividing potential drop of chlorine in gas phase that can realize under said temperature-32 ℃ ,-42 ℃ and-51 ℃ is respectively 1.11,0.71 and 0.45 bar.
Usually, the pressure that liquid hydrogenchloride material stream a exists is 1 to 30 bar, and preferably 5 to 15 bar, and the temperature of liquid hydrogenchloride should be-80 to-10 ℃ mutually, preferably-50 to-20 ℃.
The chlorine that can realize under above-mentioned low temperature divides to be pressed in to be used in hydrogen chloride oxidation with oxygen advantageous particularly by deacon process (Deacon process), this is to issue raw food because of the existence at process gas and rare gas element to coagulate, and chlorine utmost point from residual gas separates and expects completely simultaneously.At first, the major portion of remaining uncooled air-flow is recycled in chloration hydro-oxidation; The chlorine that is not separated and stays in air-flow will be reduced in HCl conversion possible in the HCl oxidation reactor.Secondly, the uncooled air-flow of part is discharged the gathering with restriction rare gas element (particularly nitrogen and carbonic acid gas) from process.But the chlorine be included in gaseous purge stream has improved the expense for the aftertreatment gaseous purge stream.Relative chlorine loss has also reduced the chlorine output in the process.
Liquid hydrogenchloride material stream easily mode by under 10 to 25 bar under the condensing temperature of-10 ℃ to-40 ℃ the conventional refrigeration equipment condensation of use prepare.This is combined with for example isocyanic ester or polycarbonate equipment is favourable, but this be because in these equipment, obtain make the hydrogenchloride simple condensation as the rare gas element lower than the low ratio of 10 volume % in the hydrogenchloride of by product.With by distillation purifying hydrogenchloride, combine advantageous particularly, this be because this obtained near the hydrogenchloride that there is higher degree dew point.
The HCl as by product of gained in polycarbonate or isocyanic ester equipment is compressed in the treatment step of the method, purifying (for example passing through distillation purifying) and condensation.After decompression, during the chlorine of HCl after the HCl oxidation of liquefaction is separated for cooling and therefore evaporation.Gaseous state HCl material stream is divided into for the feed stream of HCl oxidation and is recycled to polycarbonate or isocyanic ester equipment again in the recycle stream of this liquefaction according to manipulation require.
Usually, use in the methods of the invention the hydrogenchloride as tail gas stream of gained in the process that forms hydrogenchloride as co-product.These processes are for for example
(1) prepare isocyanic ester by phosgene and amine,
(2) prepare chloride of acid,
(3) prepare polycarbonate,
(4) prepare vinyl chloride by Ethylene Dichloride,
(5) chlorination of aromatic substance.
The HCl material stream of evaporation needn't all circulate (i.e. all compression and condensations again), but can be used as gaseous feed, is fed in the HCl oxidation.For the refrigeration of raising amount is provided in the HCl oxidation furnaces, all with the HCl of part evaporation, can again be compressed and condensation.For example, the HCl air-flow can be recycled to HCl compression stage or the HCl purification phase of polycarbonate or isocyanic ester equipment.
Usually, as the have>95 volume % of hydrogenchloride of refrigeration agent, the purity of preferably>99 volume %.Can comprise carbonic acid gas and micro CO or nitrogen as submember.
In an embodiment of the inventive method, prepared by liquid hydrogenchloride material stream a in the method for the preparation of polycarbonate.In another embodiment of the inventive method, prepared by liquid hydrogenchloride material stream a in the method for the preparation of isocyanic ester.
About the method for the preparation of isocyanic ester, WO04/056758 has put down in writing a kind of method of the mixture that comprises hydrogenchloride, phosgene, possible solvent, low-boiling-point substance and rare gas element for fractionation partially or completely, described mixture usually by amine with obtain during reacting of phosgene prepares isocyanic ester.Put down in writing and removed phosgene so that the hydrogenchloride as by product obtained is purified to the degree that can be used for other purposes.Herein, phosgene obtains as bottoms in distillation tower.Except as described by the solvent with suitable in this application---preferably synthesizing isocyanate solvent---washing be further purified HCl, the enriching section of tower can be equally under suitable pressure and temperature condition by distillation be further purified HCl and at the top of tower as liquid state discharge expect to flow acquisition HCl.This also can realize by the air-flow that compresses and distill subsequently gained.
In an embodiment of the inventive method, in step b), gaseous hydrogen chloride material stream a ' is fed to oxidation zone as the material stream b1 that contains hydrogenchloride at least partly.This part is generally 10 to 90% of hydrogenchloride material stream a.
In another embodiment of the invention, gaseous hydrogen chloride material stream a ' again liquefies and reuses as refrigerant stream at least partly.This part is generally 10 to 90% of hydrogenchloride material stream a.
At oxidation step b) in, the material stream b1 that contains hydrogenchloride is fed to oxidation zone catalyzed oxidation together with the material stream b2 that contains oxygen.
Hydrogenchloride b1 at least part of introducing step b) can come from chlorine separating step e) in the evaporation refrigerant stream a.
In catalytic process, hydrogenchloride becomes chlorine by dioxygen oxidation in the exothermic equilibrium reaction, produces water vapour.The popular response temperature is 150 to 500 ℃, and popular response pressure is 1 to 25 bar.In addition, advantageously use superstoichiometric oxygen.For example, excessive the commonly using of twice to four times oxygen.
Suitable catalyzer comprises ruthenium oxide, ruthenium chloride or other the ruthenium compound on silicon-dioxide, aluminum oxide, titanium dioxide or the zirconium dioxide for example loaded on as carrier.Suitable catalyzer can be for example by being carried on ruthenium chloride on carrier and subsequent drying or drying and roasting acquisition.
Except ruthenium compound or replace ruthenium compound, suitable catalyzer also can comprise the compound of other precious metals, for example gold, palladium, platinum, osmium, iridium, silver, copper or rhenium.Suitable catalyzer also can comprise chromic oxide (III).
The popular response device that carries out the catalyzed oxidation of hydrogenchloride is fixed bed or fluidized-bed reactor.Oxidation of hydrogen chloride can carry out in a plurality of stages.
The catalyzed oxidation of hydrogenchloride can be adiabatic or preferably isothermal or approximate isothermal ground, in batches (preferably continuously) as fluidized-bed or fixed bed process, carry out.Preferably in fluidized-bed reactor, at the temperature of 320 to 450 ℃, under the pressure of 2 to 10 bar, carry out.
When this reaction is carried out in fixed bed, also can use a plurality of (2 to 10, preferably 2 to 6, particularly preferably 2 to 5, particularly 2 to the 3) reactor be connected in series with other intercooling.Oxygen or can with together with the hydrogenchloride of the first reactor upstream, introduce or this introducing can be distributed in each reactor.Each reactors in series connection also can be combined in a device.
Suitable heterogeneous catalyst is in particular ruthenium compound or the copper compound be carried on solid support material, and it also can be adulterated; The ruthenium catalyst preferably optionally adulterated.Suitable solid support material for for example silicon-dioxide, graphite, there is rutile or anatase structured titanium dioxide, zirconium dioxide, aluminum oxide or its mixture, preferred titanium dioxide, zirconium dioxide, aluminum oxide or its mixture, particularly preferably gama-alumina or Alpha-alumina or its mixture.
The copper of load or ruthenium catalyst can be for example by using CuCl
2or RuCl
3optionally promote the solution impregnating carrier material of the promotor (promoter)---preferably with its muriatic form---of doping.The moulding of catalyzer can be after the dipping of solid support material or is preferably carried out before it.
The promotor that is suitable for doping is for example lithium, sodium, potassium, rubidium and caesium of basic metal, preferred lithium, sodium and potassium, particularly preferably potassium; Alkaline-earth metal is magnesium, calcium, strontium and barium for example, preferably magnesium and calcium, particularly preferably magnesium; Rare earth metal is scandium, yttrium, lanthanum, cerium, praseodymium and rubidium for example, preferably scandium, yttrium, lanthanum and cerium, particularly preferably lanthanum and cerium, or its mixture.
Preferred promotor is calcium, silver and nickel.Particularly preferably the combination of the combination of ruthenium and silver and calcium and ruthenium and nickel is as promotor.
Hydrogenchloride and oxygen are generally 1:1 to 20:1 in the volume ratio at reactor inlet place, preferably 2:1 to 8:1, particularly preferably 2:1 to 5:1.
In step c), product gas flow b3 contacts in the device that contacts with hydrochloric acid soln I, and part is isolated water and hydrogenchloride from material stream b3, obtains containing the air-flow b of hydrogenchloride, chlorine, water, oxygen, carbonic acid gas and possible rare gas element.In this step---it also can be described as and quenches and absorption step, cooled product air-flow b3 and separate at least partly water outlet and hydrogenchloride as hydrochloric acid soln from product gas flow b3.Hot product stream b3 for example, by contacting and cooling with the dilute hydrochloric acid I as quenchant in the device that contacts suitable (packing tower or tray column, jet scrubber or spray column), and partial oxidation hydrogen is absorbed in quenchant simultaneously.Quenching and absorbing medium are the hydrochloric acid that non-hydrogenchloride is saturated.
Usually, the circulation hydrochloric acid I operation for device that contacts.In a preferred embodiment, the hydrochloric acid soln that (for example 1 to 20%) circulates in the device that contacts at least partly shifts out from the device that contacts and distillation subsequently obtains gaseous hydrogen chloride and exhausts the hydrochloric acid soln II of hydrogenchloride, simultaneously hydrogenchloride be recycled in step b) and at least partly hydrochloric acid soln II be recycled in the device that contacts.
The air-flow c that leaves the device that contacts comprises chlorine, hydrogenchloride, water, oxygen, carbonic acid gas and usually also comprises rare gas element.Can be by drying stage d subsequently) in contact the micro-moisture of removal with suitable siccative.Suitable siccative is for example vitriol oil, molecular sieve or water absorbability absorption agent.Acquisition comprises chlorine, oxygen, carbonic acid gas and possible rare gas element and substantially water-free air-flow d.
In step e), by dry air-flow d, cooling and optional compression is to obtain material stream e cooling and optional compression.
According to the present invention, cooling by optionally the air-flow d of compressed and pre-cooled drying is cooling in advance by what use liquid hydrogenchloride material to flow in one or more interchanger.Cooling material stream e has 2 to 35 bar, the preferably pressure of 3 to 10 bar, and the temperature of-80 to-10 ℃, preferred-50 to-20 ℃ usually.
Usually the air-flow d of cooling drying being compressed in some stages.At first air-flow d this drying and optional compression can be cooled to the approximately temperature of 40 to 5 ℃ with water coolant or cold water.Can in the interchanger of the liquid hydrogenchloride of one or more uses as refrigeration agent, make subsequently this optional also pre-cooled air-flow d compressed be cooled to and be generally-80 to-10 ℃, preferably the outlet temperature of-50 to-20 ℃.At cold water cooling and with liquid chlorination hydrogen-cooled but between, the air-flow d of compression also available not liquefaction air-flow f1 pre-cooled.
Separate f in gas/liquid subsequently) in, material stream e is divided into the air-flow f1 that comprises chlorine, oxygen, carbonic acid gas and possible rare gas element and the liquid stream f2 that contains chlorine, hydrogenchloride, oxygen and carbonic acid gas.
In step g), the material stream g2 that liquid stream f2 is divided into cl gas flow g1 by distillation in tower and mainly is comprised of hydrogenchloride, oxygen and carbonic acid gas.In a preferred embodiment, during partial oxidation hydrogen is back to tower in the condensation of the top of tower and as anti-stream, obtain thus chlorine content for the material of<1 % by weight stream g2.
At another, in optional step h, the solution that is 7 to 9 as the isolated subflow of gaseous purge stream with the pH that contains sodium bicarbonate and sodium bisulfite from material stream f1 contacts, and removes thus chlorine and hydrogenchloride from air-flow.
The present invention also provides liquid hydrogenchloride as for carry out the purposes of the refrigeration agent of cooling and optional liquefied chlorine gas by indirect heat exchange in the preparation of chlorine process.
The preparation of chlorine process is for for example using oxygen heterogeneous catalytic oxidation hydrogenchloride or electrochemical oxidation hydrogenchloride (hydrogen chloride electrolysis).
Liquid hydrogenchloride can be used as refrigeration agent and use interchanger to conduct heat to primary cooling circuit in secondary coolant circuit, uses the cryocooled primary cooling circuit simultaneously, even also its heat is passed to refrigerator and therefore finally is passed to surrounding environment.Can use conventional refrigeration agent (for example hydrocarbon of part halo) as the refrigeration agent for primary cooling circuit.
For example, Fig. 1 a, b and c show and comprise the primary cooling circuit that uses hydrogenchloride to move as refrigeration agent and the diagrammatic layout of secondary coolant circuit.This use conventional refrigeration agent (for example hydrocarbon of part halo) and the operation refrigerator comprise with lower device: coolant compressor V1, refrigerant condenser (for example water-cooled) W1, reducing valve and the interchanger W2 shared with secondary coolant circuit.Described secondary coolant circuit comprises interchanger W2 and W3, and the heat absorbed from the process of interchanger W3 is passed in the refrigeration agent in refrigerator by interchanger W2.
The process material stream that is gained in preparation of chlorine by the material of 1 expression stream, make its cooling and optional condensation, and the liquid process material stream that is cooling or condensation by the material stream of 2 expressions.
Fig. 1 a, b and c are different on the mode of operation secondary coolant circuit.
In Fig. 1 a, HCl evaporates and condensation again in interchanger W2 in interchanger W3.Only convection current or fluid pressure type ground carry out the conveying of gas or liquid.
In Fig. 1 b, in Fig. 1 a, HCl evaporates and condensation again in interchanger W2 in interchanger W3.Due to the pressure reduction between interchanger W2 and W3, therefore the way from W3 to W2, gaseous state HCl must be by compressor V2 compression.Pressure in W2 is regulated by pressure regulator valve, makes the liquid HCl decompression of condensation in the way that flows to interchanger W3 by described pressure regulator valve.
In Fig. 1 c, use the HCl of liquefaction fully to move secondary coolant circuit without phase transformation.Liquid HCl only is heated to not reach the degree of boiling point in interchanger W3.This liquid is cooling in W2 subsequently.The conveying of liquid HCl in secondary coolant circuit carried out with pump P1.
Claims (10)
1. the method by preparation of hydrogen chloride chlorine, it comprises the following steps:
A) provide liquid hydrogenchloride material stream a as refrigerant stream;
B) the material stream b2 that introduces at least one material stream b1 that comprises hydrogenchloride to the chloration hydro-oxidation district and comprise oxygen, and the catalytic oxidation of hydrogen chloride is become to chlorine, obtain the product gas flow b3 that comprises chlorine, water, oxygen, carbonic acid gas and rare gas element;
C) product gas flow b3 is contacted in the device that contacts with hydrochloric acid soln I and from material stream b3 part isolate water and hydrogenchloride, obtain comprising the air-flow c of hydrogenchloride, chlorine, water, oxygen, carbonic acid gas and possible rare gas element;
D) drying air stream c, obtain the substantially anhydrous air-flow d that comprises hydrogenchloride, chlorine, oxygen, carbonic acid gas and possible rare gas element;
E), by compressing and the cooling partial liquefaction air-flow d of coming, obtain the material stream e of liquefaction at least partly;
F) will expect that stream e gas/liquid is separated into air-flow f1 and the liquid stream f2 that comprises hydrogenchloride, chlorine, oxygen and carbonic acid gas that comprises chlorine, oxygen, carbonic acid gas, hydrogenchloride and possible rare gas element and optionally at least part of air-flow f1 is recycled in step b);
G) by distillation in tower, liquid is flowed to the material stream g2 that f2 is separated into cl gas flow g1 and mainly is comprised of hydrogenchloride, oxygen and carbonic acid gas,
Wherein in step e), the cooling and partial liquefaction of air-flow d, by carrying out with liquid hydrogenchloride material stream a indirect heat exchange, causes at least part of liquid hydrogenchloride material stream a evaporation and this part to obtain as gaseous hydrogen chloride material stream a '.
2. the process of claim 1 wherein that described liquid hydrogenchloride material flows under the pressure in 1 to 30 bar and has the temperature of-10 to-80 ℃.
3. claim 1 or 2 method, wherein gaseous hydrogen chloride material stream a ' is fed in the chloration hydro-oxidation district as the material stream b1 that comprises hydrogenchloride at least partly.
4. the method for any one in claims 1 to 3, wherein gaseous hydrogen chloride material stream a ' is again liquefied and is reused as refrigerant stream at least partly.
5. the method for any one in claim 1 to 4 prepared by wherein said liquid hydrogenchloride material stream a in the method for the preparation of polycarbonate or the method for the preparation of isocyanic ester.
6. the method for claim 5 prepared in the distillation purifying to the hydrogenchloride that obtains as by product by wherein said liquid hydrogenchloride material stream a in preparing polycarbonate or preparing isocyanic ester.
7. the purposes of liquid hydrogenchloride, as for carrying out the cooling and refrigeration agent of liquefied chlorine gas optionally in the preparation of chlorine process by indirect heat exchange.
8. the purposes of claim 7, the heterogeneous catalytic oxidation process that wherein said preparation of chlorine process is hydrogenchloride or the electrochemical oxidation process of hydrogenchloride.
9. claim 7 or 8 purposes, wherein liquid hydrogenchloride is as the refrigeration agent in secondary coolant circuit and by interchanger, heat is passed to primary cooling circuit.
10. the purposes of claim 9 is wherein used the hydrocarbon of part halo as refrigeration agent in described primary cooling circuit.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11155048 | 2011-02-18 | ||
| EP11155048.9 | 2011-02-18 | ||
| PCT/EP2012/052684 WO2012110597A1 (en) | 2011-02-18 | 2012-02-16 | Use of liquid hydrogen chloride as a refrigerant in methods for producing chlorine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103476705A true CN103476705A (en) | 2013-12-25 |
Family
ID=45592415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012800189953A Pending CN103476705A (en) | 2011-02-18 | 2012-02-16 | Use of liquid hydrogen chloride as a refrigerant in methods for producing chlorine |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP2675751A1 (en) |
| JP (1) | JP2014514228A (en) |
| KR (1) | KR20140007899A (en) |
| CN (1) | CN103476705A (en) |
| BR (1) | BR112013021065A2 (en) |
| WO (1) | WO2012110597A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109453764A (en) * | 2018-11-16 | 2019-03-12 | 西安元创化工科技股份有限公司 | Ruthenic oxide catalyst and preparation method thereof for preparing chlorine by oxidizing hydrogen chloride |
| CN109879251A (en) * | 2019-03-07 | 2019-06-14 | 南京工程学院 | A kind of hydrogen chloride synthesis system based on total energy approach |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3421426A1 (en) * | 2017-06-29 | 2019-01-02 | Covestro Deutschland AG | Energy-efficient process for providing phosgene steam |
| JP2024515354A (en) * | 2021-04-21 | 2024-04-09 | ベーアーエスエフ・エスエー | Process for preparing chlorine |
| CN115583631A (en) * | 2022-10-13 | 2023-01-10 | 鹤壁德瑞科技有限公司 | Method and device for preparing chlorine trifluoride |
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| GB1139523A (en) * | 1966-02-10 | 1969-01-08 | Pullman Inc | Recovery of halogens from gaseous mixtures |
| CN101128392A (en) * | 2005-02-23 | 2008-02-20 | 巴斯福股份公司 | Method for producing chlorine |
| CN101374760A (en) * | 2006-01-27 | 2009-02-25 | 巴斯夫欧洲公司 | Method for the production of chlorine |
| CN101448733A (en) * | 2006-05-19 | 2009-06-03 | 拜尔材料科学股份公司 | Method for separating chlorine from product gas of HCl oxidation process |
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| US5490390A (en) | 1994-05-13 | 1996-02-13 | Ppg Industries, Inc. | Liquefaction of chlorine or other substances |
| DE19535716A1 (en) | 1995-09-26 | 1997-03-27 | Bayer Ag | Process for working up the reaction gases in the oxidation of HCl to chlorine |
| DE10260084A1 (en) | 2002-12-19 | 2004-07-01 | Basf Ag | Separation of a mixture of hydrogen chloride and phosgene |
-
2012
- 2012-02-16 WO PCT/EP2012/052684 patent/WO2012110597A1/en active Application Filing
- 2012-02-16 JP JP2013553944A patent/JP2014514228A/en active Pending
- 2012-02-16 BR BR112013021065A patent/BR112013021065A2/en not_active IP Right Cessation
- 2012-02-16 CN CN2012800189953A patent/CN103476705A/en active Pending
- 2012-02-16 KR KR1020137024242A patent/KR20140007899A/en not_active Application Discontinuation
- 2012-02-16 EP EP12703847.9A patent/EP2675751A1/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1139523A (en) * | 1966-02-10 | 1969-01-08 | Pullman Inc | Recovery of halogens from gaseous mixtures |
| CN101128392A (en) * | 2005-02-23 | 2008-02-20 | 巴斯福股份公司 | Method for producing chlorine |
| CN101374760A (en) * | 2006-01-27 | 2009-02-25 | 巴斯夫欧洲公司 | Method for the production of chlorine |
| CN101448733A (en) * | 2006-05-19 | 2009-06-03 | 拜尔材料科学股份公司 | Method for separating chlorine from product gas of HCl oxidation process |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109453764A (en) * | 2018-11-16 | 2019-03-12 | 西安元创化工科技股份有限公司 | Ruthenic oxide catalyst and preparation method thereof for preparing chlorine by oxidizing hydrogen chloride |
| CN109879251A (en) * | 2019-03-07 | 2019-06-14 | 南京工程学院 | A kind of hydrogen chloride synthesis system based on total energy approach |
| CN109879251B (en) * | 2019-03-07 | 2024-05-03 | 南京工程学院 | Hydrogen chloride synthesis system based on energy comprehensive utilization |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012110597A1 (en) | 2012-08-23 |
| BR112013021065A2 (en) | 2019-09-24 |
| EP2675751A1 (en) | 2013-12-25 |
| JP2014514228A (en) | 2014-06-19 |
| KR20140007899A (en) | 2014-01-20 |
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