CN102216207A - Chlorine production method - Google Patents

Chlorine production method Download PDF

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Publication number
CN102216207A
CN102216207A CN2009801459534A CN200980145953A CN102216207A CN 102216207 A CN102216207 A CN 102216207A CN 2009801459534 A CN2009801459534 A CN 2009801459534A CN 200980145953 A CN200980145953 A CN 200980145953A CN 102216207 A CN102216207 A CN 102216207A
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gas
hydrogenchloride
chloropropane
ruthenium
chloride
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C.G.克纳普布杰伦
关航平
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46Ruthenium, rhodium, osmium or iridium
    • B01J23/462Ruthenium
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00Halogens; Halogen acids
    • C01B7/01Chlorine; Hydrogen chloride
    • C01B7/03Preparation from chlorides
    • C01B7/04Preparation of chlorine from hydrogen chloride
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/19Catalysts containing parts with different compositions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

Provided is a method to produce chlorine by satisfactorily oxidizing chlorinated propane or chlorinated propene, as well as by oxidizing hydrogen chloride at a satisfactory conversion rate. Disclosed is a method to produce chlorine wherein a mixed gas containing chlorinated propane and/or chlorinated propene and hydrogen chloride is brought into contact with a gas that contains oxygen in the presence of a catalyst wherein ruthenium and/or a ruthenium compound is carried in titanium oxide, the chlorinated propane and/or chlorinated propene is oxidized, and the hydrogen chloride is also oxidized. The method to produce chlorine is characterized in that the content of the chlorinated propane and/or chlorinated propene in the mixed gas is 0.1 vol% or less, relative to the hydrogen chloride.

Description

The preparation method of chlorine
Technical field
Present patent application is speciallyyed permit out hope 2008-294305 number (application on November 18th, 2008) based on Japan, advocates right of priority according to Treaty of Paris, and by quoting at this, all contents described in the above-mentioned application are all quoted in this specification sheets.
The present invention relates to prepare the method for chlorine, this method is ruthenium and/or ruthenium compound to be supported in the presence of catalyzer that titanium oxide forms, the gas that contains hydrogenchloride is being contacted, with the method for chloration hydro-oxidation with the gas that contains aerobic.
Background technology
The known method for preparing chlorine is ruthenium and/or ruthenium compound to be supported in the presence of catalyzer that titanium oxide forms, the gas (gas that contains hydrogenchloride) that contains hydrogenchloride is contacted, with chloration hydro-oxidation (for example with reference to patent documentation 1-4) with the gas that contains aerobic.Also known use by the gas that contains hydrogenchloride of the thermal decomposition process by-product of the synthesis technique of various organic compound or chlorine compound as the gas (for example with reference to patent documentation 4) that contains hydrogenchloride.
Patent documentation 1: TOHKEMY 2000-281314 communique
Patent documentation 2: TOHKEMY 2002-79093 communique
Patent documentation 3: TOHKEMY 2004-181408 communique
Patent documentation 4: TOHKEMY 2005-289800 communique.
Summary of the invention
But there is the situation of the transformation efficiency reduction that causes hydrogenchloride in the employed gas that contains hydrogenchloride.
The inventor finds through further investigation, if in the employed gas that contains hydrogenchloride, contain chloropropane or this predetermined compound of propenyl chloride in a large number, then bringing out the hydrogenchloride transformation efficiency reduces, further find, content by using this compound is the gas that contains hydrogenchloride below 0.1% volume with respect to hydrogenchloride, can prevent the reduction of above-mentioned transformation efficiency.
But also find, when in containing the gas of hydrogenchloride, containing chloropropane or propenyl chloride, the derivative of this compound itself or this compound chlorination gained is brought into follow-up reactions steps, may cause the obstruction of pipeline thus, at this moment, content by using above-claimed cpd is the gas that contains hydrogenchloride below 0.1% volume with respect to hydrogenchloride, and this compound can be prevented worrying line clogging by oxidation well.
Promptly, the invention provides the preparation method of chlorine, this method is ruthenium and/or ruthenium compound to be supported in the presence of catalyzer that titanium oxide forms, the mixed gas that contains chloropropane and/or propenyl chloride and hydrogenchloride is contacted with the gas that contains aerobic, with chloropropane and/or propenyl chloride oxidation, simultaneously with chloration hydro-oxidation, thereby prepare the method for chlorine, the method is characterized in that: the content of chloropropane and/or propenyl chloride is below 0.1% volume with respect to hydrogenchloride in the mixed gas.
According to the present invention, can make the oxidation well of chloropropane or propenyl chloride, simultaneously can be with good transformation efficiency with chloration hydro-oxidation, preparation chlorine.
Embodiment
The catalyzer that uses among the present invention is that ruthenium and/or ruthenium compound are supported the catalyzer that forms in titanium oxide.Ruthenium described here and/or ruthenium compound can be enumerated: as metal Ru, ruthenium oxide, ruthenium chloride, ruthenium chloride hydrate, nitrosyl nitric acid ruthenium, the ruthenium carbonyl complex compound of the monomeric ruthenium of metal and contain in them the mixture of combination arbitrarily.Wherein preferred ruthenium oxide promptly, preferably supports ruthenium oxide the ruthenium oxide loaded body catalyzer that forms in titanium oxide as catalyzer.
Titanium oxide among the present invention also comprises the composite oxides of titanium oxide and other metal oxide except that titanium oxide itself, or the mixture of other metal oxide such as titanium oxide and aluminum oxide, zirconium white, silicon oxide.Wherein preferred titanium oxide itself.In addition, as titanium oxide, comprise amorphousness or anatase octahedrite crystalline form, rutile crystal form.The titanium oxide that wherein preferably contains rutile crystal form.
Should illustrate, when in oxidizing reaction, using catalyzer, also can use for the dilution of inert material reaction with aluminum oxide, zirconium white, silicon oxide etc.
The shape of catalyzer can be granular with sphere, cylindrical particle shape, the uses such as particulate state of extruding the modest size that crushing and classification forms after shape, annular shape, the cellular or moulding.At this moment, below preferred 5 mm of the diameter of catalyzer.If the diameter of catalyzer is excessive, then exist the transformation efficiency of the oxidizing reaction of chloropropane and/or propenyl chloride to reduce, or hydrogenchloride is converted into the transformation efficiency reduction of chlorine.The diameter lower limit of catalyzer is not particularly limited, if but too small then increase in the pressure-losses of catalyst layer, therefore use the above catalyzer of 0.5 mm usually.Should illustrate, for the diameter of catalyzer described here, if spherical granular then be the diameter of ball, if the cylindrical particle shape then is the diameter of rounded section, if other shape then is the maximum diameter in cross section.
Described catalyzer for example can be according to TOHKEMY 2000-229239 communique, TOHKEMY 2000-281314 communique, the described method preparation of TOHKEMY 2002-79093 communique.
Among the present invention,, the mixed gas that contains chloropropane and/or propenyl chloride and hydrogenchloride is contacted with the gas that contains aerobic ruthenium and/or ruthenium compound being supported in the presence of catalyzer that titanium oxide forms.Chloropropane can for example can be enumerated: n-propyl chloride, 2 cbloropropane isopropyl chloride, 1, propylidene chloride 1,1,2-propylene dichloride, 1,3-propylene dichloride, 2,2-propylene dichloride, 1 by the propane of at least one chlorine atom replacement, 1,1-trichloropropane, 1,1,2-trichloropropane, 1,1,3-trichloropropane, 1,2,2-trichloropropane, 1,1,2,2-tetrachloro propane, 1,1,2,3-tetrachloro propane, 1,2,2,3-tetrachloro propane, 1,1,2,2,3-pentachloropropane, 1,1,2,2,3,3-chlordene propane.Wherein, chloropropane is 2 cbloropropane isopropyl chloride or 1, during the 2-propylene dichloride, is fit to adopt the present invention.
Propenyl chloride can for example can be enumerated: chlorallylene (chlorallylene by the propylene of at least one chlorine atom replacement; 3-chloro-1-propene), 2-chloro-1-propylene, 1-chloro-1-propylene, 1,3-two chloro-1-propylene, 1,2-two chloro-1-propylene, 1,1-two chloro-1-propylene, 3,3-two chloro-1-propylene, 1,1,2-three chloro-1-propylene, 1,1,3-three chloro-1-propylene, 1,2,3-three chloro-1-propylene, 2,3,3-three chloro-1-propylene, 1,1,2,3-tetrachloro-1-propylene, 1,2,3,3-tetrachloro propylene, 1,1,2,3,3-pentachloro--1-propylene.Wherein, propenyl chloride is a chlorallylene, 1, when 3-two chloro-1-propylene, 2-chloro-1-propylene, is fit to adopt the present invention.
Represent with the ratio (GHSV) of the feed speed of the mixed gas of hydrogenchloride if the usage quantity of catalyzer is used with the chloropropane and/or the propenyl chloride that contain under the standard state, then be generally 10-50000 h -1
The invention is characterized in: during above-mentioned oxidizing reaction, the content of chloropropane and/or propenyl chloride is below 0.1% volume with respect to hydrogenchloride in the above-mentioned mixed gas.
Thus, in this reaction system, can be with chloropropane or propenyl chloride oxidation well, the while with chloration hydro-oxidation, prepares chlorine with good transformation efficiency.Preferred described content is below 0.05% volume with respect to hydrogenchloride.Should illustrate that when containing the compound more than 2 kinds in chloropropane and/or the propenyl chloride in the above-mentioned mixed gas, their total content is below 0.1% volume with respect to hydrogenchloride, can make the content of each compound simultaneously is below 0.1% volume with respect to hydrogenchloride.If then there is the situation that catalyst activity is reduced in the too high levels of chloropropane and/or propenyl chloride.
The chloropropane in the above-mentioned mixed gas and/or the content of propenyl chloride are according to the source of this gas and difference can contain more than the 0.1 ppm volume with respect to hydrogenchloride usually, and the present invention is also effective in this case.
Contain the mixed gas of chloropropane and/or propenyl chloride and hydrogenchloride so long as can contain the gas that contains hydrogenchloride of chloropropane and/or propenyl chloride and get final product, can be any, mainly can enumerate the hydrogenchloride that produces in the pyrolysis of chlorination reaction at organic compound, chlorine compound or combustion reactions, the phosgenation reaction of organic compound, the preparation of chlorofluoro-alkane etc.And, for the hydrogenchloride that produces in the reaction of hydrogen and chlorine or in the heating of hydrochloric acid, the burning in the incinerator etc., in this hydrogenchloride, to contain when accumulating chloropropane and/or propenyl chloride as impurity, they also can be used as the use object.
Chlorination reaction as organic compound can be enumerated: propylene and chlorine prepared in reaction chlorallylene, ethane and chlorine prepared in reaction ethyl chloride, 1,2-ethylene dichloride and chlorine prepared in reaction trieline and zellon etc.
Pyrolysis as chlorine compound can be enumerated: by 1, the 2-ethylene dichloride prepares vinylchlorid, prepares tetrafluoroethylene etc. by chlorodifluoromethane.
Phosgenation reaction as organic compound can be enumerated: amine and phosgene reaction prepare isocyanic ester, alcohol and/or aromatic alcohol and phosgene reaction prepares carbonic ether.
Preparation as chlorofluoro-alkane can be enumerated: tetracol phenixin and hydrogen fluoride reaction prepare Refrigerant 12 and the single fluoromethane of trichlorine, methane prepare Refrigerant 12 and the single fluoromethane of trichlorine etc. with chlorine and hydrogen fluoride reaction.
Contain in the mixed gas of chloropropane and/or propenyl chloride and hydrogenchloride, the content of hydrogenchloride is generally more than 50% volume with respect to the mixed gas total amount, more than preferred 80% volume, more preferably more than 90% volume.Should illustrate that can contain nitrogen, argon gas etc. in the above-mentioned mixed gas is inert gasses to oxidizing reaction.
Consumption for oxygen is not particularly limited, but with respect to the total amount of chloropropane and/or propenyl chloride and hydrogenchloride, the mol ratio of preferred oxygen is more than 0.2, more preferably more than 0.5.If the consumption of oxygen is very few, the situation that then exists the transformation efficiency of the oxidizing reaction of chloropropane and/or propenyl chloride to reduce.Should illustrate that among the present invention, above-mentioned mixed gas is contacted with the gas that contains aerobic, the gas that contains aerobic can be pure oxygen, also can be to be gas that inert gasses dilution form with nitrogen or argon gas etc. to oxidizing reaction with pure oxygen, can also be air.Oxygen can be by air transformation method or conventional commercial run such as low temperature separation process obtain.
The temperature of reaction of oxidizing reaction of the present invention is generally 200-500 ℃, and preferred 250-450 ℃, further preferred 300-400 ℃.If reaction temperature is spent low, the situation that then exists the transformation efficiency of the oxidizing reaction transformation efficiency of chloropropane and/or propenyl chloride or hydrogenchloride to reduce.On the other hand, if temperature of reaction is too high, then there is catalyst component evaporable situation.
The pressure of oxidizing reaction is generally 0.1-5 MPa, preferred 0.1-1 MPa.
Empty tower gas velocity is generally 0.1-20 m/s.Should illustrate that among the present invention, empty tower gas velocity is meant all gas of supply response device under standard state, the ratio that the total amount of feed speed is long-pending with reactor cross section.
Can enumerate as reactive mode: Fixed Bed Gas Phase circulation reactive mode or fluidized layer gas phase circulation reactive mode.
In the Fixed Bed Gas Phase circulation reactive mode, temperature control can be undertaken by heat exchange method.Among the present invention, heat exchange method is meant in the outside of the reaction tubes that is filled with catalyzer to have overcoat (ジ ャ ケ ッ ト) portion, removes the mode of the reaction heat that generates in the dereaction by the thermal medium in the shell.In the heat exchange method, the temperature of the catalyzer packing layer in the reaction tubes is controlled by the thermal medium in the shell.The industrial fixed bed multitube reactor that can use with the multi tube heat exchanger type that reaction tubes is arranged side by side, the outside has outer race section.
Among the present invention, can obtain chlorine by following steps usually.
(1) reactions steps: the mixed gas that contains chloropropane and/or propenyl chloride and hydrogenchloride is contacted with the gas that contains aerobic, with chloropropane and/or propenyl chloride oxidation, is the step of chlorine with chloration hydro-oxidation simultaneously
(2) absorption step: with the gas of gained in the reactions steps, by cooling, contact with water and/or hydrochloric acid by making it, perhaps by contacting postcooling with water and/or hydrochloric acid, recovery is the solution of principal constituent with hydrogenchloride and water, and obtaining with chlorine and unreacted oxygen simultaneously is the step of the gas of principal constituent
(3) drying step:, obtain the step of exsiccant gas by removing the moisture in the gas that obtains in the absorption step
(4) purification step: the exsiccant gas delivery of gained in the drying step is become with chlorine to be the liquid of principal constituent or gas and to be the gas of principal constituent with unreacted oxygen, obtain the step of chlorine thus
(5) circulation step: is the step of part or all supply response step of the gas of principal constituent with gained in the purification step with unreacted oxygen
Among the present invention, be used for reactions steps after can making above-mentioned mixed gas and activated carbon contacting.
Gained is that the solution of principal constituent can be directly or remove after the chlorine contained in the solution by the bubbling of rare gas elementes such as heating and/or nitrogen with hydrogenchloride in the above-mentioned absorption step, be used for the neutralization of pH regulator, the boiler water supply of electrolyzer, the condensation rearrangement reaction preparation 4 by aniline and formaldehyde, the raw material of 4'-ditan diamines and electrolysis of hydrochloric acid.In addition, can implement to be used to reclaim the distillation of hydrogenchloride, recovered overhead hydrogenchloride by distillation tower, part as this mixed gas is used for reaction, part or all of the liquid of the bottom of distillation tower dewatered with distillation, by the recovered overhead water of distillation tower, part or all of the liquid of distillation tower bottom supplied with to the above-mentioned distillation tower that is used to reclaim hydrogenchloride.
Can be by loosing the gas member, with gained in the above-mentioned purification step be that part or all of gas of principal constituent blasts in the absorption liquid with unreacted oxygen, remove fumes of sulphuric acid.
The chlorine of gained can be used for following in the above-mentioned purification step: with ethylene reaction preparation 1, the 2-ethylene dichloride, with reaction of carbon monoxide prepare phosgene, with propylene prepared in reaction chlorallylene.Phosgene can be used for following: with amine prepared in reaction isocyanic ester, with alcohol and/or aromatic alcohol prepared in reaction carbonic ether.Can enumerate as isocyanic ester: tolylene diisocyanate, 4,4'-diphenylmethanediisocyanate, hexa-methylene-1,6-vulcabond.
Can enumerate as carbonic ether: diphenyl carbonate, methylcarbonate.
Embodiment
The present invention is described by the following examples.
Embodiment 1
With the 50 parts by weight of titanium oxide [STR-60R of Sakai chemistry (strain) preparation, 100% rutile-type], 100 weight part Alpha-aluminas [Sumitomo Chemical (strain) preparation AES-12], the 19.2 parts by weight of titanium oxide colloidal sols [CSB of Sakai chemistry (strain) preparation, titanium oxide content 38% weight] and 3 weight part methylcellulose gum [the メ ト ロ ー ズ 65SH-4000 of SHIN-ETSU HANTOTAI's chemistry (strain) preparation] mixing, add pure water then and carry out mixing.This mixture is extruded cylindric into diameter 3.0 mm φ, and drying is broken for about long 4-6 mm then.The gained formed body was burnt till 3 hours in air, under 800 ℃, obtain containing the carrier of the mixture of titanium oxide and Alpha-alumina.In this carrier the infiltration ruthenium chloride the aqueous solution, drying, then in air, under 250 ℃, burnt till 2 hours, obtaining ruthenium oxide thus is the ruthenium oxide loaded body catalyzer of 1% weight.
Use the ruthenium oxide loaded body catalyzer of gained, the following propylene dichloride that makes contacts with oxygen with hydrogenchloride, carries out oxidizing reaction.That is, in axial crystal reaction tube (internal diameter 14 mm), fill 2.37 g (1.8 cm 3) (ニ ッ カ ト ー (strain) preparation, mixture SSA995) are further filled 1.19 g (0.9 cm above this catalyzer for the Alpha-alumina ball of catalyzer and 3.7g diameter 2 mm 3) catalyzer and the mixture of this Alpha-alumina ball of 5.5 g diameters, 2 mm.
With 100 ml/ minute hydrogen chloride gas, 50 ml/ minute oxygen (all be scaled absolute pressure 0.1 MPa, 0 ℃), 2.5 ml/ minutes be the flow of the 2 cbloropropane isopropyl chloride gas of 2.0% volume with nitrogen dilution, supply with continuously by this reaction tubes top.2 cbloropropane isopropyl chloride gas is 0.05% volume with respect to the cubage of the hydrogen chloride gas in the raw material.Temperature of reaction is 339-350 ℃, and reaction pressure is 0.1 MPa, is 2277 h with respect to the GHSV of catalyst volume -1
Feed 30% quality potassium iodide aqueous solution by gas and collect above-mentioned gas,, measure unreacted hydrogenchloride amount, measure the outlet amount of carbon dioxide by gas chromatographic analysis by neutralization titration by the growing amount of iodimetry mensuration chlorine with the reaction tubes outlet.Begin reaction, the transformation efficiency and the carbonic acid gas of the hydrogenchloride during through about 48 hours are as shown in table 1 with respect to the yield of 2 cbloropropane isopropyl chloride.
Comparative example 1
With nitrogen dilution is that the flow of the 2 cbloropropane isopropyl chloride gas of 2.0% volume is 10 ml/ minutes, in addition carries out operation similarly to Example 1.Should illustrate that 2 cbloropropane isopropyl chloride gas is 0.2% volume with respect to the cubage of the hydrogen chloride gas in the raw material.Begin reaction, the transformation efficiency and the carbonic acid gas of the hydrogenchloride during through about 48 hours are as shown in table 1 with respect to the yield of 2 cbloropropane isopropyl chloride.
Comparative example 2
Supplying with nitrogen dilution with 10 ml/ minutes flows is the 2 cbloropropane isopropyl chloride gas of 4.9% volume, in addition carries out operation similarly to Example 1.Should illustrate that 2 cbloropropane isopropyl chloride gas is 0.5% volume with respect to the cubage of the hydrogen chloride gas in the raw material.Begin reaction, the transformation efficiency and the carbonic acid gas of the hydrogenchloride during through about 48 hours are as shown in table 1 with respect to the yield of 2 cbloropropane isopropyl chloride.
[table 1]
? 2 cbloropropane isopropyl chloride is with respect to the content (%) of hydrogenchloride The transformation efficiency of hydrogenchloride (%) Carbonic acid gas is with respect to the yield (%) of 2 cbloropropane isopropyl chloride
Embodiment 1 0.05 35.1 67.3
Comparative example 1 0.2 29.4 35.7
Comparative example 2 0.5 27.9 37.9
Embodiment 2
Supplying with continuously with nitrogen dilution with 10 ml/ minute flow is the chlorallylene gas of 0.5% volume, replaces 2 cbloropropane isopropyl chloride gas with this, in addition carries out operation similarly to Example 1.Should illustrate that chlorallylene gas is 0.05% volume with respect to the cubage of the hydrogen chloride gas in the raw material.Begin reaction, the transformation efficiency and the carbonic acid gas of the hydrogenchloride during through about 48 hours are as shown in table 2 with respect to the yield of chlorallylene.
Comparative example 3
Supplying with continuously with nitrogen dilution with 40 ml/ minute flow is the chlorallylene gas of 0.5% volume, replaces 2 cbloropropane isopropyl chloride gas with this, in addition carries out operation similarly to Example 1.Should illustrate that chlorallylene gas is 0.2% volume with respect to the cubage of the hydrogen chloride gas in the raw material.Begin reaction, the transformation efficiency and the carbonic acid gas of the hydrogenchloride during through about 48 hours are as shown in table 2 with respect to the yield of chlorallylene gas.
[table 2]
? Chlorallylene is with respect to the content (%) of hydrogenchloride The transformation efficiency of hydrogenchloride (%) Carbonic acid gas is with respect to the yield (%) of chlorallylene
Embodiment 2 0.05 37.1 46.9
Comparative example 3 0.2 31.3 11.1

Claims (7)

1. the preparation method of chlorine, it is ruthenium and/or ruthenium compound to be supported in the presence of catalyzer that titanium oxide forms, the mixed gas that contains chloropropane and/or propenyl chloride and hydrogenchloride is contacted with the gas that contains aerobic, with chloropropane and/or propenyl chloride oxidation, simultaneously chloration hydro-oxidation is prepared the method for chlorine; It is characterized in that: the chloropropane in the mixed gas and/or the content of propenyl chloride are below 0.1% volume with respect to hydrogenchloride.
2. the described preparation method of claim 1, wherein, above-mentioned catalyzer is that ruthenium oxide is supported the ruthenium oxide loaded body catalyzer that forms in titanium oxide.
3. claim 1 or 2 described preparation methods, wherein, titanium oxide is the titanium oxide that contains rutile crystal type.
4. each described preparation method among the claim 1-3, wherein, above-mentioned chloropropane is for being selected from 2 cbloropropane isopropyl chloride and 1, at least a compound in the 2-propylene dichloride.
5. each described preparation method among the claim 1-4, wherein, above-mentioned propenyl chloride is for being selected from chlorallylene, 1, at least a compound in 3-two chloro-1-propylene and the 2-chloro-1-propylene.
6. each described preparation method among the claim 1-5, wherein, the content of the hydrogenchloride in the mixed gas is more than 80% volume with respect to the mixed gas total amount.
7. each described preparation method among the claim 1-6, wherein, oxidizing temperature is 250-450 ℃.
CN2009801459534A 2008-11-18 2009-11-17 Chlorine production method Pending CN102216207A (en)

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JP2008294305A JP5169763B2 (en) 2008-11-18 2008-11-18 Chlorine production method
JP2008-294305 2008-11-18
PCT/JP2009/069463 WO2010058761A1 (en) 2008-11-18 2009-11-17 Chlorine production method

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005289800A (en) * 2004-03-22 2005-10-20 Sumitomo Chemical Co Ltd Method of producing chlorine
WO2006135074A1 (en) * 2005-06-13 2006-12-21 Sumitomo Chemical Company, Limited Method for producing oxidation catalyst, method for producing chlorine, and method for oxidizing carbon monoxide and/or unsaturated hydrocarbon

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4438771B2 (en) * 2005-06-13 2010-03-24 住友化学株式会社 Method for producing oxidation catalyst, method for producing chlorine, and method for oxidizing carbon monoxide and / or unsaturated hydrocarbon

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005289800A (en) * 2004-03-22 2005-10-20 Sumitomo Chemical Co Ltd Method of producing chlorine
WO2006135074A1 (en) * 2005-06-13 2006-12-21 Sumitomo Chemical Company, Limited Method for producing oxidation catalyst, method for producing chlorine, and method for oxidizing carbon monoxide and/or unsaturated hydrocarbon

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