CN102224101A - Chlorine manufacturing method - Google Patents
Chlorine manufacturing method Download PDFInfo
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- CN102224101A CN102224101A CN2009801463915A CN200980146391A CN102224101A CN 102224101 A CN102224101 A CN 102224101A CN 2009801463915 A CN2009801463915 A CN 2009801463915A CN 200980146391 A CN200980146391 A CN 200980146391A CN 102224101 A CN102224101 A CN 102224101A
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
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- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0209—Impregnation involving a reaction between the support and a fluid
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Disclosed is a method whereby at least one compound selected from a group comprised of carbon monoxide, phosgene, hydrogen and an organic compound is suitably oxidized and hydrogen chloride is suitably oxidized to manufacture chlorine. This invention pertains to a method whereby the aforementioned compound is oxidized and hydrogen chloride is oxidized to manufacture chlorine by bringing into contact an oxygen-containing gas and a gas which contains hydrogen chloride and at least one compound selected from the group comprised of carbon monoxide, phosgene, hydrogen and an organic compound, in the presence of a catalyst wherein silica and a ruthenium compound are carried in titanium oxide.
Description
Technical field
Present patent application is speciallyyed permit out hope 2008-297758 number based on Japan, and (application on November 21st, 2008) and Japan specially permit out hope 2009-104041 number (application on April 22nd, 2009), advocate right of priority according to Treaty of Paris, by quoting at this, all contents described in the above-mentioned application are all quoted in this specification sheets.
The present invention relates to the preparation method of chlorine, this method is ruthenium compound to be supported in the presence of catalyzer that titanium oxide forms, to contain at least a compound that is selected from carbon monoxide, phosgene, hydrogen and the organic compound and the mixed gas of hydrogenchloride contacts with the gas that contains aerobic, thus with the above-claimed cpd oxidation, simultaneously with chloration hydro-oxidation.
Background technology
Contact with the gas that contains aerobic as containing at least a compound that is selected from carbon monoxide, phosgene, hydrogen and the organic compound and the mixed gas of hydrogenchloride, thus with the above-claimed cpd oxidation, simultaneously with the preparation method of the chlorine of chloration hydro-oxidation, known in TOHKEMY 2005-289800 communique (patent documentation 1), the method for carrying out above-mentioned oxidizing reaction in that ruthenium and/or ruthenium compound are supported in the presence of catalyzer that titanium oxide forms is arranged.
Patent documentation 1: TOHKEMY 2005-289800 communique.
Summary of the invention
But, in above-mentioned method in the past, aspect the transformation efficiency of the oxidizing reaction of at least a compound in being selected from carbon monoxide, phosgene, hydrogen and organic compound, may not be abundant.
The inventor has carried out deep research, find: carry out above-mentioned oxidizing reaction silicon-dioxide and ruthenium compound being supported in the presence of catalyzer that titanium oxide forms, thus can be with above-claimed cpd oxidation well, simultaneously with hydrogenchloride oxidation well, prepare chlorine, thereby finished the present invention.
Promptly, the invention provides the preparation method of chlorine, this method is silicon-dioxide and ruthenium compound to be supported in the presence of catalyzer that titanium oxide forms, make and contain at least a compound that is selected from carbon monoxide, phosgene, hydrogen and the organic compound and the mixed gas of hydrogenchloride contacts with the gas that contains aerobic, thus with the above-claimed cpd oxidation, simultaneously with chloration hydro-oxidation.
According to the present invention, at least a compound oxidation well that is selected from carbon monoxide, phosgene, hydrogen and the organic compound can be prepared chlorine with hydrogenchloride oxidation well simultaneously.
Embodiment
As containing at least a compound that is selected from carbon monoxide, phosgene, hydrogen and the organic compound and the mixed gas of hydrogenchloride, for example can use the heating of hydrolysis reaction, the hydrochloric acid of preparation, the chlorinated hydrocarbon of the phosgenation reaction of the pyrolysis of reaction at hydrogen and chlorine, chlorine compound or combustion reactions, organic compound or chlorination reaction, chlorofluoro-alkane, any material that contains hydrogenchloride that in the burning of incinerator etc., produces.Should illustrate, can also can be used in combination by oxygen or the rare gas element that these each reactions or hydrogen chloride oxidation reaction reclaim.
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.
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, benzene and chlorine prepared in reaction chlorobenzene etc.
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.
Hydrolysis reaction as chlorinated hydrocarbon can be enumerated: chlorobenzene and water prepared in reaction phenol.
Among the present invention, make and contain at least a compound that is selected from carbon monoxide, phosgene, hydrogen and the organic compound and the mixed gas of hydrogenchloride contacts with the gas that contains aerobic.Carbon monoxide described here, phosgene, hydrogen, the such compound of organic compound contain as the impurity in the above-mentioned hydrogenchloride usually, but among the present invention, be not only the impurity that is contained in the hydrogenchloride, contained carbon monoxide, phosgene, hydrogen and organic compound also can oxidation in the employed all gas when the preparation of chlorine.
Above-mentioned organic compound can suitably be selected, and is preferably to be selected from least a in aliphatic hydrocrbon, chlorination aliphatic hydrocrbon, aromatic hydrocarbon, chlorinating aromatic hydrocarbon, alcohols and the phenols.Aliphatic hydrocrbon described here for example can be enumerated: aliphatic saturated hydrocarbons such as methane, ethane, propane, butane, hexane, aliphatic unsaturated hydrocarbons such as ethene, propylene, butylene, hexene, acetylene.Wherein optimization methane, ethane, ethene, propylene, acetylene.
For example can enumerate as the chlorination aliphatic hydrocrbon: methyl chloride, methylene dichloride, trichloromethane, tetracol phenixin, ethyl chloride, as 1, the ethylene dichloride of 2-ethylene dichloride, trichloroethane, tetrachloroethane, pentaline, hexachloroethane, as the chloropropane of 2 cbloropropane isopropyl chloride, vinylchlorid, chlorallylene, 1 as vinylchlorid, Ethylene Dichloride, trieline, zellon, dichloropropylenes such as 3-two chloro-1-propylene etc.Wherein preferable methyl chlorine, methylene dichloride, trichloromethane, tetracol phenixin, ethyl chloride, vinylchlorid, ethylene dichloride, chloropropane, propylene dichloride, chlorallylene, dichloropropylene.
For example can enumerate benzene,toluene,xylene etc. as aromatic hydrocarbon.In addition, can enumerate as the chlorinating aromatic hydrocarbon: mono chloro benzene, dichlorobenzene, trichlorobenzene, tetrachlorobenzene, pentachlorobenzene, Perchlorobenzene, phenyl chloroformate etc. as orthodichlorobenzene.Wherein preferred mono chloro benzene, dichlorobenzene.
Can enumerate methyl alcohol, ethanol, propyl alcohol etc. as alcohol.
Can enumerate phenol, cresols etc. as aromatic alcohol.
When containing organic compound in the above-mentioned mixed gas, its content is generally below 5% volume with respect to hydrogenchloride, below preferred 1% volume, further below preferred 0.1% volume.When the content of organic compound is too much, the situation that then exists activity of such catalysts to reduce.On the other hand, the content of organic compound is 0.1 ppm volume when above with respect to hydrogenchloride, suitablely adopts the present invention.
When containing carbon monoxide in the above-mentioned mixed gas, its content is generally below 5% volume with respect to hydrogenchloride, below preferred 1% volume, further below preferred 0.1% volume.When the content of carbon monoxide is too much, the situation that exists activity of such catalysts to reduce.On the other hand, the content of carbon monoxide is 0.1ppm volume when above with respect to hydrogenchloride, suitablely adopts the present invention.
When containing hydrogen in the above-mentioned mixed gas, its content is generally below 5% volume with respect to hydrogenchloride, below preferred 2% volume, further below preferred 1% volume.When the content of hydrogen is too much, the situation that exists activity of such catalysts to reduce.On the other hand, the content of hydrogen is 0.1ppm volume when above with respect to hydrogenchloride, suitablely adopts the present invention.
When containing phosgene in the above-mentioned mixed gas, its content is generally below 5% volume with respect to hydrogenchloride, below preferred 1% volume, further below preferred 0.5% volume.When the content of phosgene is too much, the situation that exists activity of such catalysts to reduce.On the other hand, the content of phosgene is 0.1ppm volume when above with respect to hydrogenchloride, suitablely adopts the present invention.
Hydrogenchloride can be this with nitrogen or argon gas is that the inert gasses dilution is used to oxidizing reaction, and in this case, the hydrogen cloride concentration in the above-mentioned mixed gas is generally more than 30% volume, more than preferred 50% volume, further more than preferred 60% volume.
As oxygen source, use air or pure oxygen usually.Pure oxygen can be by air transformation method or preparation such as separation by deep refrigeration.Oxygen is preferably more than 0.1 with respect to the mol ratio of hydrogenchloride, and is further preferred more than 0.2.If the oxygen amount is very few, then there is the low situation of transformation efficiency of the oxidizing reaction in carbon monoxide, phosgene, hydrogen or the organic compound.
The present invention can be by carrying out above-mentioned oxidizing reaction silicon-dioxide and ruthenium compound being supported in the presence of catalyzer that titanium oxide forms, with carbon monoxide, phosgene, hydrogen, the such compound oxidation well of organic compound, simultaneously hydrogenchloride oxidation is well prepared chlorine.Ruthenium compound described here 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.
Titanium oxide of 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.Comprise amorphousness or anatase octahedrite crystalline form (anatase-type titanium oxide), rutile crystal form (Titanium Dioxide (Rutile) Top grade) as titanium oxide.Wherein preferably contain Titanium Dioxide (Rutile) Top grade and/or anatase-type titanium oxide.Further preferred Titanium Dioxide (Rutile) Top grade is a titanium oxide more than 20% with respect to the ratio of Titanium Dioxide (Rutile) Top grade and anatase-type titanium oxide, the more preferably titanium oxide more than 30%, the further more preferably titanium oxide more than 90%.The high more then gained of Titanium Dioxide (Rutile) Top grade ratio activity of such catalysts is good more.
As among the present invention silicon-dioxide and ruthenium compound being supported the catalyzer that forms in titanium oxide, for example can exemplify following.
(1) support silicon compound in titanium oxide, the supported ruthenium compound then burns till acquisition under oxidizing gas atmosphere then.
(2) under oxidizing gas atmosphere, halogenated titanium and silicon halide are heat-treated, obtain supporting the titanium dioxide carrier of silicon-dioxide,, burn till acquisition then in this supported carrier ruthenium compound.
(3) in titanium oxide supported ruthenium compound, support silicon compound then, then under oxidizing gas atmosphere, burn till acquisition.
(4) support silicon compound and ruthenium compound in titanium oxide, burn till acquisition then.
In above-mentioned (1), also can after having supported silicon compound, under oxidizing gas atmosphere, burn till, in above-mentioned (3), also can after having supported ruthenium compound, under oxidizing gas atmosphere, burn till.Promptly, above-mentioned catalyzer can be the ruthenium oxide loaded body catalyzer, this catalyzer is that silicon compound or ruthenium compound are being supported in titanium oxide, under the atmosphere of oxidizing gas, burn till then, obtain supporting the titanium dioxide carrier of silicon-dioxide or ruthenium, in this supported carrier ruthenium compound or silicon compound, under the atmosphere of oxidizing gas, be fired into then.In addition, in above-mentioned (2), can enumerate: titanium chloride (TiCl as halogenated titanium
4), titanium bromide (TiBr
4) etc., can enumerate as silicon halide: silicon chlorides (SiCl
4), silicon bromide (SiBr
4) etc.Among the present invention, in the catalyzer of above-mentioned (1)-(4) gained, the catalyzer of especially preferably above-mentioned (1) gained.
Can enumerate as Si (OR) as above-mentioned silicon compound
4The silicon alkoxide compound of (below, R represents the alkyl of carbonatoms 1-4) is as silicon chlorides (SiCl
4), silicon bromide (SiBr
4) silicon halide, as Si (OR)
3, SiCl
2(OR)
2, SiCl
3(OR)
2Silicon halide alkoxide cpd etc.In addition, can use its hydrate as required, also can use they more than 2 kinds.Among the present invention, wherein preferred silicon alkoxide compound, more preferably tetraethoxide silicon, i.e. tetraethyl orthosilicate [Si (OC
2H
5)
4].
The silicon-dioxide that the usage quantity of above-mentioned silicon compound suitably is adjusted in the catalyzer is generally 0.001-0.3 mol with respect to 1 mol titanium oxide, preferred 0.004-0.03 mol.
In addition, can enumerate: each compound dissolution in appropriate solvent, is infiltrated gained solution in the method for titanium oxide as the method that supports silicon compound or ruthenium compound in titanium oxide; Perhaps titanium oxide is immersed in this solution, adsorbs the method for each compound etc.
Can use mixing, the moulding of Powdered or molten gelationus titanium oxide as titanium oxide, then burn till the titanium oxide of gained.The titanium oxide that burns till can prepare according to known method, for example that shaping assistants such as Powdered or molten gelationus titanium oxide and organic binder bond and water is mixing, extrusion moulding is the noodles shape, dry, broken then, obtain formed body, then, the gained formed body is burnt till under oxidizing gas atmosphere such as air and prepare.
For example can enumerate as ruthenium compound: as RuCl
3, RuBr
3Halogenide, as K
3RuCl
6, K
2RuCl
6Halate, as K
2RuO
4Oxysalt, as Ru
2OCl
4, Ru
2OCl
5, Ru
2OCl
6Oxyhalogenide, as K
2[RuCl
5(H
2O)
4], [RuCl
2(H
2O)
4] Cl, K
2[Ru
2OCl
10], Cs
2[Ru
2OCl
4] halogen close complex compound, as [Ru (NH
3)
5H
2O] Cl
2, [Ru (NH
3)
5Cl] Cl
2, [Ru (NH
3)
6] Cl
2, [Ru (NH
3)
6] Cl
3, [Ru (NH
3)
6] Br
3Ammonia complex, as Ru (CO)
5, Ru
3(CO)
12Carbonylcomplex, as [Ru
3O (OCOCH
3)
6(H
2O)
3] OCOCH
3, [Ru
2(OCOR)
4] carboxylate radical of Cl (alkyl of R=carbonatoms 1-3) closes complex compound, as K
2[RuCl
5(NO)], [Ru (NH
3)
5(NO)] Cl
3, [Ru (OH) (NH
3)
4(NO)] (NO
3)
2, [Ru (NO)] (NO
3)
3Nitrosyl complex, phosphine complex compound, amine complex, acetylacetonate complex etc.Wherein preferably use halogenide, especially preferably use muriate.Should illustrate that ruthenium compound can use its hydrate as required, can also use in addition they more than 2 kinds.
The usage ratio of ruthenium compound and titanium oxide can suitably be adjusted to: the weight ratio of ruthenium compound/titanium oxide is generally 0.1/99.9-20/80, preferred 0.3/99.7-10/90, more preferably 0.5/99.5-5/95.And preferably the usage quantity with ruthenium compound is adjusted to: the silicon-dioxide that the ruthenium compound in the catalyzer supports with respect to 1 mol is 0.1-4 mol, more preferably is adjusted to 0.3-2 mol.
Above-mentioned oxidizing gas is meant the gas that contains oxidizing substance, for example can enumerate oxygen containing gas.Its oxygen concn is generally about the 1-30% capacity.As this oxygen source, use air or pure oxygen usually, use inert gas dilution as required.In the oxidizing gas, preferred air.Firing temperature is generally 100-500 ℃, preferred 200-350 ℃.
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 carbon monoxide, phosgene, hydrogen and organic oxidizing reaction to reduce, or hydrogenchloride is converted into the situation of the transformation efficiency reduction of chlorine.The diameter lower limit of catalyzer is not particularly limited, if too small then increase in the pressure-losses of catalyst layer, therefore uses 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.
More than can be attained at titanium oxide and support the catalyzer that silicon-dioxide or ruthenium compound form.Should illustrate that this Preparation of catalysts method for example can be with reference to TOHKEMY 2008-155199 communique, TOHKEMY 2002-292279 communique.
The usage quantity of catalyzer use with standard state under be selected from ratio (GHSV) expression of the feed speed of at least a compound in carbon monoxide, phosgene, hydrogen and the organic compound and hydrogenchloride, be generally 10-50000 h
-1
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 transformation efficiency of oxidizing reaction of carbon monoxide, phosgene, hydrogen or organic compound or hydrogenchloride to reduce.On the other hand, temperature of reaction is too high, then has catalyst component evaporable situation.
The pressure of oxidizing reaction is generally 0.1-5 MPa, preferred 0.1-1 MPa.
The gas line speed of void tower benchmark is generally 0.1-20 m/s.Should illustrate that among the present invention, the gas line speed of void tower benchmark is meant the ratio of total amount and the sectional area of reactor of the feed speed of all gas under standard state of supply response device.
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 overcoat.In heat exchange method, the temperature of the catalyzer packing layer in the reaction tubes is controlled by the thermal medium in the overcoat.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: making and contain at least a compound that is selected from carbon monoxide, phosgene, hydrogen and the organic compound and the mixed gas of hydrogenchloride contacts with the gas that contains aerobic, thus with the above-claimed cpd oxidation, is the step of chlorine with chloration hydro-oxidation simultaneously
(2) absorption step: the gas of gained in the reactions steps is passed through cooling, by it is contacted with water and/or hydrochloric acid, perhaps by contacting postcooling with water and/or hydrochloric acid, reclaiming with hydrogenchloride and water is the solution of principal constituent, 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 part or all step of supplying with to reactions steps 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 and water 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'-dipropyl methane diamines and electrolysis of hydrochloric acid.In addition, can also 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 distillation tower bottom 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 benzene prepared in reaction chlorobenzene, 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.Should illustrate that among the following embodiment, if no special instructions, the part and the % of expression content or usage quantity are weight basis.
Embodiment 1
(preparation of catalyst A)
With 100 parts of titanium dioxide powders [clear F-1R that makes with タ イ タ ニ ウ system (strain), Titanium Dioxide (Rutile) Top grade ratio 93%], 0.5 part of セ ラ ン ダ ー (Cerander) [ユ ケ Application industry (strain) make YB-152A] and 2 parts of sugar esters [the フ ー ズ of Mitsubishi Chemical (strain) S-1570] mixing, then add 25.5 parts of pure water, 12.5 parts of titanium oxide sol [CSB that Sakai chemistry (strain) is made, titanium oxide content 40%], carry out mixing.This mixture is extruded noodles shape into diameter 3.0 mm φ, 110 ℃ dry 2 hours down, be broken for then about length 3-5 mm.In air, with 1.7 hours the gained formed body is warming up to 600 ℃ by room temperature, under this temperature, keep then burning till in 3 hours.With the 31.93g tetraethyl orthosilicate [Si (OC that makes with the pure pharmaceutical worker of light industry (strain)
2H
5)
4] be dissolved in the 137.70 g ethanol, further gained solution is infiltrated in the burned material of 900.0 g gained, placement is 3.3 hours under air atmosphere, under 22 ℃.Under airiness, with 2 hours 900.0 g gained solids are warming up to 300 ℃ by room temperature, under this temperature, keep then burning till in 2 hours, [the Titanium Dioxide (Rutile) Top grade ratio is more than 90% to obtain 898.2 g dioxide-containing silicas and be 1.0% white titanium dioxide carrier, sodium content is 12 ppm weight, and calcium contents is 8 ppm weight].
With the 2.16 g ruthenium chloride hydrates [RuCl that NE ケ system キ ャ ッ ト (strain) makes
3NH
2O, Ru content 40.0%] be dissolved in the 20.5 g pure water, the aqueous solution for preparing is infiltrated in the titanium dioxide carrier of the above-mentioned gained of 90.0 g, placement is 6.2 hours under air atmosphere, under 35 ℃.Under airflow, with 1.3 hours 18.2 g gained solids are warming up to 250 ℃ by room temperature, under this temperature, keep then burning till in 2 hours, the content that obtains ruthenium oxide is 1.25% catalyst A.
(reaction)
Use catalyst A, by utilizing the reaction of oxygen with chloration hydro-oxidation, make catalyst activity stable, the following then tetracol phenixin that makes contacts with oxygen with hydrogenchloride, carries out oxidizing reaction.That is, in axial crystal reaction tube (internal diameter 14 mm), fill 3.4 g (2.7 cm
3) catalyst A, further above this catalyst A, fill 7.8 g (6.1 cm
3) catalyst A and the mixture of the Alpha-alumina ball of 6.4 g diameters, 2 mm.
With the flow of 80 ml/ minute hydrogen chloride gas, 40 ml/ minute oxygen (all be scaled absolute pressure 0.1 MPa, 0 ℃), supply with continuously by this reaction tubes top.Temperature of reaction is 334-350 ℃, and reaction pressure is 0.1 MPa, is 549 h with respect to the GHSV of catalyst volume
-1
After the supply of hydrogen chloride gas and oxygen begins 23 hours, will be that the carbon tetrachloride gas of 13.1% volume begins to supply with 4.9ml/ minute flow with nitrogen dilution.Tetracol phenixin is calculated as 0.8% volume with respect to the amount of hydrogenchloride in the raw material.
Feed in the 30% quality potassium iodide aqueous solution by gas and to collect above-mentioned gas reaction tubes outlet, measure the growing amount of chlorine by iodimetry, measure unreacted hydrogenchloride amount by neutralization titration, measure the outlet amount of carbon dioxide by gas chromatographic analysis.The supply of beginning carbon tetrachloride gas, the transformation efficiency and the carbonic acid gas of the hydrogenchloride during through 51 hours are as shown in table 1 with respect to the yield of tetracol phenixin.
Embodiment 2
To be that the methyl chloride gas of 2.6% volume is supplied with 10.0 ml/ minutes flow with nitrogen dilution, replace tetracol phenixin, in addition carry out operation similarly to Example 1 with this.Methyl chloride is calculated as 0.3% volume with respect to the amount of the hydrogenchloride in the raw material.In addition, begin to supply with methyl chloride gas, the transformation efficiency and the carbonic acid gas of the hydrogenchloride during through 44 hours are as shown in table 1 with respect to the yield of methyl chloride.
Embodiment 3
To be that the ethylene gas of 3.9% volume is supplied with 4.1 ml/ minutes flow with nitrogen dilution, replace tetracol phenixin, in addition carry out operation similarly to Example 1 with this.Ethene is calculated as 0.2% volume with respect to the amount of the hydrogenchloride in the raw material.In addition, begin to supply with ethylene gas, the transformation efficiency and the carbonic acid gas of the hydrogenchloride during through 42 hours are as shown in table 1 with respect to the yield of ethene.
Embodiment 4
To be that the phenol gas of 0.5% volume is supplied with 15.6 ml/ minutes flow with nitrogen dilution, replace tetracol phenixin, in addition carry out operation similarly to Example 1 with this.Phenol is calculated as 0.1% volume with respect to the amount of the hydrogenchloride in the raw material.In addition, begin to supply with phenol gas, the transformation efficiency and the carbonic acid gas of the hydrogenchloride during through 45 hours are as shown in table 1 with respect to the yield of phenol.
Comparative example 1
(preparation of catalyst B)
Titanium oxide and Alpha-alumina are with weight ratio 34:66 (titanium oxide: aluminum oxide) mix, then add pure water and carry out mixing.This mixture is extruded cylindric into diameter 1.5 mm φ, and drying is broken for about length 2-4 mm then.In air, under 700-730 ℃, the gained formed body was burnt till 3 hours, obtain containing the carrier of the mixture of titanium oxide and Alpha-alumina.To the aqueous solution of this carrier infiltration ruthenium chloride, drying, then in air, under 250 ℃, burnt till 2 hours, the content that obtains ruthenium oxide thus is the catalyst B of 2% weight.
(preparation of catalyzer C)
With titanium oxide and Alpha-alumina with weight ratio 50:50 (titanium oxide: aluminum oxide) mix, then, the titanium oxide with respect to 100 and the mixture of Alpha-alumina are that the titanium oxide sol (CSB that Sakai chemistry (strain) is made contains 39% titanium oxide) of 12.8 weight ratios dilutes with pure water, and be mixing.This mixture is extruded cylindric into diameter 1.5 mm φ, and drying is broken for about length 2-4 mm then.In air, under 650-680 ℃, the gained formed body was burnt till 3 hours, obtain containing the carrier of the mixture of titanium oxide and Alpha-alumina.To the aqueous solution of this carrier infiltration ruthenium chloride, drying, then in air, under 250 ℃, burnt till 2 hours, the content that obtains ruthenium oxide thus is the catalyzer C of 4% weight.
(reaction)
Use catalyst B and C, by utilizing the reaction of oxygen with chloration hydro-oxidation, make catalyst activity stable, the following then tetracol phenixin that makes contacts with oxygen with hydrogenchloride, carries out oxidizing reaction.That is, in axial crystal reaction tube (internal diameter 14 mm), fill 3.7 g (2.7 cm
3) catalyzer C, further above catalyzer C, fill 8.1 g (6.1 cm
3) mixture of Alpha-alumina ball (SSA995 that ニ ッ カ ト ー (strain) makes) of catalyst B and 6.0 g diameters, 2 mm.
With the flow of 80 ml/ minute hydrogen chloride gas, 40 ml/ minute oxygen (all be scaled absolute pressure 0.1 MPa, 0 ℃), supply with continuously by this reaction tubes top.Temperature of reaction is 331-359 ℃, and reaction pressure is 0.1 MPa, is 549 h with respect to the GHSV of catalyst volume
-1
After the supply of hydrogen chloride gas and oxygen begins 20 hours, will be that the carbon tetrachloride gas of 4.4% volume begins to supply with 14.5 ml/ minutes flow with nitrogen dilution.Tetracol phenixin is calculated as 0.8% volume with respect to the amount of hydrogenchloride in the raw material.
Feed in the 30% quality potassium iodide aqueous solution by gas and to collect above-mentioned gas reaction tubes outlet, measure the growing amount of chlorine by iodimetry, measure unreacted hydrogenchloride amount by neutralization titration, by measure the outlet amount of carbon dioxide with gas chromatographic analysis.The supply of beginning carbon tetrachloride gas, the transformation efficiency and the carbonic acid gas of the hydrogenchloride during through 48 hours are as shown in table 1 with respect to the yield of tetracol phenixin.
Comparative example 2
To be that the methyl chloride gas of 2.6% volume is supplied with 10.0 ml/ minutes flow with nitrogen dilution, replace tetracol phenixin, in addition carry out the operation same with comparative example 1 with this.Methyl chloride is calculated as 0.3% volume with respect to the amount of the hydrogenchloride in the raw material.In addition, begin to supply with methyl chloride gas, the transformation efficiency and the carbonic acid gas of the hydrogenchloride during through 29 hours are as shown in table 1 with respect to the yield of methyl chloride.
Comparative example 3
To be that the ethylene gas of 3.9% volume is supplied with 4.1 ml/ minutes flow with nitrogen dilution, replace tetracol phenixin, in addition carry out the operation same with comparative example 1 with this.Ethene is calculated as 0.2% volume with respect to the amount of the hydrogenchloride in the raw material.In addition, begin to supply with ethylene gas, the transformation efficiency and the carbonic acid gas of the hydrogenchloride during through 46 hours are as shown in table 1 with respect to the yield of ethene.
Comparative example 4
To be that the phenol gas of 0.4% volume is supplied with 20.0 ml/ minutes flow with nitrogen dilution, replace tetracol phenixin, in addition carry out the operation same with comparative example 1 with this.Phenol is calculated as 0.1% volume with respect to the amount of the hydrogenchloride in the raw material.In addition, begin to supply with phenol gas, the transformation efficiency and the carbonic acid gas of the hydrogenchloride during through 43 hours are as shown in table 1 with respect to the yield of phenol.
[table 1]
Claims (15)
1. the preparation method of chlorine, it is supporting silicon-dioxide and ruthenium compound in the presence of catalyzer that titanium oxide forms, make and contain at least a compound that is selected from carbon monoxide, phosgene, hydrogen and the organic compound and the mixed gas of hydrogenchloride contacts with the gas that contains aerobic, thus with the above-claimed cpd oxidation, simultaneously with chloration hydro-oxidation.
2. the described preparation method of claim 1, wherein, above-mentioned catalyzer is that ruthenium compound is being supported after titanium dioxide carrier, burns till under the atmosphere of oxidizing gas and the ruthenium oxide loaded body catalyzer that obtains, and described titanium dioxide carrier forms in titanium oxide silica supported.
3. the described preparation method of claim 1, wherein, above-mentioned catalyzer is the ruthenium oxide loaded body catalyzer, this ruthenium oxide loaded body catalyzer is that silicon compound is being supported after titanium oxide, under the atmosphere of oxidizing gas, burn till, obtain supporting the titanium dioxide carrier that silicon-dioxide forms, ruthenium compound is being supported after this carrier, under the atmosphere of oxidizing gas, burn till and obtain.
4. each described preparation method among the claim 1-3, wherein, the content of the organic compound in the mixed gas is below 1% volume with respect to hydrogenchloride.
5. each described preparation method among the claim 1-4, wherein, organic compound is to be selected from least a in aliphatic hydrocrbon, chlorination aliphatic hydrocrbon, aromatic hydrocarbon, chlorinating aromatic hydrocarbon, alcohols and the phenols.
6. the described preparation method of claim 5, wherein, aliphatic hydrocrbon is to be selected from least a in methane, ethane, propane, ethene, propylene and the acetylene.
7. the described preparation method of claim 5, wherein, the chlorination aliphatic hydrocrbon is to be selected from least a in methyl chloride, methylene dichloride, trichloromethane, tetracol phenixin, ethyl chloride, vinylchlorid, ethylene dichloride, chloropropane, propylene dichloride, chlorallylene and the dichloropropylene.
8. the described preparation method of claim 5, wherein, aromatic hydrocarbon is to be selected from least a in benzene, toluene and the dimethylbenzene.
9. the described preparation method of claim 5, wherein, the chlorination aliphatic hydrocrbon is mono chloro benzene and/or dichlorobenzene.
10. the described preparation method of claim 5, wherein, alcohols is to be selected from least a in methyl alcohol, ethanol and the propyl alcohol.
11. the described preparation method of claim 5, wherein, phenols is a phenol.
12. each described preparation method among the claim 1-3, wherein, the content of the carbon monoxide in the mixed gas is below 1% volume with respect to hydrogenchloride.
13. each described preparation method among the claim 1-3, wherein, the content of the phosgene in the mixed gas is below 1% volume with respect to hydrogenchloride.
14. each described preparation method among the claim 1-3, wherein, the content of the hydrogen in the mixed gas is below 2% volume with respect to hydrogenchloride.
15. each described preparation method among the claim 1-14, wherein, oxidizing temperature is 250-450 ℃.
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| JP2008297758 | 2008-11-21 | ||
| JP2009104041A JP5267305B2 (en) | 2008-11-21 | 2009-04-22 | Chlorine production method |
| JP2009-104041 | 2009-04-22 | ||
| PCT/JP2009/069606 WO2010058810A1 (en) | 2008-11-21 | 2009-11-19 | Chlorine manufacturing method |
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