Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
  • C01B15/01—Hydrogen peroxide
  • C01B15/029—Preparation from hydrogen and oxygen
• • 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
• • 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
• • 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
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/66—Silver or gold
• • 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
  • B01J37/0203—Impregnation the impregnation liquid containing organic compounds

Definitions

• the present invention relates to a method for producing hydrogen peroxide by directly reacting hydrogen and oxygen in the presence of a radical scavenger.
• Hydrogen peroxide is used as a bleaching agent and disinfectant for paper, pulp, fiber, etc. because it has an oxidizing power and a strong bleaching and disinfecting action. It also includes epoxidation and hydroxylation. It is an important industrial product used extensively in oxidation reactions.
• hydrogen peroxide is used in the semiconductor industry for cleaning the surface of semiconductor substrates and the like, for chemical polishing of copper, tin and other copper alloy surfaces, and for etching electronic circuits. And since hydrogen peroxide is a decomposition product of water and oxygen, it is positioned as important from the viewpoint of green chemistry and attracts attention as an alternative material for chlorine bleach.
• an anthraquinone method an electrolytic method, a method using oxidation of isopropyl alcohol, and the like are known as methods for producing hydrogen peroxide, and the anthraquinone method is mainly employed industrially.
• the anthraquinone method is a multi-step method such as hydrogenation of anthraquinone, oxidation with air, extraction of hydrogen peroxide produced with water, and further purification and concentration. Therefore, this method is not necessarily an ideal method for producing hydrogen peroxide because it requires high capital investment, uses a large amount of energy, and releases an organic solvent for dissolving anthraquinone to the atmosphere. I can't say that.
• the catalyst In such a method for producing hydrogen peroxide directly from oxygen and hydrogen using a noble metal catalyst, the catalyst also functions as a decomposition catalyst for hydrogen peroxide, so that the generated hydrogen peroxide is simultaneously decomposed. . Therefore, in this method, some compound is often used to suppress decomposition.
• Patent Document 1 in addition to the non-acidic oxygen-containing organic compound, ions such as sulfate ion, chlorine ion, bromine ion are reacted. It has been proposed to be present in the liquid phase of the medium.
• Patent Document 2 discloses a method for producing hydrogen peroxide using a platinum group metal catalyst supported on an oxide support in a method for producing hydrogen peroxide catalytically from hydrogen and oxygen in a reaction medium.
• water is usually suitable as the reaction medium, and hydrochloric acid aqueous solution, hydrobromic acid aqueous solution, phosphoric acid aqueous solution, sulfuric acid aqueous solution, etc., particularly hydrochloric acid aqueous solution, It has been reported that an aqueous hydrogen acid solution can be suitably used.
• a mixed aqueous solution of sodium chloride, potassium chloride or the like as a chloride ion component and sulfuric acid or phosphoric acid as a hydrogen ion component can be suitably employed instead of the hydrochloric acid aqueous solution.
• a combination of a mixed aqueous solution of sodium bromide, potassium bromide or the like as the bromide ion component and sulfuric acid, phosphoric acid or the like as the hydrogen ion component can be suitably employed instead of the hydrobromic acid aqueous solution.
• Patent Document 3 is a method for producing an aqueous hydrogen peroxide solution directly from hydrogen and oxygen in a stirred reactor, in which hydrogen and oxygen are separately made into small bubbles, made acidic by adding an inorganic acid in advance, and hydrogen and oxygen.
• a method has been proposed in which the amount of oxygen introduced is a constant molar ratio.
• the aqueous reaction medium may include a stabilizer against hydrogen peroxide (eg, phosphonate or tin) and a decomposition inhibitor (eg, halide).
• bromides are particularly preferred decomposition inhibitors among the halides, and are advantageously used in combination with free bromine (Br 2 ).
• Patent Document 4 is a method for producing an organic hydrogen peroxide solution or an organic hydrogen peroxide aqueous solution by a direct synthesis method, in which a non-explosive gaseous mixture containing hydrogen and oxygen and a liquid reaction medium are used.
• a production process is disclosed for passing through a fixed bed comprising a mixture containing a noble metal catalyst.
• the document also discloses that the liquid reaction medium contains a strong acid and a halide.
• Patent Document 5 is a method for directly synthesizing an aqueous solution of hydrogen peroxide from hydrogen and oxygen by heterogeneous catalysis in a three-phase system, which is a solid heterogeneous catalyst suspended in a granular state in a liquid aqueous phase.
• the catalyst reacts directly on the surface of the catalyst and the catalyst comprises a pure compound of palladium or a combination of metal and at least one other noble metal.
• the document discloses that in this method, the metal compound is supported on a carrier containing at least one compound selected from zirconium dioxide and superacid zirconium dioxide, and the liquid aqueous phase is 0.1% relative to the aqueous phase. It discloses that it contains bromide ions at a concentration of 05-3 mmol / l and its pH is in the range of 0-4.
• the industrial production method of hydrogen peroxide using halogen ions as a decomposition inhibitor is not limited to an economically satisfactory level due to various limitations.
• the present invention has an object to provide a method capable of producing hydrogen peroxide at a level that is industrially and economically satisfactory without requiring excessive purification equipment and without requiring excessive production facilities.
• the present inventors have intensively studied compounds having an effect of inhibiting the decomposition of hydrogen peroxide other than halogen, and as a result, radical scavengers are useful for suppressing the decomposition of hydrogen peroxide. As a result, the present invention was completed.
• ⁇ 1> A method for producing hydrogen peroxide, in which hydrogen and oxygen are reacted in the presence of a noble metal catalyst and a radical scavenger in a reaction medium.
• ⁇ 2> The method for producing hydrogen peroxide according to ⁇ 1>, wherein the radical scavenger is a nitrone compound, a nitroso compound, a dithiocarbamate derivative or an ascorbic acid derivative.
• the radical scavenger is a nitrone compound, a nitroso compound, a dithiocarbamate derivative or an ascorbic acid derivative.
• the radical scavenger is a nitrone compound represented by the following general formula (1), (2) or (3), a nitroso compound represented by the following general formula (4), or the following general formula (5).
• R 1 and R 2 each independently, alkyl group having 1 carbon atoms which may 10 have a branch, a phosphoric acid group or phosphoric acid ester group
• R 3 and R Each of 4 is independently hydrogen, an optionally branched alkyl group having 1 to 10 carbon atoms, an optionally substituted branched hydroxyl group or an amino group and having 1 to 10 carbon atoms.
• R 5 is an alkyl group having 1 carbon atoms which may 10 have a branch
• Each R 10 is independently hydrogen or an alkyl group having 1 to 10 carbon atoms which may have a branch
• R 11 may have 1 to carbon atoms which may have a branch
• 10 is an alkyl group, R 12 ⁇ R 15 it Independently, they have a hydrogen or a branched alkyl group which may having 1 to 10 carbon atoms
• the alkyl group of R 16 is ⁇ carbon atoms 1 may have a branch 10 Or an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen, a sulfonic acid group or an optionally substituted alkyl group having 1 to 10 carbon atoms, and in the general formula (5), R 17 and R 18 are each independently a branched
• R 1 and R 2 are each a methyl group
• R 3 and R 4 are each independently a methyl group, hydrogen, a 2-oxo-1-pyridylmethyl group, or an amino group
• R 5 is a methyl group, an ethyl group, an isopropyl group, an n-propyl group, a cyclopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, or a cyclobutyl group.
• R 6 to R 10 are hydrogen, in the general formula (3), R 11 is a tert-butyl group, R 12 to R 15 are hydrogen, and in the general formula (4), R 16 is a tert-butyl group, a 3,5-dibromo-1-sulfophenyl group, or a 2,3,5,6-tetramethylphenyl group, and in the general formula (5), R 17 and R 18 are each independently Methyl group, ethyl group or A Rubokishimechiru group, X + is a sodium ion, method for producing hydrogen peroxide according to ⁇ 3>.
• ⁇ 5> The peroxide according to any one of ⁇ 1> to ⁇ 4>, wherein the radical scavenger is 5,5-dimethyl-1-pyrroline ⁇ ⁇ ⁇ N-oxide or N-tert-butyl- ⁇ -phenylnitrone.
• the radical scavenger is 5,5-dimethyl-1-pyrroline ⁇ ⁇ ⁇ N-oxide or N-tert-butyl- ⁇ -phenylnitrone.
• ⁇ 6> The amount of the hydrogen peroxide according to any one of ⁇ 1> to ⁇ 5>, wherein the amount of the radical scavenger used is 0.01 to 0.05 parts by weight with respect to 100 parts by weight of the reaction medium. Production method.
• the noble metal catalyst is a catalyst in which at least one metal selected from the group consisting of platinum, palladium, silver and gold is supported on silica, alumina, silica alumina, titanium oxide or zirconia, ⁇ The method for producing hydrogen peroxide according to any one of 1> to ⁇ 6>.
• the production method of the present invention by using a radical scavenger that has not been studied at all in the past, the load of purification of hydrogen peroxide does not become excessive, and an excessive production facility is required. Therefore, it is possible to achieve an industrially and economically satisfactory level.
• the present invention is characterized in that hydrogen and oxygen are reacted in a reaction medium in the presence of a noble metal catalyst and a radical scavenger.
• ⁇ Radical scavenger> In the direct synthesis method of hydrogen peroxide represented by the conventional anthraquinone method, it is important to suppress this decomposition because the noble metal catalyst is active in the generation of hydrogen peroxide and at the same time in the decomposition reaction. is there.
• the decomposition mechanism of hydrogen peroxide is due to the generation of OH radicals accompanying the cleavage of the oxygen-oxygen bond of hydrogen peroxide. By the generation of OH radicals, hydrogen radicals of hydrogen peroxide present in the vicinity are extracted, and the decomposition reaction proceeds in a chain manner.
• the present inventors think that if the OH radical generated by the above reaction can be captured, the progress of the decomposition of the surrounding hydrogen peroxide can be suppressed, and if a radical scavenger is used, It came to the idea that decomposition
• the radical scavenger captures the OH radicals generated by the decomposition of hydrogen peroxide on the surface of the noble metal catalyst and suppresses the spread of the decomposition reaction to the surrounding hydrogen peroxide by forming a radical scavenger-OH adduct. It is thought that.
• the lifetime of the radical scavenger is from several minutes to several hours, and even a radical scavenger with a short lifetime has the effect of delaying the decomposition chain reaction.
• radical scavengers include nitrone compounds, nitroso compounds, dithiocarbamate derivatives and ascorbic acid derivatives. These radical scavengers may be in the form of salts, or in the form of hydrates where possible. Examples of the salt include sodium salt and potassium salt.
• nitrone compound examples include compounds represented by the following general formulas (1) to (3).
• R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms, a phosphoric acid group or a phosphoric acid ester group which may have a branch.
• Examples of the phosphoric acid ester group include those having various structures, such as those having the following structures.
• R 19 and R 20 are each independently an alkyl group having 1 to 10 carbon atoms which may have a branch, or R 19 and R 20 together may form a 5- to 6-membered ring with O to which they are attached and P to which O is attached, and the ring thus formed may have a branch It may be substituted with an alkyl group having 1 to 10 carbon atoms.
• R 19 and R 20 are preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably an ethyl group, and R 19 and R 20 are combined to form a nitrone compound from the viewpoint of easy availability. It is also preferred that a 6-membered ring is formed together with O to which O is bonded and P to which O is bonded, and the ring is optionally substituted with a methyl group.
• methyl groups are preferable as R 1 and R 2 from the viewpoint of the hydrogen peroxide decomposition inhibitory effect and the availability of the nitrone compound.
• R 3 and R 4 are each independently hydrogen, an optionally branched alkyl group having 1 to 10 carbon atoms, an optionally branched hydroxyl group or amino group.
• R 3 and R 4 are alkyl groups having 1 to 10 carbon atoms, 2-oxo-1-pyridylmethyl group or amino group which may be substituted with a group, from the viewpoint of easy availability of nitrone compounds.
• a methyl group, hydrogen, 2-oxo-1-pyridylmethyl group and amino group are preferred.
• R 5 is an alkyl group having 1 to 10 carbon atoms which may have a branch. From the viewpoint of easy availability of a nitrone compound, R 5 is a methyl group or an ethyl group. Isopropyl, n-propyl, cyclopropyl, n-butyl, sec-butyl, tert-butyl and cyclobutyl are preferred.
• R 6 to R 10 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms which may have a branch, from the viewpoint of easy availability of the nitrone compound.
• R 6 to R 10 are preferably hydrogen.
• R 11 is an alkyl group having 1 to 10 carbon atoms which may have a branch. From the viewpoint of easy availability of a nitrone compound, R 11 is a tert-butyl group. preferable.
• R 12 to R 15 are each independently hydrogen or an optionally substituted alkyl group having 1 to 10 carbon atoms, from the viewpoint of easy availability of the nitrone compound.
• R 12 to R 15 are preferably hydrogen.
• examples of the nitroso compound cited as the radical scavenger include compounds represented by the following general formula (4).
• R 16 is substituted with an optionally branched alkyl group having 1 to 10 carbon atoms; or a halogen, a sulfonic acid group, or an optionally substituted alkyl group having 1 to 10 carbon atoms. And an aryl group having 6 to 20 carbon atoms. When the aryl group is substituted with an alkyl group, the carbon number of the aryl group is not counted as the carbon number of the aryl group.
• R 16 is tert-butyl, 3,5-dibromo-1-sulfophenyl, and 2,3,5,6-tetramethyl.
• a phenyl group is preferred.
• Examples of the dithiocarbamate derivative exemplified as the radical scavenger include compounds represented by the following general formula (5).
• R 17 and R 18 are each independently a C 1-10 alkyl group which may have a branch or may be substituted with a hydroxyl group, or a C 1 which may have a branch. ⁇ 10 carboxyalkyl groups, and X + is a cation. In addition, the carbon number of a carboxyl group shall be counted to the carbon number of a carboxyalkyl group.
• R 17 and R 18 are preferably a methyl group, an ethyl group and a carboxymethyl group, and X + is preferably a sodium ion from the viewpoint of the availability of a dithiocarbamate derivative and the effect of suppressing the decomposition of hydrogen peroxide.
• examples of the ascorbic acid derivatives mentioned as the radical scavenger include compounds represented by the following formula (6).
• radical scavengers described above are known compounds and can be synthesized by known methods.
• nitrone compounds, nitroso compounds and dithiocarbamate derivatives mentioned above include 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), N-tert-butyl- ⁇ -phenylnitrone ( PBN), 3,3,5,5-tetramethyl-1-pyrroline-N-oxide (M4PO), 2-methyl-2-nitrosopropane, 3,5-dibromo-4-nitrosobenzenesulfonate, ⁇ - (4 -Pyridyl-1-oxide) -N-tert-butylnitrone, 5- (diethoxyphosphoryl) -5-methyl-1-pyrroline-N-oxide, 1-nitroso-2,3,5,6-tetramethylbenzene 2- (5,5-dimethyl-2-oxo-2 ⁇ 5- [1,3,2] dioxaphosphinan-2-yl) -2-methyl-3,4-dihy B-2H-pyrrole 1-oxide, 5-die
• the radical scavenger is preferably a nitrone compound from the viewpoint of the effect of inhibiting the decomposition of hydrogen peroxide, and in particular, 5,5-dimethyl-1-pyrroline-N-oxide and N-tert-butyl- ⁇ -phenylnitrone are preferred.
• the amount of radical scavenger used is preferably 0.01 to 0.05 parts by weight with respect to 100 parts by weight of the reaction medium. More preferably, the radical scavenger is used in an amount of 0.02 to 0.04 parts by weight with respect to 100 parts by weight of the reaction medium.
• Halogen / Halogen ion In the present invention, conventionally used halogen or halogen ions may be used to suppress the decomposition of hydrogen peroxide, but from the viewpoint of purification cost, the amount used does not impair the effects of the present invention. It is preferable that the range is not used.
• any conventionally known noble metal catalyst for synthesizing hydrogen peroxide can be used without particular limitation.
• the noble metal catalyst at least one selected from the group consisting of platinum, palladium, silver and gold is used from the viewpoint of catalytic activity, and palladium and / or gold is more preferably used.
• the molar ratio of palladium to gold is preferably 0.1 to 10, and more preferably 1 to 5.
• the noble metal In order to increase the catalyst efficiency and the reaction efficiency, it is preferable to support the noble metal on a support such as silica, alumina, silica alumina, titanium oxide or zirconia oxide.
• a support such as silica, alumina, silica alumina, titanium oxide or zirconia oxide.
• titanium oxide is preferably used as the carrier.
• a conventionally known method can be employed without any particular limitation, but an impregnation method or an ion exchange method is preferable.
• an impregnation method an evaporation to dryness method, an equilibrium adsorption method, a pore filling method, or the like can be employed.
• the amount of the noble metal supported on the carrier is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the carrier.
• the amount of noble metal catalyst (supported catalyst when supported on a carrier) is preferably 1 to 100 g per 1 L of reaction medium, and 1 to 1 L per 1 L. 40 g is more preferable.
• reaction medium The method for producing hydrogen peroxide of the present invention is usually carried out in a reaction medium that is in a liquid phase.
• the reaction medium can be used without particular limitation as long as it does not inhibit the reaction between hydrogen and oxygen.
• Such reaction media are well known to those skilled in the art.
• reaction medium examples include water, alcohols such as methanol and ethanol, ketones such as acetone, and mixed solvents thereof. Among these, water and alcohol are preferable.
• reaction media may contain additives for pH adjustment, stabilizer effect or gas solubility improvement, for example, phosphoric acid, sulfuric acid and other acids, fluorine inert liquids, etc. You may contain.
• the weight of the reaction medium is the weight including the additives.
• this reaction can increase the yield of hydrogen peroxide by setting the pressure high, it is usually carried out using a reaction apparatus such as a pressure-resistant autoclave.
• the reactor can be of any type such as a stirring tank type, bubble column type, fixed bed type, microreactor, etc., and the reaction can be carried out either batchwise or continuously.
• the reaction apparatus includes a gas introduction part and a gas discharge part, and usually includes a thermometer and a pressure gauge.
• a reactor made of Teflon (registered trademark) lining stainless steel, Inconel or Hastelloy is preferably used.
• an inexpensive reactor formed of stainless steel or glass lining can be used, which is economically advantageous.
• the reaction temperature of hydrogen and oxygen during the synthesis of hydrogen peroxide is preferably from 0 to 100 ° C., particularly preferably from 5 to 50 ° C.
• the pressure of the reaction is not particularly limited, but is preferably atmospheric pressure to 10M Pascal, and particularly preferably atmospheric pressure to 2M Pascal.
• the reaction time is usually 0.01 to 100 hours, preferably 0.5 to 10 hours.
• the flow rates of hydrogen gas and oxygen gas are such that the explosion range is avoided and oxygen is excessive with respect to hydrogen (for example, the volume ratio of the flow rates of hydrogen gas and oxygen gas is 1: 2 to 1:10). Is preferred). Furthermore, in order to further reduce the risk of explosion from the viewpoint of safety, it is preferable to dilute hydrogen and oxygen.
• the diluent gas that can be used in this case is an inert gas that does not affect the reaction between hydrogen and oxygen.
• nitrogen gas, argon gas, and helium gas can be used. Nitrogen gas is preferable from the viewpoint of cost.
• oxygen may be diluted with compressed air and used as an oxygen mixed gas.
• these gases are usually introduced into the liquid phase, that is, the reaction solution from the viewpoint of reaction efficiency.
• the radical scavenger may be dissolved in the reaction medium in advance and introduced into the reaction apparatus, or the reaction medium and the radical scavenger may be separately introduced into the reaction apparatus.
• reaction rate (amount of hydrogen consumed) ⁇ (total amount of hydrogen injected)
• amount of hydrogen consumed is measured by gas chromatography (equipment used: trade name “GC-8A”, manufactured by Shimadzu Corporation) and the amount of hydrogen remaining without reaction is measured and subtracted from the total amount of hydrogen blown. I asked for it.
• Hydrogen peroxide selectivity [(Molecular amount of hydrogen peroxide produced by reaction) ⁇ (Theoretical molar amount of hydrogen peroxide calculated from the amount of hydrogen consumed)] The molar amount of hydrogen peroxide produced was determined by removing a part of the reaction solution after the completion of the hydrogen peroxide synthesis reaction, using titanyl sulfate as a coloring agent for hydrogen peroxide, and an ultraviolet-visible spectrophotometer (trade name). : V-550, manufactured by JASCO Corporation).
• the suspension was transferred to a 300 ml beaker and heated to remove the solvent. Thereafter, the obtained solid was dried with an 85 ° C. drier for 2 days, sized to 0.5 to 1.8 mm, and used in the experiment.
• Example 2 In the same manner as in Example 1, an Au / Pd-supported titania catalyst was produced.
• Example 3 In the same manner as in Example 1, an Au / Pd-supported titania catalyst was produced.
• Example 4 In the same manner as in Example 1, an Au / Pd-supported titania catalyst was produced.
• the method for producing hydrogen peroxide of the present invention using a radical scavenger is efficient in using hydrogen peroxide without using a halogen as a decomposition inhibitor. Can be manufactured well. Therefore, an increase in cost due to the necessity of halogen purification can be suppressed, and industrial value is recognized in the present invention.

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