CA2008651A1 - Process for the preparation of hydrogen peroxide (i) - Google Patents
Process for the preparation of hydrogen peroxide (i)Info
- Publication number
- CA2008651A1 CA2008651A1 CA002008651A CA2008651A CA2008651A1 CA 2008651 A1 CA2008651 A1 CA 2008651A1 CA 002008651 A CA002008651 A CA 002008651A CA 2008651 A CA2008651 A CA 2008651A CA 2008651 A1 CA2008651 A1 CA 2008651A1
- Authority
- CA
- Canada
- Prior art keywords
- hydrogen
- catalyst
- working solution
- static mixer
- coated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title description 4
- 239000012224 working solution Substances 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000003068 static effect Effects 0.000 claims abstract description 28
- 239000007789 gas Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000011541 reaction mixture Substances 0.000 claims abstract description 14
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000004056 anthraquinones Chemical class 0.000 claims abstract description 11
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000011949 solid catalyst Substances 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 description 24
- 229960002163 hydrogen peroxide Drugs 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 7
- 241000264877 Hippospongia communis Species 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010517 secondary reaction Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- PCFMUWBCZZUMRX-UHFFFAOYSA-N 9,10-Dihydroxyanthracene Chemical class C1=CC=C2C(O)=C(C=CC=C3)C3=C(O)C2=C1 PCFMUWBCZZUMRX-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000001609 comparable effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C01B15/022—Preparation from organic compounds
- C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
- B01J19/2435—Loop-type reactors
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/00094—Jackets
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00761—Details of the reactor
- B01J2219/00763—Baffles
- B01J2219/00765—Baffles attached to the reactor wall
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/18—Details relating to the spatial orientation of the reactor
- B01J2219/182—Details relating to the spatial orientation of the reactor horizontal
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/19—Details relating to the geometry of the reactor
- B01J2219/194—Details relating to the geometry of the reactor round
- B01J2219/1941—Details relating to the geometry of the reactor round circular or disk-shaped
- B01J2219/1943—Details relating to the geometry of the reactor round circular or disk-shaped cylindrical
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
- B01J2219/324—Composition or microstructure of the elements
- B01J2219/32466—Composition or microstructure of the elements comprising catalytically active material
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
Abstract The invention relates to a process for the production of-hydrogen peroxide by the anthraquinone process. A reaction mixture into which there are fed hydrogen or a hydrogen-containing gas and a working solution, i.e. an anthra-quinone derivative in an organic solvent, is circulated via a tubular static mixing zone (9) which is continuous or comprises several parts, in order to hydrogenate the anthraquinone derivative in the presence of a solid cata-lyst, and by removing hydrogenated working solution (13) and gas (11) from the circulating reaction mixture (8).
According to the invention, the reaction mixture (14) is circulated (8) via a catalyst-coated static mixing zone (9), where it is simultaneously both mixed and catalyzed.
According to the invention, the reaction mixture (14) is circulated (8) via a catalyst-coated static mixing zone (9), where it is simultaneously both mixed and catalyzed.
Description
20(18651.
A process for the preparation of hydrogen peroxide (I) The present invention relates to a process for the prepara-tion of hydrogen peroxide by the anthraquinone process, and more particularly to its partial process, namely hydrogena-tion. Quite specifically the present invention relates to a process in which a reaction solution is circulated into which hydrogen or a hydrogen-containing gas and a working solution, i.e. an anthraquinone derivative in an organic solvent, are fed via a tubular static mixing zone which is either continuous or made up of several parts, in order to hydrogenate the anthra~uinone derivative in the presence of a solid catalyst and by removing hydrogenated working solu-tion and gas from the circulating reaction mixture. In ad-dition the present invention relates to a tubular static mixer comprising one or more parts and to the use of the mixer in the process mentioned above.
It is known that hydrogen peroxide can be prepared by the so-called anthraquinone process. In this process an anthra-guinone derivative is dissolved in a solvent comprising one or more components. The solution thus prepared is called the working solution. In the preparation of hydrogen per-oxide, the working solution is first fed to the hydrogena-tion step. During this step the anthraquinone derivatives are hydrogenated, in the presence of a catalyst, to the corresponding anthrahydroquinone derivatives. Thereafter the hydrogenated working solution is directed to oxidation, during which oxygen or an oxygen-containing gas is intro-duced into it, whereupon hydrogen peroxide is formed in the solution. The principal reactions of the anthraquinone process are shown below:
+ H2 catalYst > ~
o OH
.
OH
+ 2 > ~ R ' H22 OE~ O ,:
The working solution which contains hydrogen peroxide is fed to the extraction step, in which the hydrogen peroxide is caused by extraction to pass from the working solution into an aqueous solution. The extracted working solution is dried by removal of excess water and recycled to the begin-ning of the cyclic process, i.e. to hydrogenation. The aqueous solution of hydrogen peroxide, obtained by extrac-tion, is purified and concentrated.
The hydrogenation described above is a demanding step in the anthraquinone process. High activity and high selec-tivity are required of the hydrogenation catalyst. The con-version and selectivity of the reaction in the hydrogena-tion step are dependent on the partial pressure of hydro-gen, the temperature, the concentrations of the reacting components, the catalyst, and the flow conditions in the reactor. Secondary reactions may decrease the quantity of the anthraquinone derivatives which produce hydrogen perox-ide. Both suspension reactors and fixed-bed reactors have been used for the hydrogenation.
The suspended catalysts used have included porous so-called palladium black, palladium absorbed into a carrier (for example alumina, activated carbon), and Raney nickel. The porous catalyst is suspended and the hydrogen is dispersed into the working solution in, for example, a mixing-tank reactor or a tubular reactor. In a tubular reactor the rnix-ing is effected by the high linear velocity of the working solution. Usually the linear velocities are over 3 m/s and below 10 m/s in an open tube (US Patent 4,428,923). Mixing , has also been improved by using as a reactor tube an alter-nately converging and expanding tube (US Patent 3,423,176, Kabisch et al.).
From FI Patent Application 864 971 there is additionally known a process of the type mentioned in the preamble, in which a reaction mixture which contains hydrogen, working solution and a solid suspended catalyst is circulatéd in a tubular reactor system which is equipped with a static mix-er which is continuous or made up of several parts. The pressure prevailing in the tube system is below 15 bar and the temperature below 100 C. In this process the working solution is circulated in the reaction tube system at a flow velocity which is below 3 m/s.
The contact surfaces and contact periods of the catalyst, the working solution and the hydrogen gas are important for the hydrogenation reaction. By using a stationary, solid catalyst in the hydrogenation the contact period in the aatalyst reaction can be shortened, whereby the proportion of secondary reactions is decreased. The absence of the expensive filtration step is a significant advantage of using a fixed catalyst bed rather than a suspended cata-lyst. The filtration may be problematic also technically, since the catalyst particles are small.
A suspended catalyst is left partly unexploited in the hy-drogenation reaction, since for a large proportion of the time it is in a hydrogen-free part of the process cycle, for example in the circulation tank, or it may adhere to the process cycle. Also, a suspended catalyst is more sen-sitive to sintration and to mechanical wear.
In fixed-bed reactors, carrier pellets and so-called honey-comb catalysts have been used (Berglin et al., US Patent ..
4 Z0086~
4,552,748). The carrier used has usually been active alumina, but also other porous carriers having a large spe-cific surface can be used, for example SiO2 or activated carbon. A noble metal, usually palladium, has been absorbed as the active component into the carrier. Only some kind of after-filtration for the separation, from the working solu-tion, of particles detached from the bed is used in the ``fixed-bed reactor before the oxidation step.
In fixed-bed reactors there are usually used pellets (dia-meter usually 0.2-10 mm) installed between sieve sheets or nets. In pellets as large as this, the transfer of material into the deepest pores and out of them is slow, for which reason the active metal in the inner parts of the pellets remains unexploited in the reaction. Likewise, the pressure loss increases to a high level, and canalization of the flows occurs in these freely packed catalyst beds. The re-duction gas also tends to separate into a phase of its own, whereupon the hydrogenation velocity decreases. Special attention must be paid in order that no catalytic poisons will pass into the working solution or into the réduction gas.
The so-called honeycomb catalyst is made up of a cellular support structure having parallel canals. The porous car-rler is fixed as a thin layer on the support structure, and furthermore a noble metal is absorbed into it. A reactor working according to a principle such as this has the dis-advantage of a poor mixing of the hydrogen with the working solution and ~ossibly the separation of the gas bubbles into a phase of their own. Heat transfer from the inner parts of the honeycomb remains poor, in which case the tem-perature therein may rise too high, a situation which in-creases the quantity of undesirable byproducts.
.
.
.
A process for the preparation of hydrogen peroxide (I) The present invention relates to a process for the prepara-tion of hydrogen peroxide by the anthraquinone process, and more particularly to its partial process, namely hydrogena-tion. Quite specifically the present invention relates to a process in which a reaction solution is circulated into which hydrogen or a hydrogen-containing gas and a working solution, i.e. an anthraquinone derivative in an organic solvent, are fed via a tubular static mixing zone which is either continuous or made up of several parts, in order to hydrogenate the anthra~uinone derivative in the presence of a solid catalyst and by removing hydrogenated working solu-tion and gas from the circulating reaction mixture. In ad-dition the present invention relates to a tubular static mixer comprising one or more parts and to the use of the mixer in the process mentioned above.
It is known that hydrogen peroxide can be prepared by the so-called anthraquinone process. In this process an anthra-guinone derivative is dissolved in a solvent comprising one or more components. The solution thus prepared is called the working solution. In the preparation of hydrogen per-oxide, the working solution is first fed to the hydrogena-tion step. During this step the anthraquinone derivatives are hydrogenated, in the presence of a catalyst, to the corresponding anthrahydroquinone derivatives. Thereafter the hydrogenated working solution is directed to oxidation, during which oxygen or an oxygen-containing gas is intro-duced into it, whereupon hydrogen peroxide is formed in the solution. The principal reactions of the anthraquinone process are shown below:
+ H2 catalYst > ~
o OH
.
OH
+ 2 > ~ R ' H22 OE~ O ,:
The working solution which contains hydrogen peroxide is fed to the extraction step, in which the hydrogen peroxide is caused by extraction to pass from the working solution into an aqueous solution. The extracted working solution is dried by removal of excess water and recycled to the begin-ning of the cyclic process, i.e. to hydrogenation. The aqueous solution of hydrogen peroxide, obtained by extrac-tion, is purified and concentrated.
The hydrogenation described above is a demanding step in the anthraquinone process. High activity and high selec-tivity are required of the hydrogenation catalyst. The con-version and selectivity of the reaction in the hydrogena-tion step are dependent on the partial pressure of hydro-gen, the temperature, the concentrations of the reacting components, the catalyst, and the flow conditions in the reactor. Secondary reactions may decrease the quantity of the anthraquinone derivatives which produce hydrogen perox-ide. Both suspension reactors and fixed-bed reactors have been used for the hydrogenation.
The suspended catalysts used have included porous so-called palladium black, palladium absorbed into a carrier (for example alumina, activated carbon), and Raney nickel. The porous catalyst is suspended and the hydrogen is dispersed into the working solution in, for example, a mixing-tank reactor or a tubular reactor. In a tubular reactor the rnix-ing is effected by the high linear velocity of the working solution. Usually the linear velocities are over 3 m/s and below 10 m/s in an open tube (US Patent 4,428,923). Mixing , has also been improved by using as a reactor tube an alter-nately converging and expanding tube (US Patent 3,423,176, Kabisch et al.).
From FI Patent Application 864 971 there is additionally known a process of the type mentioned in the preamble, in which a reaction mixture which contains hydrogen, working solution and a solid suspended catalyst is circulatéd in a tubular reactor system which is equipped with a static mix-er which is continuous or made up of several parts. The pressure prevailing in the tube system is below 15 bar and the temperature below 100 C. In this process the working solution is circulated in the reaction tube system at a flow velocity which is below 3 m/s.
The contact surfaces and contact periods of the catalyst, the working solution and the hydrogen gas are important for the hydrogenation reaction. By using a stationary, solid catalyst in the hydrogenation the contact period in the aatalyst reaction can be shortened, whereby the proportion of secondary reactions is decreased. The absence of the expensive filtration step is a significant advantage of using a fixed catalyst bed rather than a suspended cata-lyst. The filtration may be problematic also technically, since the catalyst particles are small.
A suspended catalyst is left partly unexploited in the hy-drogenation reaction, since for a large proportion of the time it is in a hydrogen-free part of the process cycle, for example in the circulation tank, or it may adhere to the process cycle. Also, a suspended catalyst is more sen-sitive to sintration and to mechanical wear.
In fixed-bed reactors, carrier pellets and so-called honey-comb catalysts have been used (Berglin et al., US Patent ..
4 Z0086~
4,552,748). The carrier used has usually been active alumina, but also other porous carriers having a large spe-cific surface can be used, for example SiO2 or activated carbon. A noble metal, usually palladium, has been absorbed as the active component into the carrier. Only some kind of after-filtration for the separation, from the working solu-tion, of particles detached from the bed is used in the ``fixed-bed reactor before the oxidation step.
In fixed-bed reactors there are usually used pellets (dia-meter usually 0.2-10 mm) installed between sieve sheets or nets. In pellets as large as this, the transfer of material into the deepest pores and out of them is slow, for which reason the active metal in the inner parts of the pellets remains unexploited in the reaction. Likewise, the pressure loss increases to a high level, and canalization of the flows occurs in these freely packed catalyst beds. The re-duction gas also tends to separate into a phase of its own, whereupon the hydrogenation velocity decreases. Special attention must be paid in order that no catalytic poisons will pass into the working solution or into the réduction gas.
The so-called honeycomb catalyst is made up of a cellular support structure having parallel canals. The porous car-rler is fixed as a thin layer on the support structure, and furthermore a noble metal is absorbed into it. A reactor working according to a principle such as this has the dis-advantage of a poor mixing of the hydrogen with the working solution and ~ossibly the separation of the gas bubbles into a phase of their own. Heat transfer from the inner parts of the honeycomb remains poor, in which case the tem-perature therein may rise too high, a situation which in-creases the quantity of undesirable byproducts.
.
.
.
2~865~
One step limiting hydrogenation in fixed-bed reactors is the passage of hydrogen from a gas bubble into the working solution. The rate of the passage of hydrogen depends on the size of the hydrogen bubbles in the working solution.
The smaller the bubbles in which the hydrogen is in the solution, the greater the total surface area of the inter-face between the working solution and the gas phase. The mixing of hydrogen with the working solution has been im-proved by using static mixers at a point before the fixed-bed reactor (US Patent 4,428,922). In this manner the hy-drogen is in small bubbles in the working solution upon entering the reactor, but as a result of the canalization in the reactor the dispersion of the gas weakens.
A pre-mixing reactor in which the working solution is satu-rated with respect to hydrogen has also been used at a point before the hydrogenation (US Patent 21837,411).
The purpose of the present invention is thus to provide a process and an apparatus for the production of hydrogen peroxide by the anthraquinone process, in which the disad-vantages of prior-art processes and apparatuses have been eliminated. The main characteristics of the invention are given in the accompanying claims.
In the process according to the invention, a reaction mix-ture comprising hydrogen or a hydrogen-containing gas and the working solution is thus caused to circulate in a constant-diameter or alternately converging and expanding tubular reactQr system which is installed horizontally or vertically and is equipped with a static mixer which is continuous or comprises several parts and is coated with a catalytic substance, the reaction mixture being simul-taneously mixed and catalyzed in the mixer. The tubular reactor can simply be dimensioned to be so long that the , `' '.
:' - "~'--Z0(:~865~
hydrogen has time to react before reaching the end of the tubular reactor. Thus reduction gas need not be circulated in the reactor.
The static mixer according to the invention comprises a support structure of a metallic, ceramic, polymeric or other corresponding material, to the surface of which a porous carrier has been fixed. The carrier comprises, for example, alumina, SiO2, silicates or activated carbon. A
metal active in hydrogenation, for example palladium, plat-inum, rhodium, nickel or a mixture of these, has been ab-sorbed into the carrier.
In the reactor according to the invention, a sufficient transfer of material between the gas and the liquid and a sufficient transfer of heat from the reactor mixture to the tube wall are achieved by means of static mixers, which have been described in the following publications, for example: Chem.-Ing.-Tech. 52 ~1980), 4, pp. 285-291; Chem.
Eng. Prog. 82 (July 1986), 7, pp. 42-48, and 20 ~May-June 1986), 3, pp. 147-154; Perry, R.H. and Chilton, C;H., Chem-ical Engineer's Handbook, 5, New York: McGraw-Hill (1973) Section 19, p. 22. Likewise, axial mixing is minimized and the temperature and concentration profiles in the cross sectional area of the tube are made even.
The reaction occurs in a thin catalyst layer of 5-300 ~m on the surface of the mixer. The layer being thin, the propor-tion of yield-decreasing secondary reactions will remain small, since the retention times of reagents and reaction products in the pores are short. Likewise, the catalytical-ly active metal will be used efficiently in the thin cata-lyst layer. For this reason the catalyst layer according to the invention is more advantageous than a fixed bed made up of pellets.
. , ~: ,; , ,-:
20(~65~
In contrast to the honeycomb reactor according to U.S.
Patent 4,552,748, in which the catalyst pieces form mutual-ly parallel, equally long canals with no mixing effect, in the reactor according to the invention its structures serve not only as fixing surfaces for the catalyst but also as mixers, the static mixer having catalyst-coated flow baf-fles mutually in different directions, which effectively distribute the flow over the entire cross sectional area of the reactor. Such an effect is not present in the reactor according to US Patent 4,552,748, which requires separate mixers for dispersing and dissolving the hydrogen into the working solution.
In the present invention it is quite essential that the reaction solution is mixed while it is being catalyzed, since it has been observed that the hydrogenation reaction is not as effective if the catalyzing and the mixing are carried out in different steps, as in US Patent 4,552,748.
Owing to the mixing, the transfer of heat and material be-tween the liquid and the catalyst surface is more rapid than in honeycomb structures consisting of straight, paral-lel canals. By means of the catalyst the linear velocities in the reactor may be lowered to below 3 mts, since the static mixers disperse the hydrogen into the working solu-tion even at low linear velocities, for example within the range 0.1-1.5 m/s. At these velocities the pressure loss and the mechanical wear of the catalyst coating are slight.
The catalyst activities in the static mixer according to the present invention remain nearly unchanged for even long periods. This is in part due to a relatively open flow, in which case extensive impurities cannot adhere to the cata-lyst surface, the flow rinsing the canal walls clean. Like-.~ :
2008651.
wise, the nearly anhydrous liquid phase and the oxygen-free gas phase promote the maintenance of the activity of the metal.
The length of the reactor is dependent on the mixer type used. When the canals of the static mixer are smaller, the geometric surface area of the mixer is greater, whereupon more catalyst layer per volume unit can be bound, but at the same time the dynamic pressure loss in the mixer will be greater. Thus an optimum size can be found for the mixer canals.
By means of the invention, a high hydrogen peroxide yield is obtained as calculated in proportion to the active metal. This is due, first, to the fact that all of the cat-alyst is in that part of the reactor system in which the hydrogenation reaction takes place. In addition, the thin catalyst layer is advantageous for the exploiting of the active metal.
A more important advantage as compared to the closest com-parable inventions is the method of mixing the hydrogen and the working solution, advantageous in terms of the transfer of material and heat. Thus, uniform conditions are pro-duced, which are advantageous for the selectivity and speed of the hydrogenation reaction. By using a thin catalyst layer, the active metal can be used effectively in the hy-drogenation and, furthermore, the contact period between the reagents and the catalyst remains short, a factor which decreases the quantity of byproducts.
The hydrogenation process according to the invention can be implemented on an industrial scale so that the reduction is carried out in its entirety within an advantageous pressure range. The pressure in the reactor is maintained within the . '~
: :
9 20~
range 1-15 bar, preferably 2-5 bar. The temperature of the working solution is maintained within the advantageous tem-perature range 40-60 C, for example in small-scale hydro-genation by jacket cooling of the reactor.
The invention is described below in greater detail with reference to the accompanying drawing, which depicts dia-grammatically the hydrogenation process according to the invention.
The hydrogenation step comprises a circulation tank 1, into which the working solution 14 to be hydrogenated is fed by means of a pump 4. The working solution is recycled to the circulation tank 1 by means of a pump 3 in the tube system 8 via a hydrogenation reactor 2 equipped with one or more static mixers 9 coated with a catalytic material. The hy-drogenation reactor 2 is equipped with a cooling jacket 6, but it is clear that the cooling can be arranged in other ways as well. The working solution 14 to be hydrogenated can also be fed directly into the circulation tube system 8. Hydrogen is introduced from a tube 12 into the hydrogen-ation circulation tube system at a point somewhat before the hydrogenation reactor 2, and the exhaust gases are re-moved through a tube 11, which is in the upper section of the circulation tank 1. Rydrogenated working solution is removed through a tube 13 connected to the lower section of the circulation tank 1 and is fed via a pump 5 and an after-filter 7 to oxygenation. The hydrogenation conversion can be affected by adjusting the feeding rate of hydrogen 12, the pressure in the reactor, and the liquid flow 8 through it.
Example In the small-scale batch experiment which was carried out, a working solution was used which contained 2-ethylanthra-20~8651 quinone 100 g/l. The solvent used was a mixture of aromatichydrocarbons and an organic phosphorus compound. 10 static mixers coated with a catalytic material and having a length of 40 mm had been installed in the tubular reactor system, the length of which was approximately 400 mm and diameter 39 mm, in which case the reaction mixture was distributed effectively in relation to the cross sectional area of the tube, being mixed and at the same time catalyzed. A layer of about 50 micrometers of porous gamma-aluminum oxide car-rier had been fixed to the surface of the metallic static mixer. Palladium, in total approximately 0.5 percent by weight, had been absorbed into the aluminum oxide layer.
The flow rate of the working solution was approximately 2000 l/h, which corresponded to a linear velocity of 0.5 m/s. The temperature was 50 C and the pressure at the be-ginning of the reactor was 4.0 bar.
Hydrogen was fed into the reactor at 55 l/h (NTP), only part of which was consumed in the reactor. The production of hydrogen peroxide in the reactor was on average 50 kg/~kg palladium) per hour.
, .
.: . . : --: -- . .
One step limiting hydrogenation in fixed-bed reactors is the passage of hydrogen from a gas bubble into the working solution. The rate of the passage of hydrogen depends on the size of the hydrogen bubbles in the working solution.
The smaller the bubbles in which the hydrogen is in the solution, the greater the total surface area of the inter-face between the working solution and the gas phase. The mixing of hydrogen with the working solution has been im-proved by using static mixers at a point before the fixed-bed reactor (US Patent 4,428,922). In this manner the hy-drogen is in small bubbles in the working solution upon entering the reactor, but as a result of the canalization in the reactor the dispersion of the gas weakens.
A pre-mixing reactor in which the working solution is satu-rated with respect to hydrogen has also been used at a point before the hydrogenation (US Patent 21837,411).
The purpose of the present invention is thus to provide a process and an apparatus for the production of hydrogen peroxide by the anthraquinone process, in which the disad-vantages of prior-art processes and apparatuses have been eliminated. The main characteristics of the invention are given in the accompanying claims.
In the process according to the invention, a reaction mix-ture comprising hydrogen or a hydrogen-containing gas and the working solution is thus caused to circulate in a constant-diameter or alternately converging and expanding tubular reactQr system which is installed horizontally or vertically and is equipped with a static mixer which is continuous or comprises several parts and is coated with a catalytic substance, the reaction mixture being simul-taneously mixed and catalyzed in the mixer. The tubular reactor can simply be dimensioned to be so long that the , `' '.
:' - "~'--Z0(:~865~
hydrogen has time to react before reaching the end of the tubular reactor. Thus reduction gas need not be circulated in the reactor.
The static mixer according to the invention comprises a support structure of a metallic, ceramic, polymeric or other corresponding material, to the surface of which a porous carrier has been fixed. The carrier comprises, for example, alumina, SiO2, silicates or activated carbon. A
metal active in hydrogenation, for example palladium, plat-inum, rhodium, nickel or a mixture of these, has been ab-sorbed into the carrier.
In the reactor according to the invention, a sufficient transfer of material between the gas and the liquid and a sufficient transfer of heat from the reactor mixture to the tube wall are achieved by means of static mixers, which have been described in the following publications, for example: Chem.-Ing.-Tech. 52 ~1980), 4, pp. 285-291; Chem.
Eng. Prog. 82 (July 1986), 7, pp. 42-48, and 20 ~May-June 1986), 3, pp. 147-154; Perry, R.H. and Chilton, C;H., Chem-ical Engineer's Handbook, 5, New York: McGraw-Hill (1973) Section 19, p. 22. Likewise, axial mixing is minimized and the temperature and concentration profiles in the cross sectional area of the tube are made even.
The reaction occurs in a thin catalyst layer of 5-300 ~m on the surface of the mixer. The layer being thin, the propor-tion of yield-decreasing secondary reactions will remain small, since the retention times of reagents and reaction products in the pores are short. Likewise, the catalytical-ly active metal will be used efficiently in the thin cata-lyst layer. For this reason the catalyst layer according to the invention is more advantageous than a fixed bed made up of pellets.
. , ~: ,; , ,-:
20(~65~
In contrast to the honeycomb reactor according to U.S.
Patent 4,552,748, in which the catalyst pieces form mutual-ly parallel, equally long canals with no mixing effect, in the reactor according to the invention its structures serve not only as fixing surfaces for the catalyst but also as mixers, the static mixer having catalyst-coated flow baf-fles mutually in different directions, which effectively distribute the flow over the entire cross sectional area of the reactor. Such an effect is not present in the reactor according to US Patent 4,552,748, which requires separate mixers for dispersing and dissolving the hydrogen into the working solution.
In the present invention it is quite essential that the reaction solution is mixed while it is being catalyzed, since it has been observed that the hydrogenation reaction is not as effective if the catalyzing and the mixing are carried out in different steps, as in US Patent 4,552,748.
Owing to the mixing, the transfer of heat and material be-tween the liquid and the catalyst surface is more rapid than in honeycomb structures consisting of straight, paral-lel canals. By means of the catalyst the linear velocities in the reactor may be lowered to below 3 mts, since the static mixers disperse the hydrogen into the working solu-tion even at low linear velocities, for example within the range 0.1-1.5 m/s. At these velocities the pressure loss and the mechanical wear of the catalyst coating are slight.
The catalyst activities in the static mixer according to the present invention remain nearly unchanged for even long periods. This is in part due to a relatively open flow, in which case extensive impurities cannot adhere to the cata-lyst surface, the flow rinsing the canal walls clean. Like-.~ :
2008651.
wise, the nearly anhydrous liquid phase and the oxygen-free gas phase promote the maintenance of the activity of the metal.
The length of the reactor is dependent on the mixer type used. When the canals of the static mixer are smaller, the geometric surface area of the mixer is greater, whereupon more catalyst layer per volume unit can be bound, but at the same time the dynamic pressure loss in the mixer will be greater. Thus an optimum size can be found for the mixer canals.
By means of the invention, a high hydrogen peroxide yield is obtained as calculated in proportion to the active metal. This is due, first, to the fact that all of the cat-alyst is in that part of the reactor system in which the hydrogenation reaction takes place. In addition, the thin catalyst layer is advantageous for the exploiting of the active metal.
A more important advantage as compared to the closest com-parable inventions is the method of mixing the hydrogen and the working solution, advantageous in terms of the transfer of material and heat. Thus, uniform conditions are pro-duced, which are advantageous for the selectivity and speed of the hydrogenation reaction. By using a thin catalyst layer, the active metal can be used effectively in the hy-drogenation and, furthermore, the contact period between the reagents and the catalyst remains short, a factor which decreases the quantity of byproducts.
The hydrogenation process according to the invention can be implemented on an industrial scale so that the reduction is carried out in its entirety within an advantageous pressure range. The pressure in the reactor is maintained within the . '~
: :
9 20~
range 1-15 bar, preferably 2-5 bar. The temperature of the working solution is maintained within the advantageous tem-perature range 40-60 C, for example in small-scale hydro-genation by jacket cooling of the reactor.
The invention is described below in greater detail with reference to the accompanying drawing, which depicts dia-grammatically the hydrogenation process according to the invention.
The hydrogenation step comprises a circulation tank 1, into which the working solution 14 to be hydrogenated is fed by means of a pump 4. The working solution is recycled to the circulation tank 1 by means of a pump 3 in the tube system 8 via a hydrogenation reactor 2 equipped with one or more static mixers 9 coated with a catalytic material. The hy-drogenation reactor 2 is equipped with a cooling jacket 6, but it is clear that the cooling can be arranged in other ways as well. The working solution 14 to be hydrogenated can also be fed directly into the circulation tube system 8. Hydrogen is introduced from a tube 12 into the hydrogen-ation circulation tube system at a point somewhat before the hydrogenation reactor 2, and the exhaust gases are re-moved through a tube 11, which is in the upper section of the circulation tank 1. Rydrogenated working solution is removed through a tube 13 connected to the lower section of the circulation tank 1 and is fed via a pump 5 and an after-filter 7 to oxygenation. The hydrogenation conversion can be affected by adjusting the feeding rate of hydrogen 12, the pressure in the reactor, and the liquid flow 8 through it.
Example In the small-scale batch experiment which was carried out, a working solution was used which contained 2-ethylanthra-20~8651 quinone 100 g/l. The solvent used was a mixture of aromatichydrocarbons and an organic phosphorus compound. 10 static mixers coated with a catalytic material and having a length of 40 mm had been installed in the tubular reactor system, the length of which was approximately 400 mm and diameter 39 mm, in which case the reaction mixture was distributed effectively in relation to the cross sectional area of the tube, being mixed and at the same time catalyzed. A layer of about 50 micrometers of porous gamma-aluminum oxide car-rier had been fixed to the surface of the metallic static mixer. Palladium, in total approximately 0.5 percent by weight, had been absorbed into the aluminum oxide layer.
The flow rate of the working solution was approximately 2000 l/h, which corresponded to a linear velocity of 0.5 m/s. The temperature was 50 C and the pressure at the be-ginning of the reactor was 4.0 bar.
Hydrogen was fed into the reactor at 55 l/h (NTP), only part of which was consumed in the reactor. The production of hydrogen peroxide in the reactor was on average 50 kg/~kg palladium) per hour.
, .
.: . . : --: -- . .
Claims (9)
1. A process for the production of hydrogen peroxide by the anthraquinone process by circulating a reaction mixture into which there are fed hydrogen or a hydrogen-containing gas (12) and a working solution (14), i.e. an anthraquinone derivative in an organic solvent, via an oblong static mix-ing zone (2) which is continuous or made up of several parts, in order to hydrogenate the anthraquinone derivative in the presence of a solid catalyst, and by removing hydro-genated working solution (13) and gas (11) from the cir-culating reaction mixture, characterized in that the reac-tion mixture (8) is mixed, while it is being catalyzed, by circulating the reaction mixture via a catalyst-coated static mixing zone (2, 9).
2. A process according to Claim 1, characterized in that in the catalyst-coated static mixing zone (2, 9) a pressure is maintained which is 1-15 bar, preferably 2-5 bar, and a temperature is maintained which is below 100 °C, preferably 40-60 °C.
3. A process according to Claim 1 or 2, characterized in that the reaction mixture (8) is circulated through the catalyst-coated static mixing zone (2, 9) at a velocity of 0.1-1.5 m/s.
4. A tubular static mixer (9), comprising one or several parts, for the catalytic hydrogenation of a reaction mix-ture which contains hydrogen or a hydrogen-containing gas (12) and a working solution (14), i.e. an anthraquinone derivative in an organic solvent, characterized in that the static mixer (9) is coated with a solid catalyst.
5. A static mixer according to Claim 4, characterized in that it is coated with a porous carrier into which a hydrogenation-catalyzing metal has been absorbed.
6. A static mixer according to Claim 5, characterized in that the thickness of the coating is at maximum ap-proximately 300 µm and preferably at minimum 5 µm.
7. A static mixer according to Claim 5 or 6, characterized in that the porous carrier is active alumina, silica, sili-cate, and/or activated carbon.
8. A static mixer according to any of Claims 4-7, charac-terized in that hydrogenation-catalyzing palladium, pla-tinum, rhodium and/or nickel has been absorbed into the mixer (9).
9. The use of a tubular static mixer (9), comprising one or several parts, for the catalytic hydrogenation of an anthraquinone derivative in an organic solvent by means of hydrogen or a hydrogen-containing gas, the surface of the static mixer having been coated with a preferably at maxi-mum 300-µm-thick porous carrier layer into which a hydrogenation-catalyzing metal has been absorbed.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI890428 | 1989-01-27 | ||
| FI890428A FI82669C (en) | 1989-01-27 | 1989-01-27 | FOERFARANDE FOER FRAMSTAELLNING AV VAETEPEROXID. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2008651A1 true CA2008651A1 (en) | 1990-07-27 |
Family
ID=8527797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002008651A Abandoned CA2008651A1 (en) | 1989-01-27 | 1990-01-26 | Process for the preparation of hydrogen peroxide (i) |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPH02275703A (en) |
| AU (1) | AU620963B2 (en) |
| BR (1) | BR9000347A (en) |
| CA (1) | CA2008651A1 (en) |
| DE (1) | DE4002335A1 (en) |
| ES (1) | ES2019046A6 (en) |
| FI (1) | FI82669C (en) |
| FR (1) | FR2642412B1 (en) |
| GB (1) | GB2229173B (en) |
| IT (1) | IT1240869B (en) |
| NZ (1) | NZ232216A (en) |
| SE (1) | SE504578C2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4313393C2 (en) * | 1993-04-07 | 2003-06-26 | Siemens Ag | Static mixer |
| FI95457C (en) * | 1994-03-15 | 1996-02-12 | Kemira Chemicals Oy | Process for the preparation of hydrogen peroxide and the reactor used therein |
| WO2001094006A2 (en) * | 2000-06-07 | 2001-12-13 | Abb Lummus Global, Inc. | Heat exchanger/reactor apparatus |
| US20220362752A1 (en) * | 2019-06-21 | 2022-11-17 | Commonwealth Scientific And Industrial Research Organisation | Processes for catalytically coating scaffolds |
| CN111410176A (en) * | 2020-05-14 | 2020-07-14 | 福建永荣科技有限公司 | Hydrogenation tower tubular reactor for producing hydrogen peroxide |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL139013B (en) * | 1965-12-04 | 1973-06-15 | Degussa | PROCESS FOR PREPARING HYDROGEN PEROXIDE ACCORDING TO THE ANTRACHINO CIRCUIT PROCEDURE. |
| US3565581A (en) * | 1968-05-16 | 1971-02-23 | Fmc Corp | Production of hydrogen peroxide in the anthraquinone process using a novel catalytic fixed bed |
| US3615207A (en) * | 1969-06-16 | 1971-10-26 | Fmc Corp | Production of hydrogen peroxide by anthraquinone process |
| YU33554B (en) * | 1969-07-12 | 1977-08-31 | Degussa | Process for reactivating noble metal catalysts on a carrier for the synthesis of h2o2 by anthraquinone process |
| JPS4941040B1 (en) * | 1970-08-18 | 1974-11-06 | ||
| DE2042523C3 (en) * | 1970-08-27 | 1979-09-13 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Process for the regeneration of noble metal catalysts for hydrogen peroxide synthesis according to the anthraquinone process |
| US3755552A (en) * | 1970-10-21 | 1973-08-28 | Fmc Corp | Process for producing hydrogen peroxide |
| US4428922A (en) * | 1982-05-14 | 1984-01-31 | Fmc Corporation | Process for manufacturing hydrogen peroxide |
| SE431532B (en) * | 1982-09-08 | 1984-02-13 | Eka Ab | METHOD OF PRODUCING WHEAT PEROXIDE |
| FI77633B (en) * | 1986-12-05 | 1988-12-30 | Kemira Oy | FOERFARANDE FOER FRAMSTAELLNING AV VAETEPEROXID. |
-
1989
- 1989-01-27 FI FI890428A patent/FI82669C/en not_active IP Right Cessation
-
1990
- 1990-01-23 SE SE9000227A patent/SE504578C2/en unknown
- 1990-01-23 AU AU48660/90A patent/AU620963B2/en not_active Ceased
- 1990-01-24 NZ NZ232216A patent/NZ232216A/en unknown
- 1990-01-26 GB GB9001802A patent/GB2229173B/en not_active Expired - Fee Related
- 1990-01-26 JP JP2015146A patent/JPH02275703A/en active Pending
- 1990-01-26 IT IT83314A patent/IT1240869B/en active IP Right Grant
- 1990-01-26 DE DE4002335A patent/DE4002335A1/en not_active Withdrawn
- 1990-01-26 BR BR909000347A patent/BR9000347A/en not_active Application Discontinuation
- 1990-01-26 CA CA002008651A patent/CA2008651A1/en not_active Abandoned
- 1990-01-26 ES ES909000488A patent/ES2019046A6/en not_active Expired - Fee Related
- 1990-01-29 FR FR909000986A patent/FR2642412B1/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| IT1240869B (en) | 1993-12-17 |
| GB2229173B (en) | 1993-03-03 |
| IT9083314A0 (en) | 1990-01-26 |
| SE9000227D0 (en) | 1990-01-23 |
| SE9000227L (en) | 1990-07-28 |
| SE504578C2 (en) | 1997-03-10 |
| AU620963B2 (en) | 1992-02-27 |
| GB2229173A (en) | 1990-09-19 |
| FI890428A (en) | 1990-07-28 |
| FI82669B (en) | 1990-12-31 |
| FR2642412B1 (en) | 1992-11-13 |
| DE4002335A1 (en) | 1990-09-06 |
| BR9000347A (en) | 1990-12-04 |
| IT9083314A1 (en) | 1990-07-28 |
| AU4866090A (en) | 1990-08-02 |
| ES2019046A6 (en) | 1991-05-16 |
| NZ232216A (en) | 1991-10-25 |
| FR2642412A1 (en) | 1990-08-03 |
| JPH02275703A (en) | 1990-11-09 |
| FI890428A0 (en) | 1989-01-27 |
| FI82669C (en) | 1991-04-10 |
| GB9001802D0 (en) | 1990-03-28 |
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