BR102017003090A2 - direct synthesis process of methyl isobutyl ketone (mibk) from isopropanol and use of zirconia-supported copper as a catalyst - Google Patents
direct synthesis process of methyl isobutyl ketone (mibk) from isopropanol and use of zirconia-supported copper as a catalyst Download PDFInfo
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- BR102017003090A2 BR102017003090A2 BR102017003090A BR102017003090A BR102017003090A2 BR 102017003090 A2 BR102017003090 A2 BR 102017003090A2 BR 102017003090 A BR102017003090 A BR 102017003090A BR 102017003090 A BR102017003090 A BR 102017003090A BR 102017003090 A2 BR102017003090 A2 BR 102017003090A2
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- isopropanol
- mibk
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- zirconia
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 title claims abstract description 93
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 title claims abstract description 53
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 239000010949 copper Substances 0.000 title claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 239000006200 vaporizer Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 239000012263 liquid product Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 238000004508 fractional distillation Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000000622 liquid--liquid extraction Methods 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims 2
- 239000012159 carrier gas Substances 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 238000010926 purge Methods 0.000 claims 1
- 238000003860 storage Methods 0.000 claims 1
- 238000009834 vaporization Methods 0.000 claims 1
- 230000008016 vaporization Effects 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 229910052763 palladium Inorganic materials 0.000 abstract description 4
- 229910052697 platinum Inorganic materials 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- JITOKQVGRJSHHA-UHFFFAOYSA-M monosodium methyl arsenate Chemical compound [Na+].C[As](O)([O-])=O JITOKQVGRJSHHA-UHFFFAOYSA-M 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- -1 coatings Substances 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 238000010543 cumene process Methods 0.000 description 1
- 244000096108 cunha Species 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/02—Formation or introduction of functional groups containing oxygen of hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
a presente invenção se refere a um processo de síntese direta de metil isobutil cetona (mibk) a partir do isopropanol, utilizando cobre suportado em zircônia (cu/zro2) como catalisador. em nossa invenção, o processo para obtenção do mibk ultrapassa 45% de rendimento, ocorre sem a necessidade de alimentar o reator com hidrogênio, sob pressão atmosférica, em reator de fluxo contínuo, e em presença de um catalisador mais barato comparado aos comumente utilizados em processos para obtenção do mibk. o mibk está entre os dez solventes orgânicos mais utilizados na indústria com produção anual mundial de cerca de 485 milhões de toneladas em 2012. atualmente o mibk é comercialmente produzido pela hidrogenação seletiva da acetona em fase líquida. o processo industrial convencional, quando não envolve múltiplas etapas, utiliza catalisadores multifuncionais a base de metais nobres tais como paládio e platina, opera sob elevadas pressões e o rendimento não passa de 30%.The present invention relates to a process of direct synthesis of methyl isobutyl ketone (mibk) from isopropanol using zirconia-supported copper (cu / zro2) as a catalyst. In our invention, the process for obtaining mibk exceeds 45% yield, occurs without the need to feed the reactor hydrogen at atmospheric pressure in a continuous flow reactor, and in the presence of a cheaper catalyst compared to those commonly used in processes for obtaining mibk. mibk is among the top ten most commonly used organic solvents in the industry with worldwide annual production of about 485 million tons in 2012. mibk is currently commercially produced by selective hydrogenation of liquid phase acetone. The conventional industrial process, when not involving multiple steps, uses noble metal based multifunctional catalysts such as palladium and platinum, operates under high pressures and yields no more than 30%.
Description
(54) Título: PROCESSO DE SÍNTESE DIRETA DE METIL ISOBUTIL CETONA (MIBK) A PARTIR DE ISOPROPANOL E USO DE COBRE SUPORTADO EM ZIRCÔNIA COMO CATALISADOR (51) Int. Cl.: C07C 45/00; C07C 49/04; C07B 41/02 (73) Titular(es): UNIVERSIDADE FEDERAL DE VIÇOSA, FUNDAÇÃO UNIVERSIDADE FEDERAL DE SÃO CARLOS (72) Inventor(es): ANDRÉ GUSTAVO SATO; MÁRCIO JOSÉ DA SILVA; CARLOS HENRIQUE FURTADO DA CUNHA; JOSÉ MARIA CORRÊA BUENO (85) Data do Início da Fase Nacional:(54) Title: DIRECT SYNTHESIS PROCESS OF METHYL ISOBUTYL KETONE (MIBK) FROM ISOPROPANOL AND USE OF COPPER SUPPORTED IN ZIRCONIA AS CATALYST (51) Int. Cl .: C07C 45/00; C07C 49/04; C07B 41/02 (73) Holder (s): UNIVERSIDADE FEDERAL DE VIÇOSA, FOUNDATION UNIVERSIDADE FEDERAL DE SÃO CARLOS (72) Inventor (s): ANDRÉ GUSTAVO SATO; MÁRCIO JOSÉ DA SILVA; CARLOS HENRIQUE FURTADO DA CUNHA; JOSÉ MARIA CORRÊA BUENO (85) Start date of the National Phase:
15/02/2017 (57) Resumo: A presente invenção se refere a um processo de síntese direta de metil isobutil cetona (MIBK) a partir do isopropanol, utilizando cobre suportado em zircônia (Cu/ZrO2) como catalisador. Em nossa invenção, o processo para obtenção do MIBK ultrapassa 45% de rendimento, ocorre sem a necessidade de alimentar o reator com hidrogênio, sob pressão atmosférica, em reator de fluxo contínuo, e em presença de um catalisador mais barato comparado aos comumente utilizados em processos para obtenção do MIBK. O MIBK está entre os dez solventes orgânicos mais utilizados na indústria com produção anual mundial de cerca de 485 milhões de toneladas em 2012. Atualmente o MIBK é comercialmente produzido pela hidrogenação seletiva da acetona em fase líquida. O processo industrial convencional, quando não envolve múltiplas etapas, utiliza catalisadores multifuncionais a base de metais nobres tais como paládio e platina, opera sob elevadas pressões e o rendimento não passa de 30%.02/15/2017 (57) Abstract: The present invention refers to a process of direct synthesis of methyl isobutyl ketone (MIBK) from isopropanol, using copper supported on zirconia (Cu / ZrO2) as a catalyst. In our invention, the process for obtaining the MIBK exceeds 45% yield, occurs without the need to feed the reactor with hydrogen, under atmospheric pressure, in a continuous flow reactor, and in the presence of a cheaper catalyst compared to those commonly used in processes for obtaining the MIBK. MIBK is among the ten most used organic solvents in the industry with an annual worldwide production of about 485 million tons in 2012. Currently MIBK is commercially produced by the selective hydrogenation of acetone in liquid phase. The conventional industrial process, when it does not involve multiple stages, uses multifunctional catalysts based on noble metals such as palladium and platinum, operates under high pressures and the yield is no more than 30%.
1212
1/61/6
Relatório descritivoDescriptive report
PROCESSO DE SÍNTESE DIRETA DE METIL ISOBUTIL CETONA (MIBK) A PARTIR DE ISOPROPANOL E USO DE COBRE SUPORTADO EM ZIRCÔNIA COMO CATALISADORDIRECT SYNTHESIS PROCESS OF METHYL ISOBUTYL KETONE (MIBK) FROM ISOPROPANOL AND THE USE OF COPPER SUPPORTED IN ZIRCONIA AS CATALYST
CAMPO DA INVENÇÃO [1] A presente invenção se refere a um processo de síntese direta de metil isobutil cetona (MIBK) a partir do isopropanol, utilizando cobre suportado em zircônia (Cu/ZrO2) como catalisador. Em nossa invenção, o processo para obtenção do MIBK ultrapassa 45% de rendimento, ocorre sem a necessidade de alimentar o reator com hidrogênio, sob pressão atmosférica, em reator de fluxo contínuo, e em presença de um catalisador mais barato comparado aos comumente utilizados em processos para obtenção do MIBK. O processo industrial convencional, quando não envolve múltiplas etapas, utiliza catalisadores multifuncionais a base de metais nobres tais como paládio e platina, opera sob elevadas pressões e o rendimento não passa de 30%.FIELD OF THE INVENTION [1] The present invention relates to a process of direct synthesis of methyl isobutyl ketone (MIBK) from isopropanol, using copper supported on zirconia (Cu / ZrO 2 ) as a catalyst. In our invention, the process for obtaining the MIBK exceeds 45% yield, occurs without the need to feed the reactor with hydrogen, under atmospheric pressure, in a continuous flow reactor, and in the presence of a cheaper catalyst compared to those commonly used in processes for obtaining the MIBK. The conventional industrial process, when it does not involve multiple stages, uses multifunctional catalysts based on noble metals such as palladium and platinum, operates under high pressures and the yield is no more than 30%.
ESTADO DA TÉCNICA [2] O metil isobutil cetona (MIBK) é, atualmente, produzido comercialmente por um processo de três etapas, em fase líquida, na faixa de temperatura 120 - 160oC e elevadas pressões (10 - 100 atm), no qual o rendimento não passa de 30%. Embora a obtenção do MIBK possa ser realizada via processo direto “one-pot synthesis”, três etapas reacionais estão envolvidas: (i) condensação aldólica de acetona a diacetona álcool (DAA); (ii) desidratação de DAA a óxido de mesitila (MO); (iii) hidrogenação seletiva do MO a MIBK, que são catalisados por platina (Pt) ou paládio (Pd), em suportes com características ácidas ou sólidos básicos. Tais catalisadores devem apresentar funções simultâneas de condensação, desidratação e hidrogenação.STATE OF THE TECHNIQUE [2] Methyl isobutyl ketone (MIBK) is currently produced commercially by a three-stage process, in liquid phase, in the temperature range 120 - 160 o C and high pressures (10 - 100 atm), at which yield is no more than 30%. Although obtaining the MIBK can be carried out via a direct “one-pot synthesis” process, three reaction steps are involved: (i) aldolic condensation from acetone to alcohol diacetone (DAA); (ii) dehydration of DAA to mesityl oxide (MO); (iii) selective hydrogenation of MO to MIBK, which are catalyzed by platinum (Pt) or palladium (Pd), in supports with acidic or basic solids characteristics. Such catalysts must have simultaneous condensation, dehydration and hydrogenation functions.
[3] MIBK é um dos mais importantes produtos químicos, commodities, obtido via condensação aldólica catalisada por ácido ou base, depois de metacrilato de metila e bisfenol-A é o terceiro em produção obtido a partir da acetona. A maior parte da produção industrial de acetona é feita a partir do propileno, utilizando o processo Hock. Neste processo, o benzeno reage com o propileno na presença de H3PO4[3] MIBK is one of the most important chemicals, commodities, obtained via aldolic condensation catalyzed by acid or base, after methyl methacrylate and bisphenol-A is the third in production obtained from acetone. Most of the industrial production of acetone is made from propylene, using the Hock process. In this process, benzene reacts with propylene in the presence of H3PO4
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2/6 como catalisador. Em seguida, o isopropilbenzeno gerado é oxidado pelo oxigênio, gerando hidroperóxido de cumila, que é clivado em acetona e fenol na presença de ácido sulfúrico.2/6 as a catalyst. Then, the isopropylbenzene generated is oxidized by oxygen, generating cumyl hydroperoxide, which is cleaved into acetone and phenol in the presence of sulfuric acid.
[4] O MIBK é muito utilizado como: intermediário químico; solvente para tintas, revestimentos, borrachas, adesivos, produtos farmacêuticos, produtos químicos e outros produtos de limpeza industriais; e agente de extração no processo de desparafinagem de produtos petrolíferos. Também pode ser utilizado em indústria de semicondutores e na fabricação de germicidas e fungicidas. Nesse sentido, a produção de MIBK tem atraído atenção significativa, pois possui uma ampla utilização industrial.[4] MIBK is widely used as: chemical intermediate; solvent for paints, coatings, rubbers, adhesives, pharmaceuticals, chemicals and other industrial cleaning products; and extraction agent in the dewaxing process for petroleum products. It can also be used in the semiconductor industry and in the manufacture of germicides and fungicides. In this sense, the production of MIBK has attracted significant attention, as it has a wide industrial use.
[5] Na presente descrição de nosso processo inventivo, o rendimento ao MIBK passa dos 45% e a reação do isopropanol ocorre em fase gasosa, na presença de catalisador sólido de cobre suportado em zircônia. Assim, o efluente de reação sai prontamente separado do catalisador. Neste contexto, a produção de MIBK pode representar vantagens estratégicas para as indústrias, pois os custos com processos de separação podem ser reduzidos.[5] In the present description of our inventive process, the yield to MIBK exceeds 45% and the isopropanol reaction occurs in the gas phase, in the presence of a solid copper catalyst supported on zirconia. Thus, the reaction effluent is readily separated from the catalyst. In this context, the production of MIBK can represent strategic advantages for the industries, since the costs with separation processes can be reduced.
[6] Processos para a produção de MIBK a partir de isoprapanol são conhecidos, porém, os processos de produção a partir da acetona são os mais utilizados. A patente US3953517, depositada no ano de 1976, apresenta o processo para obtenção de MIBK a partir da acetona e hidrogênio, utilizando três etapas reacionais catalisadas (condensação, desidratação e hidrogenação seletiva). Diversos documentos de patentes relacionados à utilização de acetona e hidrogênio para a produção de MIBK podem ser citados, tais como US5684207, US6008416, US6762328, US8101805.[6] Processes for the production of MIBK from isoprapanol are known, however, the processes of production from acetone are the most used. The US3953517 patent, filed in 1976, presents the process for obtaining MIBK from acetone and hydrogen, using three catalyzed reaction steps (condensation, dehydration and selective hydrogenation). Several patent documents related to the use of acetone and hydrogen for the production of MIBK can be cited, such as US5684207, US6008416, US6762328, US8101805.
[7] No documento de patente CN1081937, depositado no ano de 1992, é descrito a produção de MIBK a partir de isopropanol, utilizando catalisadores sólidos de cobre, niquel, aluminio e magnésio. Neste processo, o catalisador deve ser ativado com fluxo de hidrogênio a 300°C, durante quatro horas. Em seguida, a esta mesma temperatura, alimenta-se o leito catalítico com fluxo de isopropanol e hidrogênio, com proporção de 1/1,1 (Isopropanol/hidrogenio), para produzir o MIBK.[7] The patent document CN1081937, filed in 1992, describes the production of MIBK from isopropanol, using solid copper, nickel, aluminum and magnesium catalysts. In this process, the catalyst must be activated with hydrogen flow at 300 ° C for four hours. Then, at this same temperature, the catalytic bed is fed with a flow of isopropanol and hydrogen, with a ratio of 1 / 1.1 (Isopropanol / hydrogen), to produce the MIBK.
[8] Mais recentemente, o documento de patente CN103191728, depositado no ano de 2013, descreve a produção de MIBK a partir de isopropanol utilizando[8] More recently, patent document CN103191728, filed in 2013, describes the production of MIBK from isopropanol using
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3/6 catalisador sólido de alumina. Neste processo, o catalisador é ativado com fluxo de hidrogênio a 300°C. Logo após, o leito catalítico é alimentado com fluxo de isopropanol e hidrogênio, com proporção de 2/1 (hidrogênio/isopropano), para produzir MIBK. A reação ocorre em temperaturas entre 160 e 1400°C e pressão entre 4 e 5 MPa.3/6 solid alumina catalyst. In this process, the catalyst is activated with hydrogen flow at 300 ° C. Soon after, the catalytic bed is fed with a flow of isopropanol and hydrogen, with a proportion of 2/1 (hydrogen / isopropane), to produce MIBK. The reaction takes place at temperatures between 160 and 1400 ° C and pressure between 4 and 5 MPa.
[9] Nenhum dos documentos do estado da técnica, tais como patentes ou literatura científica sob a forma de artigos, reivindicam, citam ou descrevem a produção de MIBK e/ou acetona a partir de isopropanol, utilizando cobre suportado em zircônia como catalisador em sistema heterogêneo a pressão atmosférica e em temperatura entre 150 e 250°C.[9] None of the state of the art documents, such as patents or scientific literature in the form of articles, claim, quote or describe the production of MIBK and / or acetone from isopropanol, using copper supported on zirconia as a catalyst in a system heterogeneous at atmospheric pressure and at temperatures between 150 and 250 ° C.
[10] O desempenho do catalisador de cobre suportado em zircônia (Cu/ZrO2) está relacionado às propriedades de superfície da ZrO2, influenciando fortemente a natureza do óxido de Cu, bem como sua interação com o suporte.[10] The performance of the copper catalyst supported on zirconia (Cu / ZrO 2 ) is related to the surface properties of ZrO2, strongly influencing the nature of Cu oxide, as well as its interaction with the support.
[11] O processo inédito apresentado neste presente pedido permite obter o MIBK a partir do isopropanol, apresentando a vantagem de ocorrer em pressão atmosférica, utilizar apenas uma matéria prima, ocorrer em apenas uma etapa, utilizar apenas um tipo de catalisador, e de baixo custo relativo. O presente processo apresenta a vantagem adicional de gerar coprodutos, hidrogênio e acetona, a partir do isopropanol, que podem ser armazenados, reciclados ou utilizados em outros processos integrados. A composição de saída pode apresentar seletividade a MIBK acima de 80% e conversões do isopropanol acima de 50%.[11] The unprecedented process presented in this application allows to obtain MIBK from isopropanol, presenting the advantage of occurring at atmospheric pressure, using only one raw material, occurring in only one step, using only one type of catalyst, and with low relative cost. The present process has the additional advantage of generating co-products, hydrogen and acetone, from isopropanol, which can be stored, recycled or used in other integrated processes. The output composition may have selectivity to MIBK above 80% and isopropanol conversions above 50%.
[12] Sendo assim, a presente invenção é promissora, inovadora e utiliza catalisadores sólidos, baixando o custo de produção do MIBK a partir do isopropanol, já que não necessita de estágios de separação do catalisador e do efluente de reação.[12] Therefore, the present invention is promising, innovative and uses solid catalysts, lowering the production cost of MIBK from isopropanol, since it does not require stages of separation of the catalyst and the reaction effluent.
[13] Outro aspecto do presente pedido que o diferencia dos demais documentos já descritos é o fato de utilizar o cobre suportado em zircônia, tornando o catalisador mais barato pois dispensa-se a necessidade da utilização de resinas de troca iônica, níquel e/ou metais nobres, comumente utilizado para processos comerciais de obtenção do MIBK.[13] Another aspect of the present order that sets it apart from the other documents already described is the fact that it uses copper supported on zirconia, making the catalyst cheaper as there is no need for the use of ion exchange resins, nickel and / or noble metals, commonly used for commercial MIBK obtaining processes.
[14] O desenvolvimento sem precedentes da presente invenção combina reações de desidrogenação e condensação aldólica do propanal na produção de[14] The unprecedented development of the present invention combines dehydrogenation reactions and aldolic condensation of propanal in the production of
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4/64/6
MIBK e hidrogênio e/ou acetona como subprodutos, em catalisador de cobre suportado em zircônia. O catalisador pode ser sintetizado a partir da impregnação úmida da fase ativa (cobre) no suporte (zircônia), seguido de secagem e calcinação a 400°C.MIBK and hydrogen and / or acetone as by-products, in a copper catalyst supported on zirconia. The catalyst can be synthesized from the wet impregnation of the active phase (copper) in the support (zirconia), followed by drying and calcination at 400 ° C.
[15] Estes e outros objetivos ficarão mais evidentes ao longo da descrição da invenção.[15] These and other objectives will become more evident throughout the description of the invention.
DESCRIÇÃO DAS FIGURAS [16] A Figura 1 mostra um fluxo esquemático do processo da invenção para a produção de MIBK a partir do isopropanol.DESCRIPTION OF THE FIGURES [16] Figure 1 shows a schematic flow of the process of the invention for the production of MIBK from isopropanol.
DESCRIÇÃO DA INVENÇÃO [17] A invenção trata se do processo de produção de metil isobutil cetona (MIBK), e acetona e hidrogênio como subprodutos, a partir de isopropanol, em presença do catalisador de cobre suportado em zircônia.DESCRIPTION OF THE INVENTION [17] The invention deals with the production process of methyl isobutyl ketone (MIBK), and acetone and hydrogen as by-products, from isopropanol, in the presence of the copper catalyst supported on zirconia.
[18] O processo para produção de MIBK a partir do isopropanol conforme a invenção não é particularmente restrito, ou seja, o processo descritivo no qual as reações do isopropanol ocorrem em fase gasosa com o catalisador podem ocorrer também em fase líquida, desde que se permita o contato do reagente com o catalisador em condições de temperatura entre 150°C e 250°C. Ambas as reações, em fase líquida ou fase gasosa, podem ocorrer em reatores de fluxo contínuo ou batelada.[18] The process for producing MIBK from isopropanol according to the invention is not particularly restricted, that is, the descriptive process in which isopropanol reactions take place in the gas phase with the catalyst can also occur in the liquid phase, provided that allow contact of the reagent with the catalyst at temperature conditions between 150 ° C and 250 ° C. Both reactions, in liquid or gas phase, can occur in continuous or batch flow reactors.
[19] Diferentes tipos de reatores podem ser utilizados, tais como: reatores de leito fixo, reatores de leito fluidizado, reatores de fluxo pistonado, reatores batelada e reatores semi batelada.[19] Different types of reactors can be used, such as: fixed bed reactors, fluidized bed reactors, piston flow reactors, batch reactors and semi-batch reactors.
[20] O isopropanol empregado como reagente pode ser anidro (99%) ou hidratado, com o teor de água de até 10% em massa, e com teor normal de enxofre e cloreto não superior a 1 ppm.[20] The isopropanol used as a reagent can be anhydrous (99%) or hydrated, with a water content of up to 10% by weight, and with a normal sulfur and chloride content not exceeding 1 ppm.
[21] Outras características, propriedades e vantagens da presente invenção ficam claras na descrição a seguir em conjunto com os desenhos em anexo.[21] Other characteristics, properties and advantages of the present invention are clear from the description below in conjunction with the accompanying drawings.
[22] A Figura 1 mostra o processo esquemático utilizando o reator catalítico 7. A corrente 2, que contém isopropanol fresco estocado no tanque 1, é bombeada por 3[22] Figure 1 shows the schematic process using the catalytic reactor 7. Current 2, which contains fresh isopropanol stored in tank 1, is pumped by 3
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5/6 até o vaporizador 5 pela corrente 4. A linha de reciclo, proveniente da corrente 15, a qual contém isopropanol não convertido, também alimenta o vaporizador 5, regulado pela válvula 14. Pela corrente 6, os reagentes vaporizados entram em contato com o reator catalítico 7, onde o isopropanol, por reações de condensação e desidrogenação, catalisadas por Cu/ZrO2, forma MIBK, acetona, hidrogênio e água. A corrente de saída 8 do reator 7 é resfriada por um trocador de calor 9, e os produtos líquidos da corrente 10 são separados dos produtos gasosos da corrente 16. A corrente gasosa da linha 16 contém principalmente hidrogênio, enquanto a corrente líquida 10 contém isopropanol, MIBK, acetona e água.5/6 to vaporizer 5 by chain 4. The recycle line, from chain 15, which contains unconverted isopropanol, also feeds vaporizer 5, regulated by valve 14. By chain 6, the vaporized reagents come into contact with the catalytic reactor 7, where isopropanol, by condensation and dehydrogenation reactions, catalyzed by Cu / ZrO 2 , forms MIBK, acetone, hydrogen and water. The output stream 8 of the reactor 7 is cooled by a heat exchanger 9, and the liquid products of stream 10 are separated from the gaseous products of stream 16. The gas stream of line 16 contains mainly hydrogen, while liquid stream 10 contains isopropanol , MIBK, acetone and water.
[23] O sistema de refino 11, alimentado pela corrente 10, estoca MIBK no tanque 12, acetona no tanque 13 e recicla o isopropanol não convertido para o vaporizador 5 pela corrente 15, enquanto a água é purgada do sistema pela corrente 18. O hidrogênio pode ser estocado no tanque 17 pela linha 16.[23] The refining system 11, fed by stream 10, stores MIBK in tank 12, acetone in tank 13 and recycles the unconverted isopropanol to vaporizer 5 by stream 15, while the water is purged from the system by stream 18. hydrogen can be stored in tank 17 on line 16.
[24] O sistema de refino 11 pode ser qualquer dos sistemas de refino/purificação do estado da técnica, tal como um sistema de destilação fracionada, extração líquido-líquido, ou sistemas envolvendo adsorção, etc. O reator catalítico 7 opera com o fator de tempo de residência (W/F) na faixa de 10 a 50 kgCAT min kgisopropanol, em que W é a massa de catalisador (kg) e F é o fluxo de isopropanol alimentado (kg/min). O fluxo de isopropanol em fase gasosa é arrastado por um fluxo de um gás inerte numa proporção de até 90% em volume.[24] Refining system 11 can be any of the state of the art refining / purification systems, such as a fractional distillation system, liquid-liquid extraction, or systems involving adsorption, etc. The catalytic reactor 7 operates with the residence time factor (W / F) in the range of 10 to 50 kg CAT min kg isopropanol , where W is the mass of catalyst (kg) and F is the flow of isopropanol fed (kg / min). The flow of isopropanol in the gas phase is entrained by a flow of an inert gas in a proportion of up to 90% by volume.
[25] O reator deve ser carregado com o catalisador de cobre suportado em zircônia (Cu/ZrO2), e a temperatura reacional deve se situar entre 120°C e 300°C.[25] The reactor must be charged with the copper catalyst supported on zirconia (Cu / ZrO 2 ), and the reaction temperature must be between 120 ° C and 300 ° C.
[26] Assim, a presente invenção provê um processo para a produção de, principalmente, MIBK a partir de isopropanol.[26] Thus, the present invention provides a process for producing mainly MIBK from isopropanol.
EXPERIMENTO DE DEMONSTRAÇÃO [27] A invenção será ilustrada a partir do exemplo a seguir o qual descreve a invenção de forma precisa e suficiente, mas sendo apenas ilustrativo e não deve ser entendido como limitador do escopo de proteção do presente pedido de patente:DEMONSTRATION EXPERIMENT [27] The invention will be illustrated from the following example which describes the invention precisely and sufficiently, but being only illustrative and should not be construed as limiting the scope of protection of the present patent application:
[28] O catalisador de Cu/ZrO2, com massa entre 800 e 1000 mg, foi introduzido num micro reator tubular de vidro, sendo, então, submetido ao aquecimento numa taxa de 10oC/min até a temperatura reacional. Na temperatura[28] The Cu / ZrO 2 catalyst, with a mass between 800 and 1000 mg, was introduced in a glass tubular micro reactor, and was then subjected to heating at a rate of 10 o C / min until the reaction temperature. At temperature
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6/6 reacional, uma mistura gasosa de vapor de isopropanol arrastado por Hélio foi introduzida no micro reator. A reação foi realizada no intervalo de temperatura de 150-275oC sob pressão atmosférica, com tempo de residência (W/F) de 40 kgcATmin kg''Isopropanol. A composição de saída apresentou seletividade de MIBK acima de 80%.6/6 reaction, a gas mixture of isopropanol vapor dragged by Helium was introduced into the micro reactor. The reaction was carried out in the temperature range of 150-275 o C under atmospheric pressure, with residence time (W / F) of 40 kgcA T min kg '' Isopropanol . The output composition showed MIBK selectivity above 80%.
[29] Fica, portanto, demonstrado que com o uso do catalisador de Cu/ZrO2, alta seletividade a MIBK e à acetona pode ser obtida da reação de condensação aldólica do propanal e desidrogenação do isopropanol.[29] It is therefore demonstrated that with the use of the Cu / ZrO 2 catalyst, high selectivity to MIBK and acetone can be obtained from the aldolic condensation reaction of propanal and dehydrogenation of isopropanol.
[30] O isopropanol não convertido pode ser reciclado para o reator.[30] The unconverted isopropanol can be recycled to the reactor.
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Claims (8)
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| Application Number | Priority Date | Filing Date | Title |
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| BR102017003090-3A BR102017003090B1 (en) | 2017-02-15 | 2017-02-15 | DIRECT SYNTHESIS PROCESS OF METHYL ISOBUTYL KETONE (MIBK) FROM ISOPROPANOL AND USE OF COPPER SUPPORTED ON ZIRCONIA AS CATALYST |
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| Application Number | Priority Date | Filing Date | Title |
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| BR102017003090-3A BR102017003090B1 (en) | 2017-02-15 | 2017-02-15 | DIRECT SYNTHESIS PROCESS OF METHYL ISOBUTYL KETONE (MIBK) FROM ISOPROPANOL AND USE OF COPPER SUPPORTED ON ZIRCONIA AS CATALYST |
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