ES2611360T3 - Catalizadores para la conversión de ácido hidroxipropiónico o sus derivados en ácido acrílico o sus derivados - Google Patents
Catalizadores para la conversión de ácido hidroxipropiónico o sus derivados en ácido acrílico o sus derivados Download PDFInfo
- Publication number
- ES2611360T3 ES2611360T3 ES13719327.2T ES13719327T ES2611360T3 ES 2611360 T3 ES2611360 T3 ES 2611360T3 ES 13719327 T ES13719327 T ES 13719327T ES 2611360 T3 ES2611360 T3 ES 2611360T3
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- Spain
- Prior art keywords
- derivatives
- catalyst
- acid
- acrylic acid
- catalysts
- Prior art date
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- 239000003054 catalyst Substances 0.000 title abstract description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 title description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title description 4
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 title description 4
- 150000001768 cations Chemical class 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 8
- -1 phosphate anion Chemical class 0.000 abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- 239000010452 phosphate Substances 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 238000001354 calcination Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 150000004645 aluminates Chemical class 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 239000007836 KH2PO4 Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910000393 dicalcium diphosphate Inorganic materials 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
- A61F13/534—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having an inhomogeneous composition through the thickness of the pad
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
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- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1804—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with rare earths or actinides
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- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
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- B01J27/1811—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with gallium, indium or thallium
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- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
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Abstract
Un catalizador que comprende: (a) al menos un anión fosfato condensado seleccionado del grupo que consiste en las fórmulas (I), (II), y (III), [PnO3n+1](n+2)- (I) [PnO3n]n- (II) [P(2 m+n)O(5 m+3n)]n- (III) en donde n es al menos 2 y m es al menos 1, y (b) al menos dos cationes diferentes, en donde el catalizador tiene esencialmente carga neutra; y además, en donde la relación molar de fósforo con respecto a dichos al menos dos cationes diferentes es entre 0,7 y 1,7, en donde los cationes comprenden (i) al menos un catión monovalente, y (ii) al menos un catión polivalente, en donde el catión polivalente se selecciona del grupo que consiste en Be2+, Mg2+, Ca2+, Sr2+, Ba2+, Mn2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Sn2+, Pb2+, Ti3+, Cr3+, Mn3+, Al3+, Ga3+, Y3+, In3+, Sb3+, Bi3+, Si4+, Ti4+, V4+, Ge4+, Mo4+, Pt4+, V5+, Nb5+, Sb5+, y mezclas de los mismos.
Description
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La relación molar entre los cationes está comprendida, en una realización, entre 1:50 y 50:1; y en otra realización, la relación molar entre los cationes está comprendida entre 1:4 y 4:1. Por ejemplo, cuando el catalizador incluye potasio (K+) y bario (Ba2+), la relación molar entre ellos (K:Ba), en una realización, está entre 1:4 y 4:1. También, cuando el catalizador se prepara mediante la mezcla y el calentamiento de K2HPO4, Ba(NO3)2, y H3PO4, el potasio y el bario están presentes, en otra realización, en una relación molar, K:Ba, entre 2:3 y 1:1.
En una realización, el catalizador puede incluir un soporte inerte que está construido de un material que comprende silicatos, aluminatos, carbones, óxidos metálicos, y mezclas de los mismos. Alternativamente, el vehículo es inerte con respecto a la mezcla de reacción esperada para entrar en contacto con el catalizador. En otra realización, el método para preparar el catalizador incluye adicionalmente el mezclado de un soporte inerte con el catalizador antes, durante, o después de la mezcla y el calentamiento de los compuestos que contienen fósforo, en donde el soporte inerte incluye silicatos, aluminatos, carbonos, óxidos metálicos, y mezclas de los mismos. En otra realización, el método para preparar el catalizador incluye adicionalmente el mezclado de un soporte inerte con el catalizador antes, durante, o después de la mezcla y el calentamiento de los compuestos que contienen fósforo y de los compuestos que no contienen fósforo, en donde el soporte inerte incluye silicatos, aluminatos, carbonos, óxidos metálicos, y mezclas de los mismos.
El mezclado de los compuestos que contienen fósforo del catalizador se puede llevar a cabo por cualquier método conocido por el experto en la técnica, de forma ilustrativa y no excluyente: mezclado de sólidos y precipitación simultánea. En el método del mezclado de sólidos, los diferentes componentes se mezclan físicamente entre sí con molienda opcional usando cualquier método conocido por el experto en la técnica, tal como de forma ilustrativa y no excluyente: cizalla, extensión, amasado, extrusión, y otros. En el método de coprecipitación, se prepara una solución
o suspensión acuosa de los diferentes componentes, incluidos uno o más de los compuestos de fosfato, seguido por la filtración y calentamiento opcionales para eliminar los disolventes y los materiales volátiles (por ejemplo, agua, ácido nítrico, dióxido de carbono, amoniaco, o ácido acético). El calentamiento se lleva a cabo de forma típica mediante cualquier método conocido por el experto en la técnica, tal como de forma ilustrativa y no excluyente, convección, conducción, radiación, calentamiento mediante microondas, y otros.
En una realización de la invención, el catalizador se calcina. La calcinación es un proceso que permite la reacción química y/o la descomposición térmica y/o la transición de fase y/o la eliminación de materiales volátiles. El proceso de calcinación se lleva a cabo con cualquier equipo conocidos por el experto en la técnica tal como, de forma ilustrativa y no excluyente, hornos o reactores de diferentes diseños, incluidos hornos de eje, estufas rotatorias, hornos de vagoneta, y reactores de lecho fluidizado. La temperatura de calcinación es, en una realización, de 200 °C a 1200 °C; en otra realización, la temperatura de calcinación es de 250 °C a 900 °C; y en otra realización más, la temperatura de calcinación es de 300 °C a 600 °C. El tiempo de calcinación es, en una realización, de aproximadamente una hora a aproximadamente setenta y dos horas.
Aunque los expertos en la técnica conocen muchos métodos y máquinas para fraccionar las partículas en tamaños discretos y determinar la distribución de tamaño de partículas, el tamizado es una de las formas más simples, menos caras y más habituales. Una forma alternativa de determinar la distribución de tamaño de partículas es mediante dispersión de luz. Tras la calcinación, el catalizador, en una realización, se tritura y tamiza para proporcionar un producto más uniforme. La distribución de tamaño de partículas de las partículas del catalizador incluye un intervalo de partícula que, en una realización, es inferior a 3; en otra realización, la distribución de tamaño de partículas de las partículas del catalizador incluye un intervalo de partícula que es inferior a 2; y en otra realización más, la distribución de tamaño de partículas de las partículas del catalizador incluye un intervalo de partícula que es inferior a 1,5. En otra realización de la presente invención, el catalizador se tamiza hasta un tamaño de partícula promedio de 50 µm a 500 µm. En otra realización de la presente invención, el catalizador se tamiza hasta un tamaño de partícula promedio de 100 µm a 200 µm.
En otra realización, el catalizador se prepara mediante las siguientes etapas, que comprenden: (a) combinar Ca2P2O7 y KH2PO4 en una relación molar de 3:1 para obtener una mezcla sólida, y (b) calcinar dicha mezcla sólida por etapas a 50 °C, 80 °C, 120 °C, y de 450 °C a 550 °C, para producir dicho catalizador.
Tras la calcinación y trituración y molienda opcional, el catalizador se puede utilizar para catalizar varias reacciones químicas. Los ejemplos no limitativos de reacciones son: deshidratación de ácido hidroxipropiónico a ácido acrílico (tal como se describe más detalladamente a continuación), deshidratación de glicerina a acroleína, deshidratación de alcoholes alifáticos a alquenos u olefinas, deshidrogenación de alcoholes alifáticos a éteres, otras deshidrogenaciones, hidrólisis, alquilaciones, desalquilaciones, oxidaciones, desproporcionamientos, esterificaciones, ciclaciones, isomerización, condensaciones, aromatizaciones, polimerizaciones, y otras reacciones que puede ser evidentes para una persona experta en la técnica,
IV Métodos para producir ácido acrílico, derivados de ácido acrílico o mezclas de los mismos
Se proporciona un método para deshidratar el ácido hidroxipropiónico, derivados de ácido hidroxipropiónico, o mezclas de los mismos para dar ácido acrílico, derivados de ácido acrílico, o mezclas de los mismos. El método incluye poner en contacto una corriente que comprende ácido hidroxipropiónico, derivados de ácido hidroxipropiónico, o mezclas de los mismos que los contienen con un catalizador, que comprende: (a) al menos un anión fosfato condensado seleccionado del grupo que consiste en las fórmulas (I), (II), y (III),
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| CN102516038A (zh) * | 2011-11-18 | 2012-06-27 | 浙江师范大学 | 一种多聚甘油的生产方法 |
| US9714208B2 (en) * | 2012-04-11 | 2017-07-25 | The Procter & Gamble Company | Catalysts conversion of hydroxypropionic acid or its derivatives to acrylic acid or its derivatives |
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