WO2013178834A1 - Procédé catalytique permettant d'obtenir de l'éthanol à partir de gaz de synthèse - Google Patents

Procédé catalytique permettant d'obtenir de l'éthanol à partir de gaz de synthèse Download PDF

Info

Publication number
WO2013178834A1
WO2013178834A1 PCT/ES2012/070410 ES2012070410W WO2013178834A1 WO 2013178834 A1 WO2013178834 A1 WO 2013178834A1 ES 2012070410 W ES2012070410 W ES 2012070410W WO 2013178834 A1 WO2013178834 A1 WO 2013178834A1
Authority
WO
WIPO (PCT)
Prior art keywords
synthesis gas
procedure according
compound
clauses
ethanol
Prior art date
Application number
PCT/ES2012/070410
Other languages
English (en)
Spanish (es)
Inventor
Ricardo ARJONA ANTOLÍN
Juan Luís SANZ YAGÜE
Ana Isabel VICENTE GARCÍA
Yolanda PEÑA GÓMEZ
Pedro OLLERO DE CASTRO
Fernando VIDAL BARRERO
Ángel VILLANUEVA PERALES
Mª Ángeles PORTILLO CRESPO
Francisco LADRÓN DE GUEVARA VIDAL
Original Assignee
Abengoa Bioenergía Nuevas Tecnologías, S. A.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Abengoa Bioenergía Nuevas Tecnologías, S. A. filed Critical Abengoa Bioenergía Nuevas Tecnologías, S. A.
Priority to ES201490109A priority Critical patent/ES2532888B1/es
Priority to PCT/ES2012/070410 priority patent/WO2013178834A1/fr
Publication of WO2013178834A1 publication Critical patent/WO2013178834A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/08—Ethanol

Definitions

  • the present invention relates to a process for obtaining ethanol from synthesis gas in which a sulfur multimetallic catalyst is used. Therefore, the invention could be framed in the field of chemical engineering.
  • Ethanol for use as fuel comes from the fermentation of sugars, from different plant raw materials such as cereals or sugar cane.
  • sugars from different plant raw materials such as cereals or sugar cane.
  • For use as a chemical it is obtained by catalytic hydrogenation of ethylene with sulfuric acid as a catalyst. It can also be obtained from acetylene.
  • the main petroleum-derived ethanol producing plants are in the United States, Europe and South Africa.
  • ethanol is a gaseous fuel obtained from carbon-rich substances such as coal, coal, naphtha or biomass, which contains varying amounts of carbon monoxide and hydrogen.
  • a catalytic process for obtaining short chain alcohols from synthesis gas is described, in which methanol is obtained in a first stage and ethanol in a second stage.
  • WO2010 / 068318 describes a method of obtaining ethanol in several stages from biomass in which a metal catalyst of Mo / Co / S is used.
  • the present invention describes a process for obtaining ethanol in a single stage from synthesis gas and in which a sulfur multimetallic catalyst is used.
  • This catalyst is selected from those described in international patent applications WO201 2/19973 and WO201 2/19974 and allows the synthesis of ethanol in a single stage.
  • the present invention relates to a catalytic process of ethanol synthesis from synthesis gas comprising the following steps:
  • step (b) separating the liquid products obtained in step (a) into at least one stream comprising unreacted synthesis gas, methane, CO 2 , olefins and paraffins and another stream comprising Ci-C 4 alcohols and
  • step (b) recirculating the current comprising the unreacted synthesis gas, methane, C0 2, olefins and paraffins, where the amount of unreacted synthesis gas that is recirculated is between 70 and 95% by weight of the synthesis gas not reacted separately in step (b);
  • the recirculation of the current comprising the unreacted synthesis gas, methane, C0 2 olefins and paraffins establishes new operating conditions that improve the intrinsic behavior of the catalyst by increasing the production of alcohols per kilogram of CO fed.
  • This sulfur multimetallic catalyst is selected from those described in patent applications WO201 1/029973 and WO201 1/029974 and preferably those described in examples I, II, III and IV of WO201 1/029973 and in example I of WO201 2/19974.
  • the process of the invention further comprises a step (d) in which a recirculation of methanol from the stream comprising Ci-C 4 alcohols is performed.
  • a stream reforming comprising the unreacted synthesis gas, C0 2 , methane, olefins and paraffins, is carried out prior to recirculation.
  • Catalytic reforming is carried out through the use of processes known to a person skilled in the art such as, but not limited to, SMR (steam reforming), ATR (autothermal reforming) or POX (partial oxidation) of the gas stream of synthesis prior to recirculation.
  • the synthesis gas stream supplied in step (a) is previously filtered.
  • the carbonyls that are formed from the contact of the CO with the commercial steels of the pipes and equipment are eliminated. These carbonyls would deactivate the catalyst so this filtering process is recommended to prolong the life of the catalyst.
  • the different recirculates of the different currents that are carried out in the process of the present invention can be made indistinctly to the filtration zone or the reaction zone depending on the nature of the current and the effect on the process to be achieved.
  • the separation of the different streams can be carried out by any method known to a person skilled in the art such as condensation or distillation.
  • the amount of unreacted synthesis gas that is recirculated is between 85 and 93% by weight relative to the unreacted synthesis gas separated in step (b).
  • the ratio of H 2 and CO of the synthesis gas is between 0.5 and 2. In a more preferred embodiment, the ratio of H 2 and CO of the synthesis gas is between 0.7 and 1.2. . In an even more preferred embodiment the ratio of H 2 and CO is 1. Biomass usually, once gasified, has a H 2 / CO ratio between 0.9 and 0.5. Working at H 2 / CO ratios close to the unit has the advantage that the catalyst tolerates more CO concentrations without being deactivated, apart from the fact that it is the best stoichiometric ratio for ethanol production, following the 3H 2 + 3CO reaction ⁇ EtOH + C0 2 .
  • the reaction is carried out at a temperature between 280 and 320 ° C and at a pressure between 70 and 130 bar.
  • a temperature between 280 and 320 ° C and at a pressure between 70 and 130 bar.
  • the synthesis gas comes from biomass, with biomass being understood as biological matter from living beings that is used as a renewable energy source.
  • This biological matter may include, among other things, forest plant residues, agricultural holdings or residues of manufactured agricultural products etc.
  • it is achieved that in a single catalytic stage the production of ethanol is increased from an initial value of 10 Kg of ethanol per 100 kg of synthesis gas to a final value of 30 kg ethanol per 100 kg of synthesis gas Therefore, applying the process of the present invention to obtaining ethanol can lead to an increase in ethanol production of between 150 and 200%.
  • C1-C4 alcohols is understood as one or more alcohols selected from methanol, ethanol, propanol and butanol including the possible isomers of said compounds.
  • synthesis gas or “syngas” is understood as the gaseous fuel obtained from carbon-rich substances (coal, naphtha coal, biomass, etc.) subjected to a high temperature chemical process.
  • This gas mainly contains CO and H 2 in varying amounts depending on its origin and the process in which it originated.
  • Another preferred embodiment refers to a catalyst obtainable by the procedure described in the following clauses, which are intended to be exemplary and not limiting:
  • C (ii) also comprises at least one element selected from the list comprising Re, Ru, Rh, Ir, Zn, Ga, In, Ge, Sn, La, Sm and any of their combinations.
  • the sulfur compound is selected from the list comprising: a compound of formula R 1 R 2 S where R 1 and R 2 can be the same or different from each other and are selected from among hydrogen, (C Ce) alkyl or aryl; thiophenes; mercaptans; carbonyl sulfide; and any of its combinations.
  • step (a) incorporate a compound of C (iii) into the solid of step (a).
  • stage (a) is carried out in aqueous medium, the solid is obtained by precipitation and this is separated before stage (b).
  • stage (b) is carried out by adjusting the temperature, pH, solvent volume or any combination thereof.
  • step (a) the temperature and pH of an aqueous solution of the compound of C (i) are adjusted before its combination with the compound of C (ii ).
  • step (a) The procedure according to any of clauses 25 to 36, where in addition, in step (a), a support is suspended in the liquid medium.
  • step (b) The process according to any of clauses 25 to 39, wherein the incorporation of the compound of C (iii) in step (b) is carried out by impregnating the solid using an aqueous solution of one or more precursor salts of C (iii).
  • the catalyst also comprises at least one element selected from carbon, nitrogen and combinations thereof.
  • stage (a) is carried out in aqueous medium, the solid is obtained by precipitation and it is separated before stage (b).
  • step (a) precipitation is effected by adjusting the temperature and pH of an aqueous solution comprising the compound of C (i ) before combination with the compound of C (ii) and the compound of C (iii).
  • step (a) the precipitation is carried out by means of a temperature adjustment and the pH of an aqueous solution comprising the compound of C (i) and the compound of C (iii) before its combination with the compound of C (ii).
  • step (a) The procedure according to clauses 25' and 26 ', where in step (a), the pH of an aqueous solution comprising the compound of C (i) is adjusted by the addition of the compound of C (iii) , before its combination with the compound of C (ii).
  • step (a) The procedure according to any of clauses 25' to 32 ', where in step (a) the temperature is adjusted between 50 ° C and 120 ° C.
  • FIG. one shows the scheme of a linear procedure for obtaining ethanol from synthesis gas.
  • FIG. 2. It shows the scheme of the process of the invention in which a recycle of part of the synthesis gas that has not been converted into the catalytic reaction is carried out, plus gaseous by-products of the reaction, mainly methane and CO2, minority olefins and paraffins.
  • FIG. 3. It shows the scheme of the procedure of Figure 2 in which the methanol produced in the catalytic reaction is also recycled.
  • FIG. 4 shows the process scheme of the invention in which it is performed, recirculation of the synthesis gas, methane, C0 2, olefins and paraffins subjected to a reforming step and methanol.
  • FIG. 5. Shows the comparison of product distribution and conversion in the different possibilities of the process of the invention.
  • Example 1 obtaining ethanol by way of operation A and B.
  • a total of 100 grams of granulated catalyst is loaded into a 1-inch outer diameter reactor.
  • the catalyst is activated by subjecting an additional sulphidation treatment at 400 ° C for 3 hours in 10% flow (vol.) H 2 S / H 2 before use.
  • the reaction is started by feeding synthesis gas under the operating conditions and obtaining the results presented in the column corresponding to the operating mode A (see FIG. 1).
  • the results are presented in the corresponding column of Table 1.
  • the feedback of 90% by weight of the synthesis gas that has not reacted prior to separation of the liquids by condensation takes place, according to the operating mode B (see FIG. 2), obtaining the data which are presented in the corresponding column of Table 1.
  • the methanol obtained in example 1 is separated from the rest of the alcohols and recirculated to the catalytic reactor (FIG. 3). Maintaining the same operating conditions as in example 1, it can be seen in the results corresponding to the mode of operation C presented in Table 1, that the catalyst is capable of converting all the fed methanol operating continuously, which generates an increase in the percentage of ethanol produced per kilogram of CO fed into the system, using a single catalytic reactor.
  • the total carbon balance for this experiment C is 97.5%.
  • Example 3 procedure for obtaining ethanol by way of operation D.
  • Example 3 presents an embodiment where a catalytic step of methane reforming with water vapor is introduced to transform the methane according to reaction (1) and the olefins and paraffins synthesized by the catalyst into synthesis gas according to reaction (2) according to the process configuration presented in figure 4.
  • the reformer is loaded with a commercial methane reforming catalyst.
  • a temperature of 900 ° C, a pressure of 20 bar, a steam / coal ratio of 4 and a GHSV space velocity of 50,000 h "1 50% of methane can be converted from the feed stream and 18% of CO 2 , due to the displacement of the inverse WGSR ratio (3)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un procédé permettant d'obtenir de l'éthanol en une seule étape à partir de gaz de synthèse, lequel procédé comprend l'utilisation d'un catalyseur multimétallique soufré et plus précisément certains des catalyseurs décrits dans les demandes de brevet WO2011/029973 et WO2011/029974.
PCT/ES2012/070410 2012-05-31 2012-05-31 Procédé catalytique permettant d'obtenir de l'éthanol à partir de gaz de synthèse WO2013178834A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
ES201490109A ES2532888B1 (es) 2012-05-31 2012-05-31 Procedimiento catalítico de obtención de etanol a partir de gas de síntesis
PCT/ES2012/070410 WO2013178834A1 (fr) 2012-05-31 2012-05-31 Procédé catalytique permettant d'obtenir de l'éthanol à partir de gaz de synthèse

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/ES2012/070410 WO2013178834A1 (fr) 2012-05-31 2012-05-31 Procédé catalytique permettant d'obtenir de l'éthanol à partir de gaz de synthèse

Publications (1)

Publication Number Publication Date
WO2013178834A1 true WO2013178834A1 (fr) 2013-12-05

Family

ID=46513783

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/ES2012/070410 WO2013178834A1 (fr) 2012-05-31 2012-05-31 Procédé catalytique permettant d'obtenir de l'éthanol à partir de gaz de synthèse

Country Status (2)

Country Link
ES (1) ES2532888B1 (fr)
WO (1) WO2013178834A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0253540A1 (fr) * 1986-07-15 1988-01-20 Coal Industry (Patents) Limited Procédé de conversion de gaz de synthèse
US4935547A (en) * 1988-08-19 1990-06-19 Union Carbide Chemicals And Plastics Company Inc. Homologation process making higher alcohols
WO2008048364A2 (fr) * 2006-04-13 2008-04-24 Dow Global Technologies Inc. Synthèse d'alcools mélangés avec une utilisation accrue de la valeur du carbone
US20090018371A1 (en) 2007-07-09 2009-01-15 Range Fuels, Inc. Methods and apparatus for producing alcohols from syngas
WO2010068318A1 (fr) 2008-12-11 2010-06-17 Range Fuels, Inc. Procédés et appareil pour la production sélective d'éthanol à partir de gaz de synthèse
WO2011029974A1 (fr) 2009-09-10 2011-03-17 Abengoa Bioenergía Nuevas Tecnologías, S. A. Procédé d'obtention d'un solide multimétallique sulfuré et son utilisation comme catalyseur dans un procédé de production d'alcools supérieurs à partir de gaz de synthèse
WO2011029973A1 (fr) 2009-09-10 2011-03-17 Abengoa Bioenergía Nuevas Tecnologías, S. A. Procédé d'obtention d'un catalyseur multimétallique sulfuré et son utilisation dans un procédé de production d'alcools supérieurs par conversion catalytique de gaz de synthèse

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0253540A1 (fr) * 1986-07-15 1988-01-20 Coal Industry (Patents) Limited Procédé de conversion de gaz de synthèse
US4935547A (en) * 1988-08-19 1990-06-19 Union Carbide Chemicals And Plastics Company Inc. Homologation process making higher alcohols
WO2008048364A2 (fr) * 2006-04-13 2008-04-24 Dow Global Technologies Inc. Synthèse d'alcools mélangés avec une utilisation accrue de la valeur du carbone
US20090018371A1 (en) 2007-07-09 2009-01-15 Range Fuels, Inc. Methods and apparatus for producing alcohols from syngas
WO2010068318A1 (fr) 2008-12-11 2010-06-17 Range Fuels, Inc. Procédés et appareil pour la production sélective d'éthanol à partir de gaz de synthèse
WO2011029974A1 (fr) 2009-09-10 2011-03-17 Abengoa Bioenergía Nuevas Tecnologías, S. A. Procédé d'obtention d'un solide multimétallique sulfuré et son utilisation comme catalyseur dans un procédé de production d'alcools supérieurs à partir de gaz de synthèse
WO2011029973A1 (fr) 2009-09-10 2011-03-17 Abengoa Bioenergía Nuevas Tecnologías, S. A. Procédé d'obtention d'un catalyseur multimétallique sulfuré et son utilisation dans un procédé de production d'alcools supérieurs par conversion catalytique de gaz de synthèse

Also Published As

Publication number Publication date
ES2532888B1 (es) 2016-04-21
ES2532888A2 (es) 2015-04-01
ES2532888R1 (es) 2015-07-01

Similar Documents

Publication Publication Date Title
Younas et al. Recent advancements, fundamental challenges, and opportunities in catalytic methanation of CO2
Basile et al. Methanol: science and engineering
Sahebdelfar et al. Carbon dioxide utilization for methane production: A thermodynamic analysis
JP5592250B2 (ja) 二酸化炭素の合成ガスへの接触水素化
CA2993671C (fr) Procede et systeme de catalyseur pour la production de gaz de synthese de haute qualite a partir d'hydrocarbures legers et de dioxyde de carbone
JP5143965B2 (ja) メタノール及びエタノールの製造方法
US8420564B2 (en) Sulfur-tolerant catalyst prepared through high pressure decomposition
ES2634937T3 (es) Procedimiento para la preparación continua de metilmercaptano a partir de compuestos que contienen carbono, azufre e hidrógeno
ES2767502T3 (es) Procedimiento de preparación de metilmercaptano
Palma et al. State of the art of conventional reactors for methanol production
AU2015239360B2 (en) System for manufacturing aromatic compound and method for manufacturing same
Sandoval-Diaz et al. Quo vadis dry reforming of methane?—A review on its chemical, environmental, and industrial prospects
BRPI1002970B1 (pt) processo para a produção de hidrogênio a partir do etanol
EP2922783A1 (fr) Catalyseurs pour une production d'hydrogène renouvelable à partir de charges d'alimentation oxygénées
Silva et al. Effect of carburization conditions on the activity of molybdenum carbide-supported catalysts promoted by nickel for the dry reforming of methane
ES2532888B1 (es) Procedimiento catalítico de obtención de etanol a partir de gas de síntesis
US9452931B2 (en) Process scheme for catalytic production of renewable hydrogen from oxygenate feedstocks
JP2007216178A (ja) メタノール合成用触媒及び当該触媒の製造方法、並びにメタノールの製造方法
Nascimento et al. Investigation of the Deactivation Behavior of MeMo/La2O3-Al2O3-and MeMo/Nb2O5 Supported Catalysts (Me= Pt, Ni, and Co) in Tri-Reforming of Methane
BRPI0716517B1 (pt) Processos para a produção de uma mistura em fase vapor e para a produção de metanol
Pipitone et al. Unravelling competitive adsorption phenomena in the aqueous phase reforming of carboxylic acids on Pt catalysts: An experimental and theoretical study
KR20150145412A (ko) 디메틸에테르 수증기 개질반응과 수성가스 전환반응의 촉매 및 그를 이용한 합성가스 제조방법
WO2018189637A1 (fr) Procédé intégré de production d'hydrogène à partir de sulfure d'hydrogène et de dioxyde de carbone
Iqbal Development of a ceria-based catalyst prepared by the microemulsion method for highly selective CO2 conversion via reverse water gas shift
JP2014080328A (ja) プロセスからｃｏ２を排出しない合成ガス及び水素の併産方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12735314

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: P201490109

Country of ref document: ES

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12735314

Country of ref document: EP

Kind code of ref document: A1