EP0142876A2 - Method for preparing a synthetic fuel and/or sythetic components for fuels, and the product obtained thereby - Google Patents

Method for preparing a synthetic fuel and/or sythetic components for fuels, and the product obtained thereby Download PDF

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Publication number
EP0142876A2
EP0142876A2 EP84201445A EP84201445A EP0142876A2 EP 0142876 A2 EP0142876 A2 EP 0142876A2 EP 84201445 A EP84201445 A EP 84201445A EP 84201445 A EP84201445 A EP 84201445A EP 0142876 A2 EP0142876 A2 EP 0142876A2
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EP
European Patent Office
Prior art keywords
synthetic
fuels
fuel
preparing
decarboxylation
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.)
Granted
Application number
EP84201445A
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German (de)
French (fr)
Other versions
EP0142876B1 (en
EP0142876A3 (en
Inventor
Ermanno Girardi
Riccardo Mansani
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eni SpA
Original Assignee
Eni SpA
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Filing date
Publication date
Application filed by Eni SpA filed Critical Eni SpA
Priority to AT84201445T priority Critical patent/ATE33266T1/en
Publication of EP0142876A2 publication Critical patent/EP0142876A2/en
Publication of EP0142876A3 publication Critical patent/EP0142876A3/en
Application granted granted Critical
Publication of EP0142876B1 publication Critical patent/EP0142876B1/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only

Definitions

  • This invention relates to a method for preparing a synthetic fuel and/or synthetic components for fuels, and the product obtained by said method.
  • a large percentage of the product of this oxidation consists of polycarboxylic acid mixtures.
  • Examples of methods for producing carboxylic acids by oxidising coal include those described in French patent 1,347,213 and in German patents 841,140, 864,992 and 879,103.
  • the polycarboxylic acids obtained by known methods cannot be used as fuels because of their acidic nature, so that their use is practically limited to the chemical field.
  • polycarboxylic acid mixtures can be converted into fuels and/or components for fuels by transforming them into oleophilic compounds in a simple and economical manner.
  • polycarboxylic acid mixtures obtained by oxidising coal polycarboxylic acid mixtures of any origin can obviously be used for transformation into oleophilic compounds provided that their elementary compositions, molecular weight and acidity lie within the limits indicated hereinafter.
  • a first subject matter of the present invention is a method for transforming polycarboxylic acid mixtures into oleophilic compounds which can be used as synthetic fuel and/or synthetic components for fuels.
  • the method for preparing a synthetic fuel and/or synthetic components for fuels according to the present invention starts with a polycarboxylic acid mixture obtained in any manner, and is characterised by the polycarboxylic acids having the following elementary composition: carbon from 42% to 70% by weight hydrogen from 1.5% to 6% by weight oxygen from 14.0% to 52.7% by weight, a mean molecular weight of between 120 and 800, and an acidity of between 5 and 18 meq/g, and preferably between 8 and 14 meq/g, the mixture of polycarboxylic acids or their salts being subjected to decarboxylation which in the case of acids is carried out by heat treatment over catalysts constituted by transition metal oxides, and in the case of salts by simple heat treatment, the decarboxylated product being finally subjected to esterification with one or more alcohols or one or more olefins.
  • the polycarboxylic acids having the following elementary composition: carbon from 42% to 70% by weight hydrogen from 1.5% to 6% by weight oxygen from 14.0% to 52.
  • the decarboxylation can be effected by heating, in aqueous solution, for a time of between 10 and 30 minutes, preferably 20 minutes, to a temperature of between 300° and 350°C, preferably 315°C, in the presence of one or more alkaline and/or alkaline earth carbonates.
  • the decarboxylation can be effected in the absence of water at a temperature of between 350° and 550°C, preferably 500°C, for a time of between 10 and 30 minutes, preferably 20 minutes.
  • the esterification is preferably effected with alcohols comprising 1 to 10 carbon atoms, the alcohols being in H 2 SO 4 solution at a concentration of between 5% and 20% by weight, or with olefins comprising between 2 and 10 carbon atoms.
  • a second subject matter of the present invention is the synthetic fuel and/or the synthetic components for fuels, when obtained by the aforesaid method.
  • a third subject matter of the present invention is the fuel obtained by mixing the synthetic fuel and/or synthetic components according to the invention with products chosen from a medium petroleum distillate, a medium distillate from coal hydroliquefaction, the product of coal pyrolysis and particularly the mixture of benzene, toluene and xylenes, a fuel oil of petroleum origin, a mixture of aromatic hydrocarbons or a mixture of C 1 -C 10 aliphatic alcohols.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

A synthetic fuel and/or synthetic components for fuels are prepared from a mixture of polycarboxylic acids of suitable elementary composition, having a mean molecular weight of between 120 and 800 and an acidity of between 5 and 18 meq/g, by decarboxylating them by heat treatment and subjecting the decarboxylated product to esterification with one or more alcohols or one or more olefins.

Description

  • This invention relates to a method for preparing a synthetic fuel and/or synthetic components for fuels, and the product obtained by said method.
  • Various methods are known in the art for preparing synthetic fuels, in particular starting from coal by hydroliquefaction or pyrolysis, or starting from synthesis gases.
  • However, all the known methods suffer from the drawback of involving high plant and/or operating costs.
  • Numerous methods exist for oxidising coal with oxygen, oxygen- containing gases or oxidising substances in an aqueous alkaline medium.
  • A large percentage of the product of this oxidation consists of polycarboxylic acid mixtures.
  • Examples of methods for producing carboxylic acids by oxidising coal include those described in French patent 1,347,213 and in German patents 841,140, 864,992 and 879,103.
  • The polycarboxylic acids obtained by known methods cannot be used as fuels because of their acidic nature, so that their use is practically limited to the chemical field.
  • It has been surprisingly found that polycarboxylic acid mixtures can be converted into fuels and/or components for fuels by transforming them into oleophilic compounds in a simple and economical manner. Besides polycarboxylic acid mixtures obtained by oxidising coal, polycarboxylic acid mixtures of any origin can obviously be used for transformation into oleophilic compounds provided that their elementary compositions, molecular weight and acidity lie within the limits indicated hereinafter.
  • A first subject matter of the present invention is a method for transforming polycarboxylic acid mixtures into oleophilic compounds which can be used as synthetic fuel and/or synthetic components for fuels.
  • The method for preparing a synthetic fuel and/or synthetic components for fuels according to the present invention starts with a polycarboxylic acid mixture obtained in any manner, and is characterised by the polycarboxylic acids having the following elementary composition: carbon from 42% to 70% by weight hydrogen from 1.5% to 6% by weight oxygen from 14.0% to 52.7% by weight, a mean molecular weight of between 120 and 800, and an acidity of between 5 and 18 meq/g, and preferably between 8 and 14 meq/g, the mixture of polycarboxylic acids or their salts being subjected to decarboxylation which in the case of acids is carried out by heat treatment over catalysts constituted by transition metal oxides, and in the case of salts by simple heat treatment, the decarboxylated product being finally subjected to esterification with one or more alcohols or one or more olefins.
  • The decarboxylation can be effected by heating, in aqueous solution, for a time of between 10 and 30 minutes, preferably 20 minutes, to a temperature of between 300° and 350°C, preferably 315°C, in the presence of one or more alkaline and/or alkaline earth carbonates.
  • Alternatively, the decarboxylation can be effected in the absence of water at a temperature of between 350° and 550°C, preferably 500°C, for a time of between 10 and 30 minutes, preferably 20 minutes. The esterification is preferably effected with alcohols comprising 1 to 10 carbon atoms, the alcohols being in H2SO4 solution at a concentration of between 5% and 20% by weight, or with olefins comprising between 2 and 10 carbon atoms.
  • A second subject matter of the present invention is the synthetic fuel and/or the synthetic components for fuels, when obtained by the aforesaid method.
  • A third subject matter of the present invention is the fuel obtained by mixing the synthetic fuel and/or synthetic components according to the invention with products chosen from a medium petroleum distillate, a medium distillate from coal hydroliquefaction, the product of coal pyrolysis and particularly the mixture of benzene, toluene and xylenes,a fuel oil of petroleum origin, a mixture of aromatic hydrocarbons or a mixture of C1-C10 aliphatic alcohols.

Claims (12)

1. A method for preparing a synthetic fuel and/or synthetic components for fuels from a polycarboxylic acid mixture obtained in any manner, characterised by the polycarboxylic acid mixture having the following elementary composition:
carbon from.42% to 70% by weight
hydrogen from 1.5% to 6% by weight.
oxygen from 14.0% to 52.7% by weight,
a mean molecular weight of between 120 and 800, and an acidity of between 5 and 18 meq/g, the mixture of polycarboxylic acids or their salts being subjected to decarboxylation, the decarboxylated product being finally subjected to esterification with one or more alcohols or one or more olefins.
2. A method for preparing a synthetic fuel and/or synthetic components for fuels as claimed in claim 1, characterised in that the polycarboxylic acid mixture has an acidity of between 8 and 14 meq/g.
3. A method for preparing a synthetic fuel and/or synthetic components for fuels as claimed in claim 1, characterised in that the decarboxylation is effected by heating in aqueous solution for a time of between 10 and 30 minutes to a temperature of between 300° and 350°C in the presence of one or more alkaline and/or alkaline earth carbonates.
4. A method as claimed in claim 3, characterised in that the beating is effected to a temperature of 315°C.
5. A method as claimed in claim 3, characterised in that the decarboxylation time is 20 minutes.
6. A method for preparing a synthetic fuel and/or synthetic components for fuels as claimed in claim 1, characterised in that the decarboxylation takes place in the absence of water at a temperature of between 350° and 550°C for a time of between 10 and 30 minutes.
7. A method as claimed in claim 6, characterised in that the decarboxylation time is 20 minutes.
8. A method as claimed in claim 6, characterised in that the decarboxylation temperature is 500°C.
9. A method for preparing a synthetic fuel and/or synthetic components for fuels as claimed in claim 1, characterised in that the esterification is effected with alcohols comprising from 1 to 10 carbon atoms, said alcohols being used in H2SO4 solution at a concentration of between 5% and 20% by weight.
10. A method for preparing a synthetic fuel and/or synthetic components for fuels as claimed in claim 1, characterised in that the esterification is effected with olefins comprising between 2 and 10 carbon atoms.
11. A synthetic fuel and/or synthetic component for fuels when obtained by the method of the preceding claims.
12. A fuel obtained by mixing synthetic fuel and/or the synthetic components for fuels, when obtained in accordance with claims 1 to 10, with a product chosen from:
a) medium petroleum distillate;
b) medium distillate from coal hydroliquefaction;
c) coal pyrolysis product, and in particular the mixture of benzene, toluene and xylenes;
d) fuel oil of petroleum origin;
e) mixture of aromatic hydrocarbons;
f) mixture of C1-C10 aliphatic alcohols.
EP84201445A 1983-11-10 1984-10-09 Method for preparing a synthetic fuel and/or sythetic components for fuels, and the product obtained thereby Expired EP0142876B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84201445T ATE33266T1 (en) 1983-11-10 1984-10-09 PROCESS FOR PRODUCTION OF SYNTHETIC FUEL, SYNTHETIC COMPONENTS FOR FUEL AND THE PRODUCT OBTAINED FROM THEM.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT23659/83A IT1205307B (en) 1983-11-10 1983-11-10 METHOD FOR THE PREPARATION OF A SYNTHETIC FUEL AND / OR SYNTHETIC COMPONENTS FOR FUELS AND PRODUCT OBTAINED WITH THE SAME
IT2365983 1983-11-10

Publications (3)

Publication Number Publication Date
EP0142876A2 true EP0142876A2 (en) 1985-05-29
EP0142876A3 EP0142876A3 (en) 1986-04-30
EP0142876B1 EP0142876B1 (en) 1988-03-30

Family

ID=11208955

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84201445A Expired EP0142876B1 (en) 1983-11-10 1984-10-09 Method for preparing a synthetic fuel and/or sythetic components for fuels, and the product obtained thereby

Country Status (6)

Country Link
EP (1) EP0142876B1 (en)
AT (1) ATE33266T1 (en)
AU (1) AU562295B2 (en)
DE (1) DE3470175D1 (en)
IT (1) IT1205307B (en)
ZA (1) ZA848121B (en)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2701062C3 (en) * 1976-01-13 1987-06-19 Mitsubishi Gas Chemical Co., Inc., Tokio/Tokyo Process for the preparation of esters
FR2352049A1 (en) * 1976-05-21 1977-12-16 Inst Francais Du Petrole Processing of Fischer-Tropsch synthesis products from coal - by integrated process of fractionation, polymerisation, alkylation, etc.

Also Published As

Publication number Publication date
ZA848121B (en) 1985-06-26
DE3470175D1 (en) 1988-05-05
IT8323659A0 (en) 1983-11-10
AU562295B2 (en) 1987-06-04
EP0142876B1 (en) 1988-03-30
AU3413684A (en) 1985-05-16
ATE33266T1 (en) 1988-04-15
EP0142876A3 (en) 1986-04-30
IT1205307B (en) 1989-03-15

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