EP1542960A1 - Procede et dispositif pour produire du biodiesel - Google Patents

Procede et dispositif pour produire du biodiesel

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Publication number
EP1542960A1
EP1542960A1 EP03757803A EP03757803A EP1542960A1 EP 1542960 A1 EP1542960 A1 EP 1542960A1 EP 03757803 A EP03757803 A EP 03757803A EP 03757803 A EP03757803 A EP 03757803A EP 1542960 A1 EP1542960 A1 EP 1542960A1
Authority
EP
European Patent Office
Prior art keywords
esterification
mixture
transesterification
monoalcohol
unit
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.)
Withdrawn
Application number
EP03757803A
Other languages
German (de)
English (en)
Inventor
Joosten Connemann
Jürgen Fischer
Hans Groos
Arne Philippsen
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.)
Oelmuehle Leer Connemann & Co GmbH
Original Assignee
Oelmuehle Leer Connemann & Co GmbH
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 Oelmuehle Leer Connemann & Co GmbH filed Critical Oelmuehle Leer Connemann & Co GmbH
Publication of EP1542960A1 publication Critical patent/EP1542960A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10—Ester interchange
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00004—Scale aspects
    • B01J2219/00006—Large-scale industrial plants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
    • B01J2219/324—Composition or microstructure of the elements
    • B01J2219/32491—Woven or knitted materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to a process for the continuous production of biodiesel from biogenic fat- or oil-containing starting mixtures with a high proportion of free fatty acids and a device for the production of biodiesel.
  • Vegetable oils have to be cleaned through complex process steps before being used as fuel for diesel engines.
  • the addition of phosphoric acid or citric acid removes lecithins, carbohydrates and proteins from the oils.
  • the oil treated in this way is then centrifuged to remove the so-called oil sludge.
  • extraction is carried out with sodium hydroxide solution.
  • Vegetable oils differ from the technical properties of diesel fuels in several ways. So they have a higher density than diesel fuel. The cetane number (ignitability) of rapeseed oil is lower than that of diesel fuel. This can lead to uneven running behavior of the engine, which significantly increases noise emissions. In addition, the viscosity of rapeseed oil is many times higher than that of diesel fuel. The higher viscosity of the rapeseed oil leads to poorer atomization and combustion in the combustion chamber. The use of Pure vegetable oils therefore lead to coking in conventional engines, combined with increased particle emissions.
  • Biodiesel produced on the basis of vegetable oils is, however, relatively expensive due to the raw material prices and the required refining processes and cannot compete with normal diesel fuel in terms of price. This significantly limits the use of this biodiesel as a fuel in conventional diesel engines. In order for biodiesel to be able to compete with normal diesel fuel in the long term, it is imperative to significantly reduce its production costs.
  • One way to reduce biodiesel manufacturing costs is to use raw materials that are significantly cheaper than rapeseed oil.
  • a disadvantage of this process is that relatively large amounts of methanol and sulfuric acid have to be used in relation to the fatty acid mixture (molar ratio of fatty acid mixture to methanol to sulfuric acid about 1: 30: 5 or 1: 4: 2 by weight), which is not more than can be viewed economically.
  • the free fatty acids of the starting material are first acidified
  • Esterification is converted into the esters and the fatty acid triglycerides are then subjected to a basic transesterification (Canakci and Van Gerpen, 1999).
  • the process is designed in such a way that, based on a feedstock with an acid number of 66, 10% sulfuric acid and about 400% of methanol (methanol to fatty acid mixture in a molar ratio of 40: 1) are used in weight, in order to achieve esterification to an acid number of 2.0 , The yields vary between 75% and 80%.
  • a significant disadvantage of this process is that the water formed during the esterification of the free fatty acids with alcohol is the following can significantly impair basic transesterification or even completely prevent it.
  • biodiesel made from used fats and oils often does not meet the requirements placed on fuels.
  • the content of free and bound glycerol in some of the biodiesel produced in the prior art on the basis of used oils and fats is far too high. It also turned out that the composition of the biodiesel produced is subject to strong fluctuations depending on the starting material.
  • the present invention is therefore based on the technical problem of providing cost-effective methods and means for producing biodiesel on the basis of a wide variety of biogenic oil- and fat-containing starting materials, in particular used oils and fats, which allow the starting materials to be converted into biodiesel more efficiently and the production of a enable standardized biodiesel that can be used directly as fuel without further processing steps.
  • the present invention solves the problem on which it is based by providing a pressure-free process for the continuous production of alkyl esters of higher fatty acids, in particular biodiesel, from fatty acid triglyceride starting mixtures containing free fatty acids with an integrated combination of acidic esterification and basic transesterification
  • esterifications of the free fatty acids in separate, interconnected esterification devices with a C to C 4 monoalcohol in the presence of an acidic catalyst and glycerol as entrainer at 60 ° C. to 65 ° C. to form an esterification mixture
  • partial purification of the esterification mixture by partial removal of entrainer, acid catalyst and unreacted C to C mono alcohol
  • transesterification mixture at least two transesterifications of the fatty acid triglycerides in separate, interconnected transesterification devices with a C to C 4 monoalcohol in the presence of a basic catalyst at 60 ° C. to 65 ° C. to form a transesterification mixture
  • the d- to C 4 -monoalcohol used for the esterification, the entrainer used for the esterification glycerol and the water used for the purification of the transesterification mixture are at least partially recovered from the esterification and transesterification mixtures and that the acidic and basic catalysts after purification the esterification and transesterification mixtures to form a salt suitable as a fertilizer.
  • the present invention also solves the technical problem on which it is based by providing a device for carrying out the method according to the invention, that is to say a device which has an integrated combination of units for acidic esterification and basic transesterification.
  • the method according to the invention and the device according to the invention for carrying out this method allow the production of biodiesel from a large number of cleaned or unpurified oil and / or fat-containing constituents in a simple and inexpensive manner.
  • starting materials In particular, used oils or fats with a wide variety of free fatty acids, for example deep-frying oils, technical tallow, slaughterhouse waste, etc. are preferably used, which are extremely inexpensive compared to the starting materials usually used for the production of biodiesel, such as rapeseed oil.
  • These starting materials after they have been optionally pre-cleaned, for example to remove mucilage or insoluble particles such as bone, etc., are subjected to acidic esterification with a C 1 -C 4 -monoalcohol at least once and preferably several times using an acidic catalyst and an entrainer. Through the acidic esterification one or more times, the free fatty acids present in the starting materials are almost completely converted into their corresponding alkyl esters.
  • the esterification mixture obtained in this way which contains the alkyl esters of the free fatty acids and the oils and fats present as fatty acid triglycerides, is then after at least part of the unreacted monoalcohol, the acid catalyst used and the entrainer has been removed, at least two times directly subjected to basic transesterification with the same C to C monoalcohol in the presence of a basic catalyst with the release of glycerol.
  • a basic catalyst with the release of glycerol As a result of the repeated basic transesterification, almost all of the fatty acid triglycerides contained in the starting mixture are converted into the alkyl esters of the higher fatty acids bound in the triglycerides.
  • a transesterification mixture is obtained which comprises the alkyl esters of the free fatty acids and the alkyl esters of the fatty acids bound as glycerides in the starting material.
  • the successive repeated esterification and transesterification reactions result in an almost 100% conversion of the starting mixtures used into biodiesel.
  • the method according to the invention and the device according to the invention for carrying out the method advantageously also allow the simultaneous use of several different rather raw materials with a different content of free fatty acids.
  • the esterification mixture obtained in this way can then advantageously be mixed with a starting mixture which contains hardly any fatty acids from the outset and then transesterified.
  • the number of esterification and esterification reactions to be carried out depends in particular on the nature, for example the composition and the content of free fatty acids and fatty acid triglycerides, and on the purity of the starting mixtures used. According to the invention, it is provided, for example, that a starting material with a high content of free fatty acids and a low content of fatty acid triglycerides is subjected to more esterification reactions and fewer transesterification reactions than a starting material with a lower content of free fatty acids and a higher content of fatty acid triglycerides.
  • An important advantage of the device according to the invention for carrying out the method according to the application is that the device according to the invention can be converted very easily depending on the composition of the different starting materials to be converted.
  • the device according to the invention comprises a total of about 10 columns for the esterification and transesterification of the starting materials. If the starting material has a very high proportion of free fatty acids, but a very low proportion of fatty acid triglycerides, 8 of the columns can be used for acidic esterification, but only 2 columns for basic transesterification. Contains the raw material However, a relatively low proportion of free fatty acids and a relatively high proportion of fatty acid glycerides can be used, for example, 4 of the columns for esterification and 4 to 6 of the columns for basic transesterification.
  • the device according to the invention it is also possible to switch off some of the columns of the device according to the invention completely and to carry out fewer esterification and / or transesterification reactions.
  • the device according to the invention thus allows any division of the columns depending on, in particular, the fatty acid content of the starting materials used.
  • the biodiesel produced according to the invention has a high purity with the lowest acid number and extremely low glycerol content and fulfills all quality criteria imposed on a biodiesel.
  • the quality criteria set according to the European fuel standard EN 14214 are met, with the exception of the so-called CFPP (cold property), which is specified by the raw material and can only be influenced by suitable additives.
  • the method according to the invention for producing biodiesel and the device according to the invention for carrying out this method advantageously allow considerable savings in energy and consumables compared to the methods or devices known in the prior art for producing biodiesel.
  • the energy savings result on the one hand from the relatively low reaction temperatures of 60 ° C to 65 ° C and on the other hand in particular from the fact that the individual reaction steps are carried out at normal pressure, ie no energy has to be used to generate a high pressure.
  • the savings in materials result, for example, from the fact that a part stream of the catalyst circuit of the esterification, which is constantly to be renewed, is simultaneously used to neutralize the basic catalyst of the ester interchange.
  • the C to C monoalcohol which has not been reacted in the reactions is also recovered from the esterification and transesterification mixtures and reused after recycling, in particular in the acidic esterification.
  • the water used in the purification steps or the water of reaction obtained in the acidic esterification can also be recycled after the purification and used again, thereby reducing the water consumption.
  • the process according to the invention also allows the acidic and basic catalysts used for the esterification or transesterification reactions to be disposed of without damage, these being obtained from the reaction mixtures and reacting with one another, salts which can be used as fertilizers being formed.
  • the method according to the invention for the production of biodiesel and the device according to the invention for carrying out this method also serve at the same time for the production of fertilizers.
  • the method according to the invention for the production of biodiesel and the device according to the invention thus allow a particularly environmentally friendly production of biodiesel.
  • ecologically questionable starting mixtures are recycled and, on the other hand, the agents and materials used in their production are recovered and recycled so that the environment is not polluted.
  • the process according to the invention for the production of biodiesel therefore provides that starting mixtures containing fat and / or oil with free fatty acids are converted to biodiesel by repeated acidic esterification and repeated basic transesterification.
  • biodiesel means a mixture of monoalkyl esters of fatty acids which can be obtained from starting mixtures containing oil and / or fat and which can be used directly as a fuel in diesel engines.
  • “Fatty acid triglyceride starting mixtures containing free fatty acids” are understood to mean compositions which contain fats and oils as well as unbound free fatty acids and which can be converted into biodiesel by means of esterification and / or transesterification. According to the invention, the proportion of fats and oils in the Total composition is 0% to 100%, preferably at least 20%, more preferably at least 30% and most preferably more than 40% and the proportion of free fatty acids is 100% to 0%, preferably at least 1%.
  • “free fatty acids” understood unsaturated or saturated alkane carboxylic acids with unbranched carbon chain, which are not chemically bound in the starting mixtures.
  • Fatty acids with 1 to 7 carbon atoms are referred to as lower fatty acids, fatty acids with 8 to 12 carbon atoms as medium fatty acids and fatty acids with more than 12 carbon atoms as higher fatty acids.
  • the free fatty acids can be both lower and medium and higher fatty acids.
  • Fats and oils are understood to mean solid, semi-solid or liquid fatty acid triglycerides, in particular of the plant or animal body, which chemically essentially consist of mixed glycerol esters of higher fatty acids with an even number of carbon atoms. Fats and oils are water-insoluble and always have one While vegetable fats and oils contain practically exclusively straight-chain fatty acids, fatty acids with an odd number of carbon also play a role in animal fats and oils. The unsaturated fatty acids found in vegetable fats and oils are in the cis form , while animal fatty acids are often trans-configured.
  • “Used fats and oils” are understood to mean materials containing fat or oil which, after being obtained from appropriate plant or animal starting materials, have been used in particular for technical or food production purposes and which, as a result of this use, have been chemically modified or unmodified or have additional ingredients
  • "Unused fats and oils” are understood to mean materials containing fat or oil which, after being obtained from the corresponding plant or animal starting materials, have not yet been used for any other technical purpose or which were not supplied for the purpose of food production and therefore only contain ingredients that originate from the raw materials or those that are obtained are related from the starting materials.
  • “Cleaned” means that the vegetable, animal or technical fats or oils have been pretreated prior to their use in the process according to the invention for the purpose of purifying and / or concentrating the free fatty acids or fatty acid triglycerides in order to contain other ingredients, for example proteins, dyes, etc. "Uncleaned” therefore means that the vegetable, animal or technical fats or oils were not subjected to any such pretreatment before they were used in the process according to the invention. “Vegetable oils and fats” are those which predominantly come from plant starting materials such as seeds, roots, leaves or other suitable parts of plants. Animal fats or oils mainly come from animal starting materials such as animal organs, tissues or other body parts or body fluids such as milk. "Technical oils and fats” are those which have been obtained in particular from animal or vegetable raw materials and have been prepared for technical purposes.
  • the used or unused, unpurified or cleaned oils and / or fats used according to the invention are in particular selected from the group consisting of soapstock, brown grease, yellow grease, technical tallow, technical lard, deep-frying oils, animal fat, table tallow, vegetable raw oils, for example crude Palm oil, crude animal oils or fats or mixtures thereof.
  • Soapstock is understood to mean a by-product which arises from the processing of vegetable oils, in particular a by-product of edible oil refineries based on soybean, turnip or sunflower oil. Soapstock has a proportion of free fatty acids of about 50% to 80% on.
  • “Brown Grease” is understood to mean a waste product containing animal fat, which has a proportion of free fatty acids of over 15% to 40%.
  • “Yellow Grease” contains about 5% to 15% free fatty acids.
  • “Technical sebum” and “technical lard” are animal fats that are produced for technical purposes and are obtained from slaughterhouse waste using the dry or wet melting process, for example.
  • Technical tallows are valued and traded according to their acid number, the content of free fatty acids depending on the quality being between 1 and 15 to 20% by weight and sometimes even higher.
  • Technical tallows generally have an acid number of about 10 to 40 or even higher. These include technical beef tallow, US fancy tallow, US bleachable fancy tallow, US special tallow, US tallow A and animal body fats.
  • “Animal fats” include fatty products that drop off, for example, solar stearin, when solidifying poultry, beef, pork, fish and marine mammals, a solid residue that remains after the pressing of lard oil from lard.
  • Unpurified Vegetable crude oils are understood to be liquid or solid compositions which are obtained from vegetable starting materials by pressing " , and have not undergone any treatment other than settling in the customary periods and centrifuging or filtering, in which the oil is separated from solid components only mechanical forces such as gravity, centrifugal force or pressure can be used.
  • Uncleaned vegetable crude oils can also be liquid or solid vegetable oils obtained by extraction, provided that their properties do not differ from the smell, color or taste, or through specific analytical data differentiated vegetable oils obtained by pressing.
  • the proportion of free fatty acids in unpurified vegetable fats and oils varies. So raw palm oil shows NEN content of free fatty acids from about 5% to about 15%.
  • the "unpurified vegetable crude oils” also include, for example, freshly harvested crude oils from rapeseed oil, soybean oil, sunflower oil, corn oil, cottonseed oil, palm kernel and coconut fat with a proportion of free fatty acids of 2% to 3%.
  • purified vegetable oils for example raffinates, can also be used or semi-refined, the vegetable oils mentioned above can be used as starting materials.
  • Animal crude oils or fats include, for example, milk fat, wool fat, beef tallow, lard, fish oils, fish oil, and the like. These animal fats or oils can also be used according to the invention in purified or unpurified form as starting materials for the process according to the invention for producing biodiesel.
  • the starting mixtures containing unpurified free fatty acids are cleaned before the first esterification step.
  • the pre-cleaning can be carried out using cleaning processes for fats and oils, such as clarification, filtration, treatment with bleaching earth or treatment with acids or alkali, which are customarily used in the art, in order to separate disruptive impurities such as proteins, phosphates and mucilages.
  • the optionally pre-cleaned or pretreated fat and / or oil-containing starting mixtures are esterified one or more times with a Ci to C monoalcohol, in particular methanol or ethanol, in a first step and at least twice with the same in a second step C to C 4 mono alcohol are transesterified.
  • a Ci to C monoalcohol in particular methanol or ethanol
  • esterification is understood to mean the reaction of an alcohol with an acid, in particular a free fatty acid, which leads to the formation of an ester. the.
  • the free fatty acids of the starting materials are therefore converted into the alkyl esters of the free fatty acids.
  • a “transesterification” is understood to mean a reaction in which an ester, in particular a fatty acid triglyceride, is converted into another ester, in particular an alkyl ester of a higher fatty acid, for example by alcoholysis in the presence of acids or alkalis.
  • the esterification of the free fatty acids is carried out in the presence of an acidic catalyst.
  • Catalysts are substances which reduce the activation energy for the course of a reaction and thereby increase the reaction rate without appearing in the end product of the reaction.
  • Acidic catalysts are those with a pH value of less than 7.
  • acidic, non-volatile esterification catalysts are provided, preferably low-volatile inorganic acids such as sulfuric acid, organic derivatives thereof and p-toluenesulfonic acid or other suitable acidic substances can be used.
  • the C 1 -C 4 monoalcohol is advantageously added in such an amount that, on the one hand, there is a clear excess of the monoalcohol in comparison with the free acids to be esterified and, on the other hand, that at the end of the esterification reaction a clean separation into an oil and a mono alcohol phase is guaranteed.
  • CC 4 monoalcohols such as methanol and ethanol are preferably used for the acid esterification of the free fatty acids of the starting mixtures.
  • the free fatty acids are esterified
  • an “entrainer” is understood to mean a generally inert substance, which serves to enrich a component of a mixture without forming a firm bond with it.
  • the entrainer helps with phase separation by increasing the separation effect and serves to adjust the density of a phase and to trap the water of reaction.
  • glycerin is used as entrainer. Glycerin is part of the fatty acid triglycerides and is released anyway in the subsequent transesterification reactions of the fatty acid triglycerides to alkyl esters.
  • the entrainer glycerin is obtained in the transesterification reactions and is recycled into the upstream esterification reactions, so that the entrainer glycerin essentially only has to be added at the beginning of the process according to the application.
  • the acidic esterification of the free fatty acids takes place at a temperature of about 60 ° C. to 65 ° C. under normal pressure. This means that in the case of acidic esterification, comparatively mild reaction conditions are chosen.
  • the reaction of the acidic esterification itself is carried out in one or preferably several stirred tanks or columns which are connected in cascades and through which the two liquid phases flow in cocurrent or countercurrent.
  • the acidic esterification of the free fatty acids is carried out in an esterification device designed as a column.
  • Columns are columnar or tower-like reaction vessels which also allow the separation of at least one phase.
  • the columns used according to the invention can have suitable column internals, such as adjustable or movable column plates, packing elements, liquid distributors, ordered packings of woven wire belts, reflux distributors and supporting grids Due to their elongated construction, the columns used according to the invention enable a plug flow and a continuously increasing shift in equilibrium certain implementations in cocurrent or countercurrent of two phases.
  • the columns used for the esterification can be flowed through in cocurrent from bottom to top or from top to bottom or in countercurrent, the columns being able to be used as individual reactors by pumping around.
  • the fatty acids of the starting mixtures are, according to the invention, subjected to one or more steps of acidic esterification in separate esterification columns.
  • the acidic esterification of the starting mixtures is preferably carried out at least twice. In this way, almost 100% esterification of the free fatty acids available in the starting materials is achieved.
  • the individual esterification columns are connected in series and connected to one another, the esterification mixture obtained in a column being transferred to the subsequent column for further and increasing esterification or to obtain a decreasing acid number.
  • a fresh mixture of entrainer, monoalcohol and acidic catalyst is then or simultaneously added to the last esterification column, and the acidic esterification of the free fatty acids in the upstream column is then continued with this mixture.
  • the two phases that is to say the fatty acid mixture as the light phase and the methanol-catalyst mixture weighted with the entrainer as the heavy phase, are preferably carried out in countercurrent.
  • the interconnected columns contain different concentrations of the acid catalyst. It is therefore provided according to the invention that the concentration of the acid catalyst in the individual esterification columns can be different.
  • the ratio of methanol to fatty acid mixture is 2 to 12 times, preferably 4 to 6 times that amount of methanol-catalyst mixture, in particular in the low fatty acid range, by means of a self-circulation of the methanol-catalyst mixture restricted to one or two columns increased, which is used for the fatty acid mixture with a higher acid number in the entrance area of the acid esterification.
  • this internal cycle must also have the lowest possible reaction water content (well below 1% water) in order to achieve the lowest possible acid number, this increased circulation of methanol-entrainer-catalyst mixture is passed through suitable water scavengers such as molecular sieves or membrane filters, which in turn there are at least two devices and are operated alternately due to the water enrichment.
  • suitable water scavengers such as molecular sieves or membrane filters
  • esterification columns can also be operated with such an internal cycle.
  • the esterification mixture obtained in this column is only partially transferred to the downstream column, while part of the esterification mixture is transferred to an upstream column and is esterified again there.
  • the individual columns connected in series contain different, in particular decreasing, concentrations of the acid catalyst, the part of the esterification mixture obtained which is transferred to the downstream column is further esterified in the presence of a lower concentration of the acid catalyst, while the part of the esterification mixture obtained, which is transferred to the upstream column, is esterified in the presence of a higher concentration of the acid catalyst.
  • the esterification mixture obtained in each column after the esterification has ended is pre-cleaned before transfer to the next esterification or transesterification column, in order to ensure that the subsequent reaction can take place under optimal conditions.
  • some of the esterification products formed for example water of reaction, which may impair the subsequent reaction, can be removed in this way.
  • the esterification mixture obtained in an esterification unit is pre-cleaned in that the entrainer, the acid catalyst, the water formed during the esterification and the unreacted C 1 -C 1 -monoalcohol in the form of a mixture which forms the heavy phase by means of phase separation of the esterification mixture which is in the light phase is at least partially separated off.
  • the mixture of entrainer, acid catalyst and monoalcohol, ie the heavy phase, separated during the pre-cleaning by means of phase separation, is transferred to special devices for cleaning and separating the constituents of the mixture.
  • special devices for cleaning and separating the constituents of the mixture In these purification devices, according to the invention, specific purification and recovery of the constituents of the mixture, that is, the entrainer glycerin, the acid catalyst and the monoalcohol, are carried out.
  • the components thus separated and purified can then be used again in the process steps according to the invention, in particular the acidic esterification steps.
  • the heavy phase comprising acid catalyst, entrainer and mono alcohol is first of all transferred to a drying device.
  • this drying device the unreacted monoalcohol and water are largely separated from the acid catalyst and entrainer.
  • water is either separated off in molecular sieves or microfilters or, together with the monoalcohol, is evaporated off as a water / monoalcohol mixture by means of distillation.
  • the separated in the drying device monoalcohol is then used for further purification in a Rektifikati-: onsvorraum transferred.
  • a “rectification device” is understood to mean a device for carrying out countercurrent or column de-distillation, which enables liquid or vapor mixtures to be broken down in that liquid and vapor are brought into countercurrent with one another, for example on packing, in countercurrent
  • the rectification device cleaned C 1 -C 1 -monoalcohol has a water content of about 1% to 2% and can then be recirculated from the rectification device back into the esterification device and is then available again as a reactant, again in the esterification device rectified measuring Ethanol can have a water content of 1% to 2%, because water is generated during the esterification and is then removed by the entrainer. Rectification can therefore save on reflux and thus on energy.
  • the mixture obtained in the drying device largely free of water and monoalcohol, which contains entrainer, acid catalyst and residual amounts of monoalcohol, is derived from the drying device, whereby part of this mixture can be recycled directly back into the esterification columns, while a small one Partial stream of this mixture is passed into the acidification device of the transesterification.
  • the amount of the partial flow of the entrainer-catalyst mixture freed of methanol and water of reaction intended for the acidification device of the transesterification is precisely matched to the neutralization of the basic catalyst in the heavy soap phase of the transesterification and subsequent adequate acidification thereof.
  • the mixture is transferred to a separator.
  • the fatty acids obtained are separated off in the separator and returned to the esterification device.
  • the remaining mixture which still contains glycerol and considerable residual amounts of the C-i to C monoalcohol, is then transferred from the separator to a rectification plant for further purification, in which the residual amounts of the monoalcohol are separated off and the esterification devices are returned in a purified form.
  • the last of the esterification columns connected in series can be designed as an extraction column.
  • the esterification mixture can be extracted in the extraction column using pure monoalcohol or a monoalcohol / entrainer mixture, the downward-flowing esterification mixture flowing lighter monoalcohol or inflowing lighter monoalcohol-entrainer mixture suits.
  • the extraction removes non-esterified free fatty acids, which can then be circulated back into one of the upstream esterification columns, where they can be esterified.
  • the esterification mixture obtained after the last esterification in the last esterification column or after extraction in the extraction column is characterized in that almost all free fatty acids of the fatty acid triglyceride starting mixture are esterified with the C 1 -C 4 -monoalcohol.
  • the esterification mixture obtained according to the invention has a particularly low acid number, which is preferably 0.5 to 1, before the transesterification reactions are carried out.
  • the esterification mixture obtained has a water content of at most 0.5%.
  • the esterification mixture obtained after the esterification in the last esterification column with an acid number of 0.5 to 1 and a water content of at most 0.5% for basic transesterification of the fatty acid glycerides of the starting mixture into a downstream one connected to the last esterification column Transesterification device is transferred.
  • one or more, in particular purified, fatty acid triglyceride starting mixtures are added to the esterification mixture before the transesterification, which have a very small proportion of free fatty acids, in particular from 0% to 1% and in which acidic esterification is therefore not necessary.
  • the esterification mixture obtained after the last stage of the acidic esterification and the optionally added (n) purified starting mixture (s) are, depending on the composition of the starting materials, according to the invention 2 to 6 times in separate, interconnected separate series Transesterification devices.
  • the transesterification devices are also designed as columns with or without packing.
  • the fatty acid triglycerides are preferably transesterified with the same CC 4 monoalcohol that was used for the acidic esterification of the free fatty acids.
  • the monoalcohol used for the basic transesterification is therefore preferably also methanol or ethanol.
  • the basic transesterification of the fatty acid triglycerides is preferably carried out at a temperature of 60 ° C to 65 ° C in the presence of a basic catalyst.
  • the basic catalyst is selected according to the invention such that, on the one hand, an optimal transesterification of the fatty acid triglycerides to alkyl esters of higher fatty acids can take place.
  • the basic catalyst used for the transesterification of the fatty acid triglycerides is preferably potassium hydroxide.
  • Anhydrous sodium hydroxide or sodium methylate and other alkaline substances can also be used as the basic catalyst.
  • the transesterification mixture obtained after transesterification in one column is preferably pre-cleaned before being transferred to the next column. According to the invention, the reaction mixture is first subjected to a phase separation in the column, basic catalyst, unreacted monoalcohol and the glycerol formed during the transesterification being at least partially separated as a heavy phase from the transesterification mixture present in the light phase.
  • the transesterification mixture prepurified by means of phase separation is then further purified from the column, before being transferred to the downstream column, in a separator using water.
  • the water used is preferably pH-conditioned or buffered in another suitable manner, in particular buffered condensed water or buffered softened water.
  • the water used according to the invention must not contain calcium, since otherwise calcium soaps are formed which, because of their amorphous structure, would block any filter devices during production and later use of the product.
  • further amounts of basic catalyst, unreacted monoalcohol, soap, glycerin and the water used for cleaning are separated from the transesterification mixture.
  • the pre-cleaned transesterification mixture is then transferred to a downstream column for further transesterification of the fatty acid triglycerides with monoalcohol, especially if it contains unreacted fatty acid triglycerides.
  • the purified transesterification mixture is the transesterification mixture of the last transesterification column in which almost all fatty acid triglycerides are in transesterified form, this transesterification mixture is purified in at least one further separator.
  • the transesterification mixture obtained in the last transesterification column is purified in at least three successive separators using suitable water.
  • the last transesterification mixture cleaned in the separators is then transferred to a drying plant, with residual amounts of water being removed again. After drying in the drying device, the desired end product, biodiesel, is available in purified form and can be used directly as a fuel.
  • the heavy phase obtained in a column by means of phase separation and separated from the ester mixture, which contains unreacted monoalcohol, basic catalyst and glycerol, is transferred to an acidification device for further purification and separation of the constituents from the column.
  • the aqueous mixtures of unreacted monoalcohol, basic catalyst and glycerin obtained in the separators are also transferred to this acidification device for further purification and separation of the constituents.
  • the small partial stream of the acidic catalyst mixture from the acidic esterification which has to be discharged anyway for the ongoing slight renewal of the catalyst / entrainer mixture, is used in a cost- and energy-saving manner.
  • the amount of entrainer contained goes back to the normal glycerine purification.
  • the amount of glycerin then cleaned goes back into the catalyst cycle of acidic esterification as an entrainer, which is continuously renewed in this way.
  • the acidic catalyst mixture originating from the esterification part is combined with the alkaline heavy phase for neutralization and acidification, with about 1-10% of the total mixture coming from the esterification stage and about 90-99% from the transesterification stage.
  • the mixture is transferred from the acidification device into a separator.
  • the fatty acids released by soap splitting are separated in a purified form.
  • the separated fatty acids are returned directly to the esterification device.
  • the remaining mixture, the glycerol, the salt formed from acid catalyst and basic catalyst and C 1 -C 4 monoalcohol as well as water, is transferred from the separator to a rectification device for further purification.
  • the remaining monoalcohol is separated from the glycerol and the other constituents in purified form and returned to the acidic esterification.
  • the purified monoalcohol returned to the esterification has a water content of 1% to 2%.
  • the purity of externally supplied fresh methanol is normally over 99.85%, with the water content being below 0.1% water content. This quality is used, for example, in the area of the already low acid numbers of the acid esterification, where the lowest possible water content is required. However, this is not the case in the higher acid number range of the acid esterification, in which larger amounts of water of reaction are formed anyway (for example 3-6% water, based on the fatty acid mixture).
  • methanol can therefore be used for this area, which, coming from the rectification, has a substantially higher water content than 0.1%, namely 1.0 to 2.0% water.
  • the rectification can thus be carried out with significantly less reflux of condensed methanol, which directly significantly reduces the essential steam consumption of the overall process.
  • the almost methanol-free mixture which also occurs in the rectification device, comprising glycerol, the salt formed from the esterification and transesterification catalysts, and reaction water and wash water is transferred to an evaporation device, where the water is present in purified form is separated from the other components, the so-called raw glycerin, consisting of glycerin and salt.
  • the purified water is drained from the evaporation device, condensed and returned to the separators, where it can be used again to purify the transesterification mixtures.
  • the crude glycerin is then purified via a drying and distillation device, filter device and thin-film evaporation device, the original mixture of acidic and basic catalyst being separated off to form a salt suitable as a fertilizer.
  • a small part of the freshly obtained glycerin is returned to the esterification devices as a replacement for the entrained agent that has been removed.
  • the present invention also relates to a device for producing alkyl esters of higher fatty acids, in particular biodiesel, comprising in an integrated combination an esterification unit with at least two esterification devices for esterifying the free fatty acids, a downstream transesterification unit connected with the esterification unit with at least two transesterification devices for transesterification of the fatty acid triglycerides, a downstream purification unit connected to the transesterification unit for purifying the biodiesel produced and a downstream purification unit connected to the transesterification unit for purification and separation of the agents used in the esterification unit and / or transesterification unit and / or purification unit, characterized in that the purification unit by at least one supply line and at least one Derivation is connected to the esterification unit, so that the agents used in the esterification unit and the transesterification unit are simultaneously cleaned and separated in the purification unit and the agents used for esterification are recirculated to the esterification unit.
  • the device for producing biodiesel according to the invention is particularly advantageously suitable for producing biodiesel from fresh and used vegetable, animal or technical oils or fats.
  • the device according to the invention in particular has an esterification unit and a subsequent transesterification unit connected thereto, so that the products formed in the esterification unit can be transferred to the transesterification unit and subjected to a transesterification there.
  • the esterification unit according to the invention advantageously has a plurality of esterification devices, in particular designed as columns, and a plurality of transesterification units, likewise in particular designed as columns, the esterification unit having at least two and up to, for example, seven separate columns and the transesterification unit having at least two and up to, for example, four separate columns ,
  • the device according to the application permits variable use of the individual esterification and / or transesterification columns.
  • the number of columns actually used in the operation of the device according to the invention depends in particular on the nature, ie composition and purity, of the fat or oil-containing starting mixtures used and on the desired composition and purity of the end product.
  • the entire esterification unit that is to say all the columns of the esterification unit, can be separated and switched off from the rest of the device according to the invention, so that the starting mixtures are only subjected to transesterification reactions. be opened.
  • the starting mixture used mainly comprises free fatty acids, but no or only small amounts of fatty acid triglycerides
  • the entire transesterification unit can be separated from the device according to the invention and switched off, so that only esterification reactions are carried out.
  • individual columns of the esterification unit and / or the transesterification unit can also be switched off. For example, it is possible to use only two columns per unit.
  • the device for producing biodiesel according to the invention also has two purification units, one purification unit (hereinafter referred to as biodiesel
  • Purification unit serves to purify and recover the products, ie biodiesel
  • agent purification unit serves to purify, separate and recover the agents used in the esterification unit, the transesterification unit and the biodiesel purification unit
  • the biodiesel purification unit is connected in particular to the transesterification unit, so that the products formed in the transesterification unit, that is to say the biodiesel, can be purified.
  • the biodiesel purification unit is also connected to the agent purification unit, so that the mixtures obtained in the biodiesel purification unit, which comprise the agents used in the esterification unit and the transesterification unit and the agents used in the biodiesel purification unit, are also in the agent - Purification unit can be refurbished and recovered.
  • the agents used in the esterification unit are in particular a C to C 4 monoalcohol, an acidic catalyst and an entrainer.
  • the agents used in the transesterification unit are a basic catalyst and the Ci- to C -monoalcohol.
  • the agents used in the biodiesel purification unit are in particular water.
  • the device according to the invention for producing biodiesel is characterized in particular in that the unit for purifying agents is connected both to the transesterification unit and to the esterification unit via feed lines. Mixtures formed in the esterification unit and in the transesterification unit, which are separated from the respective product mixtures in these units by phase separation and which comprise the agents and by-products used in these units, can be transferred directly to the agent purification unit, where they can be purified and purified, via the feed lines be separated.
  • the device according to the invention thus advantageously allows simultaneous purification of the agents used to carry out the esterification reactions, the transesterification reactions and the biodiesel purification in the same purification unit.
  • the agent purification unit is also advantageously connected to the esterification unit by means of discharge lines, via which the agents separated, purified and thus recovered in this purification unit can in particular be returned directly to the esterification unit via circulatory systems and reused there.
  • the device according to the invention for the production of biodiesel thus has, according to the invention, a plurality of integrated circuits which, in particular, purify, separate and recover the esterification reactions which are carried out. NEN, the transesterification reactions and / or the purification of the reaction mixture and their recycling are used in particular in the esterification unit, the individual circuits for the respective agents to be purified are partly combined with one another and partly separated from one another.
  • the esterification unit according to the invention comprises one or more esterification devices.
  • the esterification unit comprises 2 to 8 interconnected esterification devices connected in series.
  • the esterification devices are preferably designed as columns.
  • the columns according to the invention can have suitable column internals, such as adjustable or movable column plates, packing elements, liquid distributors, ordered packings of woven wire belts, reflux distributors and supporting gratings.
  • the last column can be designed as an extraction column.
  • the separate esterification devices are connected to one another by feed lines, an esterification device in each case being connected to a downstream esterification device, so that the reaction product or esterification mixture formed in the device can be transferred as a light phase into the downstream device.
  • the respective feed lines which connect the series-connected esterifications to one another each have branches which connect an esterification device to an upstream esterification device. These branches thus advantageously allow a partial flow of the product mixture formed in an esterification device into an upstream te esterification device or to be transferred again into the same esterification device.
  • At least one esterification device is also connected to a mixing device via at least one feed line, so that a mixture of C to C monoalcohol, acid catalyst and entraining agent produced in the mixing device can be transferred to the corresponding esterification device.
  • esterification devices are connected to one or more mixing devices via separate feed lines.
  • the individual esterification devices can each be connected to a separate mixing device or to the same mixing devices. In this way, different or identical mixtures containing the same or different concentrations of monoalcohol, acid catalyst and entrainer can be transferred to the individual esterification devices.
  • the esterification devices are connected to each other by a further feed line.
  • At least a partial stream of the heavy phase which was obtained after esterification in a column by means of phase separation and which contains unreacted glycerol, unconverted monoalcohol and unconverted acid catalyst, can be transferred into the upstream column via these feed lines.
  • these additional feed lines can be provided with a
  • Drying device can be connected in which water of reaction and / or monoalcohol are removed from the heavy phase.
  • These drying devices can be used, for example, as distillers. ons device for evaporating a water-monoalcohol mixture or as a molecular sieve or microfilter to remove water as a permeate.
  • the heavy phase freed from water and / or monoalcohol is then transferred to the upstream column.
  • the device according to the invention is thus designed such that, after esterification has taken place in a column, unreacted acid catalyst, unreacted glycerol and unreacted monoalcohol are each transferred to the upstream column while that formed in the column Esterification mixture is transferred in each case into the downstream column. Acidic catalyst, glycerol and monoalcohol are thus transported from column to column in the opposite direction to the esterification mixtures.
  • the last esterification device of the esterification unit is connected to the downstream transesterification unit via at least one feed line, so that the products formed in the esterification unit, in particular the last esterification device, can be transferred to the transesterification unit.
  • the transesterification unit of the device according to the invention comprises at least 2 and a maximum of 6 interconnected transesterification devices connected in series.
  • the transesterification devices are also designed as columns. Each transesterification column is connected via at least one feed line to a mixing device via which a mixture of basic catalyst and C 1 -C 4 -monoalcohol formed in the mixing device can be fed into the transesterification column.
  • each transesterification device is connected via a separate feed line to the agent purification device, in particular an acidification device of the agent purification unit.
  • the agent purification device in particular an acidification device of the agent purification unit.
  • phase separation which in particular comprises basic catalyst, soaps, excess monoalcohol and glycerol formed during the transesterification, is transferred directly to the acidification device in order to purify these compounds.
  • Each Umest fürsvortechnische is also connected beyond at least one supply line with the biodiesel purification unit, in particular a separator, the biodiesel purification unit so that the transesterification mixture formed in a Umest réellesvortechnische after partial purification by phase separation in egg ⁇ NEN separator of the biodiesel purification unit transferred and there can be further cleaned up.
  • the purified reaction mixture is transferred to the next transesterification device via a feed line between the separator and the downstream transesterification device, where it is transesterified again.
  • the individual transesterification devices of the transesterification unit are thus connected to one another via a separator of the biodiesel purification unit.
  • the last transesterification device is also connected to a separator of the biodiesel purification unit via a feed line.
  • this separator has a feed line to a downstream separator so that the transesterification mixture formed in the last transesterification device, which is biodiesel, can be further purified.
  • the last transesterification mixture is purified in at least three further separators, which in turn are each connected to the separators of the biodiesel purification unit via a feed line.
  • the biodiesel purification unit comprises at least 4 interconnected separators connected in series and a drying device.
  • the separators In the separators, the transesterification mixtures are separated from basic catalyst, excess monoalcohol, glycerol formed during the transesterification and residual amounts of acidic catalyst by means of steam.
  • the separators are connected via at least one feed line to the drying device of the biodiesel purification unit, via which the product mixture separated in the separators from basic catalyst, monoalcohol, acid catalyst and entrainer, i.e. Biodiesel to be transferred to the drying device. The cleaned end product biodiesel is then obtained in the drying device.
  • the biodiesel purification unit is connected to the agent purification unit for cleaning the agents used via special feed lines.
  • the separators of the biodiesel purification unit are connected via a feed line to the acidification device of the medium purification unit in order to feed the mixture of basic catalyst, monoalcohol, acid catalyst and entrainer separated in the separators into the medium purification device, in particular the acidification device convict.
  • the agent purification unit which serves to purify the agents used in the esterification unit, the transesterification unit and the biodiesel purification unit, has at least one drying device, an acidification device, a further separator, a rectification device, an evaporation device, a distillation device Has thin film evaporation device and a filtration device.
  • the agent purification unit is advantageously connected not only to the transesterification unit and the biodiesel purification unit, but also to the esterification unit via at least one feed line.
  • the esterification unit is connected, for example, via a feed line to the drying device of the agent purification unit, which in turn is connected to the acidification device of the agent purification unit via a further feed line.
  • the aqueous mixtures of unreacted C 1 -C 4 -monoalcohol, acid catalyst, entraining agent and water formed in the esterification are transferred into the drying device of the agent purification unit via this feed line in the esterification unit by means of phase separation.
  • the mixtures obtained in the esterification unit are further purified in the drying device, in particular the C to C 4 -monoalcohol being separated from the other constituents of the mixtures and being transferred via a feed line from the drying device into the downstream rectification device of the agent purification unit.
  • the drying unit is also connected to the acidification unit via a further feed line in order to transfer a small partial stream of the mixture of acid catalyst, entrainer and residual amounts of the C to C 4 monoalcohol separated in the drying device into the acidification device.
  • the acidification device is also connected directly to the transesterification units and the separators of the biodiesel purification unit via special feed lines.
  • the mixtures formed in the transesterification devices by means of phase separation and the mixtures formed in the separators during biodiesel purification each of which comprises water, glycerol, soaps, basic catalyst and excess monoalcohol which has not been converted during the transesterification Acidification device fed.
  • the acidification device is connected to the separator of the medium purification unit via a feed line.
  • the fatty acids released from the soap fraction are separated, which are discharged from the separator via a further line and returned to the esterification unit.
  • the separator is also connected to the rectification device of the medium purification unit via a feed line in order to transfer the water-containing mixture of acid catalyst, basic catalyst and considerable amounts of the monoalcohol formed in the separator into the rectification device.
  • the monoalcohol is then separated from the aqueous mixture and further purified in the rectification device.
  • the monoalcohol purified in the rectification device is returned to the esterification unit via a discharge line which connects the rectification device to the esterification unit and can thus be used again in the esterification unit.
  • the rectification device is also connected to the evaporation device via a feed line in order to transfer the mixture separated from the monoalcohol in the rectification device, which comprises water, residual amounts of glycerol and basic and acid catalyst, into the evaporation device for further purification. Water is separated from the transferred mixture in the evaporation device.
  • the evaporation device has a feed line for condensation, via which the water separated in the evaporation device liquefies again and from there it is transferred to the biodiesel purification unit, where it can be used again, in particular in the separators of the biodiesel purification unit.
  • the evaporation device is connected via a further feed line to the drying device of the agent purification unit and the distillation device in order to further purify the crude glycerol freed from water, the mixture of glycerol and acidic catalyst and basic catalyst and residual amounts of water.
  • the glycerol is separated from all accompanying substances, mainly the salt formed from basic and acidic catalysts. Via a feed line that connects the distillation device with a thin film
  • Evaporator connects, the salt is drained and the accompanying glycerin is recovered.
  • the salt is suitable as a fertilizer.
  • the distillation device is connected to a filtration device via a line. Via a line connecting the distillation device to the filtration device, the pure glycerin is transferred to the filtration device and further purified there to pharmaceutical glycerin for the highest demands
  • FIG. 1 shows in schematic form an apparatus according to the invention for producing biodiesel, comprising an esterification unit, a transesterification unit, a purification unit for purifying the biodiesel produced and a purification unit for purifying and separating the agents used in the esterification unit and the transesterification unit
  • FIG. 2 shows a further embodiment of the esterification unit in schematic form.
  • FIG. 1 shows a device 1 according to the invention for the production of biodiesel from oil and / or fat-containing starting mixtures containing free fatty acids, which has an integrated biodiesel purification unit 6 and an integrated agent purification unit 8.
  • the device 1 comprises an esterification unit 3 with two esterification devices 9 and 11 designed as columns.
  • the esterification column 9 is connected to a mixing device 35 via a line 37.
  • a line 41 leads from the column 9 into the esterification column (or extraction column) 11, so that the esterification mixture generated in the column 9 can be transferred into the column 11.
  • the esterification column 11 is also connected via a line 43 to a storage vessel 45 for the C 1 -C 4 -monoalcohol, so that fresh monoalcohol can be fed into the column 11.
  • the line 47 leads from the column 11 into the transesterification unit 5 with two transesterification devices 15 and 17 designed as columns.
  • the transesterification column 15 and the transesterification column 17 are each connected via lines 65 and 67 to the mixing device 63, which in turn are connected via lines 59 to the storage container 45 for the monoalcohol and via line 61 to the storage container 53 for the basic catalyst.
  • the column 15 is also connected via line 57 to the reservoir 51 for a second starting mixture with an extremely small proportion of free fatty acids.
  • the transesterification mixture generated in column 15 is subjected to a phase separation, the aqueous mixture separated from the transesterification mixture, which comprises predominantly unreacted monoalcohol, glycerol and the basic catalyst, being transferred via line 105 from column 15 to acidification device 103.
  • the transesterification mixture produced in the transesterification column 15 and prepurified by means of phase separation is transported from the column 15 via the line 69 into the separator 71 and further purified there.
  • the separator 71 receives water from the water storage container 55 via the line 93.
  • the transesterification mixture produced in the column 15 is further freed from dispersed or dissolved glycerol and basic catalyst and Cr C 4 monoalcohol, which is fed into the acid via line 107 - Transfer device 103 is transferred.
  • the reaction mixture from column 15 purified in separator 71 is transferred via line 79 into second transesterification column 17.
  • a phase separation also takes place in the transesterification column 17, the mixture of predominantly glycerol, basic catalyst and monoalcohol separated by means of phase separation being transported via line 106 into line 105 and then into acidification device 103.
  • the transesterification mixture formed in the transesterification column 17 and prepurified by phase separation is transported via line 81 into the separator 73 and further pre-cleaned there, the aqueous mixture of glycerol, acidic and basic catalyst and unreacted C 1 -C 4 -monoalcohol separated in the separator 73 containing mixture from the separator 73 via the line 109 into the line 105 and from there into the acidification device 103.
  • the separator 73 is supplied with water or condensed water vapor via the feed line 91, which is connected to the separator device 75.
  • the transesterification mixture purified in the separator 73 from the transesterification column 17 is transferred via line 83 to the separator 75, which in turn is supplied with water or condensed water vapor via line 89, which is connected to the separator 77.
  • the reaction mixture further purified in the separator 75 is then over the line 85 transferred into the separator 77.
  • the separator 77 is supplied with water from the water reservoir 55 via the line 87.
  • the transesterification mixture After the transesterification mixture has been purified, it is transferred via line 157 into the drying device 159.
  • the water formed in the drying device 159 during the drying of the purified transesterification mixture is discharged via line 161, while the end products formed are transported from the drying device 159 via line 163 into the storage container 165 for the desired end product via the purified and concentrated end products.
  • the mixture of glycerol and the acidic and basic catalysts and unreacted C 1 -C 4 -monoalcohol transported in the acidifying device 103 is transferred via line 101 into the separator 113, the fatty acids being separated in the separator 113, the fatty acid being separated off via the Line 155 is transferred to line 21 and from there it is returned to the esterification unit 3.
  • the mixture formed after the fatty acid has been separated off in the separator 113 is transferred via line 115 to a rectification device 117.
  • the rectification device 117 receives unreacted monoalcohol from the esterification unit 3 via the line 125 in the drying device 97.
  • the rectification device 117 further purifies the C 1 -C 4 -monoalcohol.
  • the mixture formed in the rectification device 117 after the monoalcohol has been separated off is transported via line 119 to the evaporation device 121, in which the water fed into the separators is evaporated from the water-containing mixture, condensed and recovered and transported back to the water container 55 via line 123 becomes.
  • the remaining constituents of the mixture produced in the evaporation device 121 are fed via line 129 into the drying system 131 and from there transported from line 193 into distillation apparatus 135.
  • the glycerin is separated from the salt formed from the acidic and basic catalyst and transferred via line 145 to the filter device 147 for further purification.
  • a small partial stream is fed via line 149 into a glycerol storage vessel 151 and from there via line 153 to line 99, which connects the drying device 97 to the entrainer storage vessel, ie glycerol storage vessel 23. that is, the glycerin cleaned in the filtering device is thus transferred to the entrainer reservoir 23, from which the entrainer glycerin required in the esterification unit 3 is removed.
  • the device according to the invention for the production of biodiesel is thus designed in such a way that the C to C 4 monoalcohol which has not been converted in the esterification unit is derived from the actual esterification devices and transferred to purification devices, into which the unreacted monoalcohol derived in the transesterification unit is also transferred is fed.
  • the unreacted monoalcohol is purified in the purification device and then transferred to the monoalcohol storage container, from which the monoalcohol required for acidic esterification in the esterification unit is removed.
  • the entraining agent required in the esterification unit is fed into the same purification devices as the unreacted monoalcohol and can be transferred from there to the entraining agent storage container, i.e.
  • FIG. 2 shows a further embodiment of the esterification unit 3 with the esterification devices 9, 171, 173, 175, 177 and 11 designed as columns.
  • the starting mixture to be esterified is fed into the first esterification column 9.
  • the esterification mixture produced in column 9 is transferred as a light phase via line 185 to the subsequent esterification column 171 for further esterification.
  • the esterification mixture formed after esterification in column 171 is then passed for further esterification via line 187 into the downstream esterification column 173 and from there via line 189 into the downstream column 175, then via line 191 into the downstream column 177 and finally transferred via line 201 into the last column 11.
  • the esterification unit 3 is supplied from the two separate mixing devices 199 and 35 with mixtures of the agents required for the esterification, ie acid catalyst, monoalcohol and glycerol.
  • the mixing devices 199 and 35 are in turn connected via line 29 to the glycerol storage container 23, via line 31 to the storage container 25 for the acid catalyst and via line 33 to the storage container 27 for used monoalcohol and are obtained from the storage containers : contain 23, 25 and 27 with glycerin, acid catalyst and mono alcohol.
  • the mixtures produced in the mixing devices 199 and 35, containing acid catalyst, glycerol and monoalcohol, can differ with regard to the concentrations of the constituents.
  • the mixture containing acidic catalyst, glycerol and mono alcohol is then fed directly into column 173 via line 169, which connects mixing device 199 to column 173.
  • the heavy phase, the unreacted glycerol, unreacted monoalcohol and contains unreacted acid catalyst separated by phase separation from the light phase containing the esterification mixture and transferred via line 181 into the upstream column 171.
  • a phase separation is also carried out in column 171, the heavy phase obtained being transferred via line 183 to the first column 9.
  • the mixture of glycerol, catalyst and monoalcohol produced in the mixing device 35 is fed directly into the esterification column 177 via the line 37.
  • phase separation takes place after the esterification, a partial stream of the heavy phase generated being transferred via line 193 to the upstream column 175 and a partial stream of the heavy phase being returned to the column 177.
  • the heavy phase obtained in column 175 after esterification and phase separation is then transported via line 195 to a drying device 197 for separating off the water of reaction and from there it is returned via line 201 to column 175, a partial stream of the purified heavy phase being fed into the upstream column 173 is transferred.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
  • Fertilizers (AREA)

Abstract

La présente invention concerne un procédé pour produire en continu du biodiesel à partir de mélanges de départ biogènes contenant des graisses ou des huiles, ayant une teneur élevée en acides gras, ainsi qu'un dispositif pour produire du biodiesel.
EP03757803A 2002-09-20 2003-09-08 Procede et dispositif pour produire du biodiesel Withdrawn EP1542960A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10243700 2002-09-20
DE10243700A DE10243700A1 (de) 2002-09-20 2002-09-20 Verfahren und Vorrichtung zur Herstellung von Biodiesel
PCT/EP2003/009965 WO2004029016A1 (fr) 2002-09-20 2003-09-08 Procede et dispositif pour produire du biodiesel

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AR (1) AR041326A1 (fr)
AU (1) AU2003273840A1 (fr)
BR (1) BR0314847A (fr)
CA (1) CA2499821A1 (fr)
DE (1) DE10243700A1 (fr)
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US20050204612A1 (en) 2005-09-22
WO2004029016A1 (fr) 2004-04-08
BR0314847A (pt) 2005-08-09
PL209695B1 (pl) 2011-10-31
AU2003273840A1 (en) 2004-04-19
AR041326A1 (es) 2005-05-11
CA2499821A1 (fr) 2004-04-08
MY148440A (en) 2013-04-30
CN100467438C (zh) 2009-03-11
DE10243700A1 (de) 2004-04-01
PL376100A1 (en) 2005-12-12
CN1741982A (zh) 2006-03-01

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