EP3112444A1 - Method for preparing acid fuel oil from the acidification of a soap stock of vegetable and/or animal origin - Google Patents
Method for preparing acid fuel oil from the acidification of a soap stock of vegetable and/or animal origin Download PDFInfo
- Publication number
- EP3112444A1 EP3112444A1 EP16177219.9A EP16177219A EP3112444A1 EP 3112444 A1 EP3112444 A1 EP 3112444A1 EP 16177219 A EP16177219 A EP 16177219A EP 3112444 A1 EP3112444 A1 EP 3112444A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- less
- oil
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- weight
- fuel
- Prior art date
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- Granted
Links
- 239000002253 acid Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 40
- 235000013311 vegetables Nutrition 0.000 title claims abstract description 9
- 230000020477 pH reduction Effects 0.000 title claims abstract description 7
- 239000000295 fuel oil Substances 0.000 title description 5
- 239000000344 soap Substances 0.000 title description 2
- 239000003921 oil Substances 0.000 claims abstract description 110
- 239000000446 fuel Substances 0.000 claims abstract description 63
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 38
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 38
- 239000011734 sodium Substances 0.000 claims abstract description 38
- 238000002485 combustion reaction Methods 0.000 claims abstract description 34
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002956 ash Substances 0.000 claims abstract description 27
- 239000011575 calcium Substances 0.000 claims abstract description 27
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 26
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 23
- 239000011593 sulfur Substances 0.000 claims abstract description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 22
- 239000011574 phosphorus Substances 0.000 claims abstract description 22
- 239000008158 vegetable oil Substances 0.000 claims abstract description 19
- 239000010775 animal oil Substances 0.000 claims abstract description 17
- 238000007670 refining Methods 0.000 claims abstract description 17
- 239000002028 Biomass Substances 0.000 claims abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 11
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 235000019198 oils Nutrition 0.000 claims description 108
- 230000002378 acidificating effect Effects 0.000 claims description 45
- 238000005119 centrifugation Methods 0.000 claims description 32
- 238000001914 filtration Methods 0.000 claims description 31
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 25
- 239000000194 fatty acid Substances 0.000 claims description 25
- 229930195729 fatty acid Natural products 0.000 claims description 25
- 150000004665 fatty acids Chemical class 0.000 claims description 24
- 239000008346 aqueous phase Substances 0.000 claims description 15
- 239000012074 organic phase Substances 0.000 claims description 15
- 238000001556 precipitation Methods 0.000 claims description 15
- 238000000605 extraction Methods 0.000 claims description 13
- 238000007127 saponification reaction Methods 0.000 claims description 13
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 9
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000000523 sample Substances 0.000 description 35
- 239000010763 heavy fuel oil Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 19
- 239000000428 dust Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 241000196324 Embryophyta Species 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000009434 installation Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 150000003626 triacylglycerols Chemical class 0.000 description 4
- UTPYTEWRMXITIN-YDWXAUTNSA-N 1-methyl-3-[(e)-[(3e)-3-(methylcarbamothioylhydrazinylidene)butan-2-ylidene]amino]thiourea Chemical compound CNC(=S)N\N=C(/C)\C(\C)=N\NC(=S)NC UTPYTEWRMXITIN-YDWXAUTNSA-N 0.000 description 3
- 240000002791 Brassica napus Species 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 244000068988 Glycine max Species 0.000 description 3
- 235000019484 Rapeseed oil Nutrition 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003225 biodiesel Substances 0.000 description 3
- 238000010908 decantation Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 235000021588 free fatty acids Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000003904 phospholipids Chemical class 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 235000019486 Sunflower oil Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- -1 fatty acid esters Chemical class 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000002600 sunflower oil Substances 0.000 description 2
- 239000003784 tall oil Substances 0.000 description 2
- 241001133760 Acoelorraphe Species 0.000 description 1
- 229930195730 Aflatoxin Natural products 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000020551 Helianthus annuus Species 0.000 description 1
- 235000003222 Helianthus annuus Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 208000034972 Sudden Infant Death Diseases 0.000 description 1
- 206010042440 Sudden infant death syndrome Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000005409 aflatoxin Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 231100000935 short-term exposure limit Toxicity 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
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, 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
-
- 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
- C10L2200/00—Components of fuel compositions
- C10L2200/04—Organic compounds
- C10L2200/0461—Fractions defined by their origin
- C10L2200/0469—Renewables or materials of biological origin
- C10L2200/0484—Vegetable or animal oils
Definitions
- the present invention relates to a process for preparing a combustible acid oil derived from biomass, in particular resulting from the acidification of a neutralization paste obtained by a process for refining a vegetable and / or animal oil.
- the invention also relates to a fuel acid oil and the use of this oil.
- the fuel acid oil of the present invention is more particularly adapted for use in combustion plants consuming exclusively, alone or as a mixture, natural gas, liquefied petroleum gases, heating oil, coal, heavy fuel oils, biomass.
- the fuel acid oil of the invention is therefore not a fuel.
- the combustible acid oil of the present invention can be used in combustion plants classified under heading 2910 A (and a fortiori 2910 B and 2910 C) of the nomenclature of classified installations for the protection of the environment (nomenclature ICPE) defined in Decree No. 2013-814 of 11 September 2013, published in the Official Journal of the French Republic of 13 September 2013.
- the heavy fuel oil generally needs to be stored at a temperature of 50 ° C to make it pumpable and to be sprayed at a temperature between 85 and 130 ° C according to burner technology, in connection with the viscosity of the product. These heating steps represent a significant energy consumption.
- the flash point of the heavy fuel oil (typically between 70 and 120 ° C) close to its operating temperature, can cause additional constraints in terms of safety (explosive atmospheres).
- the fuel compositions described in WO2013 / 098524 are a mixture of heavy fuel oil and a tall oil or neutralization oil (base neutralized and then acidified fatty acid composition), tall oil and neutralizing oil to stabilize the combustible composition.
- the compositions described in WO2014 / 102492 are mixtures of a neutralization paste and a heavy fuel of petroleum origin. These different fuel compositions are however not entirely derived from biomass.
- the document US2011 / 0203168A1 describes the manufacture of oil compositions containing triglycerides and fuels using particular microorganisms.
- the oil composition is obtained by culturing these microorganisms in the presence of a source of carbon.
- the composition of oils is therefore not derived from the chemical refining of a vegetable or animal oil but is produced by microorganisms.
- this document mentions the production of fuels (biodiesels) by transesterification of the oil produced by the microorganisms. These fuels are therefore composed of alkyl esters of C14-C18 fatty acids and do not include free fatty acids.
- the document CA2541327A1 discloses a process for purifying biodiesel using adsorbent materials.
- This biodiesel is produced by reacting triglycerides with an alcohol to form fatty acid esters.
- the fuel purification process thus obtained makes it possible in particular to remove soaps, mono- and di-glycerides as well as polymerized triglycerides.
- the biodiesel described therefore does not include free fatty acids.
- the Applicant proposes a process for preparing a fuel, in particular a liquid fuel, derived from biomass that can be substituted for an oil, in particular for being burned in an industrial boiler or an industrial oven instead of an oil .
- step b) may also make it possible to reduce also the content of alkali metals other than sodium, especially at a value of less than or equal to 1 mg / kg.
- the acidic oil supplied in step a) can be defined as resulting from the acidification of a neutralization paste.
- Acidic oils naturally have low but variable levels of sulfur and nitrogen, so that their combustion produces low SO 2 and NO x emissions. However, it is necessary to reduce the sulphate content (so sulfur) to limit particulate emissions. However, their water and ash content is important and leads, on the one hand, to a reduction in combustion efficiency and, on the other hand, to particulate emissions that do not meet environmental requirements.
- the method according to the invention makes it possible to obtain a combustible acid oil, constituting the fuel derived from the biomass of the present invention, having a good calorific value and which can be burned by producing low emissions of atmospheric pollutants. It can thus substitute for a heavy fuel type fuel.
- the invention thus makes it possible to obtain a fuel derived solely from biomass, namely neutralization pastes, the emissions of which respect high environmental constraints.
- the process according to the present invention allows to obtain a fuel with constant characteristics in terms of emissions of atmospheric pollutants, guaranteeing the use of fuel in combustion plants usually using heavy fuel oil or the other types of fuel mentioned above (in particular installations classified according to types 2910A, 2910B, 2910C ICPE nomenclature).
- the ash content may be less than or equal to 0.04% by weight.
- the fuel acid oil according to the invention may further comprise an alkali metal content other than sodium less than or equal to 1 mg / kg.
- the fuel acid oil according to the invention has a water content less than or equal to 1% by weight, or even less than or equal to 0.8% by weight, in particular from 0.1% to 0.7% by weight.
- the fuel acid oil according to the invention may have a flash point greater than or equal to 200 ° C. (measured according to standard NF EN ISO 2719 by means of a so-called Pensky Martens device).
- a high flash point makes it possible to reduce storage safety constraints compared to a heavy fuel oil with a lower flash point. This results in lower implementation costs and easier implementation.
- Such a combustible acid oil can be directly obtained by the process according to the invention.
- Another subject of the invention relates to a method of combustion of a fuel in a combustion plant, in particular of type 2910A or 2910B or 2910C according to the ICPE nomenclature, in which a fuel acid fuel directly obtained by the process according to the invention or a combustible acid oil according to the invention.
- the acidic oil supplied in step a) is derived from the refining of one or more oils chosen from a vegetable oil and / or an animal oil.
- this neutralization paste is derived from the refining of one or more oils chosen from a vegetable oil and / or an animal oil.
- the neutralization paste is preferably derived from the chemical refining of one or more vegetable oils.
- An acidic oil can be defined as base-neutralized fatty acid compositions and then acidified.
- the fatty acids advantageously come directly from the saponification of a vegetable and / or animal oil, such that, without being limiting, sunflower, soybean, rapeseed, palm, coconut, peanut, olive oil. , a fish oil, and typically comprising in the great majority saturated or unsaturated C 16 -C 18 carbon chains, of which, preferably, C 18 unsaturated carbon chains.
- Vegetable oils usually include palmitic, oleic, linoleic acid and other acids in smaller amounts.
- the base neutralized fatty acid compositions are typically neutralization pastes.
- an acidic oil contains from 30 to 70% by weight of fatty acids.
- the acidic oil supplied in stage a) advantageously has a water content of less than or equal to 1% by weight, or even less than or equal to 0.8% by weight, in particular from 0.1% to 0.7% by weight. .
- Stage a) can in particular comprise the supply of an acid oil resulting from the refining of one or more oils chosen from a vegetable oil and / or an animal oil having a water content of less than or equal to 3 % wt but greater than 1 wt%, followed by a centrifugation step making it possible to obtain a water content less than or equal to 1 wt.%, or even less than or equal to 0.8 wt.%, in particular 0.1 wt. % to 0.7% in weight.
- the organic phase recovered in step a2) constitutes an acidic oil generally having a water content of less than or equal to 3% by weight.
- the neutralization paste treated in step a1) may be a mixture of neutralization pastes obtained from the refining of different oils or may be a neutralization paste resulting from the refining of a single oil. This refining is preferably chemical.
- Such neutralization pastes come, in particular directly from the saponification of a vegetable oil and / or an animal oil.
- this saponification is carried out by adding a base, usually sodium hydroxide, and eliminates the free fatty acids present in the oil, which are found in the soapstock. form of alkaline salts of fatty acids.
- the vegetable and / or animal oil may undergo a degumming or degumming operation to eliminate phospholipids, lecithins, sugar complexes and other impurities.
- the separation of the oil and the neutralization paste resulting from the saponification can be carried out by centrifugation.
- the neutralization pastes thus essentially comprise base neutralized fatty acids. They typically comprise from 30 to 70% by weight of fatty acids.
- the neutralization pastes may contain, depending on their origin and the quality of the saponification, unreacted phospholipids or mono-, di- or tri-glycerides.
- the fatty acids have carbon chains in C 12 -C 24 , preferably C 16 -C 20 or better C 16 -C 18 .
- a neutralization paste is therefore a product derived from biomass.
- Advantages associated with such neutralization pastes lie, on the one hand, in their low cost of implementation, and, on the other hand, in the absence of undesirable toxic substances, such as pesticides, aflatoxins, heavy metals, precursors of dioxins and furans, PCBs and nitrites.
- the water content of these neutralization pastes is prohibitive as to their use alone as a fuel. Indeed, such pastes may contain significant proportions of water from the saponification reaction or addition of water for the fluidification in the industrial process. Typically, the aqueous phase represents at least 50% of the mass of the neutralization paste. Another difficulty is related to the fact that it is emulsion cases, which should be treated specifically.
- the extraction step a1) of the process according to the invention has the function of extracting the fatty acids contained in the neutralization paste. This extraction is carried out in an acidic medium under conditions that are effective for forming an aqueous phase and an organic phase comprising the fatty acids initially contained in the neutralization paste.
- This organic phase comprising the fatty acids is generally called “acid oil” or “neutralizing oil”.
- the acid used to extract the fatty acids present in the neutralization paste in the form of salts is generally an inorganic acid, such as, for example, sulfuric acid, phosphoric acid or hydrochloric acid.
- Sulfuric acid is however preferred because it allows better extraction of fatty acids at a favorable economic cost.
- the extraction is generally carried out under heating, at a temperature between 70 and 100 ° C (inclusive), preferably between 80 and 90 ° C (inclusive).
- an acidic pH is preferably maintained during the reaction time, for example a pH of less than or equal to 6, preferably less than or equal to 4.
- the reaction time is chosen to allow extraction of all the fatty acids. It is for example from 1 hour to 12 hours, depending on the geometry of the reactor, the nature and composition of the charge to be treated.
- the extraction is preferably carried out with stirring.
- step a1) the organic phase formed during step a1) is separated from the aqueous phase.
- the acidic oil which will subsequently be subjected to step b) of the process according to the invention is isolated, optionally after a centrifugation step a3 when its water content is greater than 1% but less than or equal to 3%. .
- This separation can be carried out by distillation, decantation or even centrifugation. This step can be implemented by any suitable device known and commercially available.
- this separation is carried out by decantation, followed by removal of the aqueous phase. Decantation depends on the difference in density of the liquids and their viscosity, parameters which can be modified in a manner known to those skilled in the art to promote separation if necessary.
- the acidic oil may advantageously be subjected to centrifugation prior to step b). An objective of this centrifugation is to lower the water content of the acidic oil.
- Centrifugation is advantageously performed on an acidic oil obtained by steps a1) and a2) previously described.
- This centrifugation operation makes it possible to obtain an acidic oil having very advantageously a water content of less than or equal to at 1% by weight, or even less than or equal to 0.8% by weight, in particular from 0.1% to 0.7% by weight.
- the centrifugation In addition to the removal of water, recovered in an aqueous phase, the centrifugation also allows the removal of some of the solid residues in suspension.
- the centrifugation step has the advantage of simplified implementation, avoiding resorting to complex chemical separation methods, such as distillation, which can be restrictive in terms of unwanted precautions and corrosion, and expensive.
- the centrifugation step may advantageously be a triphasic centrifugation
- the centrifugation step may itself be a combination of steps, in particular comprising a first diphasic type centrifugation step, which makes it possible to separate the suspended solids in the form of sludge, coupled with a second centrifugation step.
- triphasic which separates the organic phase, the purified aqueous phase and the residual suspended solids from the first centrifugation.
- This step can be implemented by any suitable device known and commercially available.
- the centrifugation can be carried out with speeds of 4000 - 6000 rpm.
- the duration of the centrifugation depends on the nature of the species to be separated, their partition coefficient, the difference in density between the aqueous phase, the oily organic phase and the particles, the particle size, the surface tension of the particles. species to be separated, temperature, centrifugation rate.
- the separation time (called residence time) is therefore adapted case by case by those skilled in the art by conventional means of measurement and control.
- step b) the content of ash, sulfur, calcium, phosphorus, sodium, and optionally of alkali metals other than sodium, of the acid oil supplied in step a) is reduced by means of a or several sub-stages of filtration and / or precipitation.
- This step b) can be implemented by any suitable device known and commercially available.
- Filtration can thus be carried out by means of a filter press, or a filter cartridge, or a filter membrane or be an ultra filtration, nano filtration or reverse osmosis filtration.
- Step b) may advantageously comprise at least one filtration step carried out using at least one passage through a cellulose filter.
- a cellulose filter can improve the efficiency of filtration by avoiding clogging.
- the precipitation step can advantageously be carried out under conditions that are effective for precipitating the sulphates present in the acidic oil.
- These sulphates may come from the saponification of the oil and / or the acid extraction of the fatty acids.
- the precipitation of sulphates seems to be associated with the precipitation of calcium, phosphorus, sodium, and possibly alkali metals other than sodium, which has the effect of reducing the ash content of the product. .
- the conditions for carrying out the precipitation will be determined by those skilled in the art by conventional means depending on the species to be precipitated.
- the precipitation of the sulphates can in particular be carried out by adding Ca 2+ ions, for example in the form of CaCl 2 (calcium chloride).
- step b) may comprise at least two successive filtration steps with increasingly weak mesh filters.
- the filtrations can be carried out by means of a first filter of 20 to 30 ⁇ m and a second filter of 0.5 to 1.5 ⁇ m.
- step b) may comprise a filtration step followed by a precipitation step, in particular sulphates.
- these filtration and precipitation steps may be preceded or followed by one or more other filtration steps, or even one or more precipitation steps.
- the last step may be a filtration step.
- the method may comprise a succession of filtrations by means of filters of decreasing mesh size to reach the final target, for example from 200 ⁇ m up to 25 ⁇ m.
- the last filtration step is then performed using a filter having a mesh of 0.5 to 1.5 microns.
- the ash content can be measured according to standard NF EN ISO 6245.
- the sulfur content can be measured according to standard NF EN ISO 20846.
- the calcium content can be measured according to standard NF T 60106.
- the phosphorus content can be measured according to standard NF T 60106.
- the sodium content may be measured according to standard NF T 60106.
- the alkali metal content other than sodium may be measured according to standard NF T 60106.
- the final fuel acid oil advantageously has a water content less than or equal to 1%, or even less than or equal to 0.8%, in particular from 0.1% to 0.7% by weight.
- Table 1 summarizes some physicochemical characteristics typical of an acidic oil and a heavy fuel oil SULV (Very Low Sulfur Content) (non additive heavy fuel oil), as well as the specifications imposed by the CSR 500 for a heavy fuel oil. These specifications are established by the Cincinnati Syndicale du Raffinage in France.
- Step a) of the process according to the invention may in particular provide an acidic oil having characteristics such as those shown in Table 1.
- a typical acidic oil complies with CSR 500 specifications.
- Table 1 Acidic oil Heavy fuel oil SULV Specifications
- This pilot test is carried out on a decanted oil, but which has not undergone centrifugation or filtration / precipitation.
- the oil tested corresponds to an acidic oil having a water content less than or equal to 3% by weight.
- Example A An acidic oil (Sample A) is obtained which has not undergone any subsequent treatment such as centrifugation, precipitation / filtration.
- Table 2 presents the characteristics of this acidic oil (Sample A) in comparison with that of a heavy fuel oil SULV (Very Low Sulfur Content) (Sample B, heavy fuel oil STEL not additive), and a liquid fuel according to the invention (sample D).
- Example D The liquid fuel according to the invention (sample D) is prepared according to the methodology described in Example 4 from neutralization pastes obtained essentially from rapeseed, soybean and sunflower oils.
- Table 2 Sample AT B D Unit Density at 15 ° C NF EN ISO 3675 924.7 999.9 916 kg / m 3 Viscosity at 100 ° C NF EN ISO 3104 7.614 32.67 6 cSt Flash point NF EN ISO 2719 > 200 96.5 > 200 ° C PCI (*) 35.895 40.42 35.4 MJ / kg Water content NF EN ISO 12937 2.6 0.05 0.73 wt% Sulfur content NF EN ISO 20846 ⁇ 0.1 0.68 0.005 wt% Nitrogen content ATSM D 3228 0.11 0.49 0.02 wt% Ash content NF EN ISO 6245 0.819 0,032 0,027 wt% Sodium content NF T 60106 4746 3 33 mg / kg Calcium content NF T 60106 129 4 3
- Each fuel (samples A, B and D) is burned separately in a 1 MW flue gas boiler, 1 spray burner mechanics without assistance.
- the fumes are analyzed via analyzers placed in the flue gases (analyzers placed in the exhaust ducts).
- Table 3 below summarizes the combustion conditions of this test as well as the measured emissions.
- the combustion yields of the sample A and the heavy fuel oil are substantially equivalent, showing that an acid oil can be substituted for a heavy fuel oil in a combustion plant.
- the spraying temperature and the booster temperature are lower for the acidic acid, treated (Sample D) or not (Sample A), so that the total energy consumption of the plant is reduced compared to the combustion heavy fuel oil.
- the implementation of the acidic oil is also simpler. Due to the nature of an acidic oil, NO x and SO 2 emissions are either zero or very low.
- the emission of dust from an acidic oil is greater than for a heavy fuel oil and does not allow not comply with the regulatory requirements for emissions from combustion plants (Exposure Limit Value (ELV) for dusts between 20 and 50 mg / m 3 ).
- EUV Exposure Limit Value
- the fuel according to the invention respects these constraints, with even lower emissions of NO x .
- heavy fuel oil (Sample C) is a heavy-duty SIDS fuel oil supplemented with a combustion additive that reduces dust emissions.
- Table 4 Sample AT VS D Density at 15 ° C NF EN ISO 3675 924.7 986 916 kg / m 3 Viscosity at 100 ° C NF EN ISO 3104 7.614 29.5 6 cSt Flash point NF EN ISO 2719 > 200 124.5 > 200 ° C PCI (*) 35.895 40.66 35.4 MJ / kg Water content NF EN ISO 12937 2.6 0.1 0.73 wt% Sulfur content NF EN ISO 20846 ⁇ 0.1 0.9 0.005 wt% Nitrogen content ATSM D 3228 0.11 0.43 0.02 wt% Ash content NF EN ISO 6245 0.819 0,039 0,027 wt% Sodium content NFT 60106 4746 32 33 mg / kg Calcium content NFT 60106 129 9 3 mg / kg Phosphorus content NFT 60
- Samples A and C are burned in a 39 MW water tube boiler, including 3 mechanical and steam assisted burners.
- Sample D is burned in a 52 MW water tube boiler, including 4 mechanical and air-assisted burners.
- the fuels have been burned between other fuels: the fouling of the boiler before each of the combustion tests may therefore be different.
- Table 6 summarizes the specifications required for liquid fuels other than domestic fuel oil as contained in the Decree of 26/08/13 amending the decree of 25 July 1997 on the general requirements applicable to installations classified for the protection of the environment. reporting environment under heading No. 2910 (Combustion).
- Table 7 summarizes the specifications required for liquid fuels other than domestic fuel oil as set out in the Ordinance of 26/08/13 on Combustion Plants of a Power. greater than or equal to 20 MW subject to authorization under item 2910 and item 2931.
- Sample D is prepared from neutralization pastes obtained essentially from rapeseed, soybean and sunflower oils
- sample E is prepared from neutralization paste obtained essentially from rapeseed oil.
- Table 8 Standard D E Unit Density at 15 ° C NF EN ISO 3675 916 918.2 kg / m 3 Viscosity at 50 ° C NF EN ISO 3104 19.05 21,09 cSt Flash point NF EN ISO 2719 > 200 > 200 ° C PCI (*) 35.4 36.655 MJ / kg Water content NF EN ISO 12937 0.73 0.7 wt% Sulfur content NF EN ISO 20846 0.005 0,008 wt% Nitrogen content ATSM D 3228 0.02 0.05 wt% Ash content NF EN ISO 6245 0,027 0,037 wt% Sodium content NFT 60106 33 ⁇ 1 mg / kg Calcium content NFT 60106 3 1 mg / kg Phosphorus content NFT 60106 26 129 mg
- Table 9 shows the evolution of the characteristics influencing the dust emissions during the fuel fabrication process as described in the present invention.
- Table 9 summarizes the physico-chemical characteristics of an acid oil stored in a tank (Sample No. 1). This acidic oil corresponds to an acidic oil having a water content greater than 1% by weight.
- sample No. 2 thus corresponds to an acidic oil as provided in step a) of the process according to the present invention, with a water content of less than 1% by weight.
- Sample No. 3 results from the filtration of sample No. 2 through a 25 micron filter followed by a 0.9 micron filter. Sample No. 3 corresponds to a combustible acid oil as obtained in step b) of the process according to the present invention.
- centrifugation makes it possible to significantly reduce the ash content and the sodium content (see Sample No. 2). There is also a decrease in the water content as well as in the calcium and phosphorus content. This centrifugation step can thus be used to reduce the water content but also to reduce the ash content insofar as the centrifugation also seems to reduce the phospholipid content, which is the source of phosphorus, and the content made of metals (see Table 9).
- each of the samples No. 2 and No. 3 has contents of water, ash, calcium, phosphorus and sodium lower than those of the sample A and the contents of water, ash, calcium and sodium of the same order of the sample C of Example 3. It is therefore expected that the combustion of these samples will meet the requirements for emissions, particularly dust.
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Abstract
La présente invention concerne un procédé de préparation d'une huile acide combustible issue de la biomasse, notamment issue de l'acidification d'une pâte de neutralisation obtenue par un procédé de raffinage d'une huile végétale et/ou animale. Le procédé selon l'invention permet d'obtenir une huile acide combustible à faible teneur en eau, cendres, soufre, calcium, phosphore, sodium, et éventuellement métaux alcalins autres que le sodium, adaptée pour être brûlée dans des installations de combustion industrielles.The present invention relates to a process for preparing a combustible acid oil derived from biomass, in particular resulting from the acidification of a neutralization paste obtained by a process for refining a vegetable and / or animal oil. The method according to the invention makes it possible to obtain a fuel acid oil with a low content of water, ash, sulfur, calcium, phosphorus, sodium, and possibly alkali metals other than sodium, suitable for being burned in industrial combustion plants.
Description
La présente invention concerne un procédé de préparation d'une huile acide combustible issue de la biomasse, notamment issue de l'acidification d'une pâte de neutralisation obtenue par un procédé de raffinage d'une huile végétale et/ou animale. L'invention concerne également une huile acide combustible et l'utilisation de cette l'huile.The present invention relates to a process for preparing a combustible acid oil derived from biomass, in particular resulting from the acidification of a neutralization paste obtained by a process for refining a vegetable and / or animal oil. The invention also relates to a fuel acid oil and the use of this oil.
L'huile acide combustible de la présente invention est plus particulièrement adaptée pour une utilisation dans des installations de combustion consommant exclusivement, seuls ou en mélange, du gaz naturel, des gaz de pétrole liquéfiés, du fioul domestique, du charbon, des fiouls lourds, de la biomasse. L'huile acide combustible de l'invention n'est donc pas un carburant.The fuel acid oil of the present invention is more particularly adapted for use in combustion plants consuming exclusively, alone or as a mixture, natural gas, liquefied petroleum gases, heating oil, coal, heavy fuel oils, biomass. The fuel acid oil of the invention is therefore not a fuel.
Notamment, l'huile acide combustible de la présente invention peut être utilisée dans les installations de combustion classées dans la rubrique 2910 A (et à fortiori 2910 B et 2910 C) de la nomenclature des installations classées pour la protection de l'environnement (nomenclature ICPE) définie dans le décret n° 2013-814 du 11 septembre 2013, publié dans le journal Officiel de la République Française du 13 septembre 2013.In particular, the combustible acid oil of the present invention can be used in combustion plants classified under heading 2910 A (and a fortiori 2910 B and 2910 C) of the nomenclature of classified installations for the protection of the environment (nomenclature ICPE) defined in Decree No. 2013-814 of 11 September 2013, published in the Official Journal of the French Republic of 13 September 2013.
L'industrie du raffinage de pétrole, au moins en Europe de l'ouest, a tendance à diminuer la production de fioul lourd, en raison de la baisse de la demande. Cette baisse est liée au passage à des sources d'énergie alternatives par les clients, notamment du gaz naturel, ainsi qu'aux contraintes environnementales qui tendent à limiter les quantités de NOx, SO2 et poussières émises dans l'atmosphère. Pour être en adéquation avec les prescriptions règlementaires les plus sévères, les installations de combustion de forte puissance devraient recourir à un fioul exempt d'azote, soufre et cendres ou à des techniques de traitement de fumées, ce qui n'est pas viable économiquement par rapport à d'autres énergies, telles que le gaz naturel par exemple.The petroleum refining industry, at least in Western Europe, tends to decrease the production of heavy fuel oil, due to lower demand. This decrease is related to the switch to alternative sources of energy by customers, particularly natural gas, as well as environmental constraints that tend to limit the amount of NOx, SO 2 and dust emitted into the atmosphere. In order to comply with the most stringent regulatory requirements, high-power combustion plants should use fuel oil that is free of nitrogen, sulfur and ash or smoke treatment techniques, which is unsustainable. economically compared to other energies, such as natural gas for example.
De plus, le fioul lourd nécessite généralement d'être stocké à une température voisine de 50°C afin de le rendre pompable et d'être pulvérisé à une température comprise entre 85 et 130°C selon la technologie des brûleurs, en lien avec la viscosité du produit. Ces étapes de chauffage représentent une consommation énergétique non négligeable.In addition, the heavy fuel oil generally needs to be stored at a temperature of 50 ° C to make it pumpable and to be sprayed at a temperature between 85 and 130 ° C according to burner technology, in connection with the viscosity of the product. These heating steps represent a significant energy consumption.
En outre, le point éclair du fioul lourd (typiquement compris entre 70 et 120°C) proche de sa température de mise en oeuvre, peut engendrer des contraintes supplémentaires en termes de sécurité (atmosphères explosives).In addition, the flash point of the heavy fuel oil (typically between 70 and 120 ° C) close to its operating temperature, can cause additional constraints in terms of safety (explosive atmospheres).
Il existe donc un besoin pour un combustible de substitution du fioul lourd qui soit moins contraignant lors de sa mise en oeuvre et qui permette d'atteindre les exigences de plus en plus élevées relatives aux émissions atmosphériques résultant de sa combustion.There is therefore a need for a fuel substitute for heavy fuel which is less restrictive during its implementation and which allows to meet the requirements for higher and higher atmospheric emissions resulting from its combustion.
Il existe des compositions combustibles à base de fioul lourd et de produits élaborés à partir de la biomasse, tel que par exemple les compositions combustibles élaborées par la demanderesse et décrites dans les documents
Il existe un besoin pour un combustible de substitution du fioul lourd qui soit moins contraignant lors de sa mise en oeuvre, qui permette d'atteindre les exigences de plus en plus élevées relatives aux émissions atmosphériques résultant de sa combustion et qui soit entièrement issu de la biomasse.There is a need for a fuel substitute for heavy fuel which is less restrictive during its implementation, which allows to meet the higher and higher requirements for atmospheric emissions resulting from its combustion and which is entirely derived from the biomass.
Le document
Le document
La demanderesse propose un procédé de préparation d'un combustible, notamment d'un combustible liquide, issu de la biomasse pouvant se substituer à un fioul, notamment pour être brûlé dans une chaudière industrielle ou un four industriel en lieu et place d'un fioul.The Applicant proposes a process for preparing a fuel, in particular a liquid fuel, derived from biomass that can be substituted for an oil, in particular for being burned in an industrial boiler or an industrial oven instead of an oil .
Un premier objet de l'invention concerne ainsi un procédé de préparation d'un combustible issu de la biomasse comprenant :
- a) une étape de fourniture d'une huile acide issue du raffinage d'une ou plusieurs huiles choisie(s) parmi une huile végétale et/ou une huile animale, l'huile acide ayant une teneur en eau inférieure ou égale à 1 %pds, voire inférieure ou égale à 0,8% pds, en particulier de 0,1% à 0,7% en pds,
- b) une étape de réduction des teneurs en cendres, soufre, phosphore, calcium et sodium, de l'huile acide obtenue à l'étape a), cette étape de réduction comprenant une ou plusieurs sous étapes choisie(s) parmi une filtration et une précipitation, réalisée(s) dans des conditions efficaces pour obtenir une huile acide combustible comprenant une teneur en :
- cendres inférieure ou égale à 0,1%pds, idéalement inférieure à 0,05%pds,
- soufre inférieure ou égale à 150 mg/kg, de préférence inférieure à 100 mg/kg,
- calcium inférieure ou égale à 5 mg/kg, de préférence inférieure à 1 mg/kg,
- phosphore inférieure ou égale à 150 mg/kg,
- sodium inférieure ou égale à 10 mg/kg, de préférence inférieure à 1mg/kg.
- a) a step of supplying an acidic oil resulting from the refining of one or more oils chosen from a vegetable oil and / or an animal oil, the acidic oil having a water content of less than or equal to 1% less than or equal to 0.8% by weight, in particular from 0.1% to 0.7% by weight,
- b) a step of reducing the ash, sulfur, phosphorus, calcium and sodium contents of the acid oil obtained in step a), this reduction step comprising one or more sub-steps chosen from filtration and precipitation, carried out under conditions effective to obtain a fuel acid oil comprising a content of:
- ash of less than or equal to 0.1 wt%, ideally less than 0.05 wt%,
- sulfur less than or equal to 150 mg / kg, preferably less than 100 mg / kg,
- calcium less than or equal to 5 mg / kg, preferably less than 1 mg / kg,
- phosphorus less than or equal to 150 mg / kg,
- sodium less than or equal to 10 mg / kg, preferably less than 1 mg / kg.
Avantageusement, l'étape b) peut en outre permettre de réduire également la teneur en métaux alcalins autres que le sodium, notamment à une valeur inférieure ou égale à 1mg/kg.Advantageously, step b) may also make it possible to reduce also the content of alkali metals other than sodium, especially at a value of less than or equal to 1 mg / kg.
L'huile acide fournie à l'étape a) peut être définie comme issue de l'acidification d'une pâte de neutralisation.The acidic oil supplied in step a) can be defined as resulting from the acidification of a neutralization paste.
Les huiles acides présentent ainsi naturellement des teneurs en soufre et en azote faibles mais variables, de sorte que leur combustion produit de faibles émissions de SO2 et de NOx. Il convient toutefois de diminuer la teneur en sulfate (donc en soufre) afin de limiter les émissions de particules. Leur teneur en eau et cendres est toutefois importante et conduit d'une part à une baisse du rendement de combustion et d'autre part à des émissions de particules ne respectant pas les exigences environnementales.Acidic oils naturally have low but variable levels of sulfur and nitrogen, so that their combustion produces low SO 2 and NO x emissions. However, it is necessary to reduce the sulphate content (so sulfur) to limit particulate emissions. However, their water and ash content is important and leads, on the one hand, to a reduction in combustion efficiency and, on the other hand, to particulate emissions that do not meet environmental requirements.
Le procédé selon l'invention permet d'obtenir une huile acide combustible, constituant le combustible issu de la biomasse de la présente invention, présentant un bon pouvoir calorifique et qui peut être brûlée en produisant de faibles émissions de polluants atmosphériques. Elle peut ainsi se substituer à un carburant de type fioul lourd.The method according to the invention makes it possible to obtain a combustible acid oil, constituting the fuel derived from the biomass of the present invention, having a good calorific value and which can be burned by producing low emissions of atmospheric pollutants. It can thus substitute for a heavy fuel type fuel.
L'invention permet ainsi d'obtenir un combustible issu uniquement de la biomasse, à savoir les pâtes de neutralisation, dont les émissions respectent des contraintes environnementales élevées.The invention thus makes it possible to obtain a fuel derived solely from biomass, namely neutralization pastes, the emissions of which respect high environmental constraints.
En outre, malgré des compositions variables des huiles acides en fonction de leur origine (notamment en fonction de la nature de l'huile végétale et/ou animale dont elles sont issues et de la qualité de cette huile), le procédé selon la présente invention permet d'obtenir un combustible présentant des caractéristiques constantes en termes d'émissions de polluants atmosphériques, garantissant l'utilisation du combustible dans les installations de combustion utilisant habituellement un fioul lourd ou les autres types de combustibles mentionnés plus haut (notamment les installations classées selon les types 2910A, 2910B, 2910C nomenclature ICPE).In addition, despite varying compositions of the acid oils according to their origin (in particular depending on the nature of the vegetable and / or animal oil from which they are derived and the quality of this oil), the process according to the present invention allows to obtain a fuel with constant characteristics in terms of emissions of atmospheric pollutants, guaranteeing the use of fuel in combustion plants usually using heavy fuel oil or the other types of fuel mentioned above (in particular installations classified according to types 2910A, 2910B, 2910C ICPE nomenclature).
Un autre objet de l'invention concerne une huile acide combustible, notamment issue de l'acidification d'une pâte de neutralisation obtenue par un procédé de raffinage, notamment par saponification, d'une huile végétale et/ou animale, comprenant des teneurs en :
- cendres inférieure ou égale à 0,1%pds, idéalement inférieure à 0,05%pds,
- soufre inférieure ou égale à 150 mg/kg, de préférence inférieure à 100 mg/kg,
- calcium inférieure ou égale à 5 mg/kg, de préférence inférieure à 1 mg/kg,
- phosphore inférieure ou égale à 150 mg/kg,
- sodium inférieure ou égale à 10mg/kg, de préférence inférieure à 1mg/kg.
- ash of less than or equal to 0.1 wt%, ideally less than 0.05 wt%,
- sulfur less than or equal to 150 mg / kg, preferably less than 100 mg / kg,
- calcium less than or equal to 5 mg / kg, preferably less than 1 mg / kg,
- phosphorus less than or equal to 150 mg / kg,
- sodium less than or equal to 10 mg / kg, preferably less than 1 mg / kg.
Selon des formes avantageuses, la teneur en cendres peut être inférieure ou égale à 0,04%pds.According to advantageous forms, the ash content may be less than or equal to 0.04% by weight.
Avantageusement, l'huile acide combustible selon l'invention peut en outre comprendre une teneur en métaux alcalins autres que le sodium inférieure ou égale à 1 mg/kg.Advantageously, the fuel acid oil according to the invention may further comprise an alkali metal content other than sodium less than or equal to 1 mg / kg.
Avantageusement, l'huile acide combustible selon l'invention présente une teneur en eau inférieure ou égale à 1%pds, voire inférieure ou égale à 0,8% pds, en particulier de 0,1% à 0,7% en pds.Advantageously, the fuel acid oil according to the invention has a water content less than or equal to 1% by weight, or even less than or equal to 0.8% by weight, in particular from 0.1% to 0.7% by weight.
Avantageusement, l'huile acide combustible selon l'invention peut présenter un point éclair supérieur ou égal à 200°C (mesuré selon la norme NF EN ISO 2719 au moyen d'un appareil dit de type Pensky Martens). Un point éclair élevé permet de réduire les contraintes de sécurité liées au stockage par rapport à un fioul lourd présentant un point éclair plus bas. Il en résulte des coûts de mise en oeuvre moins élevés et une mise en oeuvre plus facile.Advantageously, the fuel acid oil according to the invention may have a flash point greater than or equal to 200 ° C. (measured according to standard NF EN ISO 2719 by means of a so-called Pensky Martens device). A high flash point makes it possible to reduce storage safety constraints compared to a heavy fuel oil with a lower flash point. This results in lower implementation costs and easier implementation.
Une telle huile acide combustible peut être directement obtenue par le procédé selon l'invention.Such a combustible acid oil can be directly obtained by the process according to the invention.
Un autre objet de l'invention concerne un procédé de combustion d'un combustible dans une installation de combustion, notamment de type 2910A ou 2910B ou 2910C selon la nomenclature ICPE, dans laquelle on brûle en tant que combustible une huile acide combustible directement obtenue par le procédé selon l'invention ou une huile acide combustible selon l'invention.Another subject of the invention relates to a method of combustion of a fuel in a combustion plant, in particular of type 2910A or 2910B or 2910C according to the ICPE nomenclature, in which a fuel acid fuel directly obtained by the process according to the invention or a combustible acid oil according to the invention.
L'huile acide fournie à l'étape a) est issue du raffinage d'une ou plusieurs huiles choisie(s) parmi une huile végétale et/ou une huile animale.The acidic oil supplied in step a) is derived from the refining of one or more oils chosen from a vegetable oil and / or an animal oil.
Il s'agit notamment d'une huile issue de l'acidification d'une pâte de neutralisation, cette pâte de neutralisation étant issue du raffinage d'une ou plusieurs huiles choisie(s) parmi une huile végétale et/ou une huile animale. La pâte de neutralisation est de préférence issue du raffinage chimique d'une ou plusieurs huiles végétales.It is in particular an oil resulting from the acidification of a neutralization paste, this neutralization paste being derived from the refining of one or more oils chosen from a vegetable oil and / or an animal oil. The neutralization paste is preferably derived from the chemical refining of one or more vegetable oils.
Une huile acide peut être définie comme étant des compositions d'acides gras neutralisés par une base puis acidifiés.An acidic oil can be defined as base-neutralized fatty acid compositions and then acidified.
Les acides gras proviennent avantageusement directement de la saponification d'une huile végétale et/ou animale, telle que, sans être limitatif, une huile de tournesol, de soja, de colza, de palme, de coprah, d'arachide, d'olive, une huile de poisson, et comprenant classiquement en très grande majorité des chaînes carbonées en C16-C18, saturées ou insaturées, parmi lesquelles de préférence des chaînes carbonées insaturées en C18. Les huiles végétales comprennent habituellement de l'acide palmitique, oléique, linoléique et d'autres acides en plus faibles quantités. Les compositions d'acides gras neutralisés par une base sont typiquement des pâtes de neutralisation.The fatty acids advantageously come directly from the saponification of a vegetable and / or animal oil, such that, without being limiting, sunflower, soybean, rapeseed, palm, coconut, peanut, olive oil. , a fish oil, and typically comprising in the great majority saturated or unsaturated C 16 -C 18 carbon chains, of which, preferably, C 18 unsaturated carbon chains. Vegetable oils usually include palmitic, oleic, linoleic acid and other acids in smaller amounts. The base neutralized fatty acid compositions are typically neutralization pastes.
Typiquement, une huile acide contient de 30 à 70% en poids d'acides gras.Typically, an acidic oil contains from 30 to 70% by weight of fatty acids.
L'huile acide fournie à l'étape a) présente avantageusement une teneur en eau inférieure ou égale à 1%pds, voire inférieure ou égale à 0,8% pds, en particulier de 0,1% à 0,7% en pds.The acidic oil supplied in stage a) advantageously has a water content of less than or equal to 1% by weight, or even less than or equal to 0.8% by weight, in particular from 0.1% to 0.7% by weight. .
L'étape a) peut notamment comprendre la fourniture d'une huile acide issue du raffinage d'une ou plusieurs huiles choisie(s) parmi une huile végétale et/ou une huile animale ayant une teneur en eau inférieure à inférieure ou égale à 3 %pds mais supérieure à 1% en pds, suivie d'une étape de centrifugation permettant d'obtenir une teneur en eau inférieure ou égale à 1 %pds, voire inférieure ou égale à 0,8% pds, en particulier de 0,1% à 0,7% en pds.Stage a) can in particular comprise the supply of an acid oil resulting from the refining of one or more oils chosen from a vegetable oil and / or an animal oil having a water content of less than or equal to 3 % wt but greater than 1 wt%, followed by a centrifugation step making it possible to obtain a water content less than or equal to 1 wt.%, or even less than or equal to 0.8 wt.%, in particular 0.1 wt. % to 0.7% in weight.
Selon l'invention, l'étape a) de fourniture d'une huile acide comprend :
- a1) une étape d'extraction des acides gras présents dans une pâte de neutralisation issue du raffinage, notamment de la saponification, d'une ou plusieurs huiles choisie(s) parmi une huile végétale et/ou une huile animale, cette étape d'extraction étant réalisée en milieu acide dans des conditions efficaces pour former une phase aqueuse et une phase organique comprenant lesdits acides gras,
- a2) une étape de séparation au cours de laquelle on sépare ladite phase organique précédemment formée et on la récupère.
- a1) a step of extracting the fatty acids present in a neutralization paste resulting from the refining, in particular the saponification, of one or more oils chosen from a vegetable oil and / or an animal oil, this step of extraction being carried out in an acidic medium under conditions that are effective for forming an aqueous phase and an organic phase comprising said fatty acids,
- a2) a separation step during which said previously formed organic phase is separated and recovered.
La phase organique récupérée à l'étape a2) constitue une huile acide présentant généralement une teneur en eau inférieure ou égale à 3%pds.The organic phase recovered in step a2) constitutes an acidic oil generally having a water content of less than or equal to 3% by weight.
La pâte de neutralisation traitée à l'étape a1) peut être un mélange de pâtes de neutralisation issues du raffinage de différentes huiles ou peut être une pâte de neutralisation issue du raffinage d'une unique huile. Ce raffinage est de préférence chimique.The neutralization paste treated in step a1) may be a mixture of neutralization pastes obtained from the refining of different oils or may be a neutralization paste resulting from the refining of a single oil. This refining is preferably chemical.
De telles pâtes de neutralisation proviennent, notamment directement, de la saponification d'une huile végétale et/ou d'une huile animale. En général, cette saponification est réalisée par ajout d'une base, généralement de la soude, et permet d'éliminer les acides gras libres présents dans l'huile, lesquels se retrouvent dans la pâte de neutralisation (« soapstock » en anglais) sous forme de sels alcalins d'acides gras. Avant cette saponification, l'huile végétale et/ou animale peut subir une opération de dégommage ou démucilagination visant à éliminer les phospholipides, lécithines, complexes sucrés et autres impuretés. La séparation de l'huile et de la pâte de neutralisation résultant de la saponification peut être réalisée par centrifugation.Such neutralization pastes come, in particular directly from the saponification of a vegetable oil and / or an animal oil. In general, this saponification is carried out by adding a base, usually sodium hydroxide, and eliminates the free fatty acids present in the oil, which are found in the soapstock. form of alkaline salts of fatty acids. Before this saponification, the vegetable and / or animal oil may undergo a degumming or degumming operation to eliminate phospholipids, lecithins, sugar complexes and other impurities. The separation of the oil and the neutralization paste resulting from the saponification can be carried out by centrifugation.
Les pâtes de neutralisation comprennent ainsi essentiellement des acides gras neutralisés par une base. Elles comprennent typiquement de 30 à 70% en poids d'acides gras.The neutralization pastes thus essentially comprise base neutralized fatty acids. They typically comprise from 30 to 70% by weight of fatty acids.
En plus des acides gras neutralisés par une base, les pâtes de neutralisation peuvent contenir, selon leur origine et la qualité de la saponification, des phospholipides ou des mono-, di- ou tri-glycérides n'ayant pas réagi. Habituellement, les acides gras ont des chaînes carbonées en C12-C24, de préférence C16-C20 ou mieux C16-C18.In addition to the base-neutralized fatty acids, the neutralization pastes may contain, depending on their origin and the quality of the saponification, unreacted phospholipids or mono-, di- or tri-glycerides. Usually, the fatty acids have carbon chains in C 12 -C 24 , preferably C 16 -C 20 or better C 16 -C 18 .
Une pâte de neutralisation est donc un produit issu de la biomasse. Des avantages associés à de telles pâtes de neutralisation résident, d'une part, sur leur bas coût de mise en oeuvre, et, d'autre part, dans l'absence de substances toxiques indésirables, telles que les pesticides, les aflatoxines, les métaux lourds, les précurseurs de dioxines et furanes, les PCB et les nitrites.A neutralization paste is therefore a product derived from biomass. Advantages associated with such neutralization pastes lie, on the one hand, in their low cost of implementation, and, on the other hand, in the absence of undesirable toxic substances, such as pesticides, aflatoxins, heavy metals, precursors of dioxins and furans, PCBs and nitrites.
Cependant, la teneur en eau de ces pâtes de neutralisation est rédhibitoire quant à leur utilisation seule en tant que combustible. En effet, de telles pâtes peuvent contenir des proportions importantes d'eau provenant de la réaction de saponification ou de rajout d'eau pour la fluidification dans le process industriel. Typiquement, la phase aqueuse représente 50% au moins de la masse de la pâte de neutralisation. Une autre difficulté est liée au fait qu'il s'agit selon les cas d'émulsions, qu'il convient de traiter de façon spécifique.However, the water content of these neutralization pastes is prohibitive as to their use alone as a fuel. Indeed, such pastes may contain significant proportions of water from the saponification reaction or addition of water for the fluidification in the industrial process. Typically, the aqueous phase represents at least 50% of the mass of the neutralization paste. Another difficulty is related to the fact that it is emulsion cases, which should be treated specifically.
L'utilisation en tant que combustible nécessite par conséquent de mettre en oeuvre des méthodes d'élimination de cette eau et autres résidus solides ou liquides visqueux indésirables.The use as a fuel therefore requires methods of removing this water and other unwanted solids or viscous liquid residues.
L'étape a1) d'extraction du procédé selon l'invention a pour fonction d'extraire les acides gras contenus dans la pâte de neutralisation. Cette extraction est réalisée en milieu acide dans des conditions efficaces pour former une phase aqueuse et une phase organique comprenant les acides gras initialement contenus dans la pâte de neutralisation.The extraction step a1) of the process according to the invention has the function of extracting the fatty acids contained in the neutralization paste. This extraction is carried out in an acidic medium under conditions that are effective for forming an aqueous phase and an organic phase comprising the fatty acids initially contained in the neutralization paste.
Cette phase organique comprenant les acides gras est généralement appelée « huile acide », ou encore « huile de neutralisation ».This organic phase comprising the fatty acids is generally called "acid oil" or "neutralizing oil".
L'acide utilisé pour extraire les acides gras présents dans la pâte de neutralisation sous forme de sels est généralement un acide inorganique, tel que par exemple l'acide sulfurique, l'acide phosphorique ou l'acide chlorhydrique.The acid used to extract the fatty acids present in the neutralization paste in the form of salts is generally an inorganic acid, such as, for example, sulfuric acid, phosphoric acid or hydrochloric acid.
L'acide sulfurique est toutefois préféré car il permet une meilleure extraction des acides gras à un coût économique favorable.Sulfuric acid is however preferred because it allows better extraction of fatty acids at a favorable economic cost.
L'extraction est généralement réalisée sous chauffage, à une température comprise entre 70 et 100°C (bornes incluses), de préférence entre 80 et 90°C (bornes incluses).The extraction is generally carried out under heating, at a temperature between 70 and 100 ° C (inclusive), preferably between 80 and 90 ° C (inclusive).
Afin d'obtenir une bonne extraction des acides gras, on maintient de préférence un pH acide le temps de la réaction, par exemple un pH inférieur ou égal à 6, de préférence inférieur ou égal à 4.In order to obtain a good extraction of the fatty acids, an acidic pH is preferably maintained during the reaction time, for example a pH of less than or equal to 6, preferably less than or equal to 4.
Le temps de réaction est choisi pour permettre une extraction de la totalité des acides gras. Il est par exemple de 1 heure à 12 heures, en fonction de la géométrie du réacteur, de la nature et de la composition de la charge à traiter.The reaction time is chosen to allow extraction of all the fatty acids. It is for example from 1 hour to 12 hours, depending on the geometry of the reactor, the nature and composition of the charge to be treated.
L'extraction est de préférence réalisée sous agitation.The extraction is preferably carried out with stirring.
On obtient ainsi la formation d'une phase aqueuse et d'une phase organique contenant les acides gras.The formation of an aqueous phase and an organic phase containing the fatty acids are thus obtained.
Au cours de cette étape, on sépare la phase organique formée lors de l'étape a1) de la phase aqueuse. Autrement dit, on isole l'huile acide qui sera ultérieurement soumise à l'étape b) du procédé selon l'invention, optionnellement après une étape a3 de centrifugation lorsque sa teneur en eau est supérieure à 1% mais inférieure ou égale à 3%.During this step, the organic phase formed during step a1) is separated from the aqueous phase. In other words, the acidic oil which will subsequently be subjected to step b) of the process according to the invention is isolated, optionally after a centrifugation step a3 when its water content is greater than 1% but less than or equal to 3%. .
Cette séparation peut être réalisée par distillation, décantation, voire centrifugation. Cette étape peut être mise en oeuvre par tous dispositifs appropriés, connus et disponibles dans le commerce.This separation can be carried out by distillation, decantation or even centrifugation. This step can be implemented by any suitable device known and commercially available.
Avantageusement, cette séparation est réalisée par décantation, suivie d'une élimination de la phase aqueuse. La décantation dépend de la différence de densité des liquides et de leur viscosité, paramètres qui peuvent être modifiés de manière connue par l'homme de l'art pour favoriser la séparation le cas échéant.Advantageously, this separation is carried out by decantation, followed by removal of the aqueous phase. Decantation depends on the difference in density of the liquids and their viscosity, parameters which can be modified in a manner known to those skilled in the art to promote separation if necessary.
Avantageusement, on peut réaliser une filtration à 150 µm de l'huile acide avant toute étape ultérieure.Advantageously, it is possible to carry out a filtration at 150 μm of the acidic oil before any subsequent step.
Lorsque la teneur en eau de l'huile acide est inférieure ou égale à 3%pds mais supérieure à 1%pds, l'huile acide peut avantageusement être soumise à une centrifugation préalablement à l'étape b). Un objectif de cette centrifugation est d'abaisser la teneur en eau de l'huile acide.When the water content of the acidic oil is less than or equal to 3% by weight but greater than 1% by weight, the acidic oil may advantageously be subjected to centrifugation prior to step b). An objective of this centrifugation is to lower the water content of the acidic oil.
La centrifugation est avantageusement réalisée sur une huile acide obtenue par les étapes a1) et a2) précédemment décrites.Centrifugation is advantageously performed on an acidic oil obtained by steps a1) and a2) previously described.
Cette opération de centrifugation permet d'obtenir une huile acide présentant très avantageusement une teneur en eau inférieure ou égale à 1% en poids, voire inférieure ou égale à 0,8% en poids, en particulier de 0,1% à 0,7% en poids.This centrifugation operation makes it possible to obtain an acidic oil having very advantageously a water content of less than or equal to at 1% by weight, or even less than or equal to 0.8% by weight, in particular from 0.1% to 0.7% by weight.
Outre l'élimination d'eau, récupérée dans une phase aqueuse, la centrifugation permet également l'élimination d'une partie des résidus solides en suspension.In addition to the removal of water, recovered in an aqueous phase, the centrifugation also allows the removal of some of the solid residues in suspension.
L'étape de centrifugation présente l'avantage d'une mise en oeuvre simplifiée, en évitant de recourir à des méthodes de séparation chimiques complexes, telles que distillation, lesquelles peuvent être contraignantes en termes de précautions et de corrosion indésirables, et onéreuses.The centrifugation step has the advantage of simplified implementation, avoiding resorting to complex chemical separation methods, such as distillation, which can be restrictive in terms of unwanted precautions and corrosion, and expensive.
L'étape de centrifugation peut avantageusement être une centrifugation triphasique,The centrifugation step may advantageously be a triphasic centrifugation,
Toutefois, l'étape de centrifugation peut elle-même être une combinaison d'étapes, en particulier comprendre une première étape de centrifugation de type diphasique, qui permet de séparer les matières en suspension sous forme de boues, couplée à une deuxième étape de centrifugation triphasique, laquelle sépare la phase organique, la phase aqueuse épurée et les matières en suspension résiduelles de la première centrifugation. Cette étape peut être mise en oeuvre par tous dispositifs appropriés, connus et disponibles dans le commerce.However, the centrifugation step may itself be a combination of steps, in particular comprising a first diphasic type centrifugation step, which makes it possible to separate the suspended solids in the form of sludge, coupled with a second centrifugation step. triphasic, which separates the organic phase, the purified aqueous phase and the residual suspended solids from the first centrifugation. This step can be implemented by any suitable device known and commercially available.
Classiquement, la centrifugation peut être mise en oeuvre avec des vitesses de 4000 - 6000 t/min.Conventionally, the centrifugation can be carried out with speeds of 4000 - 6000 rpm.
La durée de la centrifugation dépend de la nature des espèces à séparer, de leur coefficient de partage, de la différence de densité entre la phase aqueuse, la phase organique huileuse et les particules, de la taille des particules, de la tension de surface des espèces à séparer, de la température, de la vitesse de centrifugation. La durée de séparation (appelée temps de séjour) est donc adaptée au cas par cas par l'homme de l'art par des moyens conventionnels de mesure et contrôle.The duration of the centrifugation depends on the nature of the species to be separated, their partition coefficient, the difference in density between the aqueous phase, the oily organic phase and the particles, the particle size, the surface tension of the particles. species to be separated, temperature, centrifugation rate. The separation time (called residence time) is therefore adapted case by case by those skilled in the art by conventional means of measurement and control.
Au cours de cette étape b), on réduit la teneur en cendres, soufre, calcium, phosphore, sodium, et éventuellement en métaux alcalins autres que le sodium, de l'huile acide fournie à l'étape a) au moyen d'une ou plusieurs sous-étapes de filtration et/ou de précipitation.During this step b), the content of ash, sulfur, calcium, phosphorus, sodium, and optionally of alkali metals other than sodium, of the acid oil supplied in step a) is reduced by means of a or several sub-stages of filtration and / or precipitation.
Cette étape b) peut être mise en oeuvre par tous dispositifs appropriés, connus et disponibles dans le commerce.This step b) can be implemented by any suitable device known and commercially available.
La filtration peut ainsi être réalisée au moyen d'un filtre presse, ou d'un filtre cartouche, ou d'une membrane filtrante ou être une ultra filtration, une nano filtration ou encore une filtration par osmose inverse.Filtration can thus be carried out by means of a filter press, or a filter cartridge, or a filter membrane or be an ultra filtration, nano filtration or reverse osmosis filtration.
L'étape b) peut avantageusement comprendre au moins une étape de filtration effectuée à l'aide d'au moins un passage à travers un filtre à cellulose. Un tel filtre à cellulose peut permettre d'améliorer l'efficacité de la filtration en évitant le colmatage.Step b) may advantageously comprise at least one filtration step carried out using at least one passage through a cellulose filter. Such a cellulose filter can improve the efficiency of filtration by avoiding clogging.
L'étape de précipitation peut avantageusement être réalisée dans des conditions efficaces pour précipiter les sulfates présents dans l'huile acide. Ces sulfates peuvent provenir de la saponification de l'huile et/ou de l'extraction à l'acide des acides gras.The precipitation step can advantageously be carried out under conditions that are effective for precipitating the sulphates present in the acidic oil. These sulphates may come from the saponification of the oil and / or the acid extraction of the fatty acids.
Sans vouloir être lié par une théorie, la précipitation des sulfates semble associée à la précipitation du calcium, du phosphore, du sodium, et éventuellement des métaux alcalins autres que le sodium, ce qui pour a pour effet de diminuer la teneur en cendres du produit.Without wishing to be bound by theory, the precipitation of sulphates seems to be associated with the precipitation of calcium, phosphorus, sodium, and possibly alkali metals other than sodium, which has the effect of reducing the ash content of the product. .
De manière générale, les conditions de réalisation de la précipitation seront déterminées par l'homme du métier par des moyens conventionnels en fonction des espèces à précipiter.In general, the conditions for carrying out the precipitation will be determined by those skilled in the art by conventional means depending on the species to be precipitated.
La précipitation des sulfates peut notamment être réalisée par ajout d'ions Ca2+, par exemple sous forme de CaCl2 (chlorure de calcium).The precipitation of the sulphates can in particular be carried out by adding Ca 2+ ions, for example in the form of CaCl 2 (calcium chloride).
Le choix et le nombre de ces sous-étapes pourra être déterminé aisément par l'homme du métier en contrôlant la teneur en cendres, soufre, calcium, phosphore et sodium de la phase organique finale, constituant l'huile acide combustible selon l'invention.The choice and the number of these sub-steps can easily be determined by those skilled in the art by controlling the content of ash, sulfur, calcium, phosphorus and sodium of the final organic phase, constituting the fuel acid oil according to the invention. .
Dans un mode de réalisation, l'étape b) peut comprendre au moins deux étapes de filtration successives avec des filtres de maillage de plus en plus faible. A titre d'exemple, les filtrations peuvent être effectuées au moyen d'un premier filtre de 20 à 30 µm et d'un deuxième filtre de 0,5 à 1,5 µm.In one embodiment, step b) may comprise at least two successive filtration steps with increasingly weak mesh filters. By way of example, the filtrations can be carried out by means of a first filter of 20 to 30 μm and a second filter of 0.5 to 1.5 μm.
Dans un autre mode de réalisation, l'étape b) peut comprendre une étape filtration suivie d'une étape de précipitation, notamment des sulfates.In another embodiment, step b) may comprise a filtration step followed by a precipitation step, in particular sulphates.
Eventuellement ces étapes de filtration et de précipitation peuvent être précédées ou suivies d'une ou plusieurs autres étapes de filtration, voire d'une ou plusieurs étapes de précipitation. Avantageusement, la dernière étape peut être une étape de filtration.Optionally, these filtration and precipitation steps may be preceded or followed by one or more other filtration steps, or even one or more precipitation steps. Advantageously, the last step may be a filtration step.
Le procédé peut comprendre une succession de filtrations au moyen de filtres de mailles décroissantes pour atteindre la cible finale, par exemple partir de 200 µm jusqu'à 25 µm. Avantageusement, la dernière étape de filtration est alors réalisée au moyen d'un filtre présentant un maillage de 0,5 à 1,5 µm.The method may comprise a succession of filtrations by means of filters of decreasing mesh size to reach the final target, for example from 200 μm up to 25 μm. Advantageously, the last filtration step is then performed using a filter having a mesh of 0.5 to 1.5 microns.
Grâce à cette étape b), il est possible d'obtenir une huile acide constituant une huile acide combustible finale présentant très avantageusement des teneurs en :
- cendres inférieure ou égale à 0,1%, idéalement inférieure à 0,05%pds,
- soufre inférieure ou égale à 150 mg/kg, de préférence inférieure à 100 mg/kg,
- calcium inférieure ou égale à 5 mg/kg, de préférence inférieure à 1 mg/kg,
- phosphore inférieure ou égale à 150 mg/kg,
- sodium inférieure ou égale à 10mg/kg, de préférence inférieure à 1mg/kg,
- ash less than or equal to 0.1%, ideally less than 0.05% wt,
- sulfur less than or equal to 150 mg / kg, preferably less than 100 mg / kg,
- calcium less than or equal to 5 mg / kg, preferably less than 1 mg / kg,
- phosphorus less than or equal to 150 mg / kg,
- sodium less than or equal to 10 mg / kg, preferably less than 1 mg / kg,
La teneur en cendres pourra être mesurée selon la norme NF EN ISO 6245.The ash content can be measured according to standard NF EN ISO 6245.
La teneur en soufre pourra être mesurée selon la norme NF EN ISO 20846.The sulfur content can be measured according to standard NF EN ISO 20846.
La teneur en calcium pourra être mesurée selon la norme NF T 60106.The calcium content can be measured according to standard NF T 60106.
La teneur en phosphore pourra être mesurée selon la norme NF T 60106.The phosphorus content can be measured according to standard NF T 60106.
La teneur en sodium pourra être mesurée selon la norme NF T 60106.The sodium content may be measured according to standard NF T 60106.
La teneur en métaux alcalins autres que le sodium pourra être mesurée selon la norme NF T 60106.The alkali metal content other than sodium may be measured according to standard NF T 60106.
On notera que le procédé selon l'invention peut permettre d'obtenir des huiles dont les teneurs en cendres, soufre, calcium, phosphore, sodium et éventuellement en métaux alcalins autres que le sodium sont très inférieures aux seuils précités, voire nulles ou quasiment nulles et indétectables par les moyens de quantification usuels.It will be noted that the process according to the invention can make it possible to obtain oils whose contents in ash, sulfur, calcium, phosphorus, sodium and optionally alkali metals other than sodium are well below the aforementioned thresholds, or even zero or virtually zero and undetectable by the usual means of quantification.
En outre, l'huile acide combustible finale présente avantageusement une teneur en eau inférieure ou égale à 1%, voire inférieure ou égale à 0,8%, en particulier de 0,1% à 0,7% en poids.In addition, the final fuel acid oil advantageously has a water content less than or equal to 1%, or even less than or equal to 0.8%, in particular from 0.1% to 0.7% by weight.
Le tableau 1 rassemble quelques caractéristiques physico-chimiques typiques d'une huile acide et d'un fioul lourd TBTS (Très Basse Teneur en Soufre) (fioul lourd non additivé), ainsi que les spécifications imposées par la CSR 500 pour un fioul lourd. Ces spécifications sont établies par la Chambre Syndicale du Raffinage en France.Table 1 summarizes some physicochemical characteristics typical of an acidic oil and a heavy fuel oil SULV (Very Low Sulfur Content) (non additive heavy fuel oil), as well as the specifications imposed by the CSR 500 for a heavy fuel oil. These specifications are established by the Chambre Syndicale du Raffinage in France.
L'étape a) du procédé selon l'invention peut notamment fournir une huile acide présentant des caractéristiques telles que celles présentées dans le tableau 1. On notera qu'une huile acide typique respecte les spécifications CSR 500.
Cet essai pilote est réalisé sur une huile décantée, mais n'ayant pas subi de centrifugation, ni de filtration/précipitation. Autrement dit, l'huile testée correspond à une huile acide présentant une teneur en eau inférieure ou égale à 3% pds.This pilot test is carried out on a decanted oil, but which has not undergone centrifugation or filtration / precipitation. In other words, the oil tested corresponds to an acidic oil having a water content less than or equal to 3% by weight.
Une pâte de neutralisation a subi le traitement suivant :
- a1) injection de 1201 d'acide sulfurique à 97% dans un réacteur contenant 4000kg de pâte de neutralisation, où la température est de 80 à 90°C. Le temps de réaction est de 24 heures, sous contrôle en continu du pH afin de maintenir le pH à une valeur inférieure à 4,
- a2) décantation de la phase aqueuse et de la phase organique formées au cours de l'étape a1) puis élimination de la phase aqueuse,
- a1) injection of 1201 of 97% sulfuric acid into a reactor containing 4000 kg of neutralization paste, where the temperature is 80 to 90 ° C. The reaction time is 24 hours under continuous pH control in order to keep the pH below 4,
- a2) decanting the aqueous phase and the organic phase formed during step a1) and then removing the aqueous phase,
On obtient une huile acide (Echantillon A) qui n'a subi aucun traitement ultérieur tel qu'une centrifugation, une précipitation/ filtration.An acidic oil (Sample A) is obtained which has not undergone any subsequent treatment such as centrifugation, precipitation / filtration.
Le tableau 2 présente les caractéristiques de cette huile acide (Echantillon A) en comparaison à celles d'un fioul lourd TBTS (Très Basse Teneur en Soufre) (Echantillon B, fioul lourd TBTS non additivé), et d'un combustible liquide selon l'invention (échantillon D).Table 2 presents the characteristics of this acidic oil (Sample A) in comparison with that of a heavy fuel oil SULV (Very Low Sulfur Content) (Sample B, heavy fuel oil STEL not additive), and a liquid fuel according to the invention (sample D).
Le combustible liquide selon l'invention (échantillon D) est préparé selon la méthodologie décrite dans l'exemple 4 à partir de pâtes de neutralisation obtenues essentiellement à partir d'huiles de colza, de soja et de tournesol.
Chaque combustible (échantillons A, B et D) est brûlé séparément dans une chaudière à tubes de fumées de 1 MW, 1 brûleur à pulvérisation mécanique sans assistance. Les fumées sont analysées via des analyseurs placés dans les fumées de combustion (analyseurs placés dans les conduits d'évacuation).Each fuel (samples A, B and D) is burned separately in a 1 MW flue gas boiler, 1 spray burner mechanics without assistance. The fumes are analyzed via analyzers placed in the flue gases (analyzers placed in the exhaust ducts).
Le tableau 3 ci-dessous rassemble les conditions de combustion de cet essai ainsi que les émissions mesurées.
On notera que les rendements de combustion de l'échantillon A et du fioul lourd sont sensiblement équivalents, montrant que l'on peut substituer une huile acide à un fioul lourd dans une installation de combustion. En outre, la température de pulvérisation et la température de gavage sont inférieures pour l'huile acide, traitée (Echantillon D) ou non (Echantillon A), de sorte que la consommation énergétique totale de l'installation est réduite par rapport à la combustion d'un fioul lourd. La mise en oeuvre de l'huile acide est également plus simple.
En raison de la nature d'une huile acide, les émissions de NOx et de SO2 sont nulles ou très faibles. En revanche, l'émission de poussières d'une huile acide est plus importante que pour un fioul lourd et ne permet pas de respecter les contraintes règlementaires relatives aux émissions des installations de combustion (Valeur Limite d'Exposition (VLE) aux poussières entre 20 et 50 mg/m3). Le combustible selon l'invention respecte ces contraintes, avec des émissions encore plus faibles de NOx.It will be noted that the combustion yields of the sample A and the heavy fuel oil are substantially equivalent, showing that an acid oil can be substituted for a heavy fuel oil in a combustion plant. In addition, the spraying temperature and the booster temperature are lower for the acidic acid, treated (Sample D) or not (Sample A), so that the total energy consumption of the plant is reduced compared to the combustion heavy fuel oil. The implementation of the acidic oil is also simpler.
Due to the nature of an acidic oil, NO x and SO 2 emissions are either zero or very low. On the other hand, the emission of dust from an acidic oil is greater than for a heavy fuel oil and does not allow not comply with the regulatory requirements for emissions from combustion plants (Exposure Limit Value (ELV) for dusts between 20 and 50 mg / m 3 ). The fuel according to the invention respects these constraints, with even lower emissions of NO x .
Les caractéristiques physico-chimiques des combustibles testés figurent dans le tableau 4.The physico-chemical characteristics of the fuels tested are shown in Table 4.
Contrairement à l'essai pilote, le fioul lourd (Echantillon C) est un fioul lourd TBTS additivé avec un additif de combustion ayant pour effet de diminuer les émissions de poussières.
Les échantillons A et C sont brûlés dans une chaudière à tubes d'eau de 39 MW, comprenant 3 brûleurs à pulvérisation mécanique et à assistance vapeur. L'échantillon D est brûlé dans une chaudière à tubes d'eau de 52 MW, comprenant 4 brûleurs à pulvérisation mécanique et à assistance air.Samples A and C are burned in a 39 MW water tube boiler, including 3 mechanical and steam assisted burners. Sample D is burned in a 52 MW water tube boiler, including 4 mechanical and air-assisted burners.
Les combustibles ont été brûlés entre d'autres combustibles : l'encrassement de la chaudière avant chacun des tests de combustion peut donc être différent.The fuels have been burned between other fuels: the fouling of the boiler before each of the combustion tests may therefore be different.
Les conditions de combustion et les émissions mesurées sont rassemblées dans le tableau 5.
(*)NF EN 14385
(*) NF EN 14385
Bien que les rendements ne soient pas directement comparables du fait d'un encrassement potentiellement différent de la chaudière avant la combustion des Echantillons A et C, on observe un rendement de combustion acceptable pour l'huile acide, pour une température d'injection très inférieure par rapport au fioul lourd.
On notera que le fioul lourd ne respecte pas la Valeur Limite d'Emission NOx : 450 mg/m3(n) imposée par la réglementation.
Les émissions de poussières de l'huile acide sont très importantes et ne respectent pas les limites des différentes législations. Notamment, les émissions de poussière sont très supérieures à la VLE de 50 mg/m3. Pour pouvoir brûler une huile acide de ce type, l'installation de combustion devrait être équipée d'un traitement de fumées, tel un électro filtre.
Sans vouloir être lié par une théorie, il est supposé que les émissions de poussières sont dues aux teneurs élevées de l'huile acide en cendres, calcium, sodium, et éventuellement en phosphore.
La combustion de l'échantillon D selon l'invention montre l'obtention d'un bon rendement de combustion et une faible émission de poussières.
A noter que la combustion d'un fioul lourd additivé dans une chaudière telle que celle dans laquelle a été brûlé l'échantillon D nécessiterait l'utilisation d'un traitement des fumées afin de respecter les VLE.
Les spécifications VLE en vigueur en France en 2016 sont reprises dans les tableaux 6 et 7 ci-dessous. On constate que ces valeurs sont respectées lors de la combustion de l'échantillon D, sans aucun traitement des fumées produites.Although the yields are not directly comparable because of a potentially different fouling of the boiler before the combustion of Samples A and C, an acceptable combustion efficiency for the acid oil is observed, for a very lower injection temperature. compared to heavy fuel oil.
It should be noted that heavy fuel oil does not comply with the NOx Emission Limit Value: 450 mg / m 3 (n) imposed by the regulations.
The dust emissions of the acid oil are very important and do not respect the limits of the different legislations. In particular, the dust emissions are much higher than the TLV of 50 mg / m 3 . In order to burn an acid oil of this type, the combustion plant should be equipped with a flue gas treatment, such as an electro-filter.
Without wishing to be bound by theory, it is assumed that dust emissions are due to the high levels of acid oil in ash, calcium, sodium, and possibly phosphorus.
The combustion of the sample D according to the invention shows the obtaining of a good combustion efficiency and a low dust emission.
It should be noted that the combustion of a heavy fuel oil additive in a boiler such as that in which the sample D was burned would require the use of a flue gas treatment in order to respect the ELVs.
The VLE specifications in effect in France in 2016 are shown in Tables 6 and 7 below. It is noted that these values are respected during the combustion of the sample D, without any treatment of the fumes produced.
Le tableau 6 rassemble les spécifications requises pour les combustibles liquides autres que le fioul domestique telles que figurant dans l'Arrêté du 26/08/13 modifiant l'arrêté du 25 juillet 1997 relatif aux prescriptions générales applicables aux installations classées pour la protection de l'environnement soumises à déclaration sous la rubrique n° 2910 (Combustion).
Le tableau 7 rassemble les spécifications requises pour les combustibles liquides autres que le fioul domestique telles que figurant dans l'Arrêté du 26/08/13 relatif aux installations de combustion d'une puissance supérieure ou égale à 20 MW soumises à autorisation au titre de la rubrique 2910 et de la rubrique 2931.
Table 7 summarizes the specifications required for liquid fuels other than domestic fuel oil as set out in the Ordinance of 26/08/13 on Combustion Plants of a Power. greater than or equal to 20 MW subject to authorization under item 2910 and item 2931.
Une pâte de neutralisation a subi le traitement suivant :
- a1) injection de 1201 d'acide sulfurique à 97% dans un réacteur contenant 4000kg de pâte de neutralisation, où la température est de 80 à 90°C. Le temps de réaction, sous agitation pour assurer un mélange homogène, est de 24 heures, sous contrôle en continu du pH afin de maintenir le pH à une valeur inférieure à 4,
- a2) décantation de la phase aqueuse et de la phase organique formées au cours de l'étape a1) puis élimination de la phase aqueuse,
- a3) centrifugation à 5000 tr.min-1 durant 5 minutes au moyen d'un appareil de centrifugation Alpha Laval®, puis élimination de la phase aqueuse,
- b) première filtration sur un filtre papier à 25 µm suivie d'une seconde filtration sur filtre cellulose à 0,9 µm, les deux filtrations étant effectuées en série avec une vitesse d'une tonne/heure.
- a1) injection of 1201 of 97% sulfuric acid into a reactor containing 4000 kg of neutralization paste, where the temperature is 80 to 90 ° C. The reaction time, with stirring to ensure a homogeneous mixture, is 24 hours, under continuous control of the pH in order to maintain the pH at a value of less than 4,
- a2) decanting the aqueous phase and the organic phase formed during step a1) and then removing the aqueous phase,
- a3) centrifugation at 5000 tr.min -1 for 5 minutes by means of a centrifugation apparatus Alpha Laval®, then removing the aqueous phase,
- b) first filtration on a paper filter at 25 μm followed by a second filtration on cellulose filter at 0.9 μm, the two filtrations being carried out in series with a speed of one ton / hour.
Les caractéristiques des combustibles ainsi obtenus sont rassemblées dans le tableau 8. L'échantillon D est préparé à partir de pâtes de neutralisation obtenues essentiellement à partir d'huiles de colza, de soja et de tournesol, l'échantillon E est préparé à partir de pâte de neutralisation obtenue essentiellement à partir d'huile de colza.
Le tableau 9 permet de visualiser l'évolution des caractéristiques influant sur les émissions de poussières au cours du procédé de fabrication du combustible tel que décrit dans la présente invention.Table 9 shows the evolution of the characteristics influencing the dust emissions during the fuel fabrication process as described in the present invention.
Le tableau 9 rassemble les caractéristiques physico-chimiques d'une huile acide stockée dans une cuve (Echantillon N°1). Cette huile acide correspond à une huile acide présentant une teneur en eau supérieure à 1%pds.Table 9 summarizes the physico-chemical characteristics of an acid oil stored in a tank (Sample No. 1). This acidic oil corresponds to an acidic oil having a water content greater than 1% by weight.
L'huile acide stockée dans la cuve subit ensuite un brassage et une étape de centrifugation (5000 tr/min dans un appareil Alpha Laval®) jusqu'à obtenir l'échantillon N°2. L'échantillon N°2 correspond ainsi à une huile acide telle que fournie à l'étape a) du procédé selon la présente invention, avec une teneur en eau inférieure à 1%pds. L'échantillon N°3 résulte de la filtration de l'échantillon N°2 à travers un filtre de 25 microns puis un filtre de 0,9 micron. L'échantillon N°3 correspond à une huile acide combustible telle qu'obtenue à l'étape b) du procédé selon la présente invention.The acid oil stored in the tank then undergoes a stirring and a centrifugation step (5000 rpm in an Alpha Laval® apparatus) until sample No. 2 is obtained. Sample No. 2 thus corresponds to an acidic oil as provided in step a) of the process according to the present invention, with a water content of less than 1% by weight. Sample No. 3 results from the filtration of sample No. 2 through a 25 micron filter followed by a 0.9 micron filter. Sample No. 3 corresponds to a combustible acid oil as obtained in step b) of the process according to the present invention.
Au vu de ces caractéristiques, on note que la centrifugation permet de réduire de manière notable la teneur en cendres et la teneur en sodium (voir Echantillon N°2). On note également une diminution de la teneur en eau ainsi que de la teneur en calcium et phosphore. Cette étape de centrifugation peut ainsi être utilisée pour réduire la teneur en eau mais également pour diminuer la teneur en cendres dans la mesure où la centrifugation semble également permettre de réduire la teneur en phospholipides, qui sont à l'origine du phosphore, et la teneur en métaux (voir tableau 9).In view of these characteristics, it is noted that the centrifugation makes it possible to significantly reduce the ash content and the sodium content (see Sample No. 2). There is also a decrease in the water content as well as in the calcium and phosphorus content. This centrifugation step can thus be used to reduce the water content but also to reduce the ash content insofar as the centrifugation also seems to reduce the phospholipid content, which is the source of phosphorus, and the content made of metals (see Table 9).
Chacune des filtrations ultérieures permet d'abaisser encore ces teneurs (voir Echantillon N°3).Each of the subsequent filtrations makes it possible to lower these contents even further (see Sample No. 3).
On note également que chacun des échantillons N°2 et N°3 présente des teneurs en eau, cendres, calcium, phosphore et sodium inférieures à celles de l'échantillon A et des teneurs en eau, cendres, calcium et sodium du même ordre de grandeur que celles de l'échantillon C de l'exemple 3. On peut donc s'attendre à ce que la combustion de ces échantillons réponde aux exigences en matière d'émissions, notamment de poussières.It is also noted that each of the samples No. 2 and No. 3 has contents of water, ash, calcium, phosphorus and sodium lower than those of the sample A and the contents of water, ash, calcium and sodium of the same order of the sample C of Example 3. It is therefore expected that the combustion of these samples will meet the requirements for emissions, particularly dust.
Le procédé selon l'invention permet ainsi de produire une huile acide combustible présentant une teneur en eau et en cendres réduite.
Claims (12)
cette étape a) comprenant :
this step a) comprising:
Applications Claiming Priority (1)
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FR1556202A FR3038323B1 (en) | 2015-07-01 | 2015-07-01 | PROCESS FOR THE PREPARATION OF A COMBUSTIBLE ACID OIL RESULTING FROM THE ACIDIFICATION OF A NEUTRALIZATION PULP OF VEGETABLE AND / OR ANIMAL ORIGIN. |
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EP3112444A1 true EP3112444A1 (en) | 2017-01-04 |
EP3112444B1 EP3112444B1 (en) | 2019-06-19 |
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EP16177219.9A Active EP3112444B1 (en) | 2015-07-01 | 2016-06-30 | Method for preparing acid fuel oil from the acidification of a soap stock of vegetable and/or animal origin |
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EP (1) | EP3112444B1 (en) |
ES (1) | ES2736103T3 (en) |
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Citations (8)
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CA2541327A1 (en) | 2003-10-09 | 2005-04-28 | The Dallas Group Of America, Inc. | Purification of biodiesel with adsorbent materials |
RU2004119053A (en) * | 2004-06-22 | 2006-01-10 | Государственное научное учреждение "Институт механики металлополимерных систем им. В.А. Белого НАН Беларуси" (BY) | COMPOSITION FOR ANTI-FRICTION COATINGS |
CN1958751A (en) * | 2006-11-21 | 2007-05-09 | 鲁希诺 | Blended fuel oil and manufacturing technique |
US20110203168A1 (en) | 2008-11-28 | 2011-08-25 | Solazyme, Inc. | Novel Triglyceride and Fuel Compositions |
WO2013098524A1 (en) | 2011-12-28 | 2013-07-04 | Total Raffinage Marketing | Fuel composition comprising a heavy fuel oil and a biomass product |
US20130216688A1 (en) * | 2006-09-26 | 2013-08-22 | Novita, Llc | Solvent extraction of oil from distillers dried grains and methods of using extraction products |
US8545703B1 (en) * | 2012-11-27 | 2013-10-01 | Menlo Energy Management, LLC | Production of glycerin from feedstock |
WO2014102492A1 (en) | 2012-12-27 | 2014-07-03 | Total Raffinage Chimie | Fuel composition comprising a heavy fuel oil, and product created from the biomass |
-
2015
- 2015-07-01 FR FR1556202A patent/FR3038323B1/en not_active Expired - Fee Related
-
2016
- 2016-06-30 ES ES16177219T patent/ES2736103T3/en active Active
- 2016-06-30 EP EP16177219.9A patent/EP3112444B1/en active Active
Patent Citations (8)
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CA2541327A1 (en) | 2003-10-09 | 2005-04-28 | The Dallas Group Of America, Inc. | Purification of biodiesel with adsorbent materials |
RU2004119053A (en) * | 2004-06-22 | 2006-01-10 | Государственное научное учреждение "Институт механики металлополимерных систем им. В.А. Белого НАН Беларуси" (BY) | COMPOSITION FOR ANTI-FRICTION COATINGS |
US20130216688A1 (en) * | 2006-09-26 | 2013-08-22 | Novita, Llc | Solvent extraction of oil from distillers dried grains and methods of using extraction products |
CN1958751A (en) * | 2006-11-21 | 2007-05-09 | 鲁希诺 | Blended fuel oil and manufacturing technique |
US20110203168A1 (en) | 2008-11-28 | 2011-08-25 | Solazyme, Inc. | Novel Triglyceride and Fuel Compositions |
WO2013098524A1 (en) | 2011-12-28 | 2013-07-04 | Total Raffinage Marketing | Fuel composition comprising a heavy fuel oil and a biomass product |
US8545703B1 (en) * | 2012-11-27 | 2013-10-01 | Menlo Energy Management, LLC | Production of glycerin from feedstock |
WO2014102492A1 (en) | 2012-12-27 | 2014-07-03 | Total Raffinage Chimie | Fuel composition comprising a heavy fuel oil, and product created from the biomass |
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ES2736103T3 (en) | 2019-12-26 |
FR3038323A1 (en) | 2017-01-06 |
EP3112444B1 (en) | 2019-06-19 |
FR3038323B1 (en) | 2019-05-17 |
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