WO2018137794A1 - Procédé d'extraction pour traiter un mélange ligneux dans une centrifugeuse - Google Patents
Procédé d'extraction pour traiter un mélange ligneux dans une centrifugeuse Download PDFInfo
- Publication number
- WO2018137794A1 WO2018137794A1 PCT/EP2017/071191 EP2017071191W WO2018137794A1 WO 2018137794 A1 WO2018137794 A1 WO 2018137794A1 EP 2017071191 W EP2017071191 W EP 2017071191W WO 2018137794 A1 WO2018137794 A1 WO 2018137794A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- centrifuge
- drum
- mixture
- extraction
- lignin
- Prior art date
Links
- 238000000605 extraction Methods 0.000 title claims abstract description 134
- 239000000203 mixture Substances 0.000 title claims abstract description 133
- 229920005610 lignin Polymers 0.000 title claims abstract description 83
- 239000012530 fluid Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920002488 Hemicellulose Polymers 0.000 claims abstract description 15
- 230000002093 peripheral effect Effects 0.000 claims abstract description 5
- 230000029087 digestion Effects 0.000 claims description 24
- 239000000284 extract Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 7
- 230000002255 enzymatic effect Effects 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 58
- 230000008569 process Effects 0.000 description 36
- 239000007788 liquid Substances 0.000 description 35
- 239000007787 solid Substances 0.000 description 23
- 239000000126 substance Substances 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000002028 Biomass Substances 0.000 description 14
- 238000005406 washing Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 238000012216 screening Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 229920002678 cellulose Polymers 0.000 description 9
- 239000001913 cellulose Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000000835 fiber Substances 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000002023 wood Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 238000000855 fermentation Methods 0.000 description 4
- 230000004151 fermentation Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003534 oscillatory effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000002029 lignocellulosic biomass Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- RYYVLZVUVIJVGH-UHFFFAOYSA-N caffeine Chemical compound CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000011122 softwood Substances 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 235000008694 Humulus lupulus Nutrition 0.000 description 1
- LPHGQDQBBGAPDZ-UHFFFAOYSA-N Isocaffeine Natural products CN1C(=O)N(C)C(=O)C2=C1N(C)C=N2 LPHGQDQBBGAPDZ-UHFFFAOYSA-N 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 241000533293 Sesbania emerus Species 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- VJEONQKOZGKCAK-UHFFFAOYSA-N caffeine Natural products CN1C(=O)N(C)C(=O)C2=C1C=CN2C VJEONQKOZGKCAK-UHFFFAOYSA-N 0.000 description 1
- 229960001948 caffeine Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
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- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 235000008216 herbs Nutrition 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
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- 239000012528 membrane Substances 0.000 description 1
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- 239000012452 mother liquor Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229960002715 nicotine Drugs 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical class CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 238000007670 refining Methods 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
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- 239000011833 salt mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 238000000194 supercritical-fluid extraction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
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- 229940088594 vitamin Drugs 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0203—Solvent extraction of solids with a supercritical fluid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0269—Solid material in other moving receptacles
- B01D11/0273—Solid material in other moving receptacles in rotating drums
- B01D11/0276—Solid material in other moving receptacles in rotating drums with the general transport direction of the solids parallel to the rotation axis of the conveyor, e.g. spirals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B04—CENTRIFUGAL APPARATUS OR MACHINES FOR CARRYING-OUT PHYSICAL OR CHEMICAL PROCESSES
- B04B—CENTRIFUGES
- B04B1/00—Centrifuges with rotary bowls provided with solid jackets for separating predominantly liquid mixtures with or without solid particles
- B04B1/20—Centrifuges with rotary bowls provided with solid jackets for separating predominantly liquid mixtures with or without solid particles discharging solid particles from the bowl by a conveying screw coaxial with the bowl axis and rotating relatively to the bowl
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B04—CENTRIFUGAL APPARATUS OR MACHINES FOR CARRYING-OUT PHYSICAL OR CHEMICAL PROCESSES
- B04B—CENTRIFUGES
- B04B15/00—Other accessories for centrifuges
- B04B15/12—Other accessories for centrifuges for drying or washing the separated solid particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B04—CENTRIFUGAL APPARATUS OR MACHINES FOR CARRYING-OUT PHYSICAL OR CHEMICAL PROCESSES
- B04B—CENTRIFUGES
- B04B3/00—Centrifuges with rotary bowls in which solid particles or bodies become separated by centrifugal force and simultaneous sifting or filtering
- B04B3/02—Centrifuges with rotary bowls in which solid particles or bodies become separated by centrifugal force and simultaneous sifting or filtering discharging solid particles from the bowl by means coaxial with the bowl axis and moving to and fro, i.e. push-type centrifuges
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B04—CENTRIFUGAL APPARATUS OR MACHINES FOR CARRYING-OUT PHYSICAL OR CHEMICAL PROCESSES
- B04B—CENTRIFUGES
- B04B3/00—Centrifuges with rotary bowls in which solid particles or bodies become separated by centrifugal force and simultaneous sifting or filtering
- B04B3/04—Centrifuges with rotary bowls in which solid particles or bodies become separated by centrifugal force and simultaneous sifting or filtering discharging solid particles from the bowl by a conveying screw coaxial with the bowl axis and rotating relatively to the bowl
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B04—CENTRIFUGAL APPARATUS OR MACHINES FOR CARRYING-OUT PHYSICAL OR CHEMICAL PROCESSES
- B04B—CENTRIFUGES
- B04B7/00—Elements of centrifuges
- B04B7/08—Rotary bowls
- B04B7/12—Inserts, e.g. armouring plates
- B04B7/16—Sieves or filters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B04—CENTRIFUGAL APPARATUS OR MACHINES FOR CARRYING-OUT PHYSICAL OR CHEMICAL PROCESSES
- B04B—CENTRIFUGES
- B04B7/00—Elements of centrifuges
- B04B7/08—Rotary bowls
- B04B7/18—Rotary bowls formed or coated with sieving or filtering elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/028—Flow sheets
- B01D11/0284—Multistage extraction
Definitions
- the invention relates to an extraction method for treating a
- centrifuges in various embodiments are widely used and are used in a variety of fields. So come
- discontinuous centrifuges such as peeler centrifuges
- pusher centrifuges are advantageously used.
- centrifuges can be aligned vertically or horizontally with respect to the gravitational field of the earth and can be very specific depending on the application.
- a solid-liquid mixture, a suspension or a wet salt or salt mixture is passed through an inlet pipe via a mixture distributor of a rapidly rotating drum, which is preferably configured as a filter, supplied, so that due to the centrifugal forces acting, the liquid phase is eliminated through the filter, while inside the drum wall under the action of the very strong centrifugal field, which is generated by the rapid rotation of the drum, a solid cake is deposited.
- Pusher centrifuges easily be achieved throughputs in the order of 100 tons per hour, with drum diameter up to 1000 mm and more are quite common and typical rotational frequencies of the drum, depending on the drum diameter of up to 2000
- Rotational frequency of the drum, the amount of mixture supplied per unit time or the drum diameter or the type of pusher centrifuge used also depend on the material to be dehumidified itself, the content of liquid and so on.
- the known from the prior art pusher centrifuges are usually continuous filter centrifuges.
- One-stage and multi-stage pusher centrifuges are known, the multi-stage pusher centrifuge from an outer Screening drum and at least one in the outer screening drum
- screening stage which is also designed as a screen drum consists.
- screening stages can be concentric
- a solid-liquid mixture to be separated passes in the operating state continuously through a fixed inlet pipe in a arranged in the innermost screening stage, also synchronously co-rotating, mixture distributor and is evenly distributed on the innermost screening stage over the entire screen circumference. Most of the liquid is already centrifuged off here and a solid cake is formed.
- a single-stage pusher centrifuge does not include any further screening stages except the outer screening drum.
- the moving soil oscillates, which simultaneously co-rotates synchronously with the outer sieve drum.
- a two-stage pusher centrifuge performs the innermost stage, which is also referred to as the first stage, in addition to the rotational movement about the axis of rotation of an oscillatory movement in the direction of the axis of rotation.
- This oscillatory movement is hydraulically via a thrust piston
- Pusher centrifuges in particular for highly abrasive products, such as e.g. Charcoal and rock phosphate known to be special
- Wear protection measures such as wear-resistant sieves
- special versions for intensive washing processes and to carry out special washing processes such as countercurrent washing at Nitrocellulose are known in the art.
- Gas-tight versions of single-stage and multi-stage pusher centrifuges for operation under a protective gas atmosphere are also used.
- peeler centrifuges The functioning of peeler centrifuges is described here using the example of horizontal peeler centrifuges.
- the solid-liquid separation in horizontal peeler centrifuges is discontinuous in a sequence of specific process steps. According to the product characteristics, the individual process steps take a few minutes to several hours. At the
- the washing liquid is uniformly over the wash tube on the
- the residual layer in the horizontal peeler centrifuge is removed application-specifically after each batch or periodically. With gas pressure surges via nozzles outside the drum, the layer can be blown off via the discharge chute. If the process space is rendered inert, the nitrogen is blown off. In other, preferably smaller centrifuges, the solid can also be removed manually after stopping the centrifuge.
- Centrifuges are particularly suitable for the washing of substances because they have a lower throughput rate as the pusher centrifuges.
- a Centrifugal screw basically consists of a rotor of one
- Full-barrel drum and a screw body mounted therein has. Both are running at a high speed, the worm a
- the mixture to be separated is supplied centrally via an inlet pipe and passes through holes in the screw body in the actual separation space. Due to the centrifugal field, a circular-cylindrical liquid space is formed in the separation space. Due to the density difference between the denser material and the less dense liquid, the solid deposits in the form of a solid cake on the inner wall of the drum. About the solid, the clarifying liquid flows into the channels formed by the screw blades and decanted into the liquid housing.
- Extracting Extractants Caffeine from coffee beans, hop resins from hops, nicotine from tobacco, flavors and dyes and ingredients from a wide variety of spices, aromatic plants and natural products. With supercritical CO2 but also the reverse process, the
- Impregnate done.
- a solid starting material is contacted with the impregnating agent dissolved in the supercritical CO2, whereby the
- Impregnating penetrates into all pores of the starting material. By slowly relaxing, the supercritical CO2 loses the ability to dissolve and the impregnating substance remains evenly distributed in the starting material.
- WO 96/33861 A1 describes a continuous extraction process and a corresponding extraction apparatus. For extracting oils by compressing and extracting an oily raw material in
- a substantially cylindrical reactor provided with inlets and outlets is provided for this purpose.
- a screw press is provided, which conveys the raw material from the inlet under compression to the outlet of the reactor, wherein at the same time the extra niksfluid is introduced under pressure into the reactor.
- an oil or an extracted substance is obtained, from which subsequently the extraction fluid can be removed.
- the devices for extraction and the need are identical to the devices for extraction and the need.
- centrifuges are known in which, for example by means of a supply line and a nozzle, a solvent on the in a in the Centrifuge drum arranged sieve sedimented mixture is sprayed.
- these centrifuges have the disadvantage that in addition to the limited volume in the centrifuge drum lines and nozzles are still to order, so that the known centrifuges are structurally complicated and expensive to manufacture in terms of manufacturing.
- centrifuges have long been well known to those skilled in the art and are e.g. in the standard work "industrial centrifuges", by Prof. W. Stahl, DRM PRESS, described in detail.
- the main components of any wood or biomass-based fiber used, for example, in the paper industry consist of
- the lignin extraction is not only of interest to the paper industry. In the near future, the extraction of lignin via various lignin digestion processes will be an integral part of industrial raw material extraction.
- the biomass is not only suitable as an energy source, but also provides a source of various polymers that can be used as adhesives or binders.
- the most widely used lignin extraction process is the sulfate process (Kraft digestion).
- sulfate process wood chips or crushed plant parts are boiled for several hours at elevated pressure (7- 10bar) in sodium hydroxide solution with sodium sulfide and sodium sulfate. This results in a cleavage of the lignin in the so-called black liquor (soluble alkali lignin).
- black liquor soluble alkali lignin
- Liquid Hot Water uses deionized water under pressure at temperatures up to 260 degrees Celsius.
- hemicellulose and lignin are dissolved out of the cellulose dressing, which then passes through Concentration and cooling are precipitated in different stages. The cellulose can then be further processed in fermentation processes.
- alkali-resistant pressure reactors needed.
- the need for high pressures in the reactors requires a lot of energy.
- a major disadvantage of the known Organosolv process is their procedurally demanding structure.
- the use of acid or bases in the prehydrolysis of the biomass requires reactors which are corrosion resistant.
- not only organic solvents are used in the process but also other reagents (redox catalysts or others), whereby recycling is required in order to minimize the environmental impact.
- a major disadvantage of the known Aquasolv process and the LHW process is the low lignin yield. For most hardwoods only up to 80% removal of lignin and softwoods up to 45-60% solubility and thus extraction of lignin is possible. Of
- Extraction process to propose an extraction process for the treatment of a lignin-containing mixture, which largely avoids the disadvantages known from the prior art, in particular to propose a centrifuge for carrying out an extraction process and an extraction process for the treatment of a mixture, the constructive and
- the process would proceed as follows.
- a decanter would be charged with the fiber reaction mixture.
- high pressures are achieved (20-100bar).
- the fiber reaction mixture migrates slowly through the decanter, the educt mixture (water, sodium hydroxide solution, sodium sulfide, sodium sulfate) being continuously sprayed onto the fiber mass located in the gravitational field, and this in the gravitational field
- Discharge tank is discharged. If several decanters are connected in series, the extracted fiber mixture can subsequently be washed with water to remove the rest of the black liquor and then optionally bleached in a following decanter. This process has the advantages, compared to the prior art, that no pressure reactors are required, which is a great deal
- a lignin-containing mixture in a centrifuge arrangement.
- Delivery opening from the conveyor into the centrifuge drum is applied to the deposited on the inside of the drum screen mixture that lignin and hemicellulose are extracted from the mixture by means of the extraction fluid.
- the centrifuge assembly includes a centrifuge with a rotatable about a drum axis
- centrifuge drum having an inlet opening and a
- the centrifuge drum can be supplied with a mixture via the inlet opening.
- a drum screen is provided, in which a standing under the drum pressure generated by the rotation mixture is deductible.
- Inside the centrifuge drum is a conveyor with a
- Solvent be fed into the centrifuge drum such that from the deposited on the inside of the drum screen mixture, an extractant can be extracted.
- the mixture of the drum can be fed, wherein the mixture due to the rotation of the centrifuge, in particular the Drum, and in particular due to the high speed and the high centrifugal force acting on the inside of the drum can be brought quickly to the rotary pressure, so that the mixture, preferably a biomass, more preferably a vapor-saturated biomass, on the inner wall of the drum of a fast , high and efficient
- the mixture is heated and acted upon with hot Extra komsfluid, in particular that the extract is rapidly separated by the rotation in the centrifuge from the mixture to prevent reconstitution of the lignin.
- the extraction fluid is water, as a lignin of particularly high quality is obtained.
- a mixture is generally to be understood as meaning that the mixture consists of at least two substances, it being possible for the mixture to be a homogeneous or heterogeneous mixture, and for the substances to be solid, liquid or gaseous.
- Mixture in particular the mixture which can be supplied via the inlet opening, can be a liquid phase and / or a solid phase, wherein the
- a solid phase may also be a colloidal liquid, and / or comprise a gas phase.
- the settable mixture which is under rotary pressure may be the solid phase or colloidal
- a lignin-containing mixture is generally understood to mean a mixture that contains a biomass, in particular a Biomass mixture of different origin and composition.
- the lignin-containing mixture comprises lignocelluloses, ie in particular lignin and its derivatives, hemicellulose and cellulose.
- a lignin-containing mixture may be understood to be woody or agricultural waste or raw material from livestock and agriculture.
- the lignin-containing mixture may be mixed with a liquid and / or a solution.
- an extractant is generally understood to mean lignin and its derivatives and hemicellulose which has been extracted from the mixture by the extraction methods described.
- an extract is generally to be understood as meaning, in general, the liquid extract from the lignin-containing mixture, which is obtained after centrifuging and contains lignin and other extractants.
- an extra komfluid is generally understood to mean water, which is in particular in gaseous and / or liquid and / or supercritical and / or vaporous state.
- a residual lignin is generally to be understood as meaning the remainder of lignin, which is not in a preceding one
- a digestion is generally understood to mean a physical and / or chemical and / or biological digestion.
- a digestion is a process in which sparingly soluble substances, with the aid of physical, chemical or biological decomposition agents, are converted into soluble compounds and / or states and / or a process for opening cells.
- a partial digestion is a process in which plant material is not defibrillated by chemical treatment alone, but the half-pulp thus obtained is further defibrated by physical methods.
- Under an enzymatic treatment is in the following generally a biochemical and / or biotechnological and / or to understand microbiological treatment with an enzyme complex.
- a solvent is generally understood to mean a substance which, in particular, is in gaseous and / or liquid and / or supercritical and / or vaporous state and dissolves out a constituent of a mixture.
- a solvent may be an aqueous solvent and / or an organic solvent,
- the rotational pressure is caused by the rotation of the centrifuge, in particular the drum, the centrifugal force acting on the inside of the drum. Under the rotary pressure, especially a high
- Rotational pressure hereinafter a rotary pressure with a with a rotary pressure range of 1 to 200 bar, preferably 1 to 100 bar, particularly preferably 10 to 100 to understand bar.
- the centrifuge may be a vertically or horizontally mounted centrifuge, a continuous or discontinuous centrifuge, in particular a peeler centrifuge, sliding centrifuge, single or multi-stage pusher centrifuge, double pusher centrifuge or vibrating centrifuge or a
- the drum can be rotatable in a first direction of rotation.
- the drum can be rotatable at a drum speed of 1 to 10,000 revolutions per minute, preferably at 500 to 10 000 revolutions per minute, more preferably at 1000 to 4000
- the drum may be hollow cylindrical, preferably formed as a first hollow cylinder.
- the drum can also have a round and / or circular and / or elliptical cross section in a radial direction, that is to say orthogonal to the drum axis.
- the drum may also have a prism-like shape and / or be formed as a prism and in the radial direction a triangular and / or have rectangular and / or polygonal cross-section.
- the tunnel may be drivable with a first motor, in particular a frequency-controlled first motor, in order to be able to use the drum to control the throughput quantity and the throughput time of the mixture.
- the drum can outside, so for example on an outside of the drum against
- the extraction process for treating a lignin-containing mixture can be carried out in various ways.
- the lignin-containing mixture may be heated to the starting temperature prior to introduction into the centrifuge, the mixture may also be heated upon delivery or a centrifuge may have a heater which brings the mixture to the desired starting temperature.
- the extraction fluid and / or the solvent may be gaseous and / or liquid and / or supercritical and / or vaporous.
- the lignin extraction process provides lignin and hemicellulose of high quality, which is not affected by the process
- the lignin extraction method provides a chemistry-free variant
- the ejection element in the form of a helical coil is formed with an ejection surface, preferably the ejection element is an ejection screw, and the ejection element is rotatable in the operating state to an ejection axis such that the mixture with the ejection surface along the ejection axis is movable, or Ejection element is a push floor device and the
- Push floor device is in the operating state so along the
- Ausausossachse arranged to move back and forth, that the mixture with the push floor device, preferably with a thrust surface of the
- the ejection element may preferably be arranged at a small distance from the inside of the drum in the drum.
- the ejection element can be arranged at least partially at the outlet opening of the drum.
- the ejection axis may preferably coincide with the drum axis, wherein the ejection axis can also assume a different position from the drum axis.
- the ejection element can, in particular the
- Ejection screw be rotatable in the first direction of rotation like the drum and with an output speed of 0 to 300 revolutions per minute Turning differential rotation to the drum speed, preferably 0 to 150 revolutions per minute, more preferably 0 to 50 revolutions per minute, in particular 5 to 15 or 0 to 20 revolutions per minute
- the ejection element may be drivable with a second motor, in particular a frequency-controlled second motor, in order to operate with the
- the ejection element can, in particular when it is designed as a sliding floor device, in the operating state either an oscillatory relative movement between the moving floor device and the immovable in the axial direction of the drum and / or between one or more possibly existing drums perform, so back and forth to be movable.
- the rotation and / or the oscillatory movement of the ejection element can preferably via a push rod or a
- the mixture is feasible in a structurally simple manner in the drum and out of the drum executable.
- the ejection element comprises a hollow shaft, wherein the hollow shaft preferably has an inlet opening and / or a
- Outlet opening particularly preferably the hollow shaft circumferentially one or more inlet openings and / or one or more
- Push rod or a conveyor shaft may preferably be designed as a hollow shaft.
- the hollow shaft may have a hollow cylindrical shape, and preferably also be designed as a second hollow cylinder.
- the hollow shaft can also have a round and / or circular and / or elliptical cross section in a radial direction, that is to say orthogonal to the ejection axis.
- the hollow shaft and a prism-like shape and / or be formed as a prism and in the radial direction have a triangular and / or rectangular and / or polygonal cross-section.
- the hollow shaft thus allows with the
- a first pressure and / or a second pressure different from the first pressure and / or a first temperature and / or a second temperature different from the first temperature can be set. If a lower pressure and / or a lower temperature are then set in the centrifuge first and then a higher pressure and / or a higher temperature, several extraction substances can be successively dissolved out of the mixture in order to avoid subsequent separation of the individual extraction substances.
- only hemicellulose can be dissolved in a centrifuge under a pressure of 10-25 bar, in particular at 20 bar and at a temperature of 100 to 180 degrees Celsius, in particular at a temperature of 120 to 160 degrees Celsius.
- a cavitation rotor is provided in the drum, the cavitation rotor preferably between the
- Inlet opening of the drum and the ejection element is arranged, particularly preferably the Kavitationsrotor in the operating state by a
- Rotor axis is rotatable.
- the cavitation rotor is rotatable in a second direction of rotation.
- the first direction of rotation and the second direction of rotation can match, wherein preferably the second direction of rotation is opposite to the first direction of rotation.
- Rotor axis may coincide or take a different position in space.
- the cavitation rotor can
- the cavitation rotor can also have a round and / or circular and / or elliptical cross section in a radial direction, that is to say orthogonal to the rotor axis.
- the cavitation rotor may also have a prism-like shape and / or be formed as a prism and have a triangular and / or rectangular and / or polygonal cross-section in the radial direction.
- the cavitation rotor can be driven by a third motor, in particular a frequency-controlled third motor, in order to be able to use the cavitation rotor to control the throughput quantity and the throughput time of the mixture.
- the first engine and the second engine and the third engine may be the same engine or different engines.
- the drive device may for the first, second and / or third motor, a direct clutch and / or a
- the mixture is additionally in a very short time, so in 1 to 10 seconds, preferably 3 to 8 seconds, mixed and cavitated, i. mechanical forces act on the mixture and thus ensure better mixing of the mixture.
- the mixture due to the rotation of the
- Cavitation rotor in the opposite direction additionally mechanically treated and / or better mixed.
- an extract can be removed into a container in the extraction process.
- the container can a
- Extractant are partially precipitated. Dominates in the container a certain pressure and / or a certain temperature can
- Hemicellulose and lignin are partially precipitated.
- hemicellulose and lignin can be partially precipitated by concentrating the extract in several steps and thus precipitating the less soluble substance first.
- at least a first centrifuge and a second centrifuge can be arranged in series in the extraction process, so that the lignin-containing mixture is first subjected to a first extraction step in the first centrifuge, and then from the first centrifuge to perform a second extraction step of the second centrifuge is supplied.
- the extraction step may be a digestion, a partial digestion or an enzymatic treatment.
- switched centrifuges can be extracted from the mixture, the extractants not only sequentially, but the extraction time can be reduced. In addition, the yield of extractants will be increased.
- the various process steps can also be carried out in a centrifuge in successive steps. In particular, in a first centrifuge under a pressure of 10-25 bar, in particular at 20 bar and at a temperature of 100 to 180 degrees Celsius, in particular at a temperature of 120 to 160 degrees Celsius, only hemicellulose can be dissolved in a second centrifuge To dissolve lignin.
- an organic solvent located on the inside of the drum screen are applied to remove the residual lignin.
- a digestion and / or partial digestion of the lignin-containing mixture can be carried out.
- the lignin-containing biomass can be mechanically disrupted by the cells are digested with a mortar and / or ultrasound and / or cavitation and / or a press and / or shear forces and / or pressure relief.
- the lignin-containing biomass can be non-mechanically digested by the cells are enzymatically digested and / or denatured and / or the membrane lipids are dissolved and / or by saponification of Membraniipide.
- the lignocellulosic biomass can be non-mechanically digested by the cells are enzymatically digested and / or denatured and / or the membrane lipids are dissolved and / or by saponification of Membraniipide.
- the lignocellulosic biomass can be non-mechanically digested by the cells are enzymatically digested and / or denatured and / or the membrane lipids are dissolved and / or by saponification of Membraniipide.
- Disintegrating agents are converted into soluble compounds.
- mechanical digestion methods such as the grinding method and / or the refining method or the chemical-technical method, such as the sulphate method and / or the sulphite method and / or the soda method can be used for digestion.
- the centrifuge assembly may in the extraction process, the centrifuge assembly and / or one of the centrifuges a
- Feed along a discharge axis of the conveyor are in particular formed as a nozzle and / or as a bore.
- the centrifuge assembly and / or a centrifuge of the assembly may include a heater to the mixture heat.
- the centrifuge assembly may also have a heater at the inlet port and / or in front of the inlet port to heat the mixture prior to introduction.
- the centrifuge assembly may consist of several series-connected centrifuges. Different temperatures and / or pressures can prevail in the different centrifuges, so that different components of the mixture, in particular lignin and
- Extraction steps take place a digestion and / or a partial digestion and / or an enzymatic treatment.
- an extraction step with an organic solvent in particular ethanol and / or methanol and / or ethylene glycol can take place.
- Tank pressure can be guided out of the drum. Because of the fast
- the lignin-containing mixture is a biomass or a
- Biomass mixture is, for example, lignocelluloses which are mixed with water or another solvent, are by the
- the relaxation tank is a
- the centrifuge arrangement may comprise a condenser, wherein the condenser is preferably arranged on the expansion tank, so that the expanded mixture, in particular the extraction fluid, by means of
- the centrifuge assembly may also comprise a further ejection screw, wherein the further ejection screw is preferably arranged on the expansion vessel, so that the relaxed mixture, in particular the relaxed solid cake, in or on or from the flash tank is feasible.
- the condenser advantageously makes it possible to liquefy the extraction fluid, in particular gases and vapors, as well as entrained substances by means of condensation and thus allows the extraction fluid to be fed to a further fractionation or recycling.
- the further ejection screw which can also be an ejection element, can be arranged on the expansion vessel, preferably connected to the expansion vessel or also in this
- the further ejection screw makes it possible to lead the mixture away from the centrifuge arrangement, in particular further
- the centrifuge assembly comprises a
- Pump preferably a high-pressure solids pump, wherein the pump
- the centrifuge assembly preferably at the inlet opening, particularly preferably outside the Drum is arranged, and / or the centrifuge assembly a
- Steam generator includes, wherein the steam generator preferably at the
- the pump may be a frequency-controlled pump and / or be controllable by a transmission.
- the pump has the advantage that the mixture, before it can be supplied to the centrifuge, in particular the drum and / or the cavitation rotor via the inlet opening of the drum, can additionally be brought to a pump pressure.
- the steam generator has the advantage that the mixture, before it can be supplied to the centrifuge, in particular the drum and / or the cavitation rotor via the inlet opening of the drum, additionally a gas, preferably a water vapor, can be supplied.
- Fig. 1 shows a first embodiment of the inventive
- Fig. 2 shows another embodiment of the inventive
- FIG. 3 shows a first embodiment of the inventive
- Fig. 4 shows a further embodiment of the inventive
- Figure 1 shows a schematic representation of a first
- Embodiment of the inventive centrifuge assembly with a centrifuge 1 for performing an extraction method Embodiment of the inventive centrifuge assembly with a centrifuge 1 for performing an extraction method.
- Centrifuge assembly comprises a centrifuge 1 with a centrifuge drum 2, which comprises an inlet opening 22 and an outlet opening 23, and has a hollow cylindrical shape, preferably formed as a first hollow cylinder. Furthermore, the centrifuge Z, Z1, Z2 comprises a
- Cavitation R which comprises an inner circumferential surface R2 and blind holes R1 and preferably between the inlet opening 22 of the
- Centrifugal drum 2 and the ejection element 4 is arranged, particularly preferably the cavitation R in the operating state about a rotor axis which is equal to the drum axis T, is rotatable.
- the cavitation rotor Through the cavitation rotor, the mixture G can be supplied to the centrifuge drum 2 while being mixed and heated.
- the addition of the extraction fluid E can also take place via the cavitation rotor R.
- the centrifuge drum 2 is in the operating state about a drum axis T such in a first
- Drum sleeve 21 in particular an inner drum shell surface, a standing under a rotary pressure mixture is deductible.
- Centrifuge drum 2 is arranged an ejection element 4, wherein the ejection element 4 is preferably at least partially disposed at the outlet opening 23.
- the centrifuge assembly comprises
- the conveyor 41 is formed as a centrifuge screw 41 1 and comprises a conveying opening 42, via which the extraction fluid E is applied to the mixture G in the operating state.
- the centrifuge assembly further comprises a
- Expansion tank 5 wherein in the expansion tank 5, a lower container pressure can be formed compared to the rotary pressure.
- Outlet opening 23 of the centrifuge drum 2 is at one
- Receiving opening of the expansion tank 5 is arranged and the offset under the rotation pressure mixture so with the ejection element 4 via the outlet opening 23 in the flash tank 5 from the
- Centrifuge drum 2 dischargeable, that the mixture G under the lower pressure vessel of the flash tank 5 explosively relaxed, and thus mechanical can be unlocked.
- the mixture in particular the settleable mixture, can be released explosively.
- a further extraction step ES, ES1, ES2 can take place in a series-connected centrifuge Z, Z1, Z2, in that the mixture G is transferred by the discharge device 51 into the subsequent centrifuge Z, Z1, Z2.
- FIG. 2 shows a schematic representation of another
- Embodiment of the inventive centrifuge assembly with a centrifuge 1 for performing an extraction method Embodiment of the inventive centrifuge assembly with a centrifuge 1 for performing an extraction method.
- Centrifuge assembly comprises a centrifuge 1 with a centrifuge drum 2, which comprises an inlet opening 22 and an outlet opening 23, and a hollow cylindrical shape with a conical part 7, in
- An ejection element 4 is arranged in the centrifuge drum 2, wherein the ejection element 4 is preferably arranged at least partially at the outlet opening 23.
- the centrifuge assembly comprises an ejection element 4 with a
- the conveyor 41 is a centrifuge screw 41 1 and comprises a conveying opening 42, via which in
- Figure 3 shows a first embodiment of the inventive
- FIG. 4 shows a further embodiment of the extraction process according to the invention in a centrifuge arrangement and can be described as follows.
- a lignin-containing mixture G becomes a first
- Centrifuge Z1 is supplied and is subjected to a digestion A and / or a partial digestion tA in a first extraction step ES1.
- the centrifuge Z1 can be a centrifuge according to FIG. 1, in which a mechanical digestion via abrupt relaxation takes place.
- the lignin-containing mixture G is transferred to a second centrifuge Z2 and extracted there in a second extraction step ES2 more of the extractant EXn.
- FIG. 5 shows a further embodiment of the extraction method according to the invention in a centrifuge arrangement and can be described as follows.
- a lignin-containing mixture G is fed to a first centrifuge Z1 and is treated in a first extraction step ES1 with an extraction fluid E, in particular water.
- the lignin-containing mixture G is transferred to a second centrifuge Z2 and extracted there in a second extraction step ES2 with a solvent L, in particular an organic solvent, the Restlignin.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Centrifugal Separators (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
La présente invention concerne un procédé d'extraction destiné à être réalisé dans une installation de centrifugation, comprenant une centrifugeuse (Z, Z1, Z2) munie d'un tambour centrifuge (2) agencé à rotation autour d'un axe de tambour (T) et qui s'étend avec une enveloppe de tambour (21) d'un orifice d'admission (22) à un orifice d'évacuation (23) le long de l'axe de tambour (T). Sur une surface périphérique intérieure (24) de l'enveloppe de tambour (21) est prévu un tambour cribleur (3) dans lequel est agencé un élément d'éjection (4) qui comprend un dispositif de transport (41) muni d'un orifice de transport (42), un mélange (G) étant acheminé par l'orifice d'admission (22) jusqu'au tambour centrifuge (2) en fonctionnement, et le tambour centrifuge (2) tournant autour de l'axe de tambour (T), de telle sorte que le mélange (G) se trouvant à une pression de tambour (P) produite par la rotation se dépose sur la face intérieure du tambour cribleur (3) et le mélange (G) est un mélange (G) ligneux qui est chauffé à une température de départ de 100 à 400 °C, et au moyen du dispositif de transport (41) au cours d'une étape d'extraction (ES, ES1, ES2), un fluide d'extraction (E), sous forme d'eau très chaude à une pression d'extraction de 1 à 150 bar et à une température d'extraction de 100 à 400 °C, est acheminé dans le tambour centrifuge (2) et est appliqué, via l'orifice de transport (42), du dispositif de transport (41) jusque dans le tambour centrifuge (2) sur le mélange déposé sur la face intérieure du tambour cribleur (3), de manière à extraire du mélange (G) la lignine et l'hémicellulose à l'aide du fluide d'extraction (E).
Applications Claiming Priority (2)
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US201762451371P | 2017-01-27 | 2017-01-27 | |
US62/451371 | 2017-01-27 |
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WO2018137794A1 true WO2018137794A1 (fr) | 2018-08-02 |
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PCT/EP2017/071191 WO2018137794A1 (fr) | 2017-01-27 | 2017-08-23 | Procédé d'extraction pour traiter un mélange ligneux dans une centrifugeuse |
PCT/EP2017/071187 WO2018137792A2 (fr) | 2017-01-27 | 2017-08-23 | Procédé d'extraction pour le traitement d'un mélange dans un ensemble de centrifugation, ensemble de centrifugation |
PCT/EP2017/071188 WO2018137793A1 (fr) | 2017-01-27 | 2017-08-23 | Ensemble centrifugeuse, procédé de détente pour le traitement d'un mélange |
PCT/EP2017/071192 WO2018137795A1 (fr) | 2017-01-27 | 2017-08-23 | Centrifugeuse, procédé d'extraction permettant de traiter un mélange et utilisation d'une centrifugeuse |
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PCT/EP2017/071187 WO2018137792A2 (fr) | 2017-01-27 | 2017-08-23 | Procédé d'extraction pour le traitement d'un mélange dans un ensemble de centrifugation, ensemble de centrifugation |
PCT/EP2017/071188 WO2018137793A1 (fr) | 2017-01-27 | 2017-08-23 | Ensemble centrifugeuse, procédé de détente pour le traitement d'un mélange |
PCT/EP2017/071192 WO2018137795A1 (fr) | 2017-01-27 | 2017-08-23 | Centrifugeuse, procédé d'extraction permettant de traiter un mélange et utilisation d'une centrifugeuse |
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CN114210091A (zh) * | 2021-11-05 | 2022-03-22 | 广州市博之越精细化工有限公司 | 一种用于克斑的植物天然成分提取工艺 |
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GB2289055A (en) | 1994-04-28 | 1995-11-08 | Steiner Hops Ltd | Extraction of hops |
FR2820735B1 (fr) | 2001-02-14 | 2004-05-14 | Vivendi Water Systems | Procede et installation pour l'hydrolyse thermique des boues |
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DE10115381A1 (de) * | 2001-03-28 | 2002-10-24 | Heinkel Ag | Stülpfilterzentrifuge |
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DE102009020745A1 (de) | 2009-05-11 | 2010-11-25 | Chemische Fabrik Budenheim Kg | Phosphatgewinnung auf Klärschlamm |
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- 2017-08-23 WO PCT/EP2017/071188 patent/WO2018137793A1/fr active Application Filing
- 2017-08-23 WO PCT/EP2017/071192 patent/WO2018137795A1/fr active Application Filing
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DE3631470C1 (de) | 1986-09-16 | 1993-05-06 | Westfalia Separator Ag | Verfahren zur Rueckgewinnung von Bier |
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WO2018137792A2 (fr) | 2018-08-02 |
WO2018137795A1 (fr) | 2018-08-02 |
WO2018137793A1 (fr) | 2018-08-02 |
WO2018137792A3 (fr) | 2019-07-18 |
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