SE543463C2 - A tall oil rosin fraction - Google Patents
A tall oil rosin fractionInfo
- Publication number
- SE543463C2 SE543463C2 SE1951007A SE1951007A SE543463C2 SE 543463 C2 SE543463 C2 SE 543463C2 SE 1951007 A SE1951007 A SE 1951007A SE 1951007 A SE1951007 A SE 1951007A SE 543463 C2 SE543463 C2 SE 543463C2
- Authority
- SE
- Sweden
- Prior art keywords
- cto
- stream
- tall oil
- column
- present
- Prior art date
Links
- 239000003784 tall oil Substances 0.000 title claims abstract description 31
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 30
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 28
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 18
- 229930195729 fatty acid Natural products 0.000 claims abstract description 18
- 239000000194 fatty acid Substances 0.000 claims abstract description 18
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims description 15
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 abstract description 9
- 238000005194 fractionation Methods 0.000 description 42
- 238000001704 evaporation Methods 0.000 description 32
- 230000008020 evaporation Effects 0.000 description 31
- 238000000034 method Methods 0.000 description 24
- 239000000203 mixture Substances 0.000 description 13
- 238000012856 packing Methods 0.000 description 13
- 241000779819 Syncarpia glomulifera Species 0.000 description 12
- 239000001739 pinus spp. Substances 0.000 description 12
- 229940036248 turpentine Drugs 0.000 description 12
- 150000007513 acids Chemical class 0.000 description 10
- 238000002203 pretreatment Methods 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 2
- MLBYBBUZURKHAW-UHFFFAOYSA-N 4-epi-Palustrinsaeure Natural products CC12CCCC(C)(C(O)=O)C1CCC1=C2CCC(C(C)C)=C1 MLBYBBUZURKHAW-UHFFFAOYSA-N 0.000 description 2
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KGMSWPSAVZAMKR-UHFFFAOYSA-N Me ester-3, 22-Dihydroxy-29-hopanoic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(=C(C)C)C=C1CC2 KGMSWPSAVZAMKR-UHFFFAOYSA-N 0.000 description 2
- KGMSWPSAVZAMKR-ONCXSQPRSA-N Neoabietic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CCC(=C(C)C)C=C2CC1 KGMSWPSAVZAMKR-ONCXSQPRSA-N 0.000 description 2
- MLBYBBUZURKHAW-MISYRCLQSA-N Palustric acid Chemical compound C([C@@]12C)CC[C@@](C)(C(O)=O)[C@@H]1CCC1=C2CCC(C(C)C)=C1 MLBYBBUZURKHAW-MISYRCLQSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000011552 falling film Substances 0.000 description 2
- 235000021588 free fatty acids Nutrition 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000010665 pine oil Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/02—Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B1/00—Production of fats or fatty oils from raw materials
- C11B1/02—Pretreatment
- C11B1/04—Pretreatment of vegetable raw material
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/12—Refining fats or fatty oils by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Microbiology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
The present invention relates to a tall oil rosin fraction comprising at least 85 wt% rosin acid content and maximum 5 wt% fatty acid content.
Description
A TALL OIL ROSIN FRACTION Field of the invention The present invention relates to continuous fractionation of CTO (crude tall oil) toRTD (refined tall diesel).
Technical Background The term Crude Tall Oil, in the following CTO, refers to a by-product stream obtainedduring pulping of wood in the Kraft pulping process. The name tall oil (TO) originated asanglicization of Swedish "tallolja" ("pine oil"). The TO comprises of fraction having acidicproperties (-COOH functional group) typically about 75- 80 wt.% and neutral fraction up to25 wt.%. The latter fraction is often referred to as unsaponifiable fraction. Theunsaponifiable fraction comprises of wide spectrum of components such as hydrocarbons,fatty alcohols, phytosterol-type alcohols, aldehydes, etc. as well as high molecular weightcomponents originating from internal reactions between constituents of acidic and neutralfractions. The fraction comprised of components with acidic functionality on the other hand,can be further subdivided into two large fractions namely, (i) fatty acids fraction and (ii)rosin acids fraction each containing a number of individual components. From thisdescription of the tall oil composition it is obvious that the CTO represents an attractive poolof renewable fine chemicals, which are nowadays gaining much attention in view ofstringent environmental regulations and rising prices of fossil oils.
At present, CTO fractionation is done typically by vacuum distillation. The objectivesare rather straight forward, to split the CTO into two fraction (i) acidic fraction up to 75 wt.%and (ii) fraction of less importance called tall oil pitch (TOP). The acidic fraction is furtherprocessed in a sequence of fractionation towers operating at high temperatures andrelatively high vacuum to obtain streams enriched in fatty acids (tall oil fatty acids, TOFA),rosin acids (tall oil rosin acids, TOR) and distilled tall oil (DTO).
Typically, the TOP is returned to the pulp mills and utilized as internal fuel or fired asbiofuel in heat and power plants. lt is important to minimize the fraction of TOP producedwithin CTO refining processes and the present invention is directed to an energy efficientprocess for CTO refining with high yield of valuable chemicals and biofuels for automotiveuse.
One process for the refining of CTO is described in WO2014/098763.WO2014/098763 discloses a process for refining of crude tall oil (CTO), said process comprising fractionation under vacuum of a refined CTO into at least one stream of refined 2tall diesel (RTD) or tall oil fatty acids (TOFA), the RTD or TOFA comprising from 2 - 30% by volume of rosin acids and from 20 - 90% by volume of fatty acids, and at least one stream ofrosin acid(s) (RA) comprising less than 5 % by volume of fatty acids. The stream of RTD orTOFA is deoxygenated forming hydrocarbon compounds in a subsequent step.
One aim of the present invention is to provide an improved process and system forcontinuous fractionation of CTO to RTD where the energy usage is lowered and optimizedand where the total yield is increased.
Summary of the invention The stated purpose above is achieved by a process for continuous fractionation ofCTO (crude tall oil) to RTD (refined tall diesel), said process comprising: - when removing a stream of TOP (tall oil pitch) the CTO is fed though at least twoevaporation zones arranged in series so that one stream of CTO is fed from a firstevaporation zone to a second evaporation zone, wherein a TOP stream is produced and fedfrom the second evaporation zone, wherein a first vapor stream is produced within the firstevaporation zone and a second vapor stream is produced within the second evaporationzone and wherein there is a temperature difference of at least 10°C between the first vaporstream and the second vapor stream; and - feeding the first vapor stream and the second vapor stream into a subsequentfractionation column to produce a stream of RTD from the fractionation column, whereinthe first vapor stream and the second vapor stream are being fed to different positions,relative to the column height, in the fractionation column, which different positions in thefractionation column are separated by packing means, such as structured packing.
The core of the present invention refers to ensuring that two vapor streamsproduced within the different evaporation zones, said two vapor streams having atemperature difference of a t least 10°C, are fed to a subsequent fractionation column atdifferent positions relative to the column height, which are separated from each other bypacking means (structured packing). We have surprisingly found that applying thisinnovative arrangement within the present invention provides means for reducing theenergy needed for fractionation. Furthermore, as the present invention enables the use oflower processing temperatures, which is particularly advantageous when treating heatsensitive components, it provides means for an improved total yield. Yet another advantagein applying the arrangement of the present invention is not only to allow for an improved total yield but also to produce a higher quality composition of the products out from the 3 fractionation column as the rate of the degradation reactions of valuable components isdecreased with the use of lower processing temperatures. The utilization of an arrangementwith two evaporation zones provides two evaporation streams, where the profile of the firstvapor stream, comparatively speaking, is fatty acid rich, and the profile of second vaporstream is rosin rich. To take advantage of this preliminary separation these two vaporstreams are then sent to a subsequent fractionation column at two different positionsrelative to the column height, where different conditions are applied to ensure suitablefractionations of a more fatty acid rich material and a more rosin rich material, respectively.The technical effect of this innovative arrangement is that the first vapor stream rich in fattyacids is sent into the column section holding similar composition and where the targetedvapor/liquid equilibrium for further fractionation are already established. The same is validfor the entry point of the second vapor stream which is sent into the column section holdingsimilar composition and where the targeted vapor/liquid equilibrium for furtherfractionation are already established. Thus, within the respective column sections, thestreams are directly exposed to fractionation without disturbing the temperature andcompositional gradients at the respective column heights hence eliminating the need oftemperature adjustment either applying heat or cooling down which in turn leads to energysavings. One alternative to the arrangement in the present invention is to combine the twovapors before or within the column but losing the advantage of the preliminary separationwithin the two evaporation zones and hence the need for an additional energy to getfractionation going. Another alternative is to send the two vapors to two separate columnshence increasing the capital cost of the unit and very likely increasing the energyconsumption because of operating at least one additional unit. Yet, another alternative is tocondense the vapors and feed these either separate or combined in fractionation column(s).The negative effects of this alternative are (i) product quality deterioration as the repetitiveexposure of the valuable components to high temperature during re-evaporation; (ii)decrease of the total yield as result of (i); (iii) the use of an additional energy to re-evaporatethe material and (iv) an increased capital costs for vapor condensation, transportation viapumping, additional pipping, etc. Thus, the arrangement within the present invention solvesall problems and avoids the negative effects associated with these alternative approacheswhile keeping the energy consumption required for the fraction to a minimum and improving both total yield and quality of the valuable components. 4 Moreover, employing two evaporation zones in series enables greater flexibilitytowards CTO feed of varying compositions. Thus, for the processing of CTO with higher fattyacid content more energy can be supplied within the first evaporation zone whereas for theprocessing of the CTO with high rosin acid content more energy would be supplied withinthe second evaporation zone.
Moreover, employing two evaporation zones in series enables for more efficientutilization of the energy needed for the vaporization of valuable CTO components as well asconsiderably lowering the peak temperatures of the heat transfer media used for energysupply within the evaporation zones. The use of lower peak temperatures minimizes theunwanted thermal decomposition of the valuable CTO components, thus decreasing thetotal yield.
Moreover, it may be said that the temperature of second vapor stream is intendedto be a higher than the temperature of first vapor stream according to the presentinvention.
Furthermore, the structured packing means may suitably be a corrugated metalplates or gauzes forcing the fluids and vapors to take complicated paths through the columnthus maximizing the contact area between different phases liquid/vapor. Furthermore, andas may be understood from fig. 1, the first and second vapor streams are sent to one andthe same fractionation column to enable continuous production of RTD.
The energy needed within the fractionation column is provided by a re-boiler wheresuitable process units are such characterized by short residence time, for example but notlimited to a thin-film evaporator, falling-film evaporator, etc.
Moreover, it may be said that the design according to the present inventionprovides means for substantial decrease in the rate of decomposition for valuable CTOcomponents hence ultimately leading to an increase of the total yield. lt is well knownwithin the art that the double bonds of fatty acids and carboxylic functionality of the rosinacids are heat sensitive and the sensitivity is further promoted by the presence of variousCTO impurities, such as residual mineral acid remaining from the CTO production, metalcontaminants, etc. As it will be disclosed later in one specific embodiment of the presentinvention, the CTO impurities may be removed by a pre-treatment step. Whereas the pre-treatment removes the promotors for thermal decomposition, the specific design accordingto the present invention with two vapor streams fed and kept separately into a fractionation column to produce RTD enables the substantial decrease in the re-boiler temperature and such a decrease lowers the rate of thermal decomposition of valuable CTO componentshence increasing the total yield.lt may be said that in WO2014/098763 it is mentioned to use two thin-film evaporators in series so that a stream from the first thin-film evaporator unit may becombined with the similar stream from a second thin-film evaporator unit into thefractionation tower, where RTD and RA (rosin acid) streams are produced. As clearly statedabove, the present invention, however, re|ates to using a process equipment providing atleast two evaporation zones in series to produce separate first and second vapor streamswith different composition and temperatures and feeding these to different positions, whichare separated by structured packing, in the subsequent fractionation column to enable anenergy efficient process to produce RTD. The innovative arrangement enables the use oflower re-boiler temperatures which preserves the valuable components from thermaldecomposition thus increasing the total yield. This inventive concept in not at all disclosedor hinted in WO2014/098763.
Brief description of the drawings ln fig. 1 there is shown a schematic sequence of process steps according to onespecific embodiment of the present invention.
Specific embodiments of the invention Below specific embodiments of the present invention are disclosed and discussedfurther.
According to one specific embodiment of the present invention, the process alsocomprises the production of a rosin rich stream from the fractionation column. One possibleexample to be produced is CTOR (crude tall oil rosin) stream. The process conditions withinthe fractionation tower can be optimized so that the CTOR yield is relatively low but theproduct is characterized with high rosin acid content, high softening point, etc. thusenabling the use of CTOR directly in formulations such as inks, adhesives, rubber, etc.Moreover, according to yet another embodiment of the present invention the conditionswithin the fractionation column are optimized so that the yield of CTOR is maximized.According to yet another embodiment, the rosin rich stream, e.g. comprising CTOR, isfurther processed in a separation unit(s) to produce a stream of TOR (tall oil rosin) ofsuperior quality, and possibly also a second stream of TOP. According to one specificembodiment, the separation unit is a thin-film evaporator. Moreover, according to another specific example the separation unit is an additional fractionation column. 6 The present invention is also directed to a tall oil rosin composition possible toproduce according to above. Therefore, according to one specific embodiment, the presentinvention is directed to a tall oil rosin fraction comprising at least 70 wt.% rosin acid contentand maximum 5 wt.% fatty acid content and where the remaining amount is normally so-called neutrals or unsaponifiables.
As should be understood, the tall oil rosin fraction is possible to obtain by theprocess according to the present invention. Furthermore, according to yet another specificembodiment, the tall oil rosin fraction is further concentrated by being processed in anykind of separation unit. Therefore, according to one specific embodiment of the presentinvention, the tall oil rosin fraction comprises at least 85 wt.% rosin acid content andmaximum 5 wt.% fatty acid content.
According to yet another specific embodiment of the present invention, the totalcontent of palustric acid, abietic acid and neoabietic acid is at least 55 wt.%. These so-calledPAN acids are important because the total content thereof specifies the reactivity of therosin fraction, because the PAN acids are most reactive in comparison to the other rosin acidisomers such as but not limited to pimaric, iso-pimaric, sandaracopimaric, etc. acids. lncomparison to known rosin fractions, the present invention provides a higher concentrationin the total content of PAN acids. According to yet another specific embodiment of thepresent invention, the tall oil fraction is further concentrated to a total content of palustricacid, abietic acid and neoabietic acid above 60 wt.%.
The process according to the present invention may also comprise removal of lightends in the CTO performed before fed to the first evaporation zone. The removal of lightends suitably involves removal of water and turpentine, in one, two or several steps.Generally, this can be done in one step, however two steps may be preferred from practicalpoint of view. lt may also allow for a more efficient energy utilization/recovery/integration.The removal of water is intended to be close to 100%, and the turpentine removal should bedriven to above 80% according to the present invention. The turpentine here is used as acollective term for various components comprised of a skeleton built of up to 15 carbonatoms. Not only hydrocarbons are included in this fraction and also oxygen containingcomponents holding -OH, carbonyl, ether, etc. functionalities can be found therein. Theprinciple components of the turpentine fractions, however, are alpha- and beta-pinene.
According to one specific embodiment, the removal of light ends involves providing a temperature in a point of at least 160°C, e.g. in around or above 180°C at which point 7 turpentine boils. According to another specific embodiment, water is removed in a first stepand turpentine is removed in a second step of the removal of light ends. Therefore, theremoval of light ends may involve increasing the temperature in at least two steps to firstremove at least water in a first step and then at least turpentine in a second step.
For the removal of light ends, not only the temperature is of relevance but e.g. alsothe pressure level. The pressure may e.g. be held at a weak vacuum, e.g. in the range of 20 -60 mbar. Moreover, the equipment used may vary. Especially for the turpentine removalany equipment providing short diffusion path for the components to be vaporized ispreferred, e.g. equipment providing thin-film of the feed over a large heated area.Moreover, any equipment providing short residence time of the material at the hightemperatures during the evaporation is also preferred. Furthermore, when the CTO issufficiently conditioned in a pre-step such as this it ensures stable vacuum conditionsdownstream e.g. within the first evaporation zone and beyond.
Moreover, the present invention may also comprise a pre-treatment step(s),performed as a first step of the process. Such a pre-treatment may also be performedbefore the removal of light ends. Therefore, according to one specific embodiment of thepresent invention, the process also comprises a pre-treatment of the CTO for removal ofimpurities, such as e.g. fibers, salts, residual inorganic acid, transition metals and/or lignin,said pre-treatment comprising a first pre-treatment step involving a CTO wash and aseparation of a first oil phase comprising refined CTO to be further treated in the continuousfractionation and an aqueous phase holding impurities, and a second step involving aseparation of a second oil phase from the aqueous phase. To give some examples onpossible parameters of this pre-treatment step it may be mentioned that the CTO wash maybe performed in a water concentration of below 5 wt.%. Moreover, at least one additivemay be added in the first pre-treatment step where the additive targets the removal ofmetal impurities present in the CTO. Furthermore, the separation of the first pre-treatmentstep may be performed in a separator unit where the separation is driven by centrifugalforce. Moreover, the separation of the second step may be performed by decantation.
The temperature difference of the first and second vapor streams is an importantparameter in relation to inter alia the total yield of RTD. According to one specificembodiment of the present invention, the temperature difference between the first vapor stream compared to the second vapor stream is at least 20°C, such as at least 25°C. 8 According to yet another specific embodiment of the present invention, the processensures the first and second evaporation zones to operate at vacuum or close to vacuum,such as at 1-20 mbar and preferably 1-10 mbar. Moreover, as the first and the second vaporstreams are fed into subsequent fractionation column at two different positions there is apressure difference between the first and second evaporation zones.
Furthermore, according to yet another specific embodiment of the presentinvention, the packing means in the fractionation column separating the first vapor streamand the second vapor stream corresponds to at least 3 theoretical stages. As may beunderstood from above, the core of the present invention is to maintain the differences(temperature, composition etc.) of the first vapor stream compared to the second vaporstream.
Not only RTD and a rosin rich stream, such as CTOR, may be produced in thefractionation column. According to one specific embodiment of the present invention, thereis a third vapor stream produced and fed from the fractionation column. This third vaporstream is recovered through condensation. According to one specific embodiment, this thirdvapor stream is fed to one or more spray condensers. The effective recovery of this vaporstream may be of advantage to ensure as little affect as possible on the operation of thevacuum system. Moreover, the recovered vapor can be combined with RTD to furtherincrease the yield.
As hinted above, also the composition of the first vapor stream and the secondvapor stream are different. According to one embodiment of the present invention, the firstvapor stream comprises higher levels of fatty acid material than the second vapor stream,and where the second vapor stream comprises higher levels of rosin acid material than thefirst vapor stream. This implies that over the structured packing separating the first vaporstream from the second vapor stream in the fractionation column there is a fatty acid richenvironment and below the structured packing there is a rosin rich environment. Thus,optimizing the conditions within the column together with the arrangement, two separatedvapor streams with different compositions, enables fine tuning of the yield and compositionof product streams.
The present invention also refers to a system. According to one aspect the presentinvention provides a system for continuous fractionation of CTO (crude tall oil) to RTD (refined tall diesel), said system comprising: 9 - means providing at least a first evaporation zone and a second evaporation zoneconnected in a series; and - a fractionation column; wherein means providing the first evaporation zone and the second evaporation zone isconnected through piping to the fractionation column so that connections from the firstevaporation zone and the second evaporation zone is made at different positions, relative tothe column height, in the fractionation column, which different positions in thefractionation column are separated by packing means.
Moreover, according to one specific embodiment of the present invention, thesystem comprises one process unit providing the first evaporation zone and another processunit providing the second evaporation zone.
According to another embodiment, the system also comprises another separationunit, positioned after the fractionation column in process terms and connected to the same,for the production of TOR (tall oil rosin) from a rosin rich stream. This separation unit maybe any process equipment enabling evaporation e.g. a thin-film evaporator, short-pathevaporator, wiped-film evaporator, distillation column or combinations thereof.
Moreover, according to yet another specific embodiment of the present invention,the system also comprises one or more process units for removal of light ends present in theCTO, present before the means providing at least a first evaporation zone and a secondevaporation zone in process terms and connected to the same. These light ends are waterand turpentine. The system may e.g. comprise one unit for the removal of water andanother unit for the removal of turpentine.
Furthermore, the system may also comprise one or more washing and separationunits for pre-treatment of the CTO. These are provided before the one or more units forremoval of light ends.
Moreover, according to yet another specific embodiment of the present invention,the structured packing in the fractionation column separating the different positions ofwhere the first vapor stream is connected through piping to the fractionation column andwhere the second vapor stream is connected through piping to the fractionation columncorresponds to at least 3 theoretical stages. Feeding two vapor streams different incomposition allows for more adequate concentration profile along the column height thusopening for more fine control over the product compositions while maintaining the energy consumption to its minimum.
Detailed description of the drawings Figure 1 shows a schematic view over one embodiment of a process according tothe present invention. ln this case the CTO 1 is processed into a section 2 for removal oflight ends 8, namely water and turpentine. Regardless of the removal approach i.e. in one ormore steps, the water and turpentine are separated from each other and are processed inthe same plant or elsewhere. lt should be noted that the CTO 1 may in fact be refined CTO 1'which has been pre-treated for removal of impurities by washing and separation (optiondenoted with a dashed line).
Subsequently to the removal of the light end fractions, the stream is fed to a firstevaporation zone 3 where two streams are produced, one first vapor stream 6 fed to thefractionation column 9 through nozzle positioned ”higher” relative to the column height andone stream fed to a second evaporation zone. Within the second evaporation zone twostreams are produced, one vapor stream 7 fed to the fractionation column through a nozzlepositioned "lower" relative to the column height and more specifically under the nozzle offirst vapor stream 6, and one TOP stream 5 which is collected and/or further processed inthe same plant or elsewhere. ln the fractionation column there is produced a RTD stream 12, a rosin rich stream11, referred to as CTOR in this case, and a vapor stream 10 which suitably is sent to one ormore spray condensers. Optionally, the CTOR is further processed in another separationunit, to yield one stream of TOR 14 and one additional stream of TOP 13, both collectedand/or further processed in the same plant or elsewhere.
Examples ln the following comparative examples 1 and 2 the CTO is continuously fractionatedinto RTD using two different set-ups.
Within the first set-up, example 1, the first and second vapor streams producedwithin the respective evaporation zone were fed into the fractionation column using nozzlesat the same height and positioned at 180 degrees relative to each other i.e. combinedwithin the column.
Within the second set-up, example 2, the first vapor produced within the firstevaporation zone is fed into the fractionation column through a nozzle positioned ”higher”relative to the column height and the second vapor produced within the second evaporationzone is fed through a nozzle positioned "lower" relative to the column height. The two vapor streams are separated by a structured packing corresponding to 3 theoretical stages. 11 Besides the structured packing separating the first vapor stream from the second vaporstream within example 2, all other column internals, type of structured packing, distributors,distances between, etc. were kept the same for examples 1 and 2. The energy necessary forfractionation was delivered by a falling-film evaporator. Further, the conditions within thecolumn for both examples were optimized to obtain the same product streams regardingquantity and quality.
Satisfying all the constrains and conditions above showed that the energy deliveredby the re-boiler could be reduced by 25 % when using the set-up described in example 2.Furthermore, the temperature at the bottom of the column for example 2 was reduced byabout 10°C. Using the relationships for thermal decomposition of CTO componentsdescribed by ”Tall Oil: A book on the processing and use of tall oil” compiled and edited byJohn Drew and Marshall Propst distributed by Pine Chemical Association, one can calculatethat decreasing the fractionation temperature by 10°C decreases the rate of thermaldecomposition by more than 30 %. Thus, the design according to the present inventionprovides means for preserving the valuable CTO components which in turn leads to anincrease of the total yield for said process.
Conclusions As mentioned above, the present invention has several advantages. First of all, thetotal yield for the processing of CTO is increased. Fact is that the set-up suggested accordingto the present invention enables that more than 95% of the free fatty acids (FFAs) and morethan 90% of the rosin acids are sent to the fraction column. As the streams are separatedwith one having a high content level of FFA and another one with a high content level ofrosin material, the produced compositions and the total yield out from the fractionationcolumn is improved while minimizing the energy consumption compared to similarprocesses.
Moreover, in relation to quality parameters, the present invention has advantagescompared to what is known and used today. By incorporating the two evaporation stagesless TOP (tall oil pitch) is sent to the fractionation column. This implies that less heavycomponents entering the fractionation column thus negatively impacting the color andsoftening point parameters for CTOR/TOR products.
Furthermore, the use of two evaporation zones according to the present invention in principle discards the necessity of recycling, which in turn has a positive effect on the 12 product quality. As less time at higher temperatures are needed this has a positive effect when both fatty acids and rosin acids are sensitive for high temperatures.
Claims (2)
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| SE1951007A SE543463C2 (en) | 2018-10-31 | 2018-10-31 | A tall oil rosin fraction |
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| SE1951007A SE543463C2 (en) | 2018-10-31 | 2018-10-31 | A tall oil rosin fraction |
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|---|---|---|---|---|
| US3277072A (en) * | 1964-07-13 | 1966-10-04 | West Virginia Pulp & Paper Co | Fluid rosin |
| US3644179A (en) * | 1967-09-28 | 1972-02-22 | Krems Chemie Gmbh | Method and apparatus for continuous fractionation of tall oil and similar mixtures of organic substances with preliminary plural stage thin film evaporation |
| EP1568760A1 (en) * | 2004-02-06 | 2005-08-31 | Härting Glade, Thomas Francis | Process for refinig a raw material comprising black liquor soap, crude tall oil or tall oil pitch |
| WO2014098763A1 (en) * | 2012-12-21 | 2014-06-26 | Sunpine Ab | Biorefining of crude tall oil |
| EP3127581A1 (en) * | 2013-11-13 | 2017-02-08 | Hankkija Oy | Feed supplement comprising a resin acid based composition |
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2018
- 2018-10-31 SE SE1951007A patent/SE543463C2/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3277072A (en) * | 1964-07-13 | 1966-10-04 | West Virginia Pulp & Paper Co | Fluid rosin |
| US3644179A (en) * | 1967-09-28 | 1972-02-22 | Krems Chemie Gmbh | Method and apparatus for continuous fractionation of tall oil and similar mixtures of organic substances with preliminary plural stage thin film evaporation |
| EP1568760A1 (en) * | 2004-02-06 | 2005-08-31 | Härting Glade, Thomas Francis | Process for refinig a raw material comprising black liquor soap, crude tall oil or tall oil pitch |
| WO2014098763A1 (en) * | 2012-12-21 | 2014-06-26 | Sunpine Ab | Biorefining of crude tall oil |
| EP3127581A1 (en) * | 2013-11-13 | 2017-02-08 | Hankkija Oy | Feed supplement comprising a resin acid based composition |
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| Title |
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| FOR90 Product Datasheet, Forchem Oy, 2015, Nov. Retrieved from the Internet: 2020-02-12 <https://www.forchem.com/wp-content/uploads/2019/12/forchem_datasheet_FOR90_007.pdf> * |
| Holmbom, B. "The Behavior of Resin Acids during Tall Oil Distillation" In: J. Am. Oil Chem.' Soc., 1978, Vol. 55, No. 12, pp. 876-880. * |
| Joye, M. N. et al. "Resin Acid Composition of Pine Oleoresins" In: J. Chem. Eng. Data, 1967, Apr., Vol. 12, No. 2, pp. 279-282. * |
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