US2235462A - Manufacture of an improved tall oil - Google Patents
Manufacture of an improved tall oil Download PDFInfo
- Publication number
- US2235462A US2235462A US224414A US22441438A US2235462A US 2235462 A US2235462 A US 2235462A US 224414 A US224414 A US 224414A US 22441438 A US22441438 A US 22441438A US 2235462 A US2235462 A US 2235462A
- Authority
- US
- United States
- Prior art keywords
- tall oil
- oil
- crude
- acid
- crude tall
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003784 tall oil Substances 0.000 title description 22
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000002253 acid Substances 0.000 description 16
- 239000003921 oil Substances 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 10
- 239000002023 wood Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 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 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- -1 has rendered the Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910021653 sulphate ion Inorganic materials 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 101100130497 Drosophila melanogaster Mical gene Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 101100345589 Mus musculus Mical1 gene Proteins 0.000 description 1
- 235000005018 Pinus echinata Nutrition 0.000 description 1
- 241001236219 Pinus echinata Species 0.000 description 1
- 235000017339 Pinus palustris Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000011364 vaporized material 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
Definitions
- This invention rent to a processor resume crude tall oil. lit is well known in the wood pulpin: that when the black liquor obtainedi'rom the pulping of coniferous woodby v the sulphate procws is evaporated, a scum. com-' mcnly mown as tall oilsoep, separates and floats upon the of theblack liquor; scum is not present on the liquors o-s t y obtained before the evaporation step, but]: pro; du' probably by'a salting out erect, the liquor becomes concentrated. In present puoctice the scum of tall ,oil soap is skimmed oil of the;
- the crude tell oil soepis usually treeted withdilutesolutions of sulphuric acid or sodium acid sulphate to liberatethis crude tall oil;
- I usually pre fer to maintain a temperature of at least about 300 for atleast an hour inor'der that the chemical reactionswhich occur during may be substantially completed. Care is taken that the tall oil does notcome in contact with air during the heating operation and. that the vaporized products are removed. After the mei chanicaily held water has been driven away the volatile products coming from the heated tall oil show an increasing volume of vapor as the temperature rises. This vapor is substantially all water, formed by pyrolysis, and also contains sulphur bodies coming from the ligninand other sulphur compounds always present in crude tall. oil as impurities. I
- theproduct' After deodorizlng with hydrogen as described above theproduct' hasa definitely sweet fatty odor fax-more desirable than the foul odor of the crudetalloil.
- the product is characterized physically, by its improved odor compared to tail oil and by its freedom from any tendency to crystallize'o'n standing. Chemically it appears to be, most distinctly characterized by its freedom from hydroxy abietic acid.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Fats And Perfumes (AREA)
Description
Patented 18,1941
This invention rent to a processor resume crude tall oil. lit is well known in the wood pulpin: that when the black liquor obtainedi'rom the pulping of coniferous woodby v the sulphate procws is evaporated, a scum. com-' mcnly mown as tall oilsoep, separates and floats upon the of theblack liquor; scum is not present on the liquors o-s t y obtained before the evaporation step, but]: pro; du' probably by'a salting out erect, the liquor becomes concentrated. In present puoctice the scum of tall ,oil soap is skimmed oil of the;
evaporated black liquor sndeither used as to produce crude sodium salts of tell oil or more frequently the scum is treeted'totformfcrude (chemical constituents of the exudation are comtall oil. The crude tell oil soepis usually treeted withdilutesolutions of sulphuric acid or sodium acid sulphate to liberatethis crude tall oil;
In orderto facilitate the sepamtlon'ofthe mixq ture into two layers, ,the,use of with the aoidto increase" thedens'ityof the I water leyer iscommon practice; Aiter the acid.
f hasreaeted the crude tall oil is theupper layer and can beseparated-from the lower aqueouszs sodimn sulphate layer byodeoantstion or any other suitable means commonly used in the'chem-' icaiindustries. i
Crude tall oil, prepared in the above manner,
, is of limited usefulness in industrial imitation.
an It posseses the "foul odor typicalof suljphwte black liquors; "it, of darkcolor;
and. an even greater; objection is its tendency to vpartially, P oducing-is thick couspastedifilcult to pump anddiulcultfto re- I move t omshlpping' 'contalners. Mllstendency to crystallize varies depending upon the" history of the wood from which it originates Conse quently, crude tall oil lacks uniformity in chemical composition'and physical characteristics.
It is the purpose {of ithisinvention to provide 9, simple economical process by which taliofl can a e mn e m w mi e hy ical appearance with an improved odorsnd colori'as compared to the crude oilnow found in commerce. The improvedtall oil producedin accordence with'in P c to be deswlbedhemmatter has been found to be free of those cryfs talline which occurin the crude prod- H v q q q crude tall on showsmoreorystalformaltion than does the untreated product. r 0
not and consequently is a smooth uniform oily Pro uct. 'It*'is" capable of standing in storage I indefinitely without crystallization."
'To understand the advantages offered by this 7 invention it is essential to appreciate the lack of uniformity found in tall oll resultinz from the 5 variations inthe kind or woodused in the Q88, and more panticularlyfrom mum in the history of this, wood. when southern pine is 1 pulped by the'sulphate process promptly after it is cut green, yields a tall oildifterent from' that produced the, loss are puiped after I they have been out and exposed to air for months. When apine tree is out it exudes resmous matter in an attemptto seal the wound. This necessarily places "a. large portion of the resinous contentlof'tl'lewood in withthelo' air. and utter longexposure the air penetrates the ,wood and oxidizes some of the constituents plex and of many types, the'che'mical changes by oxidation srenot entirely understood.
Experience has 'proyed'also that in the of fattyacids to the resin acids is considerably b1813 thanin the tall oilobtained by pulping wood whichhas been cut inthe winter when' the sap is out of the tree. Because of these variations me the wood used, crude m1 oil so: u
' wood; These variations have retarded the ingo dustrial application of. crude tall oil.
Experimentation has shown that sbietlcacid toh'ydrOXyabieticacid under mild 0x1- dlzinmconditions. This can occur to a certain extent'when the coniferous woods'tends exposed u to air utter being, cut. Hydroxyebietic acid is less soluble .in fatty acid than is abietic and consequently. it tends to crystallize out of crude tall oil. crystals probably act as a. nuclei for the crystal growth of other resinous P oducts 0 present in the nude telloil. In' any event hydmxyebietic acid is believed'to accountfonthe partial solidiflwtlon of crude tall oijldue to'crys- It is one of the objects of this invention to eliminate the presence '-of hydroxyabietic acid and other oxidized analogous orilrelated' com pounds and derivatives bychemlcally processing the crude tall oil; 11 heat the crude telloil, -'at u r wood cutln the spring of the year the ratio a first rather slowly, to drive oil water which is not chemically bound and some low-boiling odorous I then continue the heating progressively until a maximum temperature of 250450" 0. has been attained. I usually pre fer to maintain a temperature of at least about 300 for atleast an hour inor'der that the chemical reactionswhich occur during may be substantially completed. Care is taken that the tall oil does notcome in contact with air during the heating operation and. that the vaporized products are removed. After the mei chanicaily held water has been driven away the volatile products coming from the heated tall oil show an increasing volume of vapor as the temperature rises. This vapor is substantially all water, formed by pyrolysis, and also contains sulphur bodies coming from the ligninand other sulphur compounds always present in crude tall. oil as impurities. I
A variety of procedures may be employed in the heating operation as'will be apparent to one 7 skilled in the art. I have found it advantageous toheatthetalloilintwosi:ages,firsttoaternperature in the neighborhood of 100 C. to remove free water and readily vaporizable con- "stituents and then to about 325' C. to effect the chemical changes described. Each heating stage advantageously is accompanied by a flow! U ing of the heated material. in a thin layer over a splash plate or the like to facilitate the re-' moval of volatile constituents. In some in.- stances I have found it desirable to maintain a temperature of 325 C. for aboutil hours.
Ifthetalloilisdryatthestartthelossof' tall oil as a result of theheat treatment gener found to be changed from a yellowish-,brownto an iridescent green, 9. color similar to that ob-' served in petroleum lubricating oils. Also the odor is decidedly improved'because of the subally does notexceed 5%.
The heating of the crude tall'dl-rmlts in a product which will be found to havaehanged chemically and physically in characteristics. In the first place, its color after cooling will be stantial loss ofsulphur compounds found in crude tall oil. a burnt or charred organic substance. This odor, I believe,.is due to the charring of small traces of lignin usually present in tall 011. Although it is not necessary in carrying out my process, I may remove this burnt fodor by, treatment with hydrogen in the presence of a catalyst in the usual manner common in hydrogenation of oils. While one may continue the treatment with sufficient hydrogen to hydrogenate the fat-.
ty and resin acids, as well as the odorous materials, this is not essential as, the odorous materials appear to be converted to non-odorous products rapidly by hydrogen treatment. I also appreciate the possibility of removing these odorous materials by many of the known methods used in the art,- such as superheated steam, activated carbon, etc. Filtration for the removal of solid matter is not necessary. .The constituents which normally result in the deposition of solids j from crude tall oil apparently are destroyed or rendered more soluble or removed by. distillation during the heating andvaporizing treatment described.
Probably the major change which occurs in crude tall oil when processedas described is the lowering of the resin acid contentof the oil and the simultaneous substantial increase in the unsaponifiable content in the oil. Merely, as a mat- The derived odor is suggestive of V asssaes ter of possible explanation I ofler the following theory to account for this chemical change during the process. Hydrozvabietic acid has been found to be unstable at temperatures of 200' C. and higher. It 'is believed that the oxidized products in crude tall oil, among'which is probably hydroxyabietic acid, become dehydrated during the heating process. This produces anhydrohydronabietic acids and possibly po ymerized or isomerized colophonic acids. Evidence indicates that some of the carbonyl groups of'these resin type acids are destroyed in the heating process. Any one ofthe above conditions would account for the lower acid number found on theheated product, as well as the increased unsaponiflable value. It appears also that abietic acid if present probably is converted to the more stable pyroabietic acid.
The following table shows the changes produced by the above described heating and va- Theimproved'odor, together with the relatively increasedpel' cntage of fatty acids, has rendered the, product suitable for use in the manufacture of such commercialarticles as soaps, printinginks,
greases, rubber compounds, etc, where the crude tall oil hasnever been found adaptable. I
After deodorizlng with hydrogen as described above theproduct' hasa definitely sweet fatty odor fax-more desirable than the foul odor of the crudetalloil.
The product is characterized physically, by its improved odor compared to tail oil and by its freedom from any tendency to crystallize'o'n standing. Chemically it appears to be, most distinctly characterized by its freedom from hydroxy abietic acid.
I claim:
1. Process'for the production of refined tall oil which is a smooth. uniform, oily liquid capable of prolonge'dstanding without crystallization which consists in raising the temperature'of, crude tall oil from coniferous wood to a maximum between about 250 C.'and about 350 C., said heating operation'serving to vaporize and expel mechanically associated water, water produced by Pyrolysis, low boiling odorous materials and sulfur'compounds,
. the loss by vaporization from tall oil which is dry at the beginningof the heating operation generally not exceeding 5 and separating the residual liquid from the vaporized materials.v
2. Process as defined in claim 1 in which the crude tall 011' is first heated slowly todrive of! mechanically associated water and some low boiling odorous materials and then is heated progressively to a'maximum temperature of 250-350 C. and the heating iscontinued at said temperature for a time suflicient to permit completion of chemical reactions occurring at said temperature.
' 3. Processes defined in claim 1 in which the heating at said maximum temperature is carried out at atleastabout 300 C. for at leastabout 1 hour.. y
4. Process as defined in claim 1 inwhich the heating at said maximum temperature is atabout 325 C. for about 3 hours.
l needed:
1 in whiclialr isaboutfos aby weight or the weight of the dry "crude tail oil and containing the organic products oi p rroiysiaot the hydroxy abietic acid content of the crude tall oil. 1
8. Refined tall 011 as defined in claim '1 having,
as compared with crude tail oil lower acid number, saponification number, resin acid content and iodine number and higher fatty' acid content and unsaponifiabie content. 9. Refined tall oil as substantially free of hydroxy abietic acid. HAROLD R. 'MURDOCK'.
defined in claim v being 10
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US224414A US2235462A (en) | 1938-08-11 | 1938-08-11 | Manufacture of an improved tall oil |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US224414A US2235462A (en) | 1938-08-11 | 1938-08-11 | Manufacture of an improved tall oil |
Publications (1)
Publication Number | Publication Date |
---|---|
US2235462A true US2235462A (en) | 1941-03-18 |
Family
ID=22840563
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US224414A Expired - Lifetime US2235462A (en) | 1938-08-11 | 1938-08-11 | Manufacture of an improved tall oil |
Country Status (1)
Country | Link |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2421627A (en) * | 1944-02-10 | 1947-06-03 | Crosse Clifford Granville La | Rubberlike substances and compounding material |
US2423236A (en) * | 1944-02-17 | 1947-07-01 | Armour & Co | Method of treating tall oil |
US2525892A (en) * | 1947-03-12 | 1950-10-17 | Champion Paper & Fibre Co | Refining tall oil |
DE1078423B (en) * | 1958-10-14 | 1960-03-24 | Statens Skogsind Ab | Use of a decarboxylated tallow oil for the production of hard fiberboard |
US20070049727A1 (en) * | 2005-08-15 | 2007-03-01 | Pollock Charles M | Low sulfur tall oil fatty acid |
-
1938
- 1938-08-11 US US224414A patent/US2235462A/en not_active Expired - Lifetime
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2421627A (en) * | 1944-02-10 | 1947-06-03 | Crosse Clifford Granville La | Rubberlike substances and compounding material |
US2423236A (en) * | 1944-02-17 | 1947-07-01 | Armour & Co | Method of treating tall oil |
US2525892A (en) * | 1947-03-12 | 1950-10-17 | Champion Paper & Fibre Co | Refining tall oil |
DE1078423B (en) * | 1958-10-14 | 1960-03-24 | Statens Skogsind Ab | Use of a decarboxylated tallow oil for the production of hard fiberboard |
US20070049727A1 (en) * | 2005-08-15 | 2007-03-01 | Pollock Charles M | Low sulfur tall oil fatty acid |
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