US2298816A - Recovery of tar acids - Google Patents
Recovery of tar acids Download PDFInfo
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- US2298816A US2298816A US289323A US28932339A US2298816A US 2298816 A US2298816 A US 2298816A US 289323 A US289323 A US 289323A US 28932339 A US28932339 A US 28932339A US 2298816 A US2298816 A US 2298816A
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- tar
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- acid
- solution
- acids
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- 239000002253 acid Substances 0.000 title description 55
- 150000007513 acids Chemical class 0.000 title description 41
- 238000011084 recovery Methods 0.000 title description 13
- 239000011269 tar Substances 0.000 description 70
- 239000012071 phase Substances 0.000 description 63
- 239000000243 solution Substances 0.000 description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- 239000011289 tar acid Substances 0.000 description 37
- 239000002904 solvent Substances 0.000 description 29
- 239000000470 constituent Substances 0.000 description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 26
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 23
- 238000004939 coking Methods 0.000 description 23
- 238000002156 mixing Methods 0.000 description 22
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 20
- 239000012266 salt solution Substances 0.000 description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- 238000004821 distillation Methods 0.000 description 18
- 229940031826 phenolate Drugs 0.000 description 18
- 230000000694 effects Effects 0.000 description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 13
- 239000001569 carbon dioxide Substances 0.000 description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 238000001556 precipitation Methods 0.000 description 11
- 235000010269 sulphur dioxide Nutrition 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 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 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 4
- 150000008041 alkali metal carbonates Chemical class 0.000 description 4
- -1 alkali metal salt Chemical class 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 150000004707 phenolate Chemical class 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 2
- 239000002641 tar oil Substances 0.000 description 2
- 241000283986 Lepus Species 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- BJNXJPYKYOKYOR-UHFFFAOYSA-N [C].ClC(Cl)Cl Chemical compound [C].ClC(Cl)Cl BJNXJPYKYOKYOR-UHFFFAOYSA-N 0.000 description 1
- 239000000061 acid fraction Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C1/00—Working-up tar
- C10C1/18—Working-up tar by extraction with selective solvents
Definitions
- crude tar is mixed with an alkali solu-l tion to effect reaction 'between vthe alkalifand ⁇ the phenolicconstituerits of the crude tar and solu; tion of the phenolate reaction products in the aqueous phase.
- the aqueous phase is thereafter separated fromthe crudeutar by centrifugation, sprung with an acid to ⁇ freel'fhe phenolicV cornpoundsf'and subjected 1 tov distillation fori recovery of these phenolic compounds.
- Such yafprocess "affords' an important advantage in the avoidancefof the distillation step-by ⁇ which a'- tar oil fraction has heen'V inst-separated from crude* tar' in the practice of4 theprior art before treatment of this tar oil fractionseparately4 for recovery of vpheencountered inigconnectio'nA with theip'rocess of Patent ⁇ 2,081,692, however, andanV object of thel be ⁇ sprung by treatment with! carbon4 dioxide.l
- the ⁇ alkaltfifeed'by theMVM springing step combines with the sulfuric acid to form tiieJaIKalimetal salt" of the A springing-v acidl (sodium sulfate) and this alkali metal salt has'practically-no" value.
- Theaqueous'phenolate liquor discharged from centrifugal I3 is nekt passed to a ⁇ still I4, in Whiclfi ⁇ it is ⁇ concentrated; by evaporation of f a substantialproprtionoflthe Water content.-V
- the springing reaction' mayA be accomplished by passingthe aqueous phenolate lp "aisedtvnviardly through the tower i-sjwiiiiopassingcarton dioxide upwardly into that tower; as wiii ooqweii understood bytnoso skiuodf tHe-art.
- So'di-ufnli ⁇ 1 ⁇ jv ⁇ coiride may be regenerated by caustinit/.ationF with linewof the aqueous ⁇ sodium carbonatefslution dischargcdfr'om' the separator
- the tar acid phase discharged as a supernatant oil from the separator I6, is next passed to a mixer I'I Where it is mixed with sulfuric acid from tank I 8 to effect completion of the springing reaction and formation of sodium sulfate by reaction of the sulfuric acid with th'e phenolates.
- This reaction results in the formation of a mixv ture consisting of an aqueous phase comprising principally sodium sulfate solution, and an oil phase containing liberated tar acids.
- This mixture is passed to a centrifugal separator I9 which effects continuous separation'of these two phases and separate discharge thereof.
- the tar acid phase discharged from the-centrifugal I9 contains practically no alkali, but still contains constituents which would resultv in the formation of a coke-like residue in the still if this tar fraction Were to be distilled without further intermediate treatment after discharge from the centrifugal I9.
- An important feature of the invention consists in the manner in which this coking incident to distillation is avoided.
- the tar acid phase discharged from the centrifugal I 9 is passed to a mixer 28, where it is mixed with a naphthenic solvent from tank 2l.
- the mixing of the tar acid phase with the naphthenic solvent effects precipitation from solution of the constituents which would otherwise cause coking in the still, and these constituents can thereafter be removed from the tar acids by filtration in the filter 22.
- An excellent solvent for use in precipitating the undesired constituents (whichl will be referred to hereinafter in the specification and claims as coking constituents) is methylalcohol, and excellent results have been obtained in the practice of the invention in cases in which the tar acid phase discharged from the centrifugal I9 is mixed with twice its volume of methyl alcohol.
- the tar acids discharged as a filtrate from the lter 22 may be passed to a, still 23, which may be of either the batch or continuous type, and subjected to distillation in that still to remove methyl alcohol from the tar acids and effect separation of tar acids from residual oil.
- the step of distilling off water in the still I4 may be entirely eliminated.
- the purpose of this step is two-fold.
- the concentration of the phenolate fraction at this stage is desirable because of the fact that it improves the efciency of the salting outeffect on the tar acid compounds upon subsequent treatment with carbon dioxide
- the sodium carbonate solution obtained from the vseparator I6 be relatively concentrated in order'to facilitate regeneration of sodium hy- ⁇ droxide therefromQand thisobject can Abe accomplished most efficiently by Aremoval of water from the phenolate fraction prior to the treatment thereof by carbonv dioxide Since neither of the above features of ⁇ advantage is absolutely essential to the successful performance of the process, however, the material discharged as an aqueous phase from thecentrifugal I3 may be treated with carbon dioxide in the tower' I5 without the performance
- both the carbon dioxide springing step and the acid springing step be performed prior to the step of precipitating coking constituents, since the performanceof the springing step with carbon dioxide affords an important advantage in that it results in the formation of sodium carbonate, which is much more Valuable than the sodium sulfate into which the sodium content of the phenolates would be converted if sulfuric acid alone-were used for springing.
- 'I'he acid treatment, after the carbon dioxide treatment also affords an important advantage in that a much more complete springing reaction and more effective removal of sodium compounds from the mixture can be accomplished by the inclusion of the acid springing step after the carbon dioxide springing, than can be accomplished if the acid springing step is eliminated.
- tar acids in the production of tar acids, the process comprising separating from tar a fraction consisting principally of tar acids, but containing constituents which cause a coke precipitate to form upon distillation, mixing said tar acid fraction with methyl alcohol to effect precipitation of said coking constituents, and thereafter separating the precipitated coking constituents from the resulting solution of tar acids in methyl alcohol.
- tar acids in the production of tar acids, the process comprising separating from tar a fraction consisting principally of tar acids, but containing constituents which cause a coke precipitate to form upon distillation, mixing said tar acid fraction with a solvent chosen from the class consisting of methyl alcohol, chloroform, carbon disulfide and sulfur dioxide to eiect precipitation of said coking constituents from the solution of tar acids in said solvent, and thereafter separating said precipitated coking constituents from said solution.
- a solvent chosen from the class consisting of methyl alcohol, chloroform, carbon disulfide and sulfur dioxide
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Oct. 13, 1942. c. M. AMBLER, JR A 2,298,816
RECOVERY oF TAR ACIDS vFiled Aug. 95,1939
` ATTORNEY Patented Oct. 13, 1942 2,298,816 RECOVERY oF 'initzicibs Cha'rlesM.` Ambler, Jr., Jenkintown, Pauassgm `or to The Sharples Corporation, Philadelphia; Pa., a corporation of Delaware Application August 9, 1939, soi'iol iso:- esatte 11 Claims.
The present inventior'ipertans tothe recovery of tar acids 'from' phenolate-:containing liquors derived from lcrude tar. It may loel regarded as an improvement of theV process of U; S. Eatent 2,081,692'-to 'Charles M. Ambler, Jr., 'and Charles E. nderwood. i v
In accordance with the process of U. S. Patent 2,081,692, crude tar is mixed with an alkali solu-l tion to effect reaction 'between vthe alkalifand `the phenolicconstituerits of the crude tar and solu; tion of the phenolate reaction products in the aqueous phase. The aqueous phase is thereafter separated fromthe crudeutar by centrifugation, sprung with an acid to `freel'fhe phenolicV cornpoundsf'and subjected 1 tov distillation fori recovery of these phenolic compounds. Such yafprocess "affords' an important advantage in the avoidancefof the distillation step-by` which a'- tar oil fraction has heen'V inst-separated from crude* tar' in the practice of4 theprior art before treatment of this tar oil fractionseparately4 for recovery of vpheencountered inigconnectio'nA with theip'rocess of Patent` 2,081,692, however, andanV object of thel be` sprung by treatment with! carbon4 dioxide.l
When sulfuric aloiddi's used as thefspringing agent, the` alkaltfifeed'by theMVM springing step combines with the sulfuric acid to form tiieJaIKalimetal salt" of the A springing-v acidl (sodium sulfate) and this alkali metal salt has'practically-no" value.y
When carbon dioxideis used asl the springing agent; the ltari` acidsderived from the springing step and subsequent distillation arerelatvely ini-'- pura-r and? the' tar'` acid fraction obtained by springing. and distillation hasy hydrophilic? propertiesyindicating: thatthe-tar acids haveriot' been adequately-puried. They contain an undesirably-A high proportio'nilo ash, and` this is anl indication that the Aseparation of l the alkali fromfthe phenolates. in-:the springing vstep is incompletek Regardless of whether the springingy step-isaecomplished; by'l carbon `dioxide or` by sulfuric acid in: the practice off the 'process of- Patent 2,081,692, a coke'-likeresiduefisl formed" the still? incident to distillation, rendering continuous' distillation impossible, and introducing di'iculties connection with the removaloi` this re's'idue-evenfmcases inwhich the distillation` is:` accomplished b'yF-batch operation.
An object of the present inveritinL has been` (o1. zenuw) t to o'ooo"toplistn uiespritgiiig onu purification of the phen late] nbr! obtained in the pija'cticeof Patent 2,081;692 `1n "such a way 'as to avoid all'of me above=mntioiiedeinooities; Y p v i Further yobectls` and aivantagesjof the invention;` and the manner' in Vwhich they have jbeen attained; will be evident from` a Yreading of the iouoofig spcification 'in io'rimotionA with the attachedowshetrin which the single figure is a difagiaininatic representation o`f oneexnbodi- 3 theintfention; Y l
i .v/ing? by reference characinfs'olutiri (p ferably sodiunfili'ya 'iter assumed to he suchal'- oom cion reagents. may-bos'ed) from ted'with# taf from `tank vI` I in fr' of yac'lueous` phenolate` soobtainedv as a` result of lfz-, is-noxt passed tov4 a ZeiltrifiigaflE separator |-3,-` rand the equeou's phenol'a'te solution is ntiuusly separated froin the crude tar by the centrifugal separation acconplishdinthat centrifugal. These steps of llixiiig`d` aldi gati are tial with the co1i'resflacnclingfstepsl oftheabove-Inentioned patont l to Aiiibisrsiidunderwood. u
Theaqueous'phenolate liquor discharged from centrifugal I3 is nekt passed to a` still I4, in Whiclfi` it is` concentrated; by evaporation of f a substantialproprtionoflthe Water content.-V The con'centratedsolutin -r uiting from this vaporatingfstepfis' next reacted with carbon dioxide to' effect springing of` asulostantial part' of the sodiin"phenolates,` and-:formation of sodium carbonate? 'Ilhsfresults"l precipitation ofthe phenolfsf f-ree vby the springingraction from solution' eauueousi pianse;` and' solution of the sodiurncaibate forrned by the springing reactionin'the aqueous phase.I The" springing reaction'mayA be accomplished by passingthe aqueous phenolate lp "aisedtvnviardly through the tower i-sjwiiiiopassingcarton dioxide upwardly into that tower; as wiii ooqweii understood bytnoso skiuodf tHe-art. '1n-e mixture-oi sodium car- 1ibei atioriofthe-ta acids; isn z ijexi passed to o .separator` I`li*,-Wl51i'ch` maybe either a. gravity or centif'ugal"sepf'irtor,1 tofeifect subsidence of the sodiun par] oonate" solution from the sprung ta'r acids;` So'di-ufnli`1`jv`coiride may be regenerated by caustinit/.ationF with liniewof the aqueous` sodium carbonatefslution dischargcdfr'om' the separator |65, and tlief resulting sodiuirihydroxide' solution may be used in the treatment of a further quan#- bona o'soltionwitiiuiooii phase, resulting `from tity of tar in the mixer I2, or for any other desired use.
The tar acid phase, discharged as a supernatant oil from the separator I6, is next passed to a mixer I'I Where it is mixed with sulfuric acid from tank I 8 to effect completion of the springing reaction and formation of sodium sulfate by reaction of the sulfuric acid with th'e phenolates.
This reaction results in the formation of a mixv ture consisting of an aqueous phase comprising principally sodium sulfate solution, and an oil phase containing liberated tar acids. This mixture is passed to a centrifugal separator I9 which effects continuous separation'of these two phases and separate discharge thereof.,
The tar acid phase discharged from the-centrifugal I9 contains practically no alkali, but still contains constituents which would resultv in the formation of a coke-like residue in the still if this tar fraction Were to be distilled without further intermediate treatment after discharge from the centrifugal I9. An important feature of the invention consists in the manner in which this coking incident to distillation is avoided.
The tar acid phase discharged from the centrifugal I 9 is passed to a mixer 28, where it is mixed with a naphthenic solvent from tank 2l. The mixing of the tar acid phase with the naphthenic solvent effects precipitation from solution of the constituents which would otherwise cause coking in the still, and these constituents can thereafter be removed from the tar acids by filtration in the filter 22. An excellent solvent for use in precipitating the undesired constituents (whichl will be referred to hereinafter in the specification and claims as coking constituents) is methylalcohol, and excellent results have been obtained in the practice of the invention in cases in which the tar acid phase discharged from the centrifugal I9 is mixed with twice its volume of methyl alcohol.
The tar acids discharged as a filtrate from the lter 22 may be passed to a, still 23, which may be of either the batch or continuous type, and subjected to distillation in that still to remove methyl alcohol from the tar acids and effect separation of tar acids from residual oil.
The invention has been described above in the simplest and preferred embodiment thereof. Various details may be modified without departing from the spirit of the invention. For example, the step of distilling off water in the still I4 may be entirely eliminated. The purpose of this step is two-fold. In the i'lrst place, the concentration of the phenolate fraction at this stage is desirable because of the fact that it improves the efciency of the salting outeffect on the tar acid compounds upon subsequent treatment with carbon dioxide In the second place, it is desirable that the sodium carbonate solution obtained from the vseparator I6 be relatively concentrated in order'to facilitate regeneration of sodium hy-` droxide therefromQand thisobject can Abe accomplished most efficiently by Aremoval of water from the phenolate fraction prior to the treatment thereof by carbonv dioxide Since neither of the above features of `advantage is absolutely essential to the successful performance of the process, however, the material discharged as an aqueous phase from thecentrifugal I3 may be treated with carbon dioxide in the tower' I5 without the performance of the intermediate distillation step stili la. f p
The step of effecting further springing of phe- Vsteps described above and illustrated in the attached flow sheet, a substantial part of the advantages of the invention may be accomplished .in spite of the omission of the springing and separating steps performed in tower I 5 and separator I6, or of the springing and separating steps performed in the elements II, I3 and I9 of the flow sheet. Thus, the advantages in avoiding passage of coking constituents to the still may be obtained in connection with' the use of naphthenic solvent as described in connection with reference numerals 20, 2I and 22 of the flow sheet, in cases in which carbon dioxide is used as the springing reagent and the acid springing step is eliminated,A` or in cases in which an acid alone is used as the springing reagent and the carbon dioxide springing is eliminated. It is desirable, however,`that both the carbon dioxide springing step and the acid springing step be performed prior to the step of precipitating coking constituents, since the performanceof the springing step with carbon dioxide affords an important advantage in that it results in the formation of sodium carbonate, which is much more Valuable than the sodium sulfate into which the sodium content of the phenolates would be converted if sulfuric acid alone-were used for springing. 'I'he acid treatment, after the carbon dioxide treatment also affords an important advantage in that a much more complete springing reaction and more effective removal of sodium compounds from the mixture can be accomplished by the inclusion of the acid springing step after the carbon dioxide springing, than can be accomplished if the acid springing step is eliminated.
While th'e step of precipitating coking constit.
uents in a form in which they can be removed; from the tar acid phase discharged from the cen-l trifugal I 9 has been described as performed by; the addition of methyl alcohol, it will be under-.Y` stood that other naphthenic solvents, such as; chloroform, carbon disulfide or sulfur dioxide may be employed in connection with the practice.- of this step of the invention.
While the treatment of the tar in the mixer |23 has been described as being performedby the; addition of sodium. hydroxide, it will be understood th'at equivalent alkaline reagents can be: substituted in this step. Potassium hydroxide, or any alkali capable of reacting with the tar; acids to form a soluble alkaliphenolate phase which may thereafter be separated from the tar by centrifugation, may, for example, be substituted for the sodium hydroxide used in this step.
Still further modifications will be obvious to those skilled in the art and I do not therefore wish to be limited except by thescope of the subjoined claims.v
I claim:
1. In the recovery of tar acids from Vtar the process comprising mixing the tar with an aqueous alkali metal hydroxide solution, separating phase from the tar by centrifugation, concentratbonate v`solution, trom theresultng tarracid phase. mixingthetar acid. phase, from which thealkali metal 'i carbonate solution has been separated. witha springing acid, separating the resulting liar acidphase 'from the resulting saltsolutionphase to obtain a tar'acid ,phase substantially freedof` salt solution, mixing' the tar .acid phase, from which saidgsalt solution phase hasbeen separated, with a solvent chosen from the class consistingl of' methyl alcohol, chloroform carbon disuldeand sulfur dioxide to effect precipitation of., coking constituents, thereafter 'removing said precipitated c'oking constituents from thesolution of` tar aci'ds 'in said solvent, 'and separatingthe solvent'and other impurities fromth'e' taracids by distillation.'
2;. In the rrecovery `of, tar acids from tar, the Presets cmprisns mixing .the tar with an aque- Qls. ellsali metal hydroxide solution, Separating the resulting aqueous alkali Vmetal phenolate Dhase from the tar ,by` centrifugation, concentrating the resulting aqueous alkali metal phenolate phase by evaporating Water therefrom, adding carbon dioxide to the concentrated phenoe late phase, separating the resulting alkali metal carbonate solution from the resulting tar acid phase, mixing the tar acid phase, from which the alkali metal carbonate solution has been separated, with sulfuric acid, separating the resulting tar acid phase from the resulting salt solution phase to obtaina tar acid phase substantially freed of salt solution, mixing the tar acid phase, from which said salt solution phase has been separated, with a solvent chosen from the class consisting of methyl alcohol, chloroform, carbon disulfide and sulfur dioxide to effect precipitation of coking constituents, thereafter removing said precipitated coking constituents from the solution of tar acids in said solvent and separating the solvent and other impurities from the tar acids by distillation.
3. In the recovery of tar acids from tar, the process comprising mixing the tar with an aqueous alkali metal hydroxide solution, separating the resulting aqueous alkali metal phenolate phase from the tar by centrifugation, mixing the resulting aqueous alkali metal phenolate phase with a springing acid, separating the resulting tar acid phase from the resulting salt solution phase and obtaining a tar acid phase substantially freed of salt solution, mixing the tar acid phase, from which said salt solution has been separated, with a solvent chosen from the class consisting of methyl alcohol, chloroform, carbon disulfide and sulfur dioxide to effect precipitation of coking constituents, thereafter removing said precipitated coking constituents from the solution of tar acids in said solvent and separating the solvent and other impurities from the tar acids by distillation.
4. In the recovery of tar acids from tar,'the process comprising mixing the tar with an aqueous alkali metal hydroxide solution, separating the resulting aqueous lalkali metal phenolate phase from the tar by centrifugation, adding carbon dioxide to said phenolate phase, separating the resulting alkali metal carbonate solution from the resulting tar acid phase and obtaining a tar acid phase substantially freed of salt solution, mixing the tar acid phase with a solvent chosen from the class consisting of methyl alcohctchlorcforn. disiiiiisieand .Sulfur dioisidefl.. r...ctn ,.tian oi taking @sustituents, thereafter removing said precipitate," olginslcohstitilehts frein the tahitien i .tar acids 5 mtas separating. .the solventahd e., `im!! .,tiesrircm the taratiis byttilla- "5.-" In the.. recgrerveiftar acids from phthalate .d by .extraction 0f tar with an 1o inetalhrdiaxide solution, the protce. adding carbon diQXide t0 'th-e tin. separating the resulting alkali .e `Soliititil from the resulting tar hase,mixing` the tar acid phase, from which 1 @animate tahitien' has been Sep- Sniihsine acid, Vseparating the re,- ffisitfithe1esi1-1.tins salt. S0- in, tar acid phase Substanltdsolution, mixing the tar acid altsolution phase has vent chosen from the g ,l Y alcohol, chloroform, ulde and 'sulfur dioxide to effect preip tion c'okin'g constituents,A Vthereafter remoying, said precipitated ckingA V"constituents from'"the'fslutiwoftar acids'in saidsolvent and separating the solvent and other impurities from the tar acids by distillation.
6. In the recovery of tar acids from phenolate solutions obtained by extraction of tar with an aqueous alkali metal hydroxide solution, the process comprising, adding carbon dioxide to the phenolate solution, separating the resulting alkali metal carbonate solution from the resulting tar -acid phase and obtaining a tar acid phase substantially freed of salt solution, mixing the tar acid phase, from which said salt solution phase has been separated, with a solvent chosen from the class consisting of methyl'alcohol, chloroform, carbon disulfide and sulfur dioxide to effect precipitation of coking constituents, thereafter removing said precipitated coking constituents from the solution of tar acids in said solvent and separating the solvent and other impurities from the tar acids by distillation.
'7. In the recovery of tar acids from phenolate solutions obtained by extraction of tar with an aqueous alkali metal hydroxide solution, the process comprising, mixing the phenolate solution with a springing acid, thereafter separating the resulting tar acid phase from the resulting salt solution phase to obtain a tar acid phase substantially freed of salt solution, mixing the tar acid phase, from which said salt solution phase has been separated, with a solvent chosen from the class consisting of methyl alcohol, chloroform, carbon disulfide and sulfur dioxide to effect precipitation of coking constituents, thereafter removing said precipitated coking constituents from the solution of tar acids in said solvent and separating the solvent and other impurities from the tar acids by distillation.
8. In the recovery of tar acids from phenolate solutions obtained by extraction of tar with an aqueous alkali metal hydroxide solution, the process comprising, mixing the phenolate solution with a springing acid, thereafter separating the resulting tar acid phase from the resulting salt solution phase to obtain a tar acid phase substantially freed of salt solution, mixing the tar acid phase, from which said salt solution phase has been separated, with a solvent chosen from the class consisting of methyl alcohol, chloroform, carbon disulfide and sulfur dioxide to 75 effect precipitation of coking constituents and thereafter removing said precipitated coking con-` stituents from the solution of tar acids in said solvent.
9. In the production of tar acids, the process comprising separating from tar a fraction consisting principally of tar acids, but containing constituents which cause a coke precipitate to form upon distillation, mixing said tar acid fraction with methyl alcohol to effect precipitation of said coking constituents, and thereafter separating the precipitated coking constituents from the resulting solution of tar acids in methyl alcohol.
10. In the production of tar acids, the process comprising separating from tar a fraction consisting principally of tar acids, but containing constituents which cause a coke precipitate to form upon distillation, mixing said tar acid fraction with a solvent chosen from the class consisting of methyl alcohol, chloroform, carbon disulfide and sulfur dioxide to eiect precipitation of said coking constituents from the solution of tar acids in said solvent, and thereafter separating said precipitated coking constituents from said solution.
11. In the recovery of tar acids from tar, the
process comprising mixing the tar with an aque# ous sodium hydroxide solution, separating the resulting aqueous sodium phenolate phase from the tar by centrifugation, concentrating the resulting aqeuous sodium phenolate phase by evaporating water therefrom, adding carbon dioxide to the concentrated phenolate phase, separating the resulting sodium carbonate solution from the resulting tar acid phase, mixing the tar acid phase from which the sodlium carbonate solution has been separated with sulphuric acid, separating the resulting tar acid phase from the resulting salt solution phase by centrifugal force to obtain a tar acid phase substantially free of salt solution, mixing the tar acid phase, from which said salt solution phase has been separated, with a solvent chosen from the class consisting of methyl alcohol, chloroform, carbon disulphide, and sulphur dioxide to effect precipitation of the coking constituents, thereafter filtering the resulting mixture to remove precipitated coking constituents from the solution of tar acids in said solvent and separating the solvent and other impurities from the tar acids by distillation. CHARLES M. AMBLER, JR.
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US289323A US2298816A (en) | 1939-08-09 | 1939-08-09 | Recovery of tar acids |
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Application Number | Priority Date | Filing Date | Title |
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US289323A US2298816A (en) | 1939-08-09 | 1939-08-09 | Recovery of tar acids |
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US2298816A true US2298816A (en) | 1942-10-13 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2573990A (en) * | 1948-03-08 | 1951-11-06 | Crossett Lumber Company | Recovery of medicinal creosote |
US2666796A (en) * | 1950-09-12 | 1954-01-19 | Consolidation Coal Co | Refining of tar acid oil |
-
1939
- 1939-08-09 US US289323A patent/US2298816A/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2573990A (en) * | 1948-03-08 | 1951-11-06 | Crossett Lumber Company | Recovery of medicinal creosote |
US2666796A (en) * | 1950-09-12 | 1954-01-19 | Consolidation Coal Co | Refining of tar acid oil |
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