LV12214B - Paņēmiens darvu sašķidrināšanai - Google Patents
Paņēmiens darvu sašķidrināšanai Download PDFInfo
- Publication number
- LV12214B LV12214B LVP-98-168A LV980168A LV12214B LV 12214 B LV12214 B LV 12214B LV 980168 A LV980168 A LV 980168A LV 12214 B LV12214 B LV 12214B
- Authority
- LV
- Latvia
- Prior art keywords
- tar
- process according
- vvherein
- vvith
- surfactant
- Prior art date
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- 239000011269 tar Substances 0.000 title claims abstract description 220
- 238000000034 method Methods 0.000 title claims abstract description 155
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 157
- 239000000203 mixture Substances 0.000 claims abstract description 139
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
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- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 3
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- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
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- TVFWYUWNQVRQRG-UHFFFAOYSA-N 2,3,4-tris(2-phenylethenyl)phenol Chemical class C=1C=CC=CC=1C=CC1=C(C=CC=2C=CC=CC=2)C(O)=CC=C1C=CC1=CC=CC=C1 TVFWYUWNQVRQRG-UHFFFAOYSA-N 0.000 description 2
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- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- OWZREIFADZCYQD-NSHGMRRFSA-N deltamethrin Chemical compound CC1(C)[C@@H](C=C(Br)Br)[C@H]1C(=O)O[C@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 OWZREIFADZCYQD-NSHGMRRFSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- QUOSBWWYRCGTMI-UHFFFAOYSA-L disodium;2-[2-(carboxylatomethoxy)ethyl-[2-(decanoylamino)ethyl]amino]acetate Chemical compound [Na+].[Na+].CCCCCCCCCC(=O)NCCN(CC([O-])=O)CCOCC([O-])=O QUOSBWWYRCGTMI-UHFFFAOYSA-L 0.000 description 1
- WYHYDRAHICKYDJ-UHFFFAOYSA-L disodium;3-[2-(2-carboxylatoethoxy)ethyl-[2-(decanoylamino)ethyl]amino]propanoate Chemical compound [Na+].[Na+].CCCCCCCCCC(=O)NCCN(CCC([O-])=O)CCOCCC([O-])=O WYHYDRAHICKYDJ-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 235000019688 fish Nutrition 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 239000013056 hazardous product Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical class CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 229940071188 lauroamphodiacetate Drugs 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- KRTSDMXIXPKRQR-AATRIKPKSA-N monocrotophos Chemical compound CNC(=O)\C=C(/C)OP(=O)(OC)OC KRTSDMXIXPKRQR-AATRIKPKSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- UOZFSLAMWIZUEN-UHFFFAOYSA-M sodium;2-[2-(decanoylamino)ethyl-(2-hydroxyethyl)amino]acetate Chemical compound [Na+].CCCCCCCCCC(=O)NCCN(CCO)CC([O-])=O UOZFSLAMWIZUEN-UHFFFAOYSA-M 0.000 description 1
- ZKBGPOVFSMIXBF-UHFFFAOYSA-M sodium;2-[2-hydroxyethyl-[2-(octadecanoylamino)ethyl]amino]acetate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC(=O)NCCN(CCO)CC([O-])=O ZKBGPOVFSMIXBF-UHFFFAOYSA-M 0.000 description 1
- LLKGTXLYJMUQJX-UHFFFAOYSA-M sodium;3-[2-carboxyethyl(dodecyl)amino]propanoate Chemical compound [Na+].CCCCCCCCCCCCN(CCC(O)=O)CCC([O-])=O LLKGTXLYJMUQJX-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 235000020354 squash Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229940066732 stearoamphoacetate Drugs 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 235000020238 sunflower seed Nutrition 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical class CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- XQXWVKQIQQTRDJ-UHFFFAOYSA-N undecyl benzenesulfonate Chemical compound CCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 XQXWVKQIQQTRDJ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
- C10L1/326—Coal-water suspensions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/92—Recovery from acid tar or the like, e.g. alkylation acids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/924—Significant dispersive or manipulative operation or step in making or stabilizing colloid system
- Y10S516/928—Mixing combined with non-mixing operation or step, successively or simultaneously, e.g. heating, cooling, ph change, ageing, milling
Description
1. Paņēmiens darvas ūdeni saturošas suspoemuisijas iegūšanai, kas ietver sekojošas stadijas: maisījuma (M), kas satur:
viskozu darvas maisījumu, kuru veido vismaz viena darva, neorganiskas cietas vielas un, neobligāti, ūdens, ūdeni (0), vismaz vienu virsmaktīvu vielu (VAV), kuras HLB ir vismaz 10, un, neobligāti, vismaz vienu ūdenī šķīstošu biezināšanas polimēru (OŠBP) ar molekulas masu lielāku par apmēram 10,000, sajaukšanu, kur sastāvdaļu (0), (VAV) un, neobligāti, (ŪŠBP) relatīvie daudzumi ir tādi, ka maisījuma (Ū)+(VAV)+neobligāti (OŠBP) viskozitāte ir vienāda ar vai lielāka kā viena desmitdaļa minētās darvas viskozitātes.
2. Paņēmiens saskaņā ar 1. punktu, kas papildus ietver iegūtā maisījuma atšķaidīšanas stadiju ar ūdeni vai ar vismaz vienu skābes ūdens šķīdumu.
3. Paņēmiens saskaņā ar 1. punktu, kur sastāvdaļu (Ū), (VAV) un, neobligāti, (OŠBP) relatīvie daudzumi ir tādi, ka maisījuma (Ū)+(VAV)+neobligāti (ŪŠBP) viskozitāte ir vienāda ar vai lielāka par minētās darvas viskozitāti.
4. Paņēmiens saskaņā ar 3. punktu, kur minētā viskozā darva satur: no apmēram 2 līdz apmēram 70 masas % darvas;
no apmēram 5 līdz apmēram 50 masas % neorganisku cietu vielu; un no 0 līdz apmēram 70 masas % ūdens.
5. Paņēmiens saskaņā ar 1. punktu, kur minētās darvas viskozitāte ir vismaz vienāda ar apmēram 3 Pa s.
6. Paņēmiens saskaņā ar 1. punktu, kur minētais maisījums (M) papildus minētajam viskozajam darvas maisījumam satur uz 100 masas daļām darvas:
no apmēram 30 līdz apmēram 200 masas daļām ūdens (0), un no apmēram 2 līdz apmēram 20 masas daļām vismaz vienas virsmaktīvas vielas (VAV) vai kombināciju, kurā ietilpst no apmēram 0.5 līdz apmēram 10 masas daļas vismaz vienas virsmaktīvas vielas (VAV) un no apmēram 0.001 līdz apmēram 15 masas daļas vismaz viena ūdenī šķīstoša biezināšanas polimēra (ŪŠBP).
7. Paņēmiens saskaņā ar 1. punktu, kur minētā virsmaktīvā viela (VAV) ir izvēlēta no grupas, kurā ietilpst: nejonogēna, anjonu, katjonu, hibrīda vai amfotēra virsmaktīva viela(s) un to maisījumi ar HLB vismaz apmēram 10.
8. Paņēmiens saskaņā ar 1. punktu, kur minētais ūdenī šķīstošais biezināšanas polimērs (ŪŠBP) ir šķīstošs ūdenī līdz vismaz 50% un var būt izvēlēts no grupas, kurā ietilpst: polivinilspirti, polietilēnglikoli, polivinilpirolidoni, sārmu metālu poliakrilāti, karagenāni, algināti, ksantāna sveķi, karboksimetilcelulozes, metilcelulozes, hidroksipropilcelulozes vai hidroksietilcelulozes un to maisījumi.
9. Paņēmiens saskaņā ar 1. punktu, kur maisījums tiek iegūts, ievadot minēto viskozo darvas maisījumu maisījumā: ūdens (Ū)+virsmaktīva viela (VAV)+neobligāti, ūdenī šķīstošs biezināšanas polimērs(i) (ŪŠBP), tad sajaucot pie temperatūras starp apmēram ap 10° un ap 50°C.
10. Paņēmiens saskaņā ar 9. punktu, kas papildus ietver atšķaidīšanas stadiju ar ūdeni vai ar vismaz vienu skābes ūdens šķīdumu.
11. Paņēmiens saskaņā ar 1. punktu, kur sajaukšana tiek veikta, ievadot ūdeni (Ū) maisījumā: viscaur vai daļēji klātesošais viskozais darvas maisijums+virsmaktīvā viela(s) (VAV)+neobligāti, ūdenī šķīstošais biezināšanas polimērs(i) (ŪŠBP), tad sajaucot pie temperatūras starp apmēram ap 10° un ap 50°C, pie kam neobligāti palikušais viskozais darvas maisījums tiek ievadīts maisījumā pēc emulsijas “eļļa ūdenī” izveidošanas, tai laikā turpinot sajaukšanu.
12. Paņēmiens saskaņā ar 11. punktu, kas papildus ietver atšķaidīšanas stadiju ar ūdeni vai ar vismaz vienu skābes ūdens šķīdumu.
13. Paņēmiens saskaņā ar 1. punktu, kas atšķiras ar to, ka sajaukšana tiek veikta ar maisītāju apgādātā mikserī, pie kam maisītājā kustīgā daļa nerotē ātrāk kā apmēram 2500 apgriezieni/minūtē ar tangenciālo ātrumu kustīgās daļas galā, kas nepārsniedz apmēram 20 m/s.
14. Paņēmiens saskaņā ar 13. punktu, kur attiecība tangenciālais ātrums kustīgās daļas galā/attālums starp kustīgās daļas galu un sienu ir mazāka kā apmēram 50,000 s'1.
15. Paņēmiens saskaņā ar 1. punktu, kur sajaukšana tiek veikta ar maisītāju apgādātā mikserī, pie kam maisītājā kustīgā daļa nerotē ātrāk kā apmēram 1500 apgriezieni/minūtē ar tangenciālo ātrumu kustīgās daļas galā, kas nepārsniedz apmēram 5 m/s.
16. Paņēmiens saskaņā ar 15. punktu, kur attiecība tangenciālais ātrums kustīgās daļas galā/attālums starp kustīgās daļas galu un sienu ir mazāka kā apmēram 10,000 s'1.
17. Paņēmiens saskaņā ar 1. punktu, kur sajaukšana tiek veikta ar maisītāju apgādātā mikserī, pie kam maisītājā kustīgā daļa nerotē ātrāk kā apmēram 500 apgriezieni/minūtē ar tangenciālo ātrumu kustīgās daļas galā, kas nepārsniedz apmēram 2.5 m/s.
18. Paņēmiens saskaņā ar 13. punktu, kur attiecība tangenciālais ātrums kustīgās daļas galā/attālums starp kustīgās daļas galu un sienu ir mazāka kā apmēram 2500 s'1.
19. Paņēmiens saskaņā ar 1. punktu, kur viskozais darvas maisījums ir nogulsnes, kas radušās dzidro eļļu sintēzē no naftas frakcijām.
20. Paņēmiens saskaņā ar 1. punktu, kur viskozais darvas maisījums satur vismaz vienu skābi.
21. Paņēmiens saskaņā ar 20. punktu, kur minētā skābe ir sērskābe.
22. Paņēmiens viskozajā darvas maisījumā esošās sērskābes rekuperācijai, kur saskaņā ar 1. punkta paņēmienu tiek iegūta darvas ūdeni saturoša suspoemulsija, kas atšķaidīta ar ūdeni vai sērskābes ūdens šķīdumu, un tad minētā atšķaidītā, ūdeni saturošā darvas suspoemulsija tiek sadedzināta.
23. Paņēmiens darvu/nogulšņu sašķidrināšanai vai darvu/nogulšņu iztīrīšanai no rezervuāriem/traukiem, piemēram, transportēšanas konteineriem, reaktoriem, cauruļvadiem un atkritumu uzglabāšanas konteineriem, kas ietver sekojošas stadijas: darvu/nogulšņu kontaktēšanu ar neorganisku skābi un virsmaktīvu vielu.
24. Paņēmiens saskaņā ar 23. punktu, kur minētā neorganiskā skābe ir izvēlēta no grupas, kurā ietilpst sērskābe, fosforskābe un to maisījumi.
25. Paņēmiens saskaņā ar 24. punktu, kur minētā neorganiskā skābe ir sērskābe.
26. Paņēmiens saskaņā ar 23. punktu, kur minētā virsmaktivā viela ir izvēlēta no grupas, kurā ietilpst nejonogēnas virsmaktīvas vielas, katjonu virsmaktīvas vielas, amfotēras virsmaktīvas vielas, anjonu virsmaktīvas vielas un to maisījumi.
27. Paņēmiens saskaņā ar 23. punktu, kur minētā darva/nogulsnes satur skābi.
28. Paņēmiens saskaņā ar 27. punktu, kur minētā virsmaktivā viela ir izvēlēta no grupas, kurā ietilpst nejonogēnas virsmaktīvas vielas, katjonu virsmaktīvas vielas, anjonu virsmaktīvas vielas un to maisījumi.
29. Paņēmiens saskaņā ar 23. punktu, kur minētās neorganiskā skābe un virsmaktivā viela pirms kontakta ar minēto darvu/nogulsnēm tiek iepriekš sajauktas.
30. Paņēmiens saskaņā ar 23. punktu, kur minētā virsmaktivā viela pirms kontakta ar darvu/nogulsnēm tiek sajaukta ar nesēju.
31. Paņēmiens saskaņā ar 30. punktu, kur minētais nesējs ir izvēlēts no grupas, kurā ietilpst ūdens, dīzeļdegviela, ksilols, metilizobutilketons, izopropilspirts, dimetilsulfoksīds, sērskābe un to maisījumi.
32. Paņēmiens saskaņā ar 27. punktu, kur minētā darva/nogulsnes satur sērskābi.
33. Paņēmiens saskaņā ar 25. punktu, kur minētās sērskābes koncentrācija ir lielāka par apmēram 75%.
34. Paņēmiens saskaņā ar 23. punktu, kas papildus ietver sašķidrinātās dravas/nogulšņu recirkulācijas stadiju, līdz visa darva/nogulsnes ir pārvērstas sūknējamā šķidrumā, un darvas/nogulšņu aizvākšanu.
35. Paņēmiens saskaņā ar 25. punktu, kas papildus ietver minētās sērskābes rekuperācijas stadiju ar reģenerācijas palīdzību.
36. Paņēmiens saskaņā ar 32. punktu, kas papildus ietver minētās sērskābes rekuperācijas stadiju ar reģenerācijas palīdzību.
37. Paņēmiens, kas ietver skābes saturošās darvas/nogulšņu kontaktēšanas stadiju ar virsmaktīvu vielu un nesēju.
38. Paņēmiens saskaņā ar 37. punktu, kur minētā skābes saturošā darva/nogulsnes satur no apmēram 20% līdz apmēram 80% sērskābes.
39. Paņēmiens, kas ietver darvas/nogulšņu kontaktēšanas stadiju ar virsmaktīvu vielu un nesēju, ar kuras palīdzību tiek būtībā aizvākta darva/nogulsnes ar skābes stiprumu lielāku par 20%.
40. Paņēmiens saskaņā ar 39. punktu, kas papildus ietver mehāniskas maisīšanas vai ārējas recirkulācijas stadiju.
41. Paņēmiens, kas ietver darvas/nogulšņu kontaktēšanas stadiju ar skābi ar koncentrāciju no apmēram 75% līdz apmēram 90% pie temperatūras no apmēram 60°F (16°C) līdz apmēram 150°F (66°C) un ar virsmaktīvu vielu, kuras koncentrācijas ir no apmēram 0.2 masas% līdz apmēram 7.5 masas% no gala maisījuma.
42. Paņēmiens saskaņā ar 23. punktu, kur minētā virsmaktīvā viela ir izvēlēta no grupas, kurā ietilpst jaukti oktil/deciispirti, kuri ir etoksilēti un propoksilēti, nonilfenoksipoli(etilēnoksil)etanols, polietoksilēti cieto tauku amīni, izopropilamīnalkilsulfonāts, dinonilfenoksilpoli(etilēnoksi)etanols, etoksilētu un propoksilētu cieto tauku amīnu maisījumi un to maisījumi.
43. Paņēmiens saskaņa ar 23. punktu, kur minēta virsmaktīvā viela ir izvēlēta no grupas, kurā ietilpst katjonu virsmaktīvās vielas.
44. Paņēmiens saskaņā ar 43. punktu, kur minētā katjonu virsmaktīvā viela ir izvēlēta no grupas, kurā ietilpst taukrindas amīnu etoksilātu virsmaktīvās vielas ar vispārējo formulu:
(CH—CH2—0)— (CH2—CH—O)x—H
I ch3
R—N i
(CH — CH2—0)b— (CH— CH—O)y—H CH3 kur R piemēroti apzīmē ogļūdeņražu grupas, kas satur caurmērā 1 līdz 30 oglekļa atomus, un kur a ar b apzīmē no 0 līdz apmēram 50 moliem etilēnoksīda (EO), un x un y apzīmē no 0 līdz apmēram 20 moliem propiiēnoksīda (PO), a, b, x un y summa ir neatkarīga un apzīmē caurmēra vērtības, pie kam a, b, x un y summa ir vismaz 2.
45. Paņēmiens saskaņā ar 26. punktu, kur minētā virsmaktīvā viela ir izvēlēta no grupas, kurā ietilpst:
i) sārmu metālu alkilbenzosulfonāti, alkilsulfāti, alkilēteru sulfāti, alkilarilēteru sulfāti, dialkilsulfosukcināti, alkilfosfāti un ēteru fosfāti;
ii) alifātiskie vai aromātiskie taukrindas amīni, alifātiskie taukrindas amīdi un kvartārie amonija atvasinājumi;
iii) betaīni un to atvasinājumi, sultaīni un to atvasinājumi, lecitīni, imidazola atvasinājumi, glicināti un to atvasinājumi, amīdpropionāti un taukrindas amīnu oksīdi;
iv) alkoksilētas taukskābes, polialkoksilēti alkilfenoli, polialkoksilēti taukrindas spirti, polialkoksilēti vai poliglicerēti taukrindas amīdi, poliglicerēti spirti un «-dioli vai etilēnoksīda/propilēnoksīda blokkopolimēri, alkilglikozīdi, alkilpoliglikozīdi, saharozes ēteri, saharozes esteri, saharozes glicerīdi un sorbīta esteri; un
v) to maisījumi.
46. Paņēmiens saskaņā ar 26. punktu, kur minētās virsmaktīvās vielas HLB vērtība ir vismaz apmēram 10.
METHOD FOR FLUIDIZING TARS
Prioritv to U.S. Provisional Application Senai Number 60/011,977, filed February 20, 1996, is hereby claimed and said application is incorporated herein by reference.
Field of Invention
The present invention relates to methods for fluidizing tars and siudges. Specificallv, the invention relates to processes for cleaning tars, such as spent acid tars, from reaction vessels, process equipment, transportation containers and storage tanks utilizing sulfuric acid, surfactants and optionallv a carrier.
Background of the Invention
Undesirabie products/by products are formed in several Chemical reaction processes. In many cases these undesirabie products tend to separate in storage containers. reactors and other process equipment as highly viscous, stickv or sometimes soiid matter of unknown Chemical composition. These are typically referred to by those skilled in the art as tars or siudges. Their phvsicai nature often times makes them difficult to remove from the containers/vessels vvhere they occur (reactors, storage tanks, transportation containers, pipes or the like) by normai material handling processes such as pumping. Build up over time subtracts from the liquid load carrving or storage capacity of the containers/vessels. Tars can be formed either during a Chemical reactjon process, a phvsicai process such as distillation or during storage and/or transportation. The tars can be classified as organic, acidic etc. based on the physical and Chemical characteristics thev exhibit. Manv organic substances, other than those having a simple structure and a low boiiing point, result after pyrolysis. that is to say heating in the absence of air, in very viscous liquids known as tars.
Large amounts of tar residues are thus produced bv industrial processes. These tars can thus consist of residues resulting from the destructive distillation of organic matter. The distillation of crude oil producēs tar residues knovvn as bitumens or altematively asphalts. These bitumens are generally mixtures of hydrocarbons of high molecular mass (in particular from 500 to 3000), most often of asphaltenes (which can represent up to 25% by vveight of the tar), and of organic substances vvhich are very rich in carbon and in hydrogen but vvhich can also contain oxygen, sulfur or nitrogen, as vvell as' traces of mētai elements, in particular nickel and vanadium. Mention may be made, as examples, of the viscous tar residues resulting from the synthesis of white oils from Petroleum fractions. These viscous tars can contain an acid, in particular sulfuric acid.
These tars constitute vvaste vvhich, because ofits verv high viscositv, is impossibie or extremeiv difficult to pump and to sprav and cannot be easily and inexpensivelv incinerated; this is highlv disadvantageous. in particular vvhen it is desired to recover the vvaste acids vvhich it mav contain. The tars must thus be handled like solīds Their incineration in a rotarv fumace is a substantial cost and can potentiallv contribute to air pollution.
The present invention provides a process for treating these tars vvhich makes it possible to remove the above-mentioned disadvantages. One process of the present invention makes it possible to condition these residues in a fluid form vvhich can be diluted vvith vvater or vvith acid, in highlv varied proportions, and vvhich is stable on storage.
Sulfuric acid is used in reactions such as sulfonations, nitration. or as a cataivst such as in alkvlation in the petroleum refinerv operations or for other uses such as drving, pickling etc. At the end of these processes, the sulfuric acid remains in a form vvhich is not usable and has to be recovered or disposed. This sulfuric acid is commonly referred to as spent acid or spent sulfuric acid. The spent acid can be processed to recover usable sulfuric acid bv a number of processes including the process of regeneration.
It is common practice to store the spent acid in storage tanks prior to recovery of the sulfuric acid either at site or transport them off-site for recovery or disposal. Common transportation modes are tank trucks, raii cars, barges and pipelines.
Tars have been found to be present in some spent acids. When spent acid is associated with tars, thev pose operational problems in material handling and recovery during storage and transportation. When tars are formed in reactors and process equipment, such as heat exchangers, thev reduce the operational capabilitv of the process and the equipment. The tars are a heavv, viscous material which tend to stick to the containers, and in some instances, over a period of time increase in viscosity and react to form solid deposits in the containers. Removal of such tars by normai pumping techniques from storage tanks, reactors or pressure transfer from tank trucks and rail cars, is difficult due to the high viscositv and in some cases the solid nature of the material.
In industrial practice, it is common to remove such tars by physical means such as cutting and opening a passage into the Container follovved bv phvsical removal or by a vacuum technique. A highlv viscous tar is not transportable vvith ordinarv small diameter four or five inch lines using Standard available vacuum trucks, most of vvhich are usuallv capable of creating a vacuum of about tvventv seven to tvventv eight inches of vvater column. Where masses of material cannot be suctioned, personnel are required to manuallv enter and remove the material.
Having to place personnel in intimate phvsical contact vvith the tar/sludge can result in significant health, safetv and environmental issues. When the tar is laden vvith volatile or hazardous materiāls personnel safety and protective equipment can significantlv slovv the removal process. Often ali of the tar/sludge can not be removed and the problem of disposal or transportation remains.
A process of the present invention is advantageous in that it does not involve anv phvsical alteration to the tank to remove the tar/sludge. Instead, it involves treating the tar vvith sulfuric acid and a surfactant to allovv blending of the tar/sludge vvith the sulfuric acid. The process provides a safer alternative to the existing methods of cleaning, especialiv tank cleaning, in that it does not involve anv confined space entrv or othervvise exposing individuāls to potential safetv hazards. Another advantage of the process is the abilitv to recover the tar/sludge in a form vvhich can be easily transported. handled and pumped. Further, it is rendered in a condition for recoverv of saleable sulfuric acid by the regeneration process.
Summarv of the Invention
The present invention relates to a process for the preparation of an aqueous tar suspoemulsion, characterized in that a mixture (M) comprising:
a viscous tar composition formed (i) from at least one tar generally exhibiting a viscosity at least equal to about 3 Pa-s, preferablv at least equal to about 30 Pa-s. (ii) from inorganic solids and, optionaily, (iii) from water, vvater (W), at least one surface-active aģent (SA) exhibiting an HLB (hydrophilicity/ lipophilicitv balance) of at least about 10, for example of at least about 12. and. optionally, at least one thickening water-soluble polymer (TWP) vvith a molecular mass greater than about 10,000, generally greater than about 100,000, is mixed, the relative amounts of constituents (W), (SA) and, optionaliy, (TWP) being such that the viscosity of the (W) + (SA) + optional (TWP) mixture is equal to or greater than about one tenth of the viscositv of said tar, preferablv equal to or greater than the viscositv of said tar, and in that the mixture obtained is optionallv diluted vvith vvater or vvith at least one aqueous acidic solution.
The present invention also relates to a method for fluidizing acidic tars/sludges comprising contact vvith sulfuric acid and a surfactant. Optionally, a carrier for the surfactant’s incorporation into the tar/sludge can be utilized. This provides an effective process for cleaning sulfuric acid tars/sludges from containers/vessels such as transportation containers, pipes and storage tanks.
A process for cleaning sulfuric acid tars/sludges from containers/vessels comprises the steps of contacting the tar/sludge vvith sulfuric acid and surfactant. recirculating the fluidized tar/sludge until ali of the tar/sludge has been fluidized to a pumpable media, and removing the fluidized tar/sludge from the container/vessel. Preferablv. the process comprises the additional step of incineration of the sludge and regeneration of the sulfuric acid.
Unless othervvise stated, ali parts or percents are parts or percents respectivelv by vveight.
Viscosity is understood to mean, in the present account. the dvnamic viscositv measured at 25°C using a Brookfield viscometer according to AFNOR Standard NFT 76102 of Fēbruary 1972.
The term suspoemulsion is employed here to denote an emulsion containing inorganic solīds or pārticies.
“Comprising,” as used herein, means various components can be conjointlv employed. Accordingly, the terms “consisting essentially of’ and “consisting of’ are embodied in the term comprising.
Detailed Description of the Invention
The present invention relates to a process for the preparation of an aqueous tar suspoemulsion, characterized in that a mixmre (M) comprising:
a viscous tar composition formed (i) from at least one tar generally exhibiting a viscositv at least equal to about 3 Pa-s, preferablv at least equal to about 30 Pa-s, (ii) from inorganic solids and. optionallv. (iii) from vvater, vvater (W), at least one surface-active aģent (SA) exhibiting an HLB (hydrophilicitv/lipophilicity balance) of at least about 10, for exampie of at least about 12. and. optionally, at least one tnickening vvater-soluble polymer (TWT) vvith a molecular mass greater than about 10,000, generally greater than about 100,000, is mixed, the relative amounts of constituents (W), (SA) and, optionallv, (TWP) being such that the viscositv of the (W) - (SA) - optional (TWP) mixture is equal to or greater than one tenth of the viscositv of the said tar. preferablv equal to or greater than the viscositv of said tar, and in that the mixture obtained is optionallv diluted vvith vvater or vvith at least one aqueous acidic solution.
The viscous tar composition can generallv contain:
from about 2 to about 70%, preferablv from about 5 to about 30%. for example from about 10 to about 25%. bv vveisht of tar;
from about 5 to about 50%, preferablv from about 10 to about 45%, for example from about 25 to about 40%, by vveight of inorganic solīds;
from 0 to about 70%, preferablv from about 5 to about 65%, for example from about 30 to about 65%, by vveight of vvater.
The viscous tar composition thus preferentially contains vvater. The tar + inorganic solīds combination forms a water-immiscible phase. These inorganic solids generally result from the svnthesis of the tar.
Mention may be made, as examples of inorganic solids present in the viscous tar composition to be emulsified, of in particular diatomaceous earths, silica povvders, quartz, sand, sand-gravel mix, calcium carbonate, mica, talc, sulfur or traces of mētai elements; the particle size of these inorganic solids is generallv from approximately 0.001 to 300 gm.
The mixture (M) to be mixed verv advantageouslv comprises, in addition to the viscous tar composition, per 100 pans bv vveight of tar;
from about 30 to about 200, preferablv from about 40 to about 120. parts by vveight of vvater (W), and either from about 2 to about 20. preferablv from about 3 to about 15. pans bv vveight of at least one surface-active aģent (SA) or. preferably, on the one hand, from about 0.5 to about 10, preferablv from about 1 to about 10, pans bv vveight of at least one surface-active aģent (SA) and. on the other hand, from about 0.001 to about 15, preferablv from about 0.1 to about 10, parts by vveight of at least one thickening vvater-solubie polvmer (TWP).
In particular, the mixture (M) to be mixed can comprise, in addition to the viscous tar composition, per 100 pans by vveight of tar:
from about 45 to about 100. for example from about 60 to about 100. pans by vveight of vvater (W), and either from about 5 to about 10 parts by vveight of at least one surface-active aģent (SA) or. preferably, on the one hand, from about 2 to about 5 parts bv vveight of at least one surface active aģent (SA) and. on the other hand. from about 0.5 to about 5 parts bv vveight of at least one thickening vvater-solubie polvmer (TWP).
According to one alternative form of the invention, it will be possible to use, depending on the tar content of the viscous tar composition, preferably of betvveen about 2 and about 70% bv weight. an amount of mixture containing about 2 to about 6% of surface-active agent(s) (SA) and from about 0.5 to about 2.5% of thickenmg vvatersoluble polvmer(s) (TWP) in water (W) of between about 1/20 and about 1/4, in particular betvveen about 1/15 and about 1/5, for example betvveen about 1/13 and about 1/6, of the amount of viscous tar composition; it vvill be possible in particular for this ratio to be betvveen about 1/9 and about 1/7.
Besides the viscous tar composition and the vvater (W), the mixture (M) to be mixed comprises at least one surface-active aģent (SA) exhibiting an HLB of at least about 10, for example of at least about 12. The surface-active aģent (SA) can be chosen from nonionic, anionic, cationic, zvvitterionic or amphoteric surface-active aģents having an HLB of at least about 10, or their mixtures.
It is thus possible to emplov at least one anionic surface-active aģent with an HLB of at least about 10 chosen from alkali mētai alkylbenzenesulphonates, alkyl sulphates, alkvl ether sulphates, alkylaryl ether sulphates, dialky 1 sulphosuccinates, alkyl phosphates or ether phosphates.
It is possible to use at least one cationic surface-active aģent vvith an HLB at least equal to about 10 chosen from aliphatic or aromatic fattv amines, aliphatic fattv amides or quatemarv ammonium derivatives.
Ionic surface-active aģents vvith an HLB greater than 20 may be suitable. It is also possible to emplov at least one zvvitterionic or amphoteric surface-active aģent vvith an HLB of at least about 10 chosen from betaines and their derivatives, sultaines and their derivatives, lecithins, imidazoline derivatives, glycinates and their derivatives, amidopropionates or fattv amine oxides.
Use is preferablv made of at least one nonionic surface-active aģent exhibiting an HLB of at least about 10 chosen, for example, from alkoxylated fatty acids, polyalkoxylated alkylphenols, polvalkoxylated fattv alcohols, polyalkoxvlated or polyglycerolated fattv amides, polyglycerolated alcohols and α-diols or ethylene oxide/propylene oxide block copolvmers, as vvell as alkvlglucosides, alkvlpolvglucosides, sucroethers. sucroesters, sucroglvcendes or sorbitan esters.
The mixture (M) to be mixed preferably also comprises at least one thickeninu water-soluble polvmer (TWP) vvith a molecular mass greater than about 10.000 (g/mol), generallv greater than about 100.000 (g/mol).
The said thickening vvater-soluble polymer (ΤλΥΡ) is generally soluble to at least about 50% in water. Mention mav in particular be made, as examples of thickening vvatersoluble polymers (TWP) vvhich can be used, of;
those obtained by Chemical svnthesis, such as poly(vinyl alcohol)s, poly(ethylene glycol)s, polyvinylpyrrolidones or poly(alkali mētai acrylate)s, those extracted from plants and optiona!ly modified, such as carrageenans, alginates, carboxymethyl celluloses, methyl celluloses, hydroxypropyl celluloses or hydroxvethyl celluloses. and those obtained by biosvnthesis. such as xanthan gum.
The surface-active agent(s) (SA) + thickening vvater-soluble polvmer(s) (TWP) svstem constitutes a verv effective stabilizing/dispersing aģent for the viscous tar composition.
The relative amounts of water fW), of surface-active agent(s) (SA) and of optional vvater-soluble polvmer(s) (TWP) are a function of the viscositv of the tar of the viscous tar composition, as vvell as of the nature of the (mixture of) surfactant(s) (SA) and of the nature of the (mixture of) optional thickening vvater-soluble polvmer(s) (TWP). These relative amounts are such that the viscositv of the (W) + (SA) + optional (TWP) mixture is equal to or greater than about one tenth of the viscosity of the tar. preferablv equal to or greater than the viscosity of the tar.
The amounts of surface-active agent(s) (SA) and of thickening vvater-soluble polvmer(s) to be used are generallv low, v/hich is very advantageous. in particular from an economic vievvpoint.
The mixing operation is carried out for a time and under shear conditions vvhich are sufficient for an emulsion of oil-in-vvater type to be obtained. The mixing time. vvhich generallv increases as the viscous tar composition becomes richer in tar. can be onlv betvveen about 0.5 and about 4 hours. Slovv stirring is. moreover, generallv sufficient.
The operation of emulsifving the tar can be carried out by:
- introducing the viscous tar composition into a vvater (W) + surface-active agent(s) (SA) + optional thickening water-soluble polymer(s) (TWP) mixture and then mixing at a temperature generallv of betvveen approximately about 10 and about 50°C; or introducing the water (W) into a viscous tar composition entirely or partially present + surface-active agent(s) (SA) + optional thickening vvater-soluble polymer(s) (TWP) mixture and then mixing at a temperature generally of betvveen approximately about 10 and about 50°C, the amount of viscous tar composition optionally remaining being introduced into the mixture after the formation of an emulsion of oil-in-water type while maintaining the mixing.
Any conventional mixing device can be utilized, particularly slovv-stimng devices.
Thus, the mixing operation can be carried out in a mixer equipped with a stirrer, a stirrer in vvhich the mobile part does not rotate at more than about 2500 revolutions/min (preferably not at more than about 1500 revolutions/min and, more particularly, not at more than about 500 revolutions/min) vvith a tangential velocity at the end of the mobile part not exceeding about 20 m/s /preferablv not exceeding about 5 m/s and, more particularly, not exceeding about 2.5 m/s); advantageouslv, the tangential velocity at the end of the mobile parv'distance betvveen the end of the mobile part and the vvail of the mixer ratio is less than about 50.000 s_i, preferablv less than about 10,000 s'1 and, more particularly, less than about 2500 s‘!. Mention mav be made, by way of examples, of single- or multiple-screvv extruders, planetarv mixers. hook mixers, s!ow dispersers, stātie mixers or paddle, propeller, arm or anehor mixers.
The viscous tar composition can also contain a hydrocarbon phase vvhich exhibits a viscosity vvhich is much lovver than that of the tar or a viscositv in the region of or equal to that of the tar.
Monitoring of the distribution of the sizes of the pārticies vvhich thev contain shovvs that the tar suspoemulsions obtained according to the process of the invention are stable on storage.
The tar suspoemulsions obtained according to the process of the invention are completelv dilutable vvith vvater or vvith an aqueous acidic solution (in particular a nīcration vvaste acid), for example an aqueous sulfuric acid solution. Thev can thus be easilv pumped and can be easily spraved into an incineration fumace for Iiquids.
Thev can generally exhibit a viscositv of less than about 80 mPa-s (in particular for a vvater content of greater than about 55% by weight), in particular of less than about 6 mPa-s (in particular for a water content of greater than about 65% by weight), for example at a gradient of about 3s'1.
The starting viscous tar composition can in particular be a residue resulting from the svnthesis of vvhite oils from petroleum fractions. The process according to the invention finds a particularly advantageous application vvhen the starting viscous tar composition contains at least one acid. in particular sulfuric acid, as often in the case of a residue resulting from the synthesis of vvhite oils from petroleum fractions. It is then in particular possible, and this constitutes another object of the invention. to recover the sulfuric acid by preparing, according to the process described above, an aqueous tar suspoemulsion. diluted vvith vvater or vvith an aqueous sulfuric acid solution, and bv then incinerating the dilute aqueous tar suspoemulsion.
The follovving example illustrates the invention vvithout, hovvever, limiting the scope thereof. It is realized that charges and variations may be made that are not shovvn belovv. Such changes vvhich do not materiallv alter the process, formulation or function are stili considered to fall vvithin the spirit and scope of the invention as recited bv the claims that follovv.
EXAMPLE
Use is made of a viscous tar composition vvith the follovving composition (% by vveight):
• tar 16% inorganic solids 34% • vvater 50%
The inorganic solids content is determined bv combustion at 950°C and the vvater content by thermogravimetnc analvsis at 100°C.
0
The viscosity of the tar is greater than 50 Pa-s.
A mixture is prepared vvhich contains, in vvater (% bv vveight):
• 1.5% of Guar CSA 200/50 (thickening vvater-soiuble polvmer);
• 2% of Soprophor B.S.U.* (ethoxylated tristyrylphenol vvith an HLB equal to 12.5 (non-ionic surface-active aģent));
• 2% of Soprophor 3D33 (phosphated and ethoxylated tristyrylphenol vvith an HLB equal to 16 (anionic surface-active aģent)).
For this, the Guar is added to vvater vvith vigorous stirring, the surfactants are then introduced and the mixture is homogenized vvith gentle stirring in order not to generate foam. The viscositv of the mixture after 1 hour is approximately 21 Pa-s.
grams of this mixture are placed in a mixer equipped vvith a gate-type paddle rotating at 500 revolutions/min and 7 times 50 grams of the abovementioned viscous tar composition are added thereto; stirring is maintained until the mixture is homogeneous.
An aqueous tar suspoemulsion is then obtained vvhich has the follovving composition (% by vveight):
• tar + other organic matter 28.5% inorganic solīds 14.5% • vvater 57.0%
This dispersion contains pārticies vvith a mean size of 4.0 pm. Monitoring the distribution of the sizes of the pārticies shovvs that this aqueous suspoemulsion is stable for at least 48 hours. This dispersion is then easilv diluted vvith a vvaste acid containing 60% of H,SO4 in vvater.
A fluid aqueous suspoemulsion is obtained vvhich contains (% by vveight):
20.5% of tar + other organic matter • 7.0% of inorganic soiids • 72.5% of vvater + acid.
This aqueous suspoemulsion is easilv pumped and then spraved into a fumace in order to be incinerated therein.
As previousiy mentioned. tars/siudges originate from different sources. Acid tars/sludges are formed in rēactions vvhich use sulfuric acid. oleum (fuming sulfuric acid)
1 and sulfurtrioxide (SO3) as reactant, medium or catalvst. A tvpical process using sulfunc acid, oleum or sulfurtrioxide as a reactant is the sulfonation reaction where these react vvith organic compounds resulting in sulfonic acids. There are several instances of organic sulfonic acids in chemistry and industrial practice. In many cases, excess sulfunc acid is used for the sulfonation in order to fullv utilizē the organic compound being sulfonated and the sulfuric acid also acts as a solvent and reaction medium during the sulfonation process. After the desired product, namelv, the sulfonic acid has been recovered. the process has to deal vvith the handling and disposai of the spent acid. Both during the sulfonation process and thereafter during storage of the spent acid, tars/sludges are formed.
Another source of tar/sludge vvould be a reaction vvhere sulfuric acid is not the primary reactant but acts as a medium for the reaction. A typical example of such a reaction vvould be a nitration reaction vvhere nitric acid is the primary reactant and sulfuric acid is necessarv to promote the reaction of the organic compound vvith the nitric acid. Nitrations are typically done vvith what is called a nitrating acid vvhich is a mixture of nitric acid and sulfuric acid. Here again, as in sulfonation. both during the nitration and after the nitro compound has been isolated. the spent acid vvhich contains sulfuric acid and other impurities has to be recovered. This is another source for tar/sludge.
In the process of manufacture of high grade gasoline, sulfuric acid is used as a catalvst in the reaction called alkvlation. The alkvlation process involves the reaction of “light” olefms containing 3.4 and/or 5 carbon atoms vvith isobutane in the presence of an acid catalvst. Typicallv, the olefms are propylene, 2-butene and 2-methyl butene and the predominant products are a mixture of 2,4 Dimethylpentane, 2,2,4 Trimethvlpentane and 2,2,5 Trimethylpentane. There are competing side-reactions vvhich result in polvmerizations. After the recovery of the gasoline, the spent acid (commonly knovvn as “alkv spent” to designate the origin of the spent acid) is transferred to storage tanks and then transported for sulfuric acid regeneration. Tars are knovvn to form during the alkvlation reaction and tend to accumulate in the storage tanks and transportation containers.
The sulfuric acid present in the tars and sludges from the above processe.^ tvpicallv ranges from about 15% to about 90%. preferablv from about 20% to about 80%
2 in strength. Typicallv the tar/'sludge can contain sulfuric acid in the range of 20% to 80%, vvater from 10% to 35% a carrier such as diesel. xvlene or other organic Chemicals in the range of from about 1% to about 30% and carbonaceous matter commonlv referred to as tar in the range of 10% to 55%. The tars/sludges can have a viscosity of from about 2000 to greater than 10,000 centipoise.
The first component of the present invention is an inorganic acid. The inorganic acid employed in this invention is a strong acid. such as sulfuric acid (H2SO4). Sulfuric acid suitable for use is anv commercially available sulfuric acid. Typicallv, this can be any of the commercially available concentrations - 77.7%, 93.2%, 99%, 100%, 104.5%, 109% and 114.6%. The last three concentrations are also referred to in commerce as 20%, 40% and 65% Oleum. The strength of the acid utilized can vary depending on the type of tar to be treated. Strengths below 77.7% can be utilized, such as ranging below about 76% or belovv about 70% or less. Generally, the preferred strength for use herein is the 93% sulfuric acid. Phosphonc acid can be utilized in the place of sulfuric acid. Mixtures of sulfuric and phospnoric can also be utilized.
The second component of the invention is the surface-active aģent, othervvise referred to herein as “surfactant. Suitable surfactants for use are nonionic surfactants, cationic surfactants. amphoteric (including zvvinerionics) surfactants, anionic surfactants and mixtures thereof. Preferred surfactants for use are nonionic surfactants, cationic surfactants, anionic surfactants and mixtures thereof. Amphoterics are not preferred for use vvith acidic tars/sludges, particularly spent sulfuric acid tars/sludges. Preferably, the surfactant is compatible vvith the acid environment and more preferably also stable in non-acid environments. Preferablv, compatibilitv is determined by the absence of any reaction betvveen the surfactant and the acid and tar system and also by the stability of the fluidized tar resulting from the use of the surfactant system. Some degree of reaction can be acceptable and it is vvithin the skill of an artisan to determine the compatibilitv'.
Preferred surfactants useful herein include: mixed octvl/decvl alcohols vvhich are ethoxylated and propoxylated. nonlyphenoxypoly(ethyleneoxy)ethanol, polyethoxylated tallovv amine, isopropvlaminealkvlarvlsulfonate. dinonylphenoxypoly(ethvleneoxy)ethanol. mixtures of ethoxvlated and propoxylated tallovv amine and mixtures thereof. Amphoteric surfactants vvhich can be utilized include: sodiumlauriminodipropionate,
3 cocamidopropvlbetaine, cocoamphohydroxypropyl sulfonate and mixtures thereof. Based on the composition of the tars. selection of the appropriate surfactant is made and experimentally tested for the stabilitv (gelling, heat evolution and reaction vvith the tar components) of the mix of the tar with the acid svstem.
Surfactants having an HLB of at least about 10 or their mixtures are preferred for use. Ionic surfactants with an HLB greater than about 20 are also preferred.
Examples of useful nonionic surfactants include condensates of ethvlene oxide vvith a hydrophobic moiety vvhich has an average hydrophilic lipophilic balance (HLB) betvveen about 8 to about 16, and more preferably, betvveen about 10 and about 12.5. These surfactants include the condensation products of primary or secondary aliphatic alcohols having from about 8 to about 24 carbon atoms, in either straight or branched chain conftguration, vvith from about 2 to about 40, and preferablv betvveen about 2 and about 9 moles of ethylene oxide per mole of aicohol.
In a preferred embodiment the aliphatic aicohol comprises betvveen about 9 and about 18 carbon atoms and is ethoxvlated vvith betvveen about 3 and about 12 moles of ethvlene oxide per mole of aliphatic aicohol.
Preferred nonionic surfactants exhibiting an HLB of at least about 10 can be chosen. for example, from alkoxylated fattv acids, polyalkoxylated alkylphenols, polyalkoxylated fattv alcohols. polyalkoxvlated or polvelvcerolated fattv amides, poivglvcerolated alcohols and χ-diols or ethylene oxide/propylene oxide block copolvmers, as vvell as alkylglucosides, alkylpoiyglucosides. sucroethers. sucroesters, sucroglvcerides or sorbitan esters.
Other suitable nonionic surfactants include the condensation products of about 6 to about 12 carbon atom alkvl phenols vvith about 3 to about 30, and preferablv betvveen about 4 and 14 moles of ethylene oxide. Examples of such surfactants are sold under the trade names Igepal CO 430, Igepal CO 530, Igepal CO 630, Igepal CO 720 and Igepal CO 730 by Rhone-Poulenc Inc. Stili other suitable nonionic surfactants are described in U.S. Patent No. 3,976.586. To the extent necessarv, this patent is expresslv incorporated by reference.
Other suitable nonionic surfactant for use herein are sold under the trade names Antarox TA 4400 and Antarox BL 240 bv Rhone-Poulenc Inc.
4
Cationic surfactants suitable for use include the quatemary compounds imidazoiines. dialkvl quats and benzvl quats as well as the amine oxides, fatty imidazoiines and ethoxvlated amines.
Cationic surfactants suitable for use are ethoxvlated tallow amines disclosed in U.S. Patent No. 5,409,574, issued April 25, 1995, to Razac et al. and to the extent necessary incorporated herein by reference.
The propoxylated fattv amine ethoxylate surfactants used in the invention can be represented by the general average formuia:
(CH,-CH2-O)a-(CH,-CH-O)x-H | I | CHj
R-N (CH?-CH,-O)b-(CH2-CH-O)z-H
I
CH, where R suitably represents hvdrocarbon groups containing an average value of between
1-30 carbon atoms, and wherein a plus b represent from 0 to about 50 moies ethvlene oxide (EO), and x and y represent from 0 to about 20 moles propylene oxide (PO), the sum of a. b, x. and v being at least 2, and preferablv from about 6 to about 22, it being understood that a, b, x, and v represent average numerical values and that the formula is an average representation. the various groups being disposed independently in each amine substituent chain, e.g., EO-PO-EO. EO-EO-PO. EO-EO-EO, ΡΟ-ΡΟ-ΡΟ, EO-PO-PO, PO-EO-PO and the like.
The hydrocarbon groups can be aliphatic or aromatic, and, if aliphatic, can be linear, branched or cyclic in nature, and can be the same or different particularlv in the case of fatty radicals which are a composite of various chain length materiāls. The aliphatic hydrocarbon radical can contain ethvlenic unsaturation. Preferably the aliphatic groups are selected from among alkvl groups. and substituted alkvl groups thereof, such as long chain alkvl groups, preferablv having from ό to 30, preferablv 6 to 22, carbon atoms, such as stearvl. lauryl, devi. cetvl. tridecvl. tetradecvl, hexadecyl, dodecyl,
5 octadecvl, nonadecyl, tallow, coco, šova, mvristvl and other natūrai fatty radicals from animal, fish, vegetable and oil seed sources (coconut oil, palm kemel oil, babassu oil, rape seed oil. sunflower seed oil and the like) or substituted groups thereof, derived from natūrai or synthetic sources. These compounds can be illustrated by cocamine ethoxylate propoxylate, laurylamine ethoxylate propoxvlate, tallowamine ethoxylate propoxylate, oleylamine ethoxylate propoxylate, stearylamine ethoxylate propoxylate, myristyiamine ethoxylate propoxylate, cetyiamine ethoxylate propoxylate and the like.
Preferred cationic surfactants vvith an HLB at least equal to about 10 can be chosen from alipatic or aromatic fatty amines, aliphatic fatty amides or quatemary ammonium derivatives.
Commercially available cationic surfactants for use are RHODAMEEN® PN 430. RHODAMEEN® VP-532/SPB and RHODAMEEN® ethoxylated fatty amines. ALKAQUAT® and RHODAQUAT® cationic quatemaries, RHODAMOX® amine oxides. and MIRAMīNE® cationic imidazolines and fatty amine condensates sold bv RhonePoulenc Inc.. Cranbury, New Jersev.
Examples of suitable amphoteric surfactants include the alkali mētai, alkaline earth mētai, ammonium or substituted ammonium salts of alkvl amphocarboxv glvcinates and alkyl amphocarboxypropionates. alkvl amphodipropionates, alkvl amphodiacetates. alkyl amphogiycinates and alkvl amphopropionates vvherein alkvl represents an alkvl group having 6 to 20 carbon atoms. Other suitable amphoteric surfactants include alkvl iminopropionates, alkvl iminodipropionates and alkyl ampnopropvlsulfonates having betvveen 12 and 18 carbon atoms; alkvl betaines and amidopropyl betaines and alkvl sultaines and alkylamidopropyihydroxy sultaines wherein alkyl represents an alkvl group having 6 to 20 carbon atoms.
Particularlv useful amphoteric surfactants include both mono and dicarboxylatcs such as those of the formulae:
6
O CH,CH,OH
H / '
R - C - NHCH2CH2N (I); and (CH2)X coom
CH,CH,OH (CH,)xCOOM ļļ ‘ ' X
R - C - NCH-.CH-.N (II) (CH2)xCOOM vvherein R is an alkyl group of 6-20 carbon atoms, x is l or 2 and M is hydrogen or sodium. Mixtures of the above structures are particulariy preferred.
Other formulae for the above amphoteric surfactants include the follovving:
AIkyl betaines
CH,
RVN-CH,COOM (III);
CHa ch3
Amidopropvl betaines
O ll
R-C-NH-CH2CH-*N-CH2COOM (IV);
CH,
Alkvl sultaines
CH3
R-NTcH2-CH-CH2SO3M (V); and tH, OH
Alkyl amidopropylhydroxv sultaines
O CH3
U i
R-C-NH-CH->CH-,-’N-CH-,-CH-CH-1SO1M (VI);
‘ i ‘i
CH3 OH vvhere R is a alkvl group of 6-20 carbon atoms and M is potassium, sodium or a 35 monovalent cation.
7
Of the above amphoteric surfactants, particularly preferred are the alkali salts of alkyl amphocarboxyglycinates and alkyl amphocarboxypropionates, alkyl amphodipropionates, alkvl amphodiacetates. alkyl amphoglycinates, alkyl amphopropvl sulfonates and alkyl amphopropionates vvherein alkyl represents an alkyl group having 6 to 20 carbon atoms. Even more preferred are compounds vvherein the alkyl group is derived from coconut oil or is a lauryl group, for exampie cocoamphodipropionate. Such cocoamphodipropionate surfactants are commercially sold under the trademarks MIRANOL C2M-SF CONC. and MIRANOL FBS by Rhone-Poulenc Inc.
Other commercially useful amphoteric surfactants include:
cocoamphoacetate (sold under the trademarks MIRANOL ULTRA C-32 and MIRAPON FA), cocoamphopropionate (sold under the trademarks MIRANOL CMSF CONC. and MIRAPON FAS), cocoamphodiacetate (sold under the trademarks MIRANOL C2M CONC. and
MIRAPON FB).
lauroamphoacetate (sold under the trademarks MIRANOL HM CONC. and MIRAPON LA), lauroamphodiacetate (sold under the trademarks MIRANOL H2M CONC. and MIRAPON LB), lauroamphodipropionate (sold under the trademarks MIRANOL H2M-SF CONC. AND MIRAPON LBS), lauroamphodiacetate obtained from a mixture of lauric and myristic acids (sold under the trademark MIRANOL BM CONC.), and cocoamphopropyl sulfonate (sold under the trademark MIRANOL CS CONC. ) caproamphodiacetate (sold under the trademark MIRANOL S2M CONC.), caproamphoacetate (sold under the trademark MIRANOL SM CONC.), caproamphodipropionate (sold under the trademark MIRANOL S2M-SF CONC.). and stearoamphoacetate (sold under the trademark MIRANOL DM).
Also useful herein are the betaines and amidobetaines vvhich are compounds of the general structure:
8
CH3 CH, l I
R2-N-CR3R4-CO2 and R2-C0-NHiCHU, - N’-CR3R4-CO2 l ’ I
CH3 CH3 respectivelv wherein R2 is C8 - C22 aikyl or alkenvl; R3 is H or C1 - C4 alkyi; and R4 is 10 HorCl-C-4 alkyl.
The betaines useful herein include the high alkyl betaines such as cocodimethyl carboxymethyl betaine. laurvl dimethyl carboxymethyl betaine, lauryl dimethyl alphacarboxy-ethyl betaine, cetvl dimethvl carboxymethyl betaine, lauryl bis-(2-hydroxyethyl)carboxy methvl betaine, stearyl bis-(2-hydroxy-propyi)carboxymethyl betaine, olevl dimethy! gamma-carboxypropyl betaine, and laurvl bis-(2-hydroxypropyl)alphacarboxyethyl betaine. The sulfobetaines are also preferred and may be represented bv cocodimethvl sulfopropvl betaine. stearyldimethyl sulfopropyl betaine, laurvl dimethvl sulfoethvl betaine, laurvl bis-('2-hydroxv-ethyl)sulfopropyl betaine and mixtures thereof. A particularlv preferred composition utilizēs cocoamidopropvl betaine.
Preferred amphoteric (including zvvitterionic) surfactants vvith an HLB of at least about 10 can be chosen from betaines and their derivatives. sultaines and their derivatives, lecithins, imidazoline derivatives, glycinates and their derivatives, amidopropionates or fattv amine oxides.
Useful anionic surfactants include anv of the knovvn hvdrophobes attached to a carboxvlate, sulfonate. sulfate or phosphate polar. solubiliztng group including salts. Salts may be the sodium, potassium, calcium. magnesium. barium, iron, ammonium and amine salts of such surfactants.
Examples of such anionic surfactants include vvater soluble salts of alkyl benzene sulfonates having betvveen 8 and 22 carbon atoms in the alkyl group, alkvl ether sulfates having betvveen 8 and 22 carbon atoms in the alkvl group, alkali mētai, ammonium and alkanolammonium salts or organic sulfuric reaction products having in their molecular strueture an alkvl. or alkarvl group containing from 8 to 22 carbon atoms and a sulfonic or sulfuric acid ester group.
9
Preferred anionic surfactants vvith an HLB of at ieast about 10 can be chosen from alkali mētai alkvlbenzenesulphonates. alkvl sulphates, alkyl ether sulphates, alkvlarvl ether sulphates. dialkvl sulp’nosuccinates. alkvl phosphates or ether phosphates.
Particularlv preferred are linear sodium and potassium alkyl ether sulfates that are svnthesized by sulfating a higher aicohol having betvveen 8 and 18 carbon atoms and having
2 to 9 moles of ethvlene oxide. Another anionic surfactant is alkyl benzene sulfonate, in vvhich the alkyl group contains betvveen about 9 to about 15, and preferably, betvveen about 11 to about 13 carbon atoms in a straight chain or branched chain configuration and most preferablv a linear straight chain having an average alkyl group of about 11 carbon atoms.
Mixtures of anionic surfactants can be utilized, including mixtures of alkyl or alkvlarvl sulfonate and sulfate surfactants. Such embodiments comprise a mixture of alkali mētai salts, preferablv sodium salts, of alkvl benzene sulfonates having from about 9 to 15. and more preferred betvveen 11 and 13 carbon atoms vvith an alkali mētai salt, preferablv sodium, of an alkvl sulfate or alkvl ethoxy sulfate having 10 to 20 and preferablv 12 to IS carbon atoms and an average ethoxyiation of2 to 4.
.Anionic surfactants vvhich mav be selected include linear alkvl benzene sulfonates such as dodecvlbenzene sulfonate. decvlbenzene sulfonate, undecvlbenzene sulfonate. tridecvlbenzene sulfonate. nonvlbenzene sulfonate and the sodium, potassium. ammonium, tnethanolammoruum and isopropvlammonium salts thereof. A preferred anionic surfactant is a linear isopropvlamine dodecvlbenzene sulfonate; one of vvhich is sold under the tradename Rhodacal® EP.AM by Rhone-Poulenc Inc.. A suitaible sulfonate salt is sodium. dodecylbenzene sulfonate. Such Chemicals are sold under the trade name Biosoft 100 by Stepan Chemicals of Northfield. Illinois. Other anionic surfactants include polyethoxylated aicohol sulfates. such as those sold under the trade name Neodol 25-3S by Shell Chemicai Companv. Examples of other anionic surfactants are provided in U.S. Patent No. 3,976,586.
To the extent necessarv. this patent is expressly incorporated bv reference.
An optional component is a carrier for the introduction of the surfactant into the tar/sludge. The camer can be aqueous or organic and is preferablv selected from the group consisting of vvater. diesel. xylene. methvl isobutvl ketone, isopropvl aicohol. an inorganic acid (e.g.. sulfuric acid) and dimethvlsulfoxide. It is used for ease of introduction of the surfactant, to provide stabilitv to the mix and result in effective clean2 0 out of the tar/sludges from the containers. Preferred carriers are vvater, diesel xviene and mixtures thereof and most preferred is diesel.
Another optional component is a suspending aģent such as guar gum, a poivsacchande blend or other similar acting poivmer can be utilized. A preferred guar is sold under the tradename Jaguar® bv Rhone-Poulenc Inc.
The process of the present invention can comprise the addition of the acid and surfactant into the container/vessel containing the tar/sludge. Preferablv, the surfactant and acid are premixed prior to introduction to the container/vessel. Another method of addition is to introduce the surfactant premixed vvith a carrier and introduce the acid separately. When the tar/sludge to be fluidized has an acid strength of greater than about
20%, preferably greater than about 30%, more preferablv greater than about 40% and most preferablv greater than about 50%, there can be sufficient acid present such that additional acid need not be added and the surfactant vvith the acid present in the tar vvill act sufficientiv to fluidize the tar/sludge and clean the container/vessel. To fluidize the tar/sludge is to provide a pumpable/flovvable mixture.
Mechanical agitation and or extemai recirculation can be utilized. Hovvever, mechanical agitation and or extemai recirculation are not necessarv. The surfactant. acid and tar/sludge can be contacted and allovved to remain in contact for a sufficient amount oftime to achieve fluidization.
The second embodiment/process of the present invention is applicable to acidic tars/sludges and to nonacidic tars/sludges. It is preferred for use vvith acidic tars/’sludges. Surprisingly. the method of the present invention cleans the containers vessels until substantially free of tar/sludge, i.e., preferablv about 90% free, more preferably about 95% free and most preferablv about 100% free of tar sludge material.
Blending the surfactant vvith the acid, preferablv sulfuric acid, is preferablv done vvithin the approximate temperature range of from about 60°F (16°C) to about 150°F (66°C) and more preferablv vvithin the approximate range of from about 75°F (24°C) to about 100°F (38°C). Excessivelv high temperatures are not emploved since they can result in charring and the formation of solid carbonaceous matter. The highest recommendec temperature bv the invention vvithout anv signifieant charring is about
150°F(66°C).
1
A process of the present invention for cleaning storage tanks and transportation containers until substantiallv free of the sludge and tars comprises contacting the tar/sludge vvith sulfuric acid of about 75% to about 98% concentration at a temperature of from about 60°F to about 150°F: introducing a surfactant into the tar/sludge/su!furic acid mix at concentrations ranging from about 0.2% to about 7.5% by weight of the final blend and optionallv contacting the tar /sludge with diesel, xylene, water or other carrier. Further, the present invention relates to a process in which the contacting is done bv mechanical agitation and or extemal recirculation in a tank, or introduction of the acidsurfactant mix in the suction side of a pump and recirculating through the tank/transportation containers via nozzles or openings at the top or sides of the tank/transportation containers.
The following examp!es are provided to better describe and define the present invention vvithout, hovvever limiting the scope thereof. They are for illustrative purposes only, and it is realized that changes and vanations may be made that are not shovvn belovv. Such changes vvhich do not materiallv alter the process, formulation or function are stili considered to fall vvithin the spint and scope of the invention as recited by the claims that follovv.
EXAMPLE 1
In this example tar is cleaned out from a rail car vvhich is full of tar. Removing the tar manuallv by cutting an access is deemed too costly and the other option vvould be to dispose of the car in a land vault. The spent acid tar cited in this exampie results from a plant vvhich manufactures a specialtv Chemical and uses sulfuric acid in the sulfonation process. The process also uses xylene among other organic species. After the process, the spent acid is transferred to a rail car for transportation to a sulfuric acid recoverv facilitv. The rail car is examined and three lavers of material are discovered in the rail car. The tar is distributed betvveen the three lavers. Laboratorv evaluation of the rail car contents reveals a flammable top laver comprtsing xylene and considerable difficultv in handling of the tar laver vvhich is the predominant laver. Based on this evaluation, the rail car is cleaned as follovvs: A batch process is utilized. Tvvo strengths of sulfuric acid are utilized. Commerciallv available sulfuric acid of 93% strength is used for blending vvith the tar and commerciallv available sulfuric acid of 78% is used to flush the transfer line. RHODACAL IPAM a commerciallv available anionic surfactant (supplied bv RhonePoulenc Inc., Cranbury, Nevv Jersev) is used for blending vvith the tar. About 66 parts of 93% sulfuric acid is charged into a batch mix tank equipped vvith an aģitator. This is follovved by the introduction of about 0.8 parts of RHODACAL IPAM (a linear isopropylamine dodecylbenzene sulfonate). About 100 parts of tar containing layer is then transferred from the rail car under a nitrogen pressure of about 50 psig into the mix tank containing the 93% sulfuric acid and the surfactant. After the transfer, the rail car is rinsed vvith about 35 parts of 78% sulfuric acid and the rinse is also transferred under nitrogen pressure to the mix tank. This flushes the transfer lines. The tank contents are agitated for about one hour. Then, the tank contents are transferred into a rail car for transportation to a facility for sulfunc acid recoverv. The resulting fluidized spent acid is stable and tar does not separate during subsequent transportation. The rail car is rendered completely cleaned.
EKAMPLE 2
In the method cited in this example, tar is cleaned out of a 25.000 gal (14 feet vvide, 22 feet tall) storage tank vvhich is used to store spent sulfuric acid from an alcohol process in a Chemical manufacturing facilitv. The process at this facilitv producēs some tar during the manufacturing operation. This tar is carried over vvith the spent acid and accumulates in the storage tank. Over a period extending over about 18 months, the tar accumulates to a point vvhere the tank is rendered unusable. The method of this invention is used for the purposes of cleaning the tank and inspecting the tank since tank inspections vvould not be meaningful in vievv of the tar coated surface. The tar in the tank is sampled and analvzed. The tank contains about 37% sulfunc acid. about 20% vvater and the remainder is carbonaceous matter of unknovvn composition. The viscositv is in excess of about 10,000 centipoise as tested bv Brookfield viscometer. The free standing acid in the tank is pumped out of the tank leaving unpumpable tar in the tank along vvith small quantities of free standing acid. Adding additional sulfuric acid is not necessarv in vievv of the ongin of the tar and the fact that the tar contains 37% sulfuric acid. Diesel is utilized as a camer to facilitate the mixing of the tar vvith the surfactant. Accordinglv about 5 parts of diesel are mixed vvith about 1 part of
3
Dinonvlphenoxy(ethyleneoxy)ethanol surfactant (commerciallv availabie as IGEPAL CO 630 supplied by Rhone-Poulenc Inc.) in a mix tank. The diesel-surfactant mix is introduced into the side of the tank by a recirculation pump. The quantities utilized result in about 94 parts of the tar being treated vvith about 5 parts of diesel and about 1 part of surfactant. The liquid from the tank is recirculated into the tank. This recirculation process is continued until the viscosity is belovv about 800 centipoise. The tank contents are then transferred to tank trucks. Inspection of the tank reveals complete removal of the tar.
EKAMPLE 3 in the method described in this example, tar from a similar alcohol process as described in Example 2 is removed from a rail car. In this example, the tar clean-out is accomplished vvithout mechanical agitation or extemal recirculation. The clean-out is achieved bv allovving the tar to stand vvith a surfactant carrier mix. There is a significant tar laver floating on the top of spent acid. Initiallv, the free acid from the rail car is transferred under air pressure. To about 750 gallons of diesel. about three 55 gallon drūms containing Polyethoxylated Tallovvamine surfactant (commerciallv availabie as RHODAMEEN PN 430 supplied bv Rhone-Poulenc Inc.) are added and mixed. Half the diesel-surfactant mix is transferred to the rail car containing the tar. This is follovved by the addition of 93?ό sulfuric acid to the rail car. The contents are allovved to stand in the rail car for 24 hours. During this time. the tar fluidized. This batch is pumped out to the storage tank for recoverv of sulfuric acid. To the residue in the rail car, the remaining half of the diesel-surfactant blend is transferred to the rail car contents follovved bv more 93% sulfunc acid. The contents in the rail car are allovved to stand for another 24 hours and then pumped to storage. This process completelv dissolves/breaks up into pumpable size the tar and allovvs for the complete removal of the tar from the rail car.
EXAMPLE 4
A 227,700 gallon storage tank accumulates tars to almost 10 feet in height on the top of the spent sulfunc acid stored in the tank, over a period of several months. Accordinglv. the free acid in the bottom laver is drained from the tank and transferred to another tank for recoverv'. This results in the tar laver dropping to the bottom of the tank. 93% Sulfunc Acid is introduced into the tank from the top using a centrifūgai pumo in ar.
amount corresponding to about 2 parts of 93% Sulfuric Acid for about 1 part of tar. Isopropylamine alkyl aryl sulfonate surfactant (RHODACAL IPAM supplied by RhonePoulenc Inc.) is introduced into the suction side of the pump and delivered into the tank over the tar-sulfuric acid layer at a ratio of about 0.013 parts of Surfactant per about 1 part of tar. Recirculation continues for approximateiy 48 hours during vvhich time the fluidization of the tar is periodically checked by inserting a rod from the top of the tank. When inspection reveals fluidization of the tar, the tank contents are transferred to storage for sulfuric acid recoverv. The tank is inspected and found to be clean and free of the tar.
Claims (11)
1. Process for the preparation of an aqueous tar suspoemulsion. comprising the steps of: mixing a mixture (M) comprising:
a viscous tar composition formed from at least one tar, from inorganic solids and. optionally, from vvater, vvater (W), at least one surface-active aģent (SA) exhibiting an HLB of at least about 10 and, optionally, at least one thickening vvater-soiuble poiymer (TWP) vvith a moiecular mass of greater than about 10,000.
vvherein the relative amounts of constituents (W), (SA) and, optionally, (TWP) being such that the viscosity of the (W) + (SA) + optional (TWP) mixture is equal to or greater than one tenth of the viscosity of said tar.
2. Process according to claim 1 further comprising the step of diluting the mixture obtained vvith vvater or vvith at least one aqueous acidic solution.
3. Process according to claim 1. vvherein the relative amounts of the constituents (W), (SA) and. optionallv. (TWP) are such that the viscositv of the (W) + (SA) + optional (TWP) mi.vture is equai to or greater than the viscositv of said tar.
4. Process according to cla:m 3, vvherein said viscous tar composition compnses:
from about 2 to about 70%. by vveight of tar;
from about 5 to about 50%. bv vveight of inorganic solids; and from 0 to about 70%, by vveight of vvater.
5. Process according to claim 1. vvherein said tar exhibits a viscositv at least equal to about 3 Pa-s.
2 6
6. Process according to claim I. vvherein said mixture (M) comprises. in addition to said viscous tar composition, per 100 parts by vveight of tar:
from about 30 to about 200 parts by vveight of vvater (W), and from about 2 to about 20parts by vveight of at least one surface-active aģent (SA) or a combination of from about 0.5 to about 10 parts by vveight of at least one surface-active aģent (SA) and from about 0.001 to about 15 parts by vveight of at least one thickening vvater-soluble polymer (TWP).
7. Process according to claim 1, vvherein said surface-active aģent (SA) is selected from the group consisting of: nonionic, anionic, cationic. zvvitterionic or amphoteric surface-active agent(s) and mixtures thereof having an HLB of at least about
10.
8. Process according to ciaim 1, vvherein said thickening vvater-soluble polvmer (TWP) is soluble to at least about 50% in vvater and can be selected from the group consisting of: poly(vinvl alcohol)s, poly(ethvlene glycol)s, polvvinylpyrTolidones, poly(alkali mētai acrvlate)s, carrageenans, alginates, xanthan gum, carboxymethyl celluloses, methyl celluloses, hvdroxypropyl celluloses or hydroxyethyl ceiluloses and mixtures thereof.
9. Process according to claim 1. vvherein the mixture is carried out bv introducing said viscous tar composition into a vvater (W) + surface-active aģent (SA) +· optional thickening vvater-soluble polymer(s) (TWP) mixture, then mixing at a temperature of betvveen approximatelv about 10 and about 50°C.
2 7
ΙΟ. Process according to claim 9, further comprising the step of dilution vvith vvater or vvith at Ieast one aaueous acidic solution.
11. Process according to claim 1, vvherein the mixing is carried out bv introducing the vvater (W) into a viscous tar composition entirely or partially present + surface-active agent(s) (SA) + optional thickening vvater-soluble polymer(s) (TWP) mixture, then mixing at a temperature of betvveen approximately about 10 and about 50° C, the amount of viscous tar composition optionally remaining being introduced into the mixture after the formation of an emulsion of oil-in-water type vvhile maintaining the mixing.
12. Process according to claim 11, further comprising the step of dilution vvith vvater or vvith at Ieast one aaueous acidic solution.
13. Process according to claim 1, characterized in that the mixing operation is carried out in a mixer equipped vvith a stirrer. a stirrer in vvhich the mobile part does not rotate at more than about 2500 revolutions/min vvith a tangential velocitv at the end of the mobile part not exceeding about 20 m/s.
14. Process according to claim 13, vvherein the tangential velocitv at the end of the mobile part/distance betvveen the end of the mobile part and the vvall of the mixer ratio is less than about 50,000 s‘\
15. Process according to claim 1, vvherein the mixing operation is carried out in a mixer equipped vvith a stirrer, a stirrer in vvhich the mobile part does not rotate at more than about 1500 revolutions/min vvith a tangential velocitv at the end of the mobile part not exceeding about 5 m/s.
16. Process according to claim 15, wherein the tangentiai velocity at the end of the mobile pāri distance betvveen the end of the mobile part and the vvall of the mixer ratio is less than about 10,000 s’1.
17. Process according to claim 1. vvherein the mixing operation is carried out in a mixer equipped vvith a stirrer, a stirrer in vvhich the mobile part does not rotate at more than about 500 revoiutions/min vvith a tangentiai velocity at the end of the mobile part not exceeding about 2.5 m/s.
18. Process according to claim 17, vvherein the tangentiai velocity at the end of the mobile part/distance betvveen the end of the mobile part and the vvall of the mixer ratio is less than about 2500 s'1.
19. Process according to claim 1. vvherein the viscous tar composition is a residue resulting from the svnthesis of vvhite oils from petroleum fractions.
20. Process according to claim 1, vvherein the viscous tar composition comprises at least one acid.
21. Process according to claim 20, vvherein said acid is sulfuric acid.
22. Process for the recoverv of sulfuric acid contained in a viscous tar composition, in vvhich an aqueous tar suspoemulsion, diluted vvith vvater or vvith an aqueous sulfuric acid solution, is prepared according to the process of claim l and then said dilute aqueous tar suspoemulsion is incinerated.
2 9
23. Process for fluidizing tars/sludges or cleaning tars/sludges from containers/vessels such as transportation containers, reactors, pipes and storage containers comprising the steps of: contacting the tar sludge vvith an inorganic acid and a surfactant.
24. Process according to claim 23. vvherein said inorganic acid is selected from the group consisting of sulfuric acid. phosphoric acid and mixtures thereof.
25. Process according claim 24. vvherein said inorganic acid is sulfuric acid.
26. Process according to claim 23 vvherein said surfactant is selected from the group consisting of nonionic surfactants. cationic surfactants, amphoteric surfactants. anionic surfactants and mixtures thereof.
27. Process according to claim 23, vvherein said tar/siudge comprises an acid.
2S. Process according to ciaim 27, vvherein said surfactant is selected from the group consisting of nonionic surfactants. cationic surfactants, anionic surfactants and mixtures thereof.
29. Process according to claim 23, vvherein said inorganic acid and surfactant are premtxed before contact vvith said tar/sludge.
30. Process according to claim 23, vvherein said surfactant is premixed vvith a carrier before contact vvith the tar/sludge.
31. A process according to claim 30, vvherein said carrier is selected from the group consisting of vvater, diesel. \ylene, methyl isobutvl ketone, isopropyl alcohol, dimethvlsufoxide, sulfuric acid and mixtures thereof.
32. Process according to ciaim 27, vvherein said tar/siudge comprises sulfuric acid.
3 0
33. Process according to claim 25. vvherein said sulfuric acid concentration is greater than about 75%.
34. Process according to claim 23 further comprising the step of recirculating the fluidized tar/sludge until ali of the tar/sludge has been converted to a pumpable media and removing the tar/sludge.
35. Process according to claim 25 further comprising the step of recovery of said sulfuric acid bv regeneration.
36. Process according to claim 32 further comprising the step of recoverv of said sulfuric acid bv regeneration.
37. Process comprising the steps of contacting an acid tar/sludge vvith a surfactant and camer.
38. Process according to claim 37. vvherein said acid tar/sludge comprises from about 20% to about 80% sulfuric acid.
39. Process comprising the steps of contacting a tar/sludge vvith a surfactant and carrier vvherebv the tar/sludge having an acid strength of greater than about 20% is substantiallv removed.
40. Process according to claim 39 further comprising the step of mechanical agitation or extemal recirculation.
41. Process comprising the steps of contacting a tar/sludge vvith acid of about 75% to about 90% concentration at a temperature of from about 60°F to about 150°F and vvith a surfactant at concentrations of from about 0.2% to about 7.5% bv vveight of the final blend.
3 1
42. Process according to claim 23. vvherein said surfactant is seiected from the group consisting of mixed octvl/decvl alcohols vvhich are ethoxvlated and propoxvlated. nonylphenoxv poly (ethyleneoxyl) ethanol. polyethoxvlated tallovv amine. isopropvlaminealkyl sulfonate. dinonvlphenoxylpoly (ethyleneoxy) ethanol. mixtures of ethoxylated and propoxylated tallovv amine and mixtures thereof.
43. Process according to claim 23. vvherein said surfactant is seiected from the group consisting of cationic surfactants.
44. Process according to claim 43. vvherein said cationic surfactant is seiected from the group consisting of fattv amine ethoxvlate surfactants represented bv the general average formula:
(CH,-CH2-O)a-(CH,-CH-O)A-H I
CHj
R-N i
(CH2-CH,-O)b-{CH2-CH-O)y-H
I
CH, vvhere R suitablv represents hvdrocarbon groups containing an average value of betvveen 1-30 carbon atoms, and vvherein a plus b represent from 0 to about 50 moles ethylene oxide (EO), and x and y represent from 0 to about 20 moles propvlene oxide (PO), the sum of a, b, x. and v being independent and representing average values. the sum of a,b.x, and v being at least 2.
45. Process according to claim 26. vvherein said surfactant is seiected from the group consisting of:
i) alkali mētai alkvlbenzene sulphonates. alkvl sulphates. alkvl ether sulphates. alkvlarvl ether sulphates. dialkvl sulphosuccinates. alkvl phosphates. and ether phosphates;
3 2
5 ii) aliphatic or aromatic fatty amines. aliphatic fattv amides and quatemary ammonium derivatives;
iii) betaines and their derivatives, sultaines and their derivatives.
lecithins, imidazoline derivatives, glycinates and their derivatives.
amidopropionates and fattv amine oxides;
10 iv) alkoxylated fatty acids, polyalkoxylated alkylphenols, polyalkoxylated fatty alcohols, polyalkoxylated or poly glvcerolated fattv amidas, polyglycerolated alcohols and °c-diols orethylene oxide/propylene oxide block copolymers. alkvlglucosides, alkylpolyglucosides, sucroethers. sucroesters, sucroglycerides and sorbitan esters; and
15 v) mixtures thereof.
46. Process according to claim 26, vvherein said surfactant has an HLB value of at ieast about 10.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US1197796P | 1996-02-20 | 1996-02-20 | |
| PCT/US1997/003793 WO1997036970A2 (en) | 1996-02-20 | 1997-02-20 | Method for fluidizing tars |
| US08/802,742 US6245216B1 (en) | 1996-02-20 | 1997-02-20 | Method for fluidizing tars |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| LV12214A LV12214A (lv) | 1999-01-20 |
| LV12214B true LV12214B (lv) | 1999-05-20 |
Family
ID=26683003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| LVP-98-168A LV12214B (lv) | 1996-02-20 | 1998-08-20 | Paņēmiens darvu sašķidrināšanai |
Country Status (22)
| Country | Link |
|---|---|
| US (2) | US6245216B1 (lv) |
| EP (1) | EP0882110B1 (lv) |
| JP (1) | JP2001527587A (lv) |
| KR (1) | KR100339993B1 (lv) |
| CN (1) | CN1085723C (lv) |
| AT (2) | ATE223951T1 (lv) |
| AU (1) | AU723738B2 (lv) |
| BG (1) | BG102713A (lv) |
| BR (1) | BR9708447A (lv) |
| CA (1) | CA2245918A1 (lv) |
| CZ (1) | CZ259598A3 (lv) |
| DE (2) | DE69715384D1 (lv) |
| HU (1) | HUP0000245A3 (lv) |
| LV (1) | LV12214B (lv) |
| MX (1) | MX9806718A (lv) |
| NO (1) | NO983791L (lv) |
| NZ (1) | NZ331467A (lv) |
| PL (1) | PL328512A1 (lv) |
| RU (1) | RU2182589C2 (lv) |
| SK (1) | SK113898A3 (lv) |
| TR (1) | TR199801621T2 (lv) |
| WO (1) | WO1997036970A2 (lv) |
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| CN110177860A (zh) * | 2016-11-29 | 2019-08-27 | 坎忒特尔产品有限责任公司 | 燃料微滴 |
| US10876060B2 (en) | 2016-11-29 | 2020-12-29 | Kamterter Products, Llc | Droplet for fuels |
| JP7360648B2 (ja) * | 2019-06-24 | 2023-10-13 | 株式会社片山化学工業研究所 | タール粘度低減剤、タール粘度低減剤を含むタール及びタール粘度低減方法 |
| JP7417990B2 (ja) * | 2019-12-13 | 2024-01-19 | 株式会社片山化学工業研究所 | コークス炉ガス流通路への汚れの付着堆積抑制方法 |
| US20220119312A1 (en) * | 2020-10-20 | 2022-04-21 | ArrMaz Products Inc. | Penetrating prime emulsion |
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-
1997
- 1997-02-20 US US08/802,742 patent/US6245216B1/en not_active Expired - Lifetime
- 1997-02-20 DE DE69715384T patent/DE69715384D1/de not_active Expired - Lifetime
- 1997-02-20 SK SK1138-98A patent/SK113898A3/sk unknown
- 1997-02-20 CZ CZ982595A patent/CZ259598A3/cs unknown
- 1997-02-20 AT AT97936007T patent/ATE223951T1/de not_active IP Right Cessation
- 1997-02-20 TR TR1998/01621T patent/TR199801621T2/xx unknown
- 1997-02-20 AT AT01203174T patent/ATE300596T1/de not_active IP Right Cessation
- 1997-02-20 EP EP97936007A patent/EP0882110B1/en not_active Expired - Lifetime
- 1997-02-20 BR BR9708447-6A patent/BR9708447A/pt not_active IP Right Cessation
- 1997-02-20 KR KR19980706461A patent/KR100339993B1/ko not_active IP Right Cessation
- 1997-02-20 CN CN97192985A patent/CN1085723C/zh not_active Expired - Fee Related
- 1997-02-20 PL PL97328512A patent/PL328512A1/xx unknown
- 1997-02-20 NZ NZ331467A patent/NZ331467A/xx unknown
- 1997-02-20 RU RU98117465/04A patent/RU2182589C2/ru active
- 1997-02-20 WO PCT/US1997/003793 patent/WO1997036970A2/en not_active Application Discontinuation
- 1997-02-20 AU AU38776/97A patent/AU723738B2/en not_active Ceased
- 1997-02-20 JP JP53124097A patent/JP2001527587A/ja active Pending
- 1997-02-20 DE DE69733847T patent/DE69733847D1/de not_active Expired - Lifetime
- 1997-02-20 HU HU0000245A patent/HUP0000245A3/hu unknown
- 1997-02-20 CA CA002245918A patent/CA2245918A1/en not_active Abandoned
-
1998
- 1998-08-19 MX MX9806718A patent/MX9806718A/es unknown
- 1998-08-19 NO NO983791A patent/NO983791L/no unknown
- 1998-08-20 LV LVP-98-168A patent/LV12214B/lv unknown
- 1998-08-21 BG BG102713A patent/BG102713A/xx unknown
-
1999
- 1999-03-05 US US09/263,641 patent/US6197837B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| AU3877697A (en) | 1997-10-22 |
| DE69733847D1 (de) | 2005-09-01 |
| CN1085723C (zh) | 2002-05-29 |
| WO1997036970A2 (en) | 1997-10-09 |
| US6197837B1 (en) | 2001-03-06 |
| NZ331467A (en) | 2000-01-28 |
| HUP0000245A1 (hu) | 2000-06-28 |
| BG102713A (en) | 1999-04-30 |
| KR100339993B1 (ko) | 2002-10-25 |
| CZ259598A3 (cs) | 1999-03-17 |
| BR9708447A (pt) | 2000-05-23 |
| PL328512A1 (en) | 1999-02-01 |
| WO1997036970A3 (en) | 1998-02-05 |
| ATE300596T1 (de) | 2005-08-15 |
| RU2182589C2 (ru) | 2002-05-20 |
| HUP0000245A3 (en) | 2001-06-28 |
| KR19990087075A (ko) | 1999-12-15 |
| JP2001527587A (ja) | 2001-12-25 |
| DE69715384D1 (de) | 2002-10-17 |
| SK113898A3 (en) | 1999-04-13 |
| NO983791D0 (no) | 1998-08-19 |
| NO983791L (no) | 1998-10-19 |
| TR199801621T2 (xx) | 1998-11-23 |
| ATE223951T1 (de) | 2002-09-15 |
| MX9806718A (en) | 1999-04-01 |
| EP0882110B1 (en) | 2002-09-11 |
| CN1213394A (zh) | 1999-04-07 |
| US6245216B1 (en) | 2001-06-12 |
| LV12214A (lv) | 1999-01-20 |
| EP0882110A2 (en) | 1998-12-09 |
| CA2245918A1 (en) | 1997-10-09 |
| AU723738B2 (en) | 2000-09-07 |
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