CN1114243A - Process for vessel decontamination - Google Patents
Process for vessel decontamination Download PDFInfo
- Publication number
- CN1114243A CN1114243A CN94107939.2A CN94107939A CN1114243A CN 1114243 A CN1114243 A CN 1114243A CN 94107939 A CN94107939 A CN 94107939A CN 1114243 A CN1114243 A CN 1114243A
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- tensio
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- water
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- 238000000034 method Methods 0.000 title claims abstract description 125
- 230000008569 process Effects 0.000 title claims description 45
- 238000005202 decontamination Methods 0.000 title description 4
- 230000003588 decontaminative effect Effects 0.000 title description 4
- 235000007586 terpenes Nutrition 0.000 claims abstract description 15
- 150000003505 terpenes Chemical class 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
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- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 101
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- 238000000605 extraction Methods 0.000 claims description 80
- 238000012545 processing Methods 0.000 claims description 68
- 239000013543 active substance Substances 0.000 claims description 61
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- 239000004215 Carbon black (E152) Substances 0.000 claims description 42
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- 238000012423 maintenance Methods 0.000 claims description 27
- 238000009833 condensation Methods 0.000 claims description 21
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- XMGQYMWWDOXHJM-JTQLQIEISA-N D-limonene Natural products CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 238000005336 cracking Methods 0.000 claims description 3
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- 238000004945 emulsification Methods 0.000 claims description 3
- 150000002632 lipids Chemical class 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 125000000545 (4R)-limonene group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 238000002513 implantation Methods 0.000 claims 2
- 238000013459 approach Methods 0.000 claims 1
- 238000003776 cleavage reaction Methods 0.000 claims 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 238000005086 pumping Methods 0.000 claims 1
- 230000007017 scission Effects 0.000 claims 1
- 125000002298 terpene group Chemical group 0.000 claims 1
- 238000013022 venting Methods 0.000 claims 1
- 238000012993 chemical processing Methods 0.000 abstract 1
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- 238000004821 distillation Methods 0.000 description 12
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- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 235000001510 limonene Nutrition 0.000 description 3
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- 241000196324 Embryophyta Species 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- -1 and wherein Substances 0.000 description 2
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- 229940077388 benzenesulfonate Drugs 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 238000012856 packing Methods 0.000 description 2
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- 238000005504 petroleum refining Methods 0.000 description 2
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- 238000007789 sealing Methods 0.000 description 2
- 239000003352 sequestering agent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- NPNUFJAVOOONJE-ZIAGYGMSSA-N β-(E)-Caryophyllene Chemical compound C1CC(C)=CCCC(=C)[C@H]2CC(C)(C)[C@@H]21 NPNUFJAVOOONJE-ZIAGYGMSSA-N 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- NVEQFIOZRFFVFW-UHFFFAOYSA-N 9-epi-beta-caryophyllene oxide Natural products C=C1CCC2OC2(C)CCC2C(C)(C)CC21 NVEQFIOZRFFVFW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000004258 Ethoxyquin Substances 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 235000010672 Monarda didyma Nutrition 0.000 description 1
- 244000179970 Monarda didyma Species 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- FAMPSKZZVDUYOS-UHFFFAOYSA-N alpha-Caryophyllene Natural products CC1=CCC(C)(C)C=CCC(C)=CCC1 FAMPSKZZVDUYOS-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- XDLDASNSMGOEMX-UHFFFAOYSA-N benzene benzene Chemical compound C1=CC=CC=C1.C1=CC=CC=C1 XDLDASNSMGOEMX-UHFFFAOYSA-N 0.000 description 1
- NPNUFJAVOOONJE-UHFFFAOYSA-N beta-cariophyllene Natural products C1CC(C)=CCCC(=C)C2CC(C)(C)C21 NPNUFJAVOOONJE-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
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- 238000004364 calculation method Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- NPNUFJAVOOONJE-UONOGXRCSA-N caryophyllene Natural products C1CC(C)=CCCC(=C)[C@@H]2CC(C)(C)[C@@H]21 NPNUFJAVOOONJE-UONOGXRCSA-N 0.000 description 1
- 229940117948 caryophyllene Drugs 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229930004069 diterpene Natural products 0.000 description 1
- 150000004141 diterpene derivatives Chemical class 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 1
- 229940093500 ethoxyquin Drugs 0.000 description 1
- 235000019285 ethoxyquin Nutrition 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000008717 functional decline Effects 0.000 description 1
- 238000003197 gene knockdown Methods 0.000 description 1
- 229960004275 glycolic acid Drugs 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
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- 238000001764 infiltration Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
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- 208000032839 leukemia Diseases 0.000 description 1
- 125000000396 limonene group Chemical group 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
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- 150000007522 mineralic acids Chemical class 0.000 description 1
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- 238000012544 monitoring process Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000008237 rinsing water Substances 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 229930004725 sesquiterpene Natural products 0.000 description 1
- 150000004354 sesquiterpene derivatives Chemical class 0.000 description 1
- 230000037384 skin absorption Effects 0.000 description 1
- 231100000274 skin absorption Toxicity 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
- C23G1/26—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions using inhibitors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B9/00—Cleaning hollow articles by methods or apparatus specially adapted thereto
- B08B9/08—Cleaning containers, e.g. tanks
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/18—Hydrocarbons
- C11D3/188—Terpenes
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/20—Industrial or commercial equipment, e.g. reactors, tubes or engines
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Cleaning By Liquid Or Steam (AREA)
- Cleaning In General (AREA)
- Wrappers (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Packages (AREA)
- Detergent Compositions (AREA)
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The method for removing the contaminant flowing through apparatus during chemical processing features that heated aqueous solution of extractant (for example, terpene) and surfactant is pumped to make it flow through the apparatus.
Description
The present invention relates to the method for during shut-down maintenance (turnaround), removing the pollutent of hydrocarbon processing equipment and container, particularly benzene, thereby cleaning equipment makes the staff carry out internal examination, maintenance and repair to equipment safely.Specifically, the present invention will add device systems, reclaim solution to handle or to utilize, all or part hydrocarbon processing equipment of flowing through is carried out integral body cleaning from its terminal based on the decontaminating solution of the extraction agent initiating terminal from device systems to be cleaned.
In chemical process and petroleum refining industry, at set intervals, factory just carries out maintenance of equipment and transformation, or once a year, once every two years or still less (if possible), in the maintenance period that operating system is stopped work fully, all respects of inspection and maintenance operating equipment system.The operating equipment system is made up of all kinds equipment that fluid is communicated with, as jar, heat exchanger, distillation tower, reactor etc.In oil refining and petrochemical industry, in order to store and to transmit conveniently, generally with an endfeed of raw material such as crude oil slave unit system and hydrocarbons product stream reclaims from the other end.Certainly, the equipment of any similar processing flow stream also can clean.This maintenance of on a large scale each equipment being carried out is known as shut-down maintenance, making operating system recovery production as early as possible is vital to factory's benefit, this be because the main loss of this maintenance (even maintenance itself costs a lot of money) be this processing units can not production refined oil product time.Must guarantee in the maintenance process that staff's safe requirement has also influenced the speed that maintenance is carried out certainly.
During shut-down maintenance, can not only stop operating process, emptying equipment system just allow the serviceman enter.Must at first make processing unit safety and remove wherein harmful even fatal resistates, make can the enter internal structure of examination and maintenance (as not rebuilding) equipment of staff.When maintenance process equipment, need before maintenance, clean usually and decontamination is single or one group of equipment.Present this cleaning (according to equipment) is to remove heavy oil and coke earlier with the light hydrocarbon solvent, injects steam-treated for some time subsequently to no longer include the gas that the serviceman is had explosion risk in monitoring device shows equipment.The method that also useful water cleaning process equipment (as suitable words) is removed pollutent, and generally be to use water vapor and water to remove the interior gas of equipment simultaneously, the maintenance so that the maintainer can enter safely.These purging methods generally need spend many hours, even a couple of days, cause the loss that a couple of days can not produce.The solvent cleaning step also can be saved generally not too effectively water vapor rinse step later on.Certainly hope can clean simultaneously effectively with the whole process flow of decontamination through equipment.
In the method for the cleaning processing equipment system of prior art, after degasification, normally with strong or weak, inorganic or organic acid or alkali or sequestrant (as HF, HCl, H
2SO
4, citric acid, acetate and hydroxyethanoic acid or EDTA, DTPA and similar sequestrant) pump is defeated by processing unit, relies on chemical reaction to remove inorganic, metal oxide dirt, corrosion product and hydro carbons settling.Unfortunately, eroding chemical can not only attack dirt and pollutent, but also the constituent material of strong corrosion equipment, and they can not pass through ready-made process pump or pipeline, because they will destroy the mechanical seal of these pumps.Need be connected into other pony pump and small pipeline and clean, make like this that cleaning speed is slow, efficient is not high.Certainly, pickling needs rinse step, neutralization procedure and rinse step---all these will handle the chemical that is difficult to handle once more, makes the time of cleaning cost longer.Active lower chemical is cleaning equipment thoroughly.The none purging method adopts gas phase to clean and remove deleterious volatile organic pollutant.
Maintainer's safety is particularly importantly removed benzene and other volatile organic carbon component from processing unit.People early have recognized that, in the environment of people's long-term exposure high-content benzene in chemical industry and petrochemical factory, will cause bone marrow function decline, underdevelopment and leukemia.Though, also having by the steam-like of skin absorption or the benzene in the water-bearing media, the benzene that benzolism the most generally is not removed owing to suction in the processing unit system causes.At present, for the staff of 8 times each workday, the safety standards of statutory regulation is 1.0ppm (on average) benzene.The National Institute For Occupational Safety AndHealth (HIOSH) recommend (1989) but the benzene in air content of occupational long-term exposure on be limited to 0.1ppm.This is also enough not good, because the workman that shut-down maintenance service company employs will be exposed in the processing unit continuously.Now, the so continuous exposure of labourer's safety rules restriction.Therefore, a main purpose of the present invention provides the method for removing pollutent in the processing unit, and it is effective and has surpassed above-mentioned standard---and in fact, it is near (as not reaching) 0ppm benzene.Benzene is present in the technical process passage usually---below dirt in pipeline, valve, pump and tower, reactor, jar and the heat exchanger or other pollutent, they only think clean later stage when having finished just from pollutant sediment thing space, ooze out or be enriched in the bullet of equipment at the bottom of gap (head space).So far, disposable integral still of no use is operated the pollutent method in the whole process flow passage of removing.
Though cleaning processing equipment has many stubborn problems, overwhelming requirement is to guarantee safety raising speed down, and the present invention has reached above-mentioned purpose when more effectively protecting environment.The present invention in many cases remove safely objectionable impurities particularly benzene even need not open processing unit in the past, just almost can thoroughly clean them---from the crude oil feeding pump to product storage tank.
The present invention has improved the old decontamination and the purging method of processing unit, it comprises, material feeding mouth to be processed adds in this processing unit when going into operation by processing unit has the extraction agent of avidity and the aqueous solution of tensio-active agent to pollutent, make this water solution flow through comprising pipeline, the whole process flow of pump and processing unit (those that select except works engineer will by the equipment of the adding of non-processing material infringement) is through equipment, reclaim this aqueous solution at the product collection place of this technical process then, or it is handled with mode free from environmental pollution, or purifying and reusing.The reagent that the inventive method is used is harmless, can not produce other refuse, just they are introduced factory sewage biological treatment system, can handle according to ordinary method.
At first, can be with the emptying in heat of processing unit system, and use the light hydrocarbon solvent washing, tentatively clean, but this is not the sin qua non in the present invention's practice.The water that need add capacity to process flow in equipment provides head for being used for that the aqueous solution is cycled through process flow to be cleaned through the pump (preferably process pump) of equipment.In this system, inject water vapor then with being heated to about 160 °F to about 270 °F at processing unit round-robin water and the processing unit from the opening for feed to the drawing mechanism.Mix to treat in water vapor and remove the extraction agent that pollutent has avidity, it is a gas under the water vapor condition, proceeds to inject, and on water vapor and the extraction agent internal surface with condensation equipment in technical process, removes and catch pollutent.Preferably also contain in said temperature scope boiling in the water vapor or have the tensio-active agent of high-vapor-pressure, promote the water of condensation and extraction agent to enter the sedimental pollutent slit that contains, improve the cleaning performance of processing unit internal surface.Also contain extraction agent and tensio-active agent (as exist) in the steam-heated recirculated water of water, also can be from this device systems the flush away pollutent, also there is cleanup action on the surface that is in contact with it.
According to boiling point, vapour pressure and the hydrocarbon solubleness therein of extraction agent, preferably use terpene to make extraction agent.Even tensio-active agent and extraction agent do not seethe with excitement in the steam temperature scope, if it is enough high that the branch of these two components is pressed under the condition of spreading out clearly, their steam will disperse and condensation in passage in process flow, enter in the slit of pollutent and hydrocarbon dirt matrix, also can extract and remove pollutent.Find that the inventive method is effective especially to the benzene of thoroughly removing in the equipment.The enough power of the condensation of this steam generation is extracted pollutent even can be pulverized dirt particles itself from the slit in airtight processing unit.This chemical formulation can in emulsion, carry under one's arms equably fine-particle solid or colloidal solid and hydrocarbon, thus make the destruction of pump seal and packing ring extremely light.When the option table surface-active agent, consider its emulsifying property to concrete pollutent.
Being used for chemical formulation of the present invention can emulsification and the various typical hydrocarbon processing industry pollutents of dissolving, as coke, resin, bituminous matter and organic polymer, they are to use aromatic hydrocarbons or fat hydrocarbon solvent (some is carcinogenic or deforming) traditionally and remove based on the alkaline stain remover.Cleaning solution of the present invention is noncorrosive, nonreactive activity, can not destroy the metal that conventional hydrocarbon processing equipment system uses.Like this, can use process pump in the original system decontaminating solution that circulates, thereby can be fully and utilize the pressure and the flow velocity of system to greatest extent, and can not destroy the sealing and the packing ring of pump, but can destroy when using reactive chemicals to clean.In fact, can control and monitor flowing of chemical formulation of the present invention in watch-keeping cubicle own from the chemical plant.Beat all is to see after the cleaning that the internal interface of equipment is bordering on new installation.Their surface is very clean, if during mild steel, will form surface film oxide fast.
Purging method of the present invention almost can be used for (if not whole words) any hydrocarbon processing equipment system.For example, use the inventive method, those skilled in the art can selective extraction agent and tensio-active agent (as using), can clean any apparatus system of tradition oil refining and hydrocarbon processing industry.This system for example includes, but is not limited to crude distillation system, viscosity breaking system, hydroeracking unit, hydrotreater (comprising reactor), fluid catalytic cracking system (except cracking unit itself), delayed coking system, ethene thermal cracker, amine treatment system and other utility appliance.For example, aforesaid device system all has auxiliary heat exchanger, and some uses direct heat oven, is listed as crude still.If use the high temperature, hydrocarbon treatment facility, will form coke, the inventive method unexpectedly can effectively be removed the coke in well heater and the equipment.
In petroleum refining industry, according to the raw material of processing and the procedure of processing of oil refining process employing, conventional oil refining process starts from the crude preheater that heat exchanger and process furnace are housed, and enters atmospheric distillation tower then and obtains straight run gasoline, passes through several processing unitss subsequently.Up to the present, these equipment or clean with the acid of aforesaid severe corrosive, or the back of stopping work uses suitable purging method to remove pollutent respectively.Unexpectedly, the inventive method is injected cleaning solution by opening for feed and is made its channel cycle along the hydrocarbon stream warp in device systems, can remove the pollutent in the equipment, makes the maintainer can go maintenance safely.Certainly, other position that also can the slave unit system adds cleaning solution, from the products export of this device systems or arbitrarily other suitable position reclaim cleaning solution.Solution is circulation time at elevated temperatures, and pollutent is caught and removed in extraction agent and tensio-active agent vaporization access arrangement and condensation.
A very big advantage of purging method of the present invention is that it can optionally clean whole processing unit system or only clean wherein arbitrary portion equipment.In brief, step of the present invention starts from during the break-down maintenance of refining of petroleum factory, petroleum chemical plant etc., earlier whole shop equipment is stopped work and emptying around here.Generally speaking, still just carried out emptying in the heat, non-imposedly with the flushing of hydrocarbon matter hydrocarbon solvent, removed solvable hydrocarbon subsequently at processing unit.The water that adds capacity in technological process apparatus, cleaning solution cycles through the pump of technological process apparatus to be cleaned, preferably process pump provides head in order to be used to make.The speed that cycles through this device systems preferably makes it be eddy current.According to equipment and the size that is used to finish the round-robin pump, this flow velocity is generally 500-5,000 gallon per minute.Preferred flow velocity is about 800-about 1,400 gallon per minute.Too low as flow velocity, the pollutent of carrying under one's arms may settle.Add and can not lack fluid when the water yield in this equipment to be cleaned generally should be enough to make pump to be operated owing to import under the flow velocity of hope the empty phenomenon in whirlpool takes place at pump.The water yield that adds be generally technological process apparatus internal system volume to be cleaned about 5% to about 25% volume, be preferably about 10% to about 18% volume.
Make water cycle subsequently, and, heat the entire equipment system by in device systems, injecting water vapor (promptly inject generally speaking, inject to the space of device systems again) to water.Based on selecting heating means easily to the experience of concrete equipment accumulation.The benefit of this type of heating is to have heated the entire equipment system of technical process, comprise that (shell side and tube side all can be heated heat exchanger, if they all are present in the technical process), heating reaches about 160 °F to about 270 °F until device temperature, preferred 185 °F to about 225 °F.For heating, steam temperature is the highest can to reach about 375 °F.In water vapor, add extraction agent as herein described and tensio-active agent then, and it is vaporized in device systems, last extraction agent and tensio-active agent condensation are in the internal surface of device systems, and, be preferably about 8 hours or until removing pollutent with the water time enough that in the whole process flow device systems, circulates of process pump with heating.When having found that the first round cleans, cycling time be about 6-about 16 hours generally just enough.In working cycle, can use currently known methods to measure the emulsifying agent activity of solution.If activity reduces, perhaps there has not been activity, can make it have emulsifying activity again by adding extraction agent and/or tensio-active agent again, perhaps replace with the aqueous solution new, that heated fully.
Measure the emulsifying agent promoting agent under the situation that adds the known quantity tensio-active agent, the active degree that reduces can show the degree of cleaning.In case show that cleaning is thorough, just discharge the logistics in the whole process flow equipment, and use water rinse.
Except bigger solid particulate, the pollutent of removing is maintained in the aqueous emulsion, can adopt currently known methods to use emulsion splitter that water and hydrocarbon and solid are separated.Because benzene---the most troubling a kind of pollutent-be water miscible, it must be extracted from water and collects.The water that the hydrocarbon of removing can deliver in the household waste jar of refinery, reclaim can be delivered in the biological tank, carries out a biological disposal upon.
If handle relatively large big solid particulate, be preferably in a certain flushing place and connect circulation filter, the solid particulate in the circulate soln is told, make circulate soln be divided into knocking-on thing (knock-down) and filtrate.For protection factory technics process pump, should remove the particle of particle diameter greater than 40 μ.Be to use outside pump to circulate if not using process pump, preferred embodiment also is to remove big solid particulate, will not be very necessary but remove this particle.
Thereby the inventive method has solved the whole issue of cleaning equipment system of factory, and available safe disposal methods solid in factory, hydrocarbon can be passed in the waste canister or in the API sludge; Can from water, extract the volatile hydrocarbon that comprises benzene and be adsorbed on the carrier as gac; Water after the extraction can be handled in factory's biological tank.So far, when using prior art method cleaning processing equipment inner, still residual many harmful wastes, particularly be the gasiform nuisance, need other processing, and can not eliminate operator and be exposed to danger in the deleterious benzene.
Compare with the prior art method, use the invention described above step can almost thoroughly clean whole processing unit system-within a short period of time, can keep standard simultaneously the strict safety of cleaning personnel to product storage tank with fresh feed pump.Compare with matting that has earlier or water vapor purging method, for the hydrocarbon treatment system, purging method of the present invention can make the time decreased of whole break-down maintenance about 3 days.
During such break-down maintenance, the remaining carcinogens as benzene, dimethylbenzene, toluene and other aromatic hydrocarbons and fat hydrocarbon usually pollutes factory.With the existence of various these gases of device monitoring, health has been set the human upper limit of concentration that can contact and can be discharged in the atmosphere respectively with environmental standard.Therefore, in work with before the serviceman enters in these equipment, must remove these carcinogenss.Other purging method and even used the trial of tensio-active agent to fail to solve the problem that these volatile organisms bring.
This processing unit system is furnished with utility appliance usually, can in them, add temperature and be about 211 °F to about 375 °F, preferred 215 °F to about 350 steam and keep the regular hour, make vapor condensation on the surface of these containers, device, pipeline and heat exchanger and all processing units, lip-deep pollutent is washed away to the position that can collect pollutent.Also can be directly in water water filling steam heat.In the present invention's practice, can reclaim wash fluid in the processing unit terminal of collecting product usually.In order to collect remaining pollutent, need water and tensio-active agent to clean once more usually.The equipment and the water vapor that are preferred for heated solution also are used to inject extraction agent (preferably being added with tensio-active agent) steam.Extraction agent can be added in the tower with water vapor, perhaps add in any technological process apparatus, here extraction agent is vaporized in water vapor and is carried under one's arms and enters in the processing unit, flows in the internal surface of these equipment and in these equipment with the water vapor condensation.Effect driving solution with pump flows along technical process, contacts the also surface of developing technique equipment with pollutent, thereby removes pollutent.
Extraction agent can add in the water vapor, in the injection device system or add in the recirculated water.Other method is at the bottom of the tower and the lower of processing unit is collected water and water cycle is returned the device systems, at the water vapor of position injection easily recirculated water is heated to about 160 °F to about 270 °F, preferred about 185 °F to about 210 °F simultaneously, add extraction agent then in recirculated water, making extraction agent concentration is about 0.10%-about 7% volume, preferred 1.5%-about 5% volume.
Extraction agent is selected from those to desiring to remove the extraction agent that pollutent has avidity.The standard of selecting is to desire to remove the solubleness of pollutent in extraction agent, the vapour pressure and the boiling point of extraction agent, make its boiling point in the scope of steam temperature, make extraction agent be preferably in water vapor condensation before condensation on the metallic surface or in the metal slit, when water of condensation is flowed with meet along equipment mobile solution, come the internal surface of cleaning equipment.Extraction agent should be nontoxic and not dangerous, the extraction agent of selecting should have high-vapor-pressure or its boiling point in the temperature range of the water vapor that concrete factory uses, when injecting with water vapor, boiling point is preferably in about 212 °F to about 375 °F, preferred about 275 °F to about 350 °F.Thereby extraction agent has enough vapor partial pressures under cleaning condition.
Have the preferred victory of avidity to get agent to dirt common in the hydrocarbon processing equipment system and pollutent and comprise various terpenes, for example comprise kautschin, limonene, cajeputene, terpenes, Oils, bergamot peel, Herba Erodii oil, pamorusa oil, oleum anethi,
Punt-pole seed oil etc. and relevant terpene such as hemiterpene (isopentene), sesquiterpene (caryophyllene), diterpene and polyterpene.Preferred extraction agent is limonene, particularly d one limonene.Also can use the mixture of several extraction agents that satisfy above-mentioned standard.As long as can select this mixture and definite relative proportion to the simple experiment of the avidity of pollutent with Vapor pressure data table and mensuration extract.
Those skilled in the art also can select the tensio-active agent that suits.The standard of boiling point and vapour pressure is identical with the said extracted agent, promptly is up to about 375 °F so that tensio-active agent almost with the condensation simultaneously of water vapor and extraction agent.Like this, the all components that cleans system can enter all metal gaps and whole processing unit internal system (gap that comprises dirt pollutent matrix), destroy dirt and pollutent is carried under one's arms in the solution (microemulsion), remove headachy pollutent, particularly as the volatile organism of benzene.So far, also there is not a kind of method of using not Hazardous substances accessible, that environment and process seal equipment, particularly pump seal are not had a damage to clean whole processing unit system.Do not have a kind of method that can remove harmful VOC, particularly benzene safely, make staff's access arrangement maintenance safely.Great advantages of the present invention is that it can not only remove pollutent and can clean whole processing unit system (from the material inlet to the products export) in single job.
The tensio-active agent of selecting can be anionic, cationic, amphoteric or non-ionic, perhaps a few class surfactant mixtures, but, according to the extraction agent of pollutent to be removed, use and in the rinse solution of vapor condensation formation or the relative quantity in the circulation flushing water, those skilled in the art can know concrete selection way.The HLB of the tensio-active agent of selecting (hydrophilic/lyophily oil balance) should be 6-18, it is about 7.5-12 to be preferably, so that the present invention has best effect.The feature of the tensio-active agent of these types is known, and they comprise chemical compound lot.According to the different process flow sheet equipment system of cleaning with the inventive method, can select many tensio-active agents and/or emulsifying agent to be used for the present invention's practice.
Preferred surfactants is selected from the alkylphenol of ethoxyquin, and wherein average band is had an appointment and 6 contained 8-10 carbon atoms to about 12 moles of ethylene oxide unit, alkyl on every mole of alkylphenol.Another preferred ingredient is that molecular weight is about oxyethane/oxypropylene block copolymer of 1,500-about 2,500 in the surfactant mixture.In particularly preferred embodiments, the 3rd component is the alkanolamide of lipid acid, and generally what buy is 50/50 mixture of it and linear alkyl benzene sulfonate from commercial.In essential scope of the present invention, many variations can be arranged, their component and proportion of composing thereof can change.The composition of above-mentioned substance is used in particular for and preferred extraction agent is that terpene, particularly d-limonene forms stable microemulsion shape liquid.Said mixture has high volatility number, and they can be used for removing many different pollutents in the hydrocarbon processing equipment system.
Above-mentioned a few class surfactant mixtures can be used, particularly under the situation of using extraction agent and tensio-active agent premixture, good effect can be obtained.The microemulsion of normally several extraction agents of this pre-composition and tensio-active agent.For prolong as uniform fluid, normally discontinuous water the successive terpene mutually in shelf-time of microemulsion of formation, need several tensio-active agents usually.Certainly, in the presence of big water gaging, will the turning around mutually of milk sap.The injection rate of such mixture is about 0.2 pound-about 0.4 pound of/pound water vapor, be preferably about 0.25 pound-about 0.33 pound of/pound water vapor.When joining in the circulating fluid, above-mentioned injection rate can make extraction agent and the tensio-active agent that has significant quantity in the fluid, and that its concentration is generally is about 0.1%-and about 7%, be preferably 1.5%-about 5%, more preferably about 2%-about 4%.Emulsifying effect to pollutent is an important index of the present invention, and those skilled in the art are after understanding pollutent and this paper explanation, and an outline is done experiment, just can select suitable mixture.
When this enforcement the inventive method, should contain have an appointment 0.06 pound-about 0.3 pound, preferred about 0.1 pound-about 0.20 pound of extraction agent in every pound of water vapor (or water).Similarly, should add about 0.001 pound-about 0.01 pound, preferred 0.003 pound-about 0.005 pound of tensio-active agent in every pound of water vapor.When using extraction agent and tensio-active agent simultaneously, their ratio is about 0.5 pound-about 30 pounds of extraction agents/pound tensio-active agent, be preferably about 1.5 pounds-about 10 pounds of extraction agents/pound tensio-active agent.As previously mentioned, all substances can add or wherein any one adds with water vapor with water vapor, make in extraction agent and the tensio-active agent any one or both be carried under one's arms, vaporize by water vapor and transmit access arrangement, until condensation.Water vapor and extraction agent can be pre-mixed before injection or inject respectively at the equipment different sites.Similarly, extraction agent, tensio-active agent and water vapor can be pre-mixed before injection.In another program, also can be or mix with water under said temperature respectively or as mixture with extraction agent and tensio-active agent, and cycle through equipment to be cleaned.
The top that the numerous processing unit system that the present invention is suitable for is included in tower has the distillation tower that return-flow system and wire netting remove the mist device, and it must remove pollutent.By making extraction agent of the present invention/tensio-active agent vapor mixing distillation tower of upwards flowing through, and near or just on the top of tower even condensation in refluxing unit, the inventive method can be washed whole distillation tower, only forms liquid residue at the bottom of tower, and it is recycled liquor and removes.Similarly, when embodiment of the present invention makes its column plate that cycles through distillation tower and/or weighting material when extraction agent and surfactant soln vaporization or after the vaporization,, just can clean distillation tower as long as handle more a spot of aqueous emulsion that contains pollutent.By after the airtight cleaning distillation tower of any mode of the present invention, can make that the staff enters to check, maintenance and repair.After cycling through whole processing unit system, reach safety standards after tested, promptly detachable this device systems is to carry out necessary maintenance.Another advantage of the inventive method is because it can reach excellent cleaning performance, can every two years carry out once the break-down maintenance of some equipment.
In one embodiment of the invention, injecting steam reaches about 2.9-8.7KPa (20-about 60psig) until pressure in equipment.Stop to inject, make steam on the internal surface of tower, carry out condensation.The steam of condensation, mention the mixture of the chemical residue of agent and tensio-active agent (as the words of using) condensation on internal surface, formation condensed fluid and pollution container, remove these sewage, whether the amount of pollutant of measuring container is suitable for the maintainer is entered to overhaul safely.As unfavorable words, repeat above-mentioned steps once more.
In another embodiment, adopt cascade or circulation means to come cleaning equipment.At first the partially filled Sealing Arrangement of water, be generally packed tower or column plate distillation tower, the water yield of adding is except that should being enough to moistening weighting material or being full of the column plate, circulation time also should be able to be full of the water filling port of pump, is generally about 8%-15% volume of tower volumetrical.Between the bottom of this equipment and top, connect pipeline, form the water cycle loop.This loop flows down water along weighting material or column plate in equipment, extract out from the bottom, upwards carry and be re-introduced into the top with pump along loop, the speed of circulation of water in circulation loop should be enough to wash away weighting material or be full of column plate, be preferably about 100GPM, water vapor is injected in the slave unit bottom simultaneously.Water temperature reaches after about 85 ℃ (185 °F), injects the extract and the tensio-active agent of significant quantity in the water cycle loop.Continue about 3 hours of circulation at about 85 ℃ (185 ℃) or higher temperature.As mentioned above, stop circulation or stirring then, circulating liquid is gathered in the bottom of tower or is removed, and uses the fresh water rinsing then.Equally, before entering, the maintainer wants testing apparatus.
The inventive method has shortened scavenging period greatly, has improved cleaning performance, and processing unit can be gone into operation as early as possible.Particularly, there are not volatile organic compound (VOC), particularly carcinogens benzene in the processing unit after the cleaning.The prior art method can not be removed remaining benzene, and wherein, VOC is gathered in the trajectory space of equipment earlier, is discharged in the atmosphere subsequently.Under environmental protection requirement at present, this discharging is no longer allowed.Adopt the inventive method, benzene to be carried under one's arms in the solution and be removed.After adopting the inventive method to handle, instrument test can not detect the existence of benzene or other VOC, can be with hazardous emission in atmosphere.After recycle-water, breakdown of emulsion, the phase-splitting, available currently known methods extracts water, and benzene and VOC are trapped in the suitable system.
For example, use following component preparation to be used for the preferred extraction agent and the surfactant mixture of cleaning reaction equipment:
Table I (mixture A)
Weight percentage
D-limonene 57%
The nonionic copolymerization
Thing1 9%
Monamulse653—C
2 17％
Butyl cellulose 3%
Nonionogenic tenside
35%
Water 9%
100％
Annotate:
1. molecular weight is 1950, HLB is oxyethane/oxypropylene block copolymer of 12 to 18
2.C
1250/50 mixture 90% and the Virahol 10% of the glycollic amide of lipid acid and linear alkyl benzene sulfonate, b.p.205 °F.
3. the adducts of nonylphenol and 10 moles of ethylene oxide.
(mixture B) in another embodiment accounts for 8% butyl cellulose and nonionogenic tenside HLB and is 10.8 the nonylphenol and the adducts of 6 moles of ethylene oxide and replace in mixture A.
Said components is mixed to a time-out, form the stable microemulsion of water in terpene, it has the long shelf-time, greasy solvability to the light hydrocarbon that comprises benzene, toluene and dimethylbenzene is good, even these pollutents can be carried under one's arms, be kept to this microemulsion under the temperature of cleaning used rising, until removing from technological process apparatus.When cleaning tower, above-mentioned any microemulsion injects tower with steam, and injection speed is 0.5kg/1.4-1.8kg water vapor (1 pound/3-4 a pounds water vapor).Continue to inject and clean the consumption of the size of tower and pollution level decision table surface-active agent/extraction agent and water vapor until tower.
The outflow logistics of purging method can be divided into hydrocarbon, solid and water, can reclaim hydrocarbon like this, and the water that contains solubility light hydrocarbon (particularly benzene) can extract operation scrubbing or extraction with suitable gas, and it is not polluted the environment.Solid can be reclaimed with calcination and processing.
The following example is intended to further specify the present invention, should not think limitation of the scope of the invention.
Embodiment 1
This embodiment describes and adopts the inventive method to clean the crude oil processing equipment system, and it comprises process furnace, atmospheric distillation tower, vacuum tower and auxiliary heat exchanger.
Heat up in a steamer between the tower in strainer trailer, a series of preheat exchanger, oil process furnace, crude oil atmospheric distillation tower, vacuum and to be linked to be circulation loop (getting back to the strainer trailer again), add hydrothermal solution by this device systems with what pump made the tensio-active agent that contains the 2% mixture B (above-mentioned) that has an appointment, extraction agent at about 210 °F with pipeline.Be connected in the hydrothermal solution that adds that pump on the strainer trailer drives tensio-active agent of the present invention, extraction agent and in circulation loop, flow, by this crude oil processing equipment system.After circulating about 10 hours, with this system evacuation, open inspection, it cleans very much.
Then, except removing burn in step, remove the coke in the process furnace according to a conventional method.Although there is not burn in step, the time of removing coke in the process furnace has still shortened about 4 hours.
Embodiment 2
This embodiment illustrates the purging method of gasoline splitter.At first rinse out liquid hydrocarbon excessive in the tower with the fire hydrant water.In tower, dose 10% volume water then.
Strainer/pump trailer is connected on the tower,, and is discharged to the top tray of tower, in tower, form successive, round-robin cascade from the suction of the tower base stream pipeline of tower.Speed with 3860 liters/minute (1000GPM) makes water cycle, makes to form between the surface of water and tower to stir, and goes into the available water vapor of refinery from the tower rising pouring simultaneously.Water temperature reaches after 85 ℃ (185 °F), injects washed mixture of the present invention (mixture B) in the water cycle loop, makes its concentration reach 2.0%.Keeping temperature is under 85 ℃ of (185) situations, continues circulation 3.5 hours.
Stop circulation then, the direct pump of liquid that will contain hydrocarbon dirt and pollutent is passed in the sewage lagoon of refinery.Water is with tower rinsing twice, and all polluted water also pump are passed in the sewage lagoon.Again dose 10% volume water in tower, it is 2.0% that adding washed mixture B makes its concentration, and recirculation is 3.5 hours again.With previous the same, lean solution and rinsing water pump are passed in the sewage lagoon.
Open at the bottom of the tower and connect, go out at the bottom of the tower in a large number, remove with the vacuum trailer than massive fragment.Finish last flushing emptying from beginning to be recycled to, clean this tower and only used 17 hours.
The refinery staff opens this tower, and when checking, they say does not have gas in the tower, do not have hydrocarbon and more any purging method was all clean than in the past.Can carry out the inside maintenance at once.Comprise installation and removal and remove strainer/pump trailer, when whole cleaning has spent 24 work.
Embodiment 3
(5 ＇ 6 "), high 19m (62 ＇), the viscosity breaking tower that contains 23 bubble cap column plates clean to diameter 1.7m.As described in the embodiment 1, use the strainer trailer that is connected in this tower that about 10598 liters (2800 gallons) (25% volume) water that contain 3.0% washed mixture B, 82 ℃ (180) were circulated 8 hours in whole tower apparatus.Every 1 hour, gather one time the recirculated water sample, do not detect the process of pollutent emulsifying effect in the tower.After 8 hours, remove lean solution in the tower, and it is pulled in removable jar with the vacuum trailer.Use this tower of fresh water rinsing then, the water after the rinsing also is pulled in removable jar with the vacuum trailer.After finishing, rinse cycle opens the manhole of tower at once.Check that this tower finds its cleaning inside such as bare metal.Touch inner wall of tower, do not have soapy feeling, and do not have hydrocarbon.In second day morning, the oil refining staff checks this tower, claims this tower can enter safely.But promptly there is not hydrocarbon gas flavor not have the hydrocarbon of instrument detected level again in the tower.
Embodiment 4
This embodiment illustrates that shell side is that viscosity breaking Tata bottoms stream, tube side are the purging method of the heat exchanger tube bundle of crude oil.Prepare the drum of a 8.2m * 2.2m * 2.9m (27 ＇ * 8 ＇ * 9.6 ＇), and filled with water steam and air line, heat exchanger tube bundle cleaned.It is the utility appliance heat exchanger of viscosity breaking tower among the embodiment 2.
In drum, dose about 30280 liters (8000 gallons) water.By water vapor pipeline injection water steam in water, reach about 92 ℃ (180 °F) until water temperature.In drum, add 4 barrels of washed mixture B, make concentration and be about 3% solution.
This tube bank has sticking tar of a thick-layer and coke at shell side, and its thickness can reach about 7.6cm-10.2cm (3 "-4 ") sometimes.The tube bank that to extract out places the above-mentioned drum that fills hot 3% aqueous solution then.Cover drum (for preventing atmospheric pollution) with tarpaulin, open the air line that is connected on the drum, stir.When forming foam, close air line.Stir, tube bank was steeped 8 hours in drum.After 8 hours, take out tube bank, be placed on water spray cleaning device, clean with high pressure water jets.
Find when the tube bank spray is clean that outer field dirt is easy to remove, still, the coke layer on pipeline enclosure and pipeline has stoped the infiltration of washed mixture, so the viscosity tarry dirt of pipeline enclosure is failed emulsified.Between first time soak period, original (for the first time promptly) 3% washed mixture solution is consumed fully.
In 3% solution of fresh washed mixture B, will restrain bubble again 4 hours.The effect of soaking tube bank is improved greatly for the second time, and current washed mixture solution can see through dirt, destroys the tar of hydrocarbon substrate and emulsification pipeline enclosure.The spray of subsequently water can be removed only and before failed the coke layer removed.The cleaning of tube bank needs about 1.5-2 days, and traditional method need spend and reaches 8 days.The refinery staff pleases oneself to this result.
Embodiment 5
The liquid circulation pipeline of two fin fan water coolers is together in series, and the volume calculation of pipeline is about 7570 liters (2000 gallons).In a container (Baker), add about 11355 liters (3000 gallons) water, and the water vapor pipeline is connected on this container.Water in the container is heated to 92 ℃ (180 °F), and in this container, adds about 303 liters (1.5 barrels, about 80 gallons) washed mixture B.The solution (about 2.75% solution of washed mixture) of about 82 ℃ (180) so making is cycled through the pipeline of placed in-line fin fan, continue 6 hours.Solution after the circulation turns back to again in this container.Fresh water flushing fin fan with fire hydrant.Check the air outlet of fin fan, find very clean.The refinery staff is also very satisfied to this result.Cleaned two other fin fan with identical method again in second day, effect is very good.Do not find hydrocarbon pollutant after the cleaning.
Embodiment 6
All methods of device of refinery hydrocracking device systems are successfully cleaned in this embodiment explanation.This hydrocracking device systems is made up of heat exchanger and pipeline on following 10 devices and these devices:
1) first step reactor feed device
2) second stage reactor feed/discharger
3) stabilizer tower cat head device
4) splitter
5) H
2The S stripping tower
6) charging surge tank
7) splitter overhead stream collector
8) low pressure tripping device
9) H
2S stripping tower cat head device
10) stabilizer tower
According to the method that previous embodiment is suitable for, working concentration is the solution of 1.0% washed mixture B, and it about 6-8 hours of 82 ℃ (180) circulation, is cleaned above-mentioned each equipment.Emptying equipment is also used the fresh water rinsing then.Lean solution and rinse water are transported in the hold tank, and are processed with other oil refinery effluent at this.
When opening equipment, find not have in above-mentioned each equipment the benzene that can measure.After the cleaning, H
2Not only do not have benzene in S stripping tower, overhead stream collector and the stripping tower, and do not have H
2S has only the FeS residue of minute quantity at the bottom of tower.The refinery staff is very satisfied to this effect.
At H
2In S stripping tower and the first step reactor feed/drawing mechanism, in 1% solution of circulating mixture B, add yellow soda ash, the acid that neutralizes and to exist.
Used 10 pumps that can move freely that filtration unit is housed respectively to come circulating mixture B solution.Each device is handled respectively.Some has used 3 reflux pumps that can move freely on pump and the tower than the stabilizer tower of large equipment such as high 49.4m (162 ＇) and the stripping tower of high 49.4m (162 ＇), comes circulating mixture B solution.
Claims (26)
1. the method for removing of carrying under one's arms the pollutent in the dirt resistates of processing unit or supplementary unit, it is characterized by, dirt on equipment or the device internal surface is contacted with water fluid washed mixture or its steam, described mixture contains the terpene extraction agent of significant quantity and the tensio-active agent of non-imposed significant quantity, and extraction agent and tensio-active agent all have sufficiently high vapour pressure under treatment condition makes that they can be scattered in the equipment under this condition; This washed mixture is heated to about 165 °F-about 230 °F, make extraction agent and surfactant-dispersed in processing unit,, extract pollutent to enter the slit of dirt resistates, destroy dirt, and pollutent and dirt resistates are carried under one's arms in the washed mixture.
2. the method for claim 1 is characterized in that, makes the washed mixture circulation in cleaning process.
3. claim 1 or 2 method, it is characterized in that, described pollutent is a benzene, it is about 6 to about 18 tensio-active agent that described water-based mixture contains HLB, described method comprises the following steps: to make this mixture to contact with the processing unit internal surface to cycle through this processing unit and keeps for some time, makes mixture have time enough to infiltrate the dirt slit and destroys dirt, and the benzene pollutent is brought in the mixture; This tensio-active agent and extraction agent are scattered in the processing unit with vapor form, and condensation is in the internal surface of processing unit, destroys dirt and the dirt resistates is brought in the mixture; From processing unit or supplementary unit, tell this mixture, from this equipment and device, remove the benzene pollutent with this mixture.
4. the method for claim 3 is characterized in that, be about 1 hour to about 8 hours the cycling time of this aqueous solution.
5. for making the serviceman can enter safely to keep in repair, remove stop work and the processing unit of emptying in the method for benzene pollutent, it is characterized in that comprising that the time length is enough to anti-the benzene amount of pollutant of chemical residue be reduced to the following step to the harmless degree of people: about at the most 375 water vapor of implantation temperature in this equipment; At the terpene extraction agent that injects this equipment chemical residue in the presence of the water vapor in this container, its boiling point is about the temperature of the water vapor of injection at the most, its consumption be about 0.06 pound to about 0.3 pound of terpene extraction agent/pound water vapor; As optional component, in this container, be injected into many about 0.2 pound of tensio-active agents/pound water vapor in the presence of the water vapor, its HLB is about 6 to about 18, but restricted condition is, when extraction agent and tensio-active agent existed simultaneously, the ratio of extraction agent and tensio-active agent was about 0.5 to about 30 pounds of extraction agents/pound tensio-active agent; Make water vapor, extraction agent and tensio-active agent condensation on the internal surface of this equipment and enter the slit that dirt is gone up on the surface, extract and catch the benzene pollutent, form the water mixture of condensed fluid and chemical residue; From this equipment, discharge condensed fluid and chemical residue.
6. the method for claim 5, it is characterized in that, inject about 0.1 pound to about 0.2 pound of terpene extraction agent/pound water vapor, 0.0003 pound of injection extremely about 0.005 pound of nonionic, positively charged ion or amphoterics or their mixture/pound water vapor, the HLB of tensio-active agent is about 7.5 to about 12.
7. the method for claim 5 is characterized in that, when condensed steam, extraction agent and tensio-active agent, prevents that water vapor from going out from this equipment.
8. the method for claim 5 is characterized in that, this equipment internal pressure stops injecting steam when reaching about 20psig to about 60psig, and keeps time enough to make the generation condensation in this container steam.
9. the method for claim 5 is characterized in that, before injection water vapor and extraction agent is pre-mixed, and preferably from different positions they is injected this equipment.
10. the method for claim 5 is characterized in that, the injection position of water vapor is different with extraction agent and tensio-active agent.
11. the method for claim 9 is characterized in that, the injection ratio of described mixture is 0.2 to about 0.4 pound of/pound water vapor.
12. the method for claim 5 is characterized in that, the concentration of extraction agent and surfactant mixture is about 1.5% to about 5%.
13. the method for arbitrary requirement in the claim 6 to 12, it is characterized in that comprising the following steps: that the bottom from this equipment connects circulation loop to the top, fill this equipment, form circulation continuously with the water section of capacity, water is circulated in circulation loop to be enough to forming even mobile speed in equipment, with the water vapor that is injected in the equipment water is heated to about 165 °F to about 230 °, extraction agent and the tensio-active agent of water in being injected into equipment of heating circulated about 1.5 to about 7 hours, and the benzene of from this equipment, removing condensed fluid and wherein carrying under one's arms.
14. the method for claim 13 is characterized in that, in extraction agent and water vapor while injection device.
15. the method for claim 13 is characterized in that, described speed of circulation is about 800-about 1400 gallon per minute.
16. remove sedimentary pollutent in chemical industry that fluid is communicated with or the oil refining process equipment, purging method when making it use or to keep in repair to clean this technological process apparatus, it is characterized in that comprising the following steps: the process fluid in the venting processing unit circulation duct to be cleaned, in this processing unit, pump into the aqueous solution of intensification and make the moving approach of its longshore current by this fluid communication device, the described aqueous solution contains significant quantity has avidity to pollutent extraction agent and at least a tensio-active agent that emulsifying activity is arranged between pollutent and water, the aqueous solution is contacted with the internal surface of this equipment, make extraction agent and tensio-active agent enter sedimental slit in sufficiently high temperature, and the maintenance time enough, in this solution that pollutent is carried under one's arms; From processing unit circulation duct to be cleaned, discharge this solution, remove pollutent in this processing unit with this solution.
17. the method for claim 16 is characterized in that, uses processing unit with pump water, extraction agent and tensio-active agent to be circulated about 6-about 16 hours in the processing unit circulation duct.
18. the method for claim 17 is characterized in that, the temperature of circulate soln is about 160 °F to about 230 °F.
19. claim 16,17 or 18 method is characterized in that this extraction agent is a terpene, the HLB of this tensio-active agent is about 6 to about 18.
20. the method for claim 19, it is characterized in that, this terpene is d-limonene, this tensio-active agent comprises: the adducts of alkylphenol and 6 to 12 moles of ethylene oxide (wherein alkyl has 8 to 10 carbon atoms), molecular weight are about 1,500 to about 2,500 the oxyethane/oxypropylene block copolymer and the alkanolamide of lipid acid.
21. in arbitrary claim of claim 16 to 18, be used for from heat exchanger by comprising that fluid is communicated with, the flowpaths processing crude oil hydrocarbon of crude oil heater and cleavage column prepares the method for cleaning hydrocarbon resistates and coke in the refining equipment system of straight run product, it is characterized in that comprising the following steps: to the refining equipment system, pumping into and contain at crude oil from the crude oil feeding mouth, the aqueous solution that the tensio-active agent of emulsifying activity is arranged between deposits of coke and the water, making it pass through this processing unit contacts with the pollution internal surface of crude stream through equipment, make extraction agent and tensio-active agent enter the slit of Marine sediments, keep time enough pollutent is brought in this solution, this solution is contacted with carbon deposits by crude oil heater and the crude oil hydrocarbon ducted coke of flowing through, the solution of pollution is entered in the crack crude tower, this solution be divided into contain the solid tower at the bottom of heavy solution and the light solution of cat head emulsification, cat head solution continues to flow through the crude Treatment pipeline of flowing through, solution is removed system by a solid at the bottom of making tower, obtains the aqueous solution of extraction agent and tensio-active agent and turns back to the crude oil hydrocarbon opening for feed.
22. the method for claim 21 is characterized in that, removes solid from the solid tower base stream that contains that cracking chamber is discharged by a skimmer and strainer, will be substantially free of the water base logistics of solid pumps into cracking chamber by connecting tube reflux line.
23. the method for claim 21, it is characterized in that, with described cat head emulsion breakdown of emulsion, contact with counter-current gas in stripping apparatus with the isolating aqueous solution of emulsive hydrocarbon and to remove the benzene pollutent, substantially do not had the water base logistics of benzene, and being further characterized in that of this method is trapped in benzene in the activated carbon filter and handles the water that does not have benzene substantially.
24. for making the staff enter to keep in repair, from all or part of method of removing chemical pollutant the system that is provided with of stopping work and the fluid of emptying is communicated with, it comprises: make to join to account for the fluid channel circulation of system volume about 5% to about 25% volume water along this device systems in the selected device systems, the while implantation temperature is up to about 375 water vapor water is heated, the terpene extraction agent that in the presence of water vapor, in round-robin water in device systems, adds chemical residue in the device systems, its consumption is about 0.06 pound-about 0.3 pound of/pound water vapor, the highest temperature of injecting water vapor that is about of its boiling point, and make it cycle through this device systems, as optional component, in the presence of water vapor, in device systems, add HLB and be about 6 to about 18 surfactant mixture, its consumption mostly is about 0.2 pound of/pound water vapor most, but restricted condition is, the ratio of extraction agent and tensio-active agent is about 0.5 pound to 30 pounds extraction agent/pound tensio-active agent when adding tensio-active agent, make and add hot water, extraction agent and tensio-active agent circulate in device systems, contact time enough with the equipment internal surface, catch chemical pollutant, form the liquid mixture that contains the pollutent of catching; With this heating liquids with low-speed pump defeated by this device systems clearing away liquid and the pollutent in the device systems, and from this device systems, remove liquid and pollutent.
25. the method for claim 24 is characterized in that, flow velocity is about 800-about 1,400 gallon per minute.
26. the method for claim 24 or 25 is characterized in that, inject about 0.06 pound to about 0.3 pound of extraction agent/pound water vapor and about 0.001 pound of about 0.01 pound of tensio-active agent/pound water vapor extremely.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP93104356A EP0604698B1 (en) | 1992-12-30 | 1993-03-17 | Process for vessel decontamination |
| AT93104356T ATE186756T1 (en) | 1992-12-30 | 1993-03-17 | METHOD FOR DECONTAMINATION OF CONTAINERS |
| DE69327034T DE69327034T2 (en) | 1992-12-30 | 1993-03-17 | Methods for decontaminating containers |
| DK93104356T DK0604698T3 (en) | 1992-12-30 | 1993-03-17 | Process for decontamination of containers |
| SG1996009473A SG59993A1 (en) | 1992-12-30 | 1993-03-17 | Process for vessel decontamination |
| PT93104356T PT604698E (en) | 1992-12-30 | 1993-03-17 | PROCESS FOR THE DECONTAMINATION OF PROCESS EQUIPMENT |
| CA002094165A CA2094165C (en) | 1992-12-30 | 1993-04-16 | Process for vessel decontamination |
| CN94107939.2A CN1114243A (en) | 1992-12-30 | 1994-06-28 | Process for vessel decontamination |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/998,556 US5356482A (en) | 1991-12-10 | 1992-12-30 | Process for vessel decontamination |
| CN94107939.2A CN1114243A (en) | 1992-12-30 | 1994-06-28 | Process for vessel decontamination |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1114243A true CN1114243A (en) | 1996-01-03 |
Family
ID=37075783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94107939.2A Pending CN1114243A (en) | 1992-12-30 | 1994-06-28 | Process for vessel decontamination |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0604698B1 (en) |
| CN (1) | CN1114243A (en) |
| AT (1) | ATE186756T1 (en) |
| CA (1) | CA2094165C (en) |
| DE (1) | DE69327034T2 (en) |
| DK (1) | DK0604698T3 (en) |
| PT (1) | PT604698E (en) |
| SG (1) | SG59993A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104364004A (en) * | 2012-05-15 | 2015-02-18 | 水动力处理科技有限公司 | Methods, plant and module for filtering contaminants from fluid |
| WO2017198232A1 (en) * | 2016-05-20 | 2017-11-23 | 深圳国宝造币有限公司 | High-precision washing process of gold and silver coin billet cake |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118043441A (en) * | 2021-09-30 | 2024-05-14 | 智能流体有限公司 | Compositions and their use in cleaning applications |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2023496A (en) * | 1928-03-12 | 1935-12-10 | Verne J Todd | Method for cleaning oil-covered surfaces |
| US1891592A (en) * | 1932-07-26 | 1932-12-20 | Gerald James W Fitz | Method of cleaning and gas-freeing hydrocarbon storage tanks |
| US2715594A (en) * | 1952-08-26 | 1955-08-16 | Standard Oil Co | Method of cleaning asphalt tanks |
| US4511488A (en) * | 1983-12-05 | 1985-04-16 | Penetone Corporation | D-Limonene based aqueous cleaning compositions |
| US4869825A (en) * | 1987-05-26 | 1989-09-26 | Werner Steiner | Process for the removal of organic contaminants from solids |
| GB2243842B (en) * | 1990-04-12 | 1993-09-22 | Electrolube Limited | Method and compositions for circuit board cleaning using ether-containing terpenoid compounds |
| JPH06511515A (en) * | 1990-12-07 | 1994-12-22 | ゴールデン テクノロジーズ カンパニー，インコーポレイテッド | Metal surface finishing method using terpenes |
-
1993
- 1993-03-17 SG SG1996009473A patent/SG59993A1/en unknown
- 1993-03-17 DK DK93104356T patent/DK0604698T3/en active
- 1993-03-17 PT PT93104356T patent/PT604698E/en unknown
- 1993-03-17 DE DE69327034T patent/DE69327034T2/en not_active Expired - Lifetime
- 1993-03-17 EP EP93104356A patent/EP0604698B1/en not_active Expired - Lifetime
- 1993-03-17 AT AT93104356T patent/ATE186756T1/en not_active IP Right Cessation
- 1993-04-16 CA CA002094165A patent/CA2094165C/en not_active Expired - Lifetime
-
1994
- 1994-06-28 CN CN94107939.2A patent/CN1114243A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104364004A (en) * | 2012-05-15 | 2015-02-18 | 水动力处理科技有限公司 | Methods, plant and module for filtering contaminants from fluid |
| CN104364004B (en) * | 2012-05-15 | 2016-12-28 | 水动力处理科技有限公司 | From method, defecator and the filtering module of filtering flow pollutant |
| WO2017198232A1 (en) * | 2016-05-20 | 2017-11-23 | 深圳国宝造币有限公司 | High-precision washing process of gold and silver coin billet cake |
| CN109072455A (en) * | 2016-05-20 | 2018-12-21 | 深圳国宝造币有限公司 | A kind of high-precision cleaning process of gold and silver coin billet cake |
Also Published As
| Publication number | Publication date |
|---|---|
| DK0604698T3 (en) | 2000-04-03 |
| DE69327034D1 (en) | 1999-12-23 |
| DE69327034T2 (en) | 2000-05-25 |
| EP0604698A2 (en) | 1994-07-06 |
| EP0604698B1 (en) | 1999-11-17 |
| CA2094165C (en) | 1999-12-07 |
| PT604698E (en) | 2000-05-31 |
| ATE186756T1 (en) | 1999-12-15 |
| EP0604698A3 (en) | 1996-12-11 |
| CA2094165A1 (en) | 1994-07-01 |
| SG59993A1 (en) | 1999-02-22 |
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