US20090223871A1 - Methodology for the chemical and mechanical treatment and cleanup of oily soils, drill cuttings, refinery wastes, tank bottoms, and lagoons/pits - Google Patents
Methodology for the chemical and mechanical treatment and cleanup of oily soils, drill cuttings, refinery wastes, tank bottoms, and lagoons/pits Download PDFInfo
- Publication number
- US20090223871A1 US20090223871A1 US12/380,665 US38066509A US2009223871A1 US 20090223871 A1 US20090223871 A1 US 20090223871A1 US 38066509 A US38066509 A US 38066509A US 2009223871 A1 US2009223871 A1 US 2009223871A1
- Authority
- US
- United States
- Prior art keywords
- hydrocarbons
- separation
- inorganic
- water
- hydrocarbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000002689 soil Substances 0.000 title claims description 7
- 239000000126 substance Substances 0.000 title claims description 3
- 239000002699 waste material Substances 0.000 title description 11
- 238000005520 cutting process Methods 0.000 title description 6
- 239000000463 material Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 5
- 239000011147 inorganic material Substances 0.000 claims abstract description 5
- 239000013049 sediment Substances 0.000 claims abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 claims abstract 19
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract 19
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract 7
- 238000005119 centrifugation Methods 0.000 claims abstract 2
- 238000010908 decantation Methods 0.000 claims abstract 2
- 239000003921 oil Substances 0.000 claims description 15
- 239000004576 sand Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 239000012071 phase Substances 0.000 claims 1
- 238000000053 physical method Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000009877 rendering Methods 0.000 abstract 1
- 239000011435 rock Substances 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 5
- 239000008186 active pharmaceutical agent Substances 0.000 description 4
- 238000005553 drilling Methods 0.000 description 3
- 239000013505 freshwater Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- 238000011021 bench scale process Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
Definitions
- API separator sludge Another source of material requiring waste minimization around refineries is API separator sludge. Again this material contains oil, salty to fresh water, bacteria, inorganic material such as dirt, clays, fine grained sand, rust, and other items. The API separator sludge also can exist as an emulsion which hampers the processing/waste minimization efforts thus resulting in costly disposal options.
- Another source of oilfield related wastes are storage pits, ponds, lagoons associated with production operations. Typically these pits, ponds and/or lagoons contain material similar to the previously described tank bottoms and/or API separator and thus inhibit cleanup of the pits, etc.
- drill cuttings Another source of material requiring cleanup and waste minimization is drill cuttings. Drill cuttings result from the drilling operations for oil wells.
- the drill cuttings contain oil, drilling mud additives, salty water and/or fresh water, crushed and groundup rock of varied lithology, and emulsions.
- the disposal of drill cuttings is difficult and expensive since the drilling mud additives and the oil typically are adsorbed onto the rock particles-thus requiring special-and expensive-disposal options.
- Another source of oilfield related wastes are oil spills on the native soil and/or ground that contaminates the soil and requires cleanup.
- a process to treat the above oily waste products to achieve separation and recovery of the salty or fresh water, the oil, and the rock and/or dirt materials and thereby achieve waste minimization has been developed and tested. Furthermore this said process can break emulsions, and more importantly is an exothermic (heat generating) process that minimizes the need for external heat sources.
- the entrained oil can be recovered as a valuable product, whereas the soil and/or rock material can be effectively cleaned of the adsorbed oil which therefore allows a multitude of inexpensive disposal options for the solids.
- the entrained water can be further processed if so desired to cleanup to disposal standards applicable to different locales. Alternately the entrained water may be reused as process water for subsequent treatment having the advantage of utilization of the residual treatment chemicals (such as alkaline agents) in the water.
- the process developed entails the following steps for emulsions and/or free liquid streams of oily material:
- the process can be operated in either a batch or continuous mode using standard tanks, or other suitable vessels.
- alkaline agents for removal of oily substrates from inorganic materials is well known process.
- peroxide to achieve partial oxidation of organic material, and thus render it more water soluble, is also well known.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
This invention relates to an improved methodology for the removal of oily hydrocarbon materials sorbed onto the surface(s) of inorganic materials. Said oily hydrocarbon materials may be partially oxidized or may be unoxidized. The invention makes use of an exothermic chemical reaction involving hydrogen peroxide and alkaline agents and hydrocarbons to partially oxidize certain reactive functional groups on the hydrocarbons and thus rendering said hydrocarbons more water soluble thereby facilitating the separation of the sorbed or free product hydrocarbons from both the surface of the inorganic material and also from between the interstitial grains (porosity). Furthermore the exothermic process facilitates the reduction of viscosity of said hydrocarbons thus further facilitating the separation of the hydrocarbons from the aqueous and inorganic phases. Said separation can be further enhanced by standard separation techniques such as settling, centrifugation, decantation, use of cyclones, and any and all other physical separation processes. Further by utilizing the hydrogen peroxide in an alkaline environment the interfacial tension of the oil is reduced further aiding said hydrocarbon-water-inorganic sediment separation and recovery of the hydrocarbons.
Description
- U.S. PROVISIONAL APPLICATION No. 61/068,412
- None
- Within the exploration, transportation, processing, and refining segments of the oil business (and other businesses), a consistently re-occurring problem exists related to waste minimization and/or cleanups of oily materials. Specifically production tanks can become partially filled with oily sediments and dirt, crude oil spills around production facilities are common requiring significant cleanup costs. In and around refineries storage tanks must be cleaned on a regular basis. These “tank bottoms” (as known in the industry) typically consist of a mixture of oil, water, salty water, clays and sand sized materials and bacteria. These items often are present as an emulsion-which is very difficult to break. Hence recovery of the entrained oil and separation of the solids under a waste minimization approach is hampered. Another source of material requiring waste minimization around refineries is API separator sludge. Again this material contains oil, salty to fresh water, bacteria, inorganic material such as dirt, clays, fine grained sand, rust, and other items. The API separator sludge also can exist as an emulsion which hampers the processing/waste minimization efforts thus resulting in costly disposal options. Another source of oilfield related wastes are storage pits, ponds, lagoons associated with production operations. Typically these pits, ponds and/or lagoons contain material similar to the previously described tank bottoms and/or API separator and thus inhibit cleanup of the pits, etc. Another source of material requiring cleanup and waste minimization is drill cuttings. Drill cuttings result from the drilling operations for oil wells. Oftentimes the drill cuttings contain oil, drilling mud additives, salty water and/or fresh water, crushed and groundup rock of varied lithology, and emulsions. The disposal of drill cuttings is difficult and expensive since the drilling mud additives and the oil typically are adsorbed onto the rock particles-thus requiring special-and expensive-disposal options. Another source of oilfield related wastes are oil spills on the native soil and/or ground that contaminates the soil and requires cleanup.
- Ideally a simple, safe and inexpensive process for the treatment of all the above items would benefit the waste minimization and resource recovery of the entrained oil. In addition the process should be applicable with minimal energy requirements to aid operation in remote locations.
- A process to treat the above oily waste products to achieve separation and recovery of the salty or fresh water, the oil, and the rock and/or dirt materials and thereby achieve waste minimization has been developed and tested. Furthermore this said process can break emulsions, and more importantly is an exothermic (heat generating) process that minimizes the need for external heat sources. The entrained oil can be recovered as a valuable product, whereas the soil and/or rock material can be effectively cleaned of the adsorbed oil which therefore allows a multitude of inexpensive disposal options for the solids. The entrained water can be further processed if so desired to cleanup to disposal standards applicable to different locales. Alternately the entrained water may be reused as process water for subsequent treatment having the advantage of utilization of the residual treatment chemicals (such as alkaline agents) in the water.
- The process developed entails the following steps for emulsions and/or free liquid streams of oily material:
-
- 1. pH adjustment to >9.0 preferably with CaO or Ca(OH)2, but in certain instances other alkaline agents may be beneficially utilized for compatibility reasons with said material to be treated;
- 2. addition of hydrogen peroxide (H2O2) preferably having a concentration greater than about 10% and in amounts equal to 0.5%, or greater, of the feed weight of the material to be processed;
- 3. monitoring of the pH and temperature
- 4. addition of additional alkaline agents and/or peroxide to achieve a temperature rise of the mixture of a minimum of 15 degrees centigrade;
- 5. mixing of the material by any appropriate manner or means;
- 6. settling of the mixture;
- 7. separation of the recovered oil and water by any means such as a clarifier and/or oil water separator;
- 8. separation of the cleaned soil, rock, dirt by any means such as a clarifier or centrifuge;
- 9. final disposal of the cleaned soil, rock, dirt in an appropriate manner.
- The process can be operated in either a batch or continuous mode using standard tanks, or other suitable vessels.
- Chemical reactions are:
-
CnH2n+2+H2O2=nCO2+H2O+heat 1. -
CnH2n+2+CaO+HOH=(CnH2n+1)−1+Ca(OH)2+(H+)+heat 2. - The use of alkaline agents for removal of oily substrates from inorganic materials is well known process. The use of peroxide to achieve partial oxidation of organic material, and thus render it more water soluble, is also well known. However the combination of the two processes to achieve lower cost cleanup of tank bottoms, drill cuttings, API separator sludges, oily pits/lagoons, and especially for the breaking of oil/water emulsions, has not previously been practiced nor discovered.
- Bench scale laboratory testing of this process has already demonstrated the efficacy of the process.
Claims (5)
1. A chemical and physical method to remove oily materials from sand, silt, grit, soil, sediments by the use of an exothermic process using hydrogen peroxide operating under alkaline conditions to liberate the oily and/or hydrocarbon material away from the surface of inorganic materials and thus allow for the separation of the hydrocarbons, water, and inorganic constituents.
2. A method to remove the liberated hydrocarbons and achieve separation of said hydrocarbons that now exist in both the aqueous phase and/or as a free phase by means of settling, decantation, filtering, centrifugation, and any other method commonly employed to achieve oil, water, solids separation.
3. A method to raise the temperature of an oily substrate to achieve lower viscosity of said hydrocarbon.
4. A method to modify the hydrocarbon chemistry to allow chemically reactive groups to form on said hydrocarbons and thus aid in the removal and separation of the hydrocarbons from the inorganic substrate.
5. A method to decrease the interfacial tension between the hydrocarbon and water to facilitate the separation of the hydrocarbon from the water and from the inorganic sediment materials.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/380,665 US20090223871A1 (en) | 2008-03-07 | 2009-03-03 | Methodology for the chemical and mechanical treatment and cleanup of oily soils, drill cuttings, refinery wastes, tank bottoms, and lagoons/pits |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US6841208P | 2008-03-07 | 2008-03-07 | |
US12/380,665 US20090223871A1 (en) | 2008-03-07 | 2009-03-03 | Methodology for the chemical and mechanical treatment and cleanup of oily soils, drill cuttings, refinery wastes, tank bottoms, and lagoons/pits |
Publications (1)
Publication Number | Publication Date |
---|---|
US20090223871A1 true US20090223871A1 (en) | 2009-09-10 |
Family
ID=41052501
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/380,665 Abandoned US20090223871A1 (en) | 2008-03-07 | 2009-03-03 | Methodology for the chemical and mechanical treatment and cleanup of oily soils, drill cuttings, refinery wastes, tank bottoms, and lagoons/pits |
Country Status (1)
Country | Link |
---|---|
US (1) | US20090223871A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11034596B2 (en) * | 2013-11-27 | 2021-06-15 | Sinomine Resources (Us) Inc. | Methods to separate brine from invert emulsions used in drilling and completion fluids |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5376182A (en) * | 1993-03-17 | 1994-12-27 | Remsol (U.S.A.) Corporation | Surfactant soil remediation |
US20050077242A1 (en) * | 2002-03-27 | 2005-04-14 | Mikael Karlsson | Soil decontamination method |
-
2009
- 2009-03-03 US US12/380,665 patent/US20090223871A1/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5376182A (en) * | 1993-03-17 | 1994-12-27 | Remsol (U.S.A.) Corporation | Surfactant soil remediation |
US20050077242A1 (en) * | 2002-03-27 | 2005-04-14 | Mikael Karlsson | Soil decontamination method |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11034596B2 (en) * | 2013-11-27 | 2021-06-15 | Sinomine Resources (Us) Inc. | Methods to separate brine from invert emulsions used in drilling and completion fluids |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |