Refining Industry Pollution Prevention Opportunities Checklist

Prepared by Philip Lo, CSDLA, 1/91.

Waste Water
Solid Waste Management
County Sanitation Districts Of Los Angeles County
1955 Workman Mill Road,
Whittier, CA 90603-4998

Mailing Address:

PO. Box 4998,
Whittier, CA 90607-4998

Charles W Carry
Chief Engineer and General Manager
Telephone (213) 699-7411, (213) 685-5217,
Fax: (213) 695-6139

Petroleum Refining Of Los Angeles County

The keys to pollution prevention for the petroleum refining industry are, for the short term, waste segregation, good operating practices and oil recovery. For the medium term, the driving force is probably product reformulation, which has resulted in production changes in meeting limitations for air toxic compounds and vapor pressure in fuel products. For the longer term, the keys may be more targeted hydrocarbon rebuilding and reforming to produce the desirable fuel components, while avoiding the undesirable toxic ones. More specifically, catalytic conversions and expanded use of hydrogenation may hold the most promise.

Y/N Opportunities Comments

(The following checklist presents a compilation of pollution prevention opportunities. However, since every refinery is unique, some of the opportunities may be more applicable to one refinery than to another. Please use the checklist with caution.)

I. Good Operating Practices

Material Input, Storage and Handling

Specify lower bottom sludge and water content for crude oil supply To minimize emulsifier carryover to API separator

Use recycled water as make-up water for crude desalter To minimize brine contamination of treated water for reuse

Reroute desalter water with emulsifiers to intermediate tankage To eliminate desalter water blowdown, which could be high in benzene and emulsifiers, while maintaining corrosion protection

Segregate and dispose of ballast water to salt water channel, if available To minimize brine contamination of treated water for reuse use corrosion resistant liners in storage and slop oil tanks install agitator in crude oil storage tanks

Replace desalting with an aggressive chemical treatment system for applicable situation, through crude oil dehydration in tankage with emulsion breaker, chloride reduction with caustic injection, ammonia replacement with neutralizing amine, film inhibitor feed rate optimization and anti-foulant injection to debutanizer heat exchanger (oil Gas Journal, 3/20/1989, pg. 60) To minimize sludge formation and need for tank cleaning

Segregate and discharge blowdown and water treatment regenerant to salt water channel or truck to ocean outlet, if available, to reduce wastes in storage tank and desalter through improved separation of water and bottom sludge at extractionl To minimize sludge accumulation

Recycled water quality is sufficient for desalting To minimize emulsion formation

Avoid high shear pumping of oily wastes; use Archimedean screw pumps as appropriate To minimize emission loss and moisture entry

Install tank cover and seal To eliminate leak losses

Install improved non-leaking seals To eliminate leaks and fugitive emissions

Install sealless pump To prevent leaks

Maintain seals regularly To minimize wastes for treatment

Recycle seal flushes and purges To minimize dirt entry to sewer

Pave process area To prevent fines from becoming wastes

Install cover for sewer drain To prevent solids entry to sewer

Collect catalytic fines during loading and unloading To minimize need for discharge

Recover coke fines for sale with coke To avoid intermediate tankage but may lose operational flexibility

Reuse recycled water for washdown if quality is desirable To avoid blending tankage

Integrate process units to pass processing streams from one unit to the next, if appropriate To flush materials back to the tank or pipeline and minimize volatile compound emissions

Bland fuels in-line

Install closed looped sampling system

Use computer software to track all hazardous materials and wastes To better manage virgin materials and waste streams

Return oily wastewater and sludge from distribution and sales terminals to refinery an permitted by federal and state recycling regulations To afford proper handling of oily wastes

Segregate scrap metals for sale To reclaim metals for reuse

Recondition valve and vessel To further reduce scrap metal reuse wastes

Recover and reuse sandblasting To minimize need for grit as blasting media or as a disposal, but beware of lead light aggregate in concrete and heavy metal contaminations product

Stormwater Management

Selectively cover loading rack and process areas to divert rainwater To preclude rainwater contamination

Segregate storm water collection system from process drainage To prevent cross contamination of storm water

Impound rainwater in collection basin or tank as appropriate To hold water pending determination of treatment need

Sweep streets and redesign catch basins to exclude dirt To prevent dirt entry to storm drain

Keep tank farm and process area clean, including secondary containment areas To avoid contaminating rainwater

Reuse rainwater after gravity recovery of oil and solids To minimize need for discharge

Discharge rainwater to public storm drain system under NPDES permit To avoid using sewer capacity

Dike process area that drains to storm water collection system as appropriate To prevent contamination of storm water

Regularly clean out drainage system to remove accumulated dirt To minimize contamination of storm water

Firefighting Water And Spillage Management

Install tank overfill prevention system To prevent spills

Pave areas under pipe rack To facilitate leak detection

Contain spillage with diking and absorbent materials To minimize spreading of spillage

Recover and reuse spillage To minimize need for disposal

Impound fire fighting water in rainwater basins or storage tanks as appropriate To hold and test before discharge or reuse

Prevent automatic crossover of storm drain to wastewater collection system To prevent spills and fire fighting water that entered the storm drain system from overwhelming the wastewater treatment system

Groundwater and Contaminated Soil Clean-up

Recover floatable oil for reuse

Pretreat and reinject treated groundwater if appropriate

Reuse hydrocarbon contaminated soil an filler in asphalt paving manufacture

Reuse soil with mineral contents similar to shale as raw material substitute for cement kiln; reuse in pre-heater and calciner kiln is preferred, to maximize volatile hydrocarbon destruction

Production Process Modifications

Separation Process

Improve separation In distillation column through various means including the following:

Increase the reflux ratio

Add a new section to the column

Match feed condition with the right feed tray

Preheat column feed

Install reusable insulation to prevent heat loss and fluctuation of column condition with weather.

Lower the reboiler temperature in distillation column through various means including the following:

Retray column to lower pressure drop To recover oil at source and avoid entrainment in transport

Increase size of vapor line to reduce pressure drop To eliminate need for discharge to sewer

Use lower pressure steam or desuperheated steam To avoid need for disposal

Install a thermocompressor To increase yield, and the separation of volatiles, e.g. benzene

Lower column pressure To minimize degradation and waste generation from high reboiler temperature

Improve overhead condensers To capture overhead losses
To minimize flaring and emissions

Conversion and Upgrading Processes

Improve conversion in reactors through various means including the following:

Distribute feeds better at inlets and outlets

Upgrade catalysts continuously, Provide separate reactor for recycled streams for more ideal reactor conditions

Better heating and cooling to avoid hot spots

Improve control to maintain optimum conditions in reactor To improve yield and conversion, and minimize the formation of undesirable compounds from side reactions

Use inhibitors to minimize unwanted side reactions. To recover and reuse catalyst

Filter catalyst fines from decanter oil from the Fluid Catalytic Cracking unit To recover the metals on the catalysts like cobalt and molybdenum, as well as those removed from oil like nickel and vanadium; the alumina carrier is also recovered

Reclaim hydroprocessing catalysts for metals and alumina

Recycle catalyst for bauxite in cement manufacturing To minimize need for disposal

Recover fluoride from spent caustics from a HIP alkylation process by calcium precipitation To produce calcium fluoride solids for use in cement industry or as fluxing agent in glass and steel industries

Reuse spent fluidized catalytic cracking unit (FCCU) catalysts in residue FCCU To reuse catalysts in another FCCU where higher metal content on the catalysts can be tolerated

Reactivate catalysts for reuse To reuse catalysts after the nickel and vanadium deposits are removed

Regenerate spent sulfuric acid by commercial reclaimer using incineration To regenerate the acid and avoid neutralization

Reclaim extraction solvents like sulfolane and sulfinol To recover solvents for reuse, with the residuals going for feed to a sulfuric acid plant because of their high BTU and sulfur contents

Product Treatment

Minimize the amount of caustic and rinse water used for product treatment through better contacting and recycling To minimize need for treatment of wastewater

Consider hydrotreating for pollutant removal To eliminate the use of caustic and water in product treatment

Send spent caustics to reclaimer To reclaim cresylic and naphthenic compounds for sale

Reuse spent sulfuric caustics for paper manufacturing To reuse the caustics if the strength is high enough

Regenerate clay from jet fuel filtration by washing with naphtha and drying by steam heating and feeding to furnace To recycle filter clay

Equipment Cleaning - Heat Exchangers

Use lower pressure steam To reduce tube-wall temperature and sludge formation

Desuperheat steam To reduce tube-wall temperature and increase the effective surface area of the exchanger because the heat transfer coefficient of condensing steam is ten times greater than that of superheated steam

Install a thermocompressor To reduce tube-wall temperature by combining high and low pressure steam

Use staged heating To minimize degradation, staged heating can be accomplished first using waste heat, then low pressure steam and finally, desuperheated high pressure steam

Use on-line cleaning techniques for exchangers Recirculating sponge balls and reversing brushes can be used to reduce exchanger maintenance and also to keep the tube surface clean so that lower temperature heat sources can be used

Use non-corroding tube Corroded tube surfaces foul more quickly than non-corroded ones

Waste Gas Treatment

Regenerate di-ethanol-amine (DEA) using slip stream filtration in addition to carbon filtration

Substitute Sulften Sulfur Recovery Process for Beavon Process

Regenerate activated carbon from gas scrubbing

Wastewater and Sludge Treatment

Add forebay skimming for API separator To remove degradation products and prolong DEA life

Use floating roof on treatment tanks and drains To avoid generation of spent Stretford Solution which contains vanadium

Use pressurized air in flotation To avoid need for disposal

Pretreat desalter water blowdown before co-mingling with other oily wastes, using absorption with light oil, or stripping with steam, nitrogen, methane or vacuum To recover more hydrocarbons for recycle

Thicken sludge In sludge tank and decant supernatant To minimize air emissions

Treat sludge with heat and chemicals to release more oil and water To pretreat the high concentration of benzene and possibly, emulsifiers in the desalter water blowdown
To minimize water content and remove some oil

Dewater sludge to cake form To aid in sludge dewatering

Reclaim hydrocarbons in sludge by feeding it to a delayed coker which produces fuel grade coke To further reduce hydrocarbon content in sludge

Use solvent extraction to remove hydrocarbons from sludge To dispose of solids and to reclaim hydrocarbon value

Use high temperature sludge drying to desorb hydrocarbons To treat sludge for disposal and recover hydrocarbons

Feed sludge cake to cement kiln for energy recovery To recycle sludge for its energy value

Evaluate gasification of oily wastes To convert waste to usable methane

Utility Production - Steam, Hydrogen

Use closed-loop cooling water system To minimize water loss

Demineralize cooling tower feed water To reduce cleaning and waste generation

Use polymers for boiler feed water treatment To reduce boiler cleaning

Collect condensate for reuse To avoid sewer discharge

Use non-chromate corrosion inhibitor To minimize chromate emissions and also chromate treatment in blowdown

Reclaim hydrogen plant catalysts To recover materials in catalysts

III. Product Reformulation and Material Substitution

Reformulate leaded gasoline to non-leaded alternative with MTBE. To eliminate lead from gasoline and product storage tanks

Reduce benzene and other volatile hydrocarbons in gasoline through re-blending with oxygenates like MTBE To decrease emissions of air toxics and smog-forming volatile organics

Y/N	Opportunities	Comments
	(The following checklist presents a compilation of pollution prevention opportunities. However, since every refinery is unique, some of the opportunities may be more applicable to one refinery than to another. Please use the checklist with caution.)
	I. Good Operating Practices
	Material Input, Storage and Handling
	Specify lower bottom sludge and water content for crude oil supply	To minimize emulsifier carryover to API separator
	Use recycled water as make-up water for crude desalter	To minimize brine contamination of treated water for reuse
	Reroute desalter water with emulsifiers to intermediate tankage	To eliminate desalter water blowdown, which could be high in benzene and emulsifiers, while maintaining corrosion protection
	Segregate and dispose of ballast water to salt water channel, if available	To minimize brine contamination of treated water for reuse use corrosion resistant liners in storage and slop oil tanks install agitator in crude oil storage tanks
	Replace desalting with an aggressive chemical treatment system for applicable situation, through crude oil dehydration in tankage with emulsion breaker, chloride reduction with caustic injection, ammonia replacement with neutralizing amine, film inhibitor feed rate optimization and anti-foulant injection to debutanizer heat exchanger (oil Gas Journal, 3/20/1989, pg. 60)	To minimize sludge formation and need for tank cleaning
	Segregate and discharge blowdown and water treatment regenerant to salt water channel or truck to ocean outlet, if available, to reduce wastes in storage tank and desalter through improved separation of water and bottom sludge at extractionl	To minimize sludge accumulation
	Recycled water quality is sufficient for desalting	To minimize emulsion formation
	Avoid high shear pumping of oily wastes; use Archimedean screw pumps as appropriate	To minimize emission loss and moisture entry
	Install tank cover and seal	To eliminate leak losses
	Install improved non-leaking seals	To eliminate leaks and fugitive emissions
	Install sealless pump	To prevent leaks
	Maintain seals regularly	To minimize wastes for treatment
	Recycle seal flushes and purges	To minimize dirt entry to sewer
	Pave process area	To prevent fines from becoming wastes
	Install cover for sewer drain	To prevent solids entry to sewer
	Collect catalytic fines during loading and unloading	To minimize need for discharge
	Recover coke fines for sale with coke	To avoid intermediate tankage but may lose operational flexibility
	Reuse recycled water for washdown if quality is desirable	To avoid blending tankage
	Integrate process units to pass processing streams from one unit to the next, if appropriate	To flush materials back to the tank or pipeline and minimize volatile compound emissions
	Bland fuels in-line
	Install closed looped sampling system
	Use computer software to track all hazardous materials and wastes	To better manage virgin materials and waste streams
	Return oily wastewater and sludge from distribution and sales terminals to refinery an permitted by federal and state recycling regulations	To afford proper handling of oily wastes
	Segregate scrap metals for sale	To reclaim metals for reuse
	Recondition valve and vessel	To further reduce scrap metal reuse wastes
	Recover and reuse sandblasting	To minimize need for grit as blasting media or as a disposal, but beware of lead light aggregate in concrete and heavy metal contaminations product
	Stormwater Management
	Selectively cover loading rack and process areas to divert rainwater	To preclude rainwater contamination
	Segregate storm water collection system from process drainage	To prevent cross contamination of storm water
	Impound rainwater in collection basin or tank as appropriate	To hold water pending determination of treatment need
	Sweep streets and redesign catch basins to exclude dirt	To prevent dirt entry to storm drain
	Keep tank farm and process area clean, including secondary containment areas	To avoid contaminating rainwater
	Reuse rainwater after gravity recovery of oil and solids	To minimize need for discharge
	Discharge rainwater to public storm drain system under NPDES permit	To avoid using sewer capacity
	Dike process area that drains to storm water collection system as appropriate	To prevent contamination of storm water
	Regularly clean out drainage system to remove accumulated dirt	To minimize contamination of storm water
	Firefighting Water And Spillage Management
	Install tank overfill prevention system	To prevent spills
	Pave areas under pipe rack	To facilitate leak detection
	Contain spillage with diking and absorbent materials	To minimize spreading of spillage
	Recover and reuse spillage	To minimize need for disposal
	Impound fire fighting water in rainwater basins or storage tanks as appropriate	To hold and test before discharge or reuse
	Prevent automatic crossover of storm drain to wastewater collection system	To prevent spills and fire fighting water that entered the storm drain system from overwhelming the wastewater treatment system
	Groundwater and Contaminated Soil Clean-up
	Recover floatable oil for reuse
	Pretreat and reinject treated groundwater if appropriate
	Reuse hydrocarbon contaminated soil an filler in asphalt paving manufacture
	Reuse soil with mineral contents similar to shale as raw material substitute for cement kiln; reuse in pre-heater and calciner kiln is preferred, to maximize volatile hydrocarbon destruction
	Production Process Modifications
	Separation Process
	Improve separation In distillation column through various means including the following:
	Increase the reflux ratio
	Add a new section to the column
	Match feed condition with the right feed tray
	Preheat column feed
	Install reusable insulation to prevent heat loss and fluctuation of column condition with weather.
	Lower the reboiler temperature in distillation column through various means including the following:
	Retray column to lower pressure drop	To recover oil at source and avoid entrainment in transport
	Increase size of vapor line to reduce pressure drop	To eliminate need for discharge to sewer
	Use lower pressure steam or desuperheated steam	To avoid need for disposal
	Install a thermocompressor	To increase yield, and the separation of volatiles, e.g. benzene
	Lower column pressure	To minimize degradation and waste generation from high reboiler temperature
	Improve overhead condensers	To capture overhead losses To minimize flaring and emissions
	Conversion and Upgrading Processes
	Improve conversion in reactors through various means including the following:
	Distribute feeds better at inlets and outlets
	Upgrade catalysts continuously, Provide separate reactor for recycled streams for more ideal reactor conditions
	Better heating and cooling to avoid hot spots
	Improve control to maintain optimum conditions in reactor	To improve yield and conversion, and minimize the formation of undesirable compounds from side reactions
	Use inhibitors to minimize unwanted side reactions.	To recover and reuse catalyst
	Filter catalyst fines from decanter oil from the Fluid Catalytic Cracking unit	To recover the metals on the catalysts like cobalt and molybdenum, as well as those removed from oil like nickel and vanadium; the alumina carrier is also recovered
	Reclaim hydroprocessing catalysts for metals and alumina
	Recycle catalyst for bauxite in cement manufacturing	To minimize need for disposal
	Recover fluoride from spent caustics from a HIP alkylation process by calcium precipitation	To produce calcium fluoride solids for use in cement industry or as fluxing agent in glass and steel industries
	Reuse spent fluidized catalytic cracking unit (FCCU) catalysts in residue FCCU	To reuse catalysts in another FCCU where higher metal content on the catalysts can be tolerated
	Reactivate catalysts for reuse	To reuse catalysts after the nickel and vanadium deposits are removed
	Regenerate spent sulfuric acid by commercial reclaimer using incineration	To regenerate the acid and avoid neutralization
	Reclaim extraction solvents like sulfolane and sulfinol	To recover solvents for reuse, with the residuals going for feed to a sulfuric acid plant because of their high BTU and sulfur contents
	Product Treatment
	Minimize the amount of caustic and rinse water used for product treatment through better contacting and recycling	To minimize need for treatment of wastewater
	Consider hydrotreating for pollutant removal	To eliminate the use of caustic and water in product treatment
	Send spent caustics to reclaimer	To reclaim cresylic and naphthenic compounds for sale
	Reuse spent sulfuric caustics for paper manufacturing	To reuse the caustics if the strength is high enough
	Regenerate clay from jet fuel filtration by washing with naphtha and drying by steam heating and feeding to furnace	To recycle filter clay
	Equipment Cleaning - Heat Exchangers
	Use lower pressure steam	To reduce tube-wall temperature and sludge formation
	Desuperheat steam	To reduce tube-wall temperature and increase the effective surface area of the exchanger because the heat transfer coefficient of condensing steam is ten times greater than that of superheated steam
	Install a thermocompressor	To reduce tube-wall temperature by combining high and low pressure steam
	Use staged heating	To minimize degradation, staged heating can be accomplished first using waste heat, then low pressure steam and finally, desuperheated high pressure steam
	Use on-line cleaning techniques for exchangers	Recirculating sponge balls and reversing brushes can be used to reduce exchanger maintenance and also to keep the tube surface clean so that lower temperature heat sources can be used
	Use non-corroding tube	Corroded tube surfaces foul more quickly than non-corroded ones
	Waste Gas Treatment
	Regenerate di-ethanol-amine (DEA) using slip stream filtration in addition to carbon filtration
	Substitute Sulften Sulfur Recovery Process for Beavon Process
	Regenerate activated carbon from gas scrubbing
	Wastewater and Sludge Treatment
	Add forebay skimming for API separator	To remove degradation products and prolong DEA life
	Use floating roof on treatment tanks and drains	To avoid generation of spent Stretford Solution which contains vanadium
	Use pressurized air in flotation	To avoid need for disposal
	Pretreat desalter water blowdown before co-mingling with other oily wastes, using absorption with light oil, or stripping with steam, nitrogen, methane or vacuum	To recover more hydrocarbons for recycle
	Thicken sludge In sludge tank and decant supernatant	To minimize air emissions
	Treat sludge with heat and chemicals to release more oil and water	To pretreat the high concentration of benzene and possibly, emulsifiers in the desalter water blowdown To minimize water content and remove some oil
	Dewater sludge to cake form	To aid in sludge dewatering
	Reclaim hydrocarbons in sludge by feeding it to a delayed coker which produces fuel grade coke	To further reduce hydrocarbon content in sludge
	Use solvent extraction to remove hydrocarbons from sludge	To dispose of solids and to reclaim hydrocarbon value
	Use high temperature sludge drying to desorb hydrocarbons	To treat sludge for disposal and recover hydrocarbons
	Feed sludge cake to cement kiln for energy recovery	To recycle sludge for its energy value
	Evaluate gasification of oily wastes	To convert waste to usable methane
	Utility Production - Steam, Hydrogen
	Use closed-loop cooling water system	To minimize water loss
	Demineralize cooling tower feed water	To reduce cleaning and waste generation
	Use polymers for boiler feed water treatment	To reduce boiler cleaning
	Collect condensate for reuse	To avoid sewer discharge
	Use non-chromate corrosion inhibitor	To minimize chromate emissions and also chromate treatment in blowdown
	Reclaim hydrogen plant catalysts	To recover materials in catalysts
	III. Product Reformulation and Material Substitution
	Reformulate leaded gasoline to non-leaded alternative with MTBE.	To eliminate lead from gasoline and product storage tanks
	Reduce benzene and other volatile hydrocarbons in gasoline through re-blending with oxygenates like MTBE	To decrease emissions of air toxics and smog-forming volatile organics

(WP, Refinery, Manual)

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Last Updated: January 8, 1996