(12) United States Patent (10) Patent No.: US 7820,069 B2 Gosselin (45) Date of Patent: Oct

US007820069B2

(12) United States Patent (10) Patent No.: US 7820,069 B2 Gosselin (45) Date of Patent: Oct. 26, 2010

(54) METHOD AND APPARATUS FOR 4,009,063 A * 2/1977 Wood ...... 156,71 CONTROLLING CONTAMINATION FROM 5,116,388 A 5, 1992 Brooks ...... 8/405 PIPE COATINGS 5,688,867 A * 1 1/1997 Scheibelhoffer et al. ... 525/168 (76) Inventor: Michael Gosselin, 22 Jefferson Cir., 5,877,389 A ck 3, 1999 Sorokinet al...... 588,316 Clinton, CT (US) O6413-1518 6,620,408 B2 9/2003 Hoeffkes et al...... 424.62 6,703,004 B2 * 3/2004 Narasimhan et al...... 424.62 (*) Notice: Subject to any disclaimer, the term of this 2002/006 1955 A1 5/2002 Colvin et al...... 524,493 patent is extended or adjusted under 35 2002/01399.57 A1* 10, 2002 Matsuo et al...... 252,186.1 U.S.C. 154(b) by 0 days. 2003/0135937 A1* 7/2003 Barrass et al...... 8,408 (21) Appl. No.: 12/460,305 2006/0269492 A1* 11/2006 Narasimhan et al...... 424.62 2006/0270761 A1* 11/2006 Gosselin ...... 523,514 (22) Filed: Jul. 16, 2009 2007/0000070 A1 1/2007 Vena et al...... 8/405 (65) Prior Publication Data US 201O/OO298.79 A1 Feb. 4, 2010 * cited by examiner Related U.S. Application Data Primary Examiner Joseph D Anthony (63) Continuation-in-part of application No. 1 1/440,897, (74) Attorney, Agent, or Firm Ober, Kaler, Grimes & filed on May 25, 2006. Shriver; Royal W. Craig (60) Provisional application No. 60/684,917, filed on May (57) ABSTRACT 26, 2005, provisional application No. 61/135,037, filed on Jul. 16, 2008. (51) Int. Cl. A combination of a styrene reduction agent and a catalyst that COB I5/08 (2006.01) effectively and economically reduces styrene emissions in A62D 3/38 (2007.01) Cured-In-Place Pipe, closed molding processes. The reduc A62D 3/30 (2007.01) tion agent generally comprises a calibrated mixture of salts A62D IOI/20 (2007.01) including sodium chloride plus three persulfate salts: ammo CO2F I/72 (2006.01) MiNR1ngredients are SN, combined inE. powderform ityand are(NPS). compresse l (52) U.S. !, 2/18637.253/186 iss5:3. into Soluble capsules containing calibrated amounts of the • 1 s 588/405. 20,758. 210,759 mixture. The capsule(s) may be prescribed through the use of s s software. The catalyst is hydrogen peroxide (HO). A cali (58) Field of Classification Search ...... 252/186.21, brated amount of the styrene reduction agent capsule(s) are 252/186.22; 5 88/320, 405 added to the cure water prior to starting the boiler equipment See application file for complete search history. for the Cured-In-Place Pipe process, and this is followed by a (56) References Cited calibrated amount of the HO catalyst in order to reduce the residual monomer content in either process or waste streams. U.S. PATENT DOCUMENTS 2.468,027 A * 4, 1949 Britton et al...... 526.93 7 Claims, 6 Drawing Sheets

Chemical Name: Styredux Physical Form: While crystallie Active oxygen content; 6,4% Minimum Chemicai Name: styredux Sr. Physica Form: liquid A.C.C. 3.1%. Minimum

Pipe diameter Length passie Irishes issi is 8E) - 3. inputdata in yellow boxesso Amount of styrene Amount of Amount of styrene Amount of styrene in the process water water used' present in the water present in the water in a 5% ?aacts: gallems) gauds 280 1873.s 0.50 3.75 3x cooling 5,521 Amount of styree styRedux in the process water Percent emountto add to the after additional Sigis Redigiri gressess was casules 39 4. exual worlsar Amount of styrene presentin the Water after treatment exunds

inaccio?o Systegus 232 0.31 amount to add to the qual to cf war s

Arnout of styrene present in the water after total Sisterisatislaounds 0.13 equatoorker

* caledissaressedupana:2%xisposite diarie? of the happa withs 301 tickTriapask coat-g time water is presentertis-ins' *Adekusatilda after process waters at 188F * War in seriesses cuts, U.S. Patent Oct. 26, 2010 Sheet 1 of 6 US 7820,069 B2

Chemical Name: StyRedux Physical Form: White, crystalline Active Oxygen Content: 6.4% Minimum Chemical Name: StyRedux SP Physical Form: Liquid A.O.C. 3.1%. Minimum

Pipe Diameter length Process" ine (inches") (feet) (hours G 180°F) Input data in yellow boxes Amount of styrene Amount of Amount of styrene Amount of styrene in the process water water used present in the water present in the water (ppm) -5% (gallons) (gallons) (pounds) 240 1873.6 0,50 3.75 3x Cooling 5,621 Amount of styrene StyRedux in the process water Percent amount to add to the after addition' (ppm) Styrene Reduction process water (Capsules) 39 D4 equal to or lower Amount of styrene present in the water after treatment pounds) in Addition to StyRedux H2O2 0.61 amount to add to the Percent System equal to or lower process water (Gallons) Styrene Reduction

Amount of styrene present in the water after Total System treatment ?pounds) 0.13 equal to or lower

Calculations are based upon a 93% composite diameter of the host pipe with a 0.01"thick thermoplastic coating "Time water is present or "cure-time". "Additive addition after process water is at 180 F, Water in boiler hoses included. F.G. 1 U.S. Patent Oct. 26, 2010 Sheet 2 of 6 US 7820,069 B2

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U.S. Patent US 7820,069 B2

U.S. Patent Oct. 26, 2010 Sheet 6 of 6 US 7820,069 B2

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*-,?• US 7,820,069 B2 1. 2 METHOD AND APPARATUS FOR styrene through the coating material is apparent as an oily CONTROLLING CONTAMINATION FROM Substance on the coating even prior to installation. This poses PIPE COATINGS grave environmental health concerns for air emissions as well as process effluents released downstream, into treatment CROSS-REFERENCE TO RELATED plants, or in the case of storm sewer rehabilitation: streams, APPLICATION(S) rivers, lakes, public and private water Supplies. During the process, employee and public Safety is at risk. The present application is a continuation-in-part of U.S. Employee exposure is tightly regulated by an Occupational application Ser. No. 1 1/440,897 filed May 25, 2006 (which in Safety and Health Administration (OSHA) workplace air turn derives priority from U.S. Provisional Application No. 10 borne threshold limit value (TLV) of 50 parts per million 60/684,917 filed May 26, 2005), and further derives priority (ppm) in many states. Releases to the air are regulated by the from U.S. Provisional Application No. 61/135,037 filed 16 Clean Air Act (CAA) National Emission Standards for Haz Jul. 2008. ardous Air Pollutants (NESHAP) for plastic composites and boat manufacturing. Releases to the water are regulated by the BACKGROUND OF THE INVENTION 15 Clean Water Act (CWA). The Environmental Protection Agency (EPA) and the local Department of Environmental 1. Field of Invention Protection (DEP) agencies have styrene listed as a reportable The present invention relates to the reduction of residual hazardous chemical. California has listed Styrene as a car styrene from a thermoset resin and, more particularly, to a cinogen. Other states have styrene listed as a possible car styrene polymerization agent in aqueous environments that cinogen and a marine pollutant. Compliance to regulating effectively and economically reduces styrene emissions and authorities can only be met by cost-effectively implementing effluents in moist environments. pollution preventive methods and technologies that reduce 2. Description of the Prior Art toxic and hazardous emissions. The composites industry today is experiencing significant The problem is highlighted in the following article: “Odour growth as an ever-increasing number of industry applications 25 Control More than Sewage when Installing Cured-In-Place are being found for reinforced plastics. This is largely owing Pipe Liners', NASTT No-Dig, March 2004, Gerry Bauer, P. to the durability, strength, cost and expected lifetime of such Eng. & David McCartney, P. Eng, City of Ottawa. The City of plastics. One application in particular is the Cured-In-Place Ottawa Canada identified five sections of sewer for rehabili Pipe (CIPP) industry, in which piping systems are repaired tation by a cured-in-place pipe methods. The contract was through the application of resin compounds to damaged pipe 30 tendered, but during lining of the initial sections, numerous Surfaces while the pipes remain buried underground. Under complaints were received from the public regarding an ground pipes are used for the transport of petroleum, natural unpleasant odor in their homes. Investigations revealed that gas, chemicals, municipal water, and the like. Due to expo the odor complaints occurred as a result of styrene. The solu Sure to a number of influences over time such as, for example, tion mentioned in this report was to dilute the air concentra temperature fluctuations, ground movements, corrosive flu 35 ids, etc., these pipes tend to crack and damage. As a result, the tion with equipment, fans above a manhole. Regulatory agen pipes often are unable to Successfully transport the above cies require reduction at the source means and not by dilution. mentioned fluids and thus become unsuitable for their No testing on the release water was implemented. intended use. The Cured-In-Place Pipe (CIPP) method for Another problem highlighting Cured-In-Place Pipe emis repair can solve this problem without expensive excavation. 40 sions is: "Fumes From Va. Sewer Work Cited In Illnesses', For example, U.S. Pat. No. 4,009,063 by Wood issued Feb. Washington Post Staff Writer, Annie Gowen, May 12, 2004, 22, 1977 shows a method of lining pipe with a hard, rigid pipe Page B08. The residents of the Warwick Village neighbor of thermosetting resin using a tubular fibrous felt immersed in hood of Alexandria, Va. were affected by styrene fumes from the resin to form a carrier for the resin. The immersed felt and a CIPP application to their sanitary sewer system. High con resin are expanded by an inflatable tube to shape the resin to 45 centrations were reported on hoses used in the operation, no the passageway Surface until the resin is cured to form a hard, testing from the source have been reported. rigid lining pipe with the felt embedded therein. The resin is Yet another problem where health officials were called into a thermosetting resin which contains a catalyst, and hot air, investigate, Schlitz Park Office Building, Milwaukee County, water, a combination of air and water or ultraviolet light (UV) Wis. Styrene fumes entered the building through drains and is used to activate the catalyst or UV initiator causing the resin 50 foundation walls. Employees were evacuated and some to cure and form a rigid liner. missed work for months. Fans were used to create airflow to Another approach involves utilizing glass fiber which is dilute concentrations of styrene. Process water testing at the woven into a tubular shape. The glass fiber is impregnated Source was not part of the investigation. with a thermosetting resin containing a catalyst, and the resin "Styrene is a common chemical component used in rubber is then cured. Carbon fiber may be interwoven with the glass 55 and plastics industries to make packaging, insulation and fiber Such that curing may be accomplished by applying an fiberglass products. It is also associated with combustion electrical current to the carbon fibers to generate heat. As a processes such as automobile exhaust and cigarette Smoke. result, the catalyst is activated and the resin cures forming a The odor threshold for styrene has been reported to be 50 rigid pipelining. In this instance, hot air or hot water is not parts per billion (Plog 1988). It has been described as having required. 60 a Sweet, sometimes irritant odor. It is slightly soluble in water There are still other methods that rely on UV curing. In all and is volatile. The most common health effects associated Such cases the higher temperature or light provides the energy with styrene exposure are mucous membrane irritation and to cure the thermosetting resin, causing it to harden into a central nervous system effects (e.g. depression, concentration structurally sound, jointless pipe-within-a-pipe. Unfortu problems, muscle weakness, tiredness, and nausea). Recov nately, during the curing process, the curing water/conden 65 ery short term effects is typically rapid upon removal from sate becomes contaminated with styrene that has permeated exposure (ATSDR 1992). Health Consultation, Schlitz Park through the film coating material. Indeed, the leaching of Office Building, WI, Sep. 13, 2005, U.S Department of US 7,820,069 B2 3 4 Health and Human Services, Agency for Toxic and Disease The present inventor's co-pending U.S. patent application Registry, Division Of Health Assessment and Consultation, Ser. No. 1 1/440,897 for “Styrene Reduction Agent” describes Atlanta, Ga. an agent including sodium chloride plus a mixture of persul There are conventional styrene reduction strategies includ fate salts: ammonium (APS), potassium (KPS), and sodium ing the following: (NPS), combined in powder form compressed into soluble 1. Using low styrene content resins: Although many of capsules for effectively and economically reducing styrene these resins are currently available from resin Suppliers, emissions in CIPP. The inventor has now discovered that a this method does not lend to every process, and the calibrated amount of hydrogen peroxide (H2O) serves as an physical properties of the final product can be affected. effective catalyst to increase reactivity and proceed to full In Some instances, the reduction of styrene is not signifi 10 reduction of toxics and pollutants. cant enough to make a difference, and in some cases, styrene emissions may even increase. SUMMARY OF THE INVENTION 2. Using controlled spay-on techniques is another method for reducing styrene emissions. This method is very It is therefore, a primary object of the present invention to effective and works by controlling the amount of surface 15 provide a styrene reduction agent, initiator or oxidizer that area of the wet resin which is exposed to the air, whether effectively and economically reduces styrene, or reactive spraying gel coat or plain resin. diluent, in Cured-In-Place Pipe, or other surface coating pro 3. Addition of paraffin wax is another method of reducing cesses, in combination with a catalyst comprising hydrogen styrene emissions. This Suppresses styrene emissions peroxide (H2O) to increase reactivity of the styrene reduc through the film it provides but, in doing so, creates the tion agent and ensure quicker and more complete reduction of problem of secondary bonding between the laminates toxics and pollutants. which can cause the further delamination of the com It is another objective to reach a higher level of effective posite resulting in a structural weakness. ness than prior art reduction agents. 4. Using alternate monomers is a forth method of reducing It is still another objective to simplify the task of imple styrene emissions. Alternate monomers such as methyl 25 menting the reactive diluent reducing agent directly into the methacrylate, vinyl toluene and butyl styrene can be curing medium in a predetermined quantity and an easy-to used, or it is possible to use olygomers, which basically calibrate manner. consist of two or three molecules that have been com It is still another objective to remove polymerized reactive bined. They work effectively but can be very expensive diluent along with Small concentrations of un-reacted dilu and, in addition, Some can be more toxic than styrene or 30 ents that may remain in the process. made from styrene derivatives, also considered HAP and It is another objective to polymerize absorbed reactive VOC compounds. diluents on the surface of said coating of reactive diluents 5. Using a closed molding process is another method. This either: miscible, soluble in water or non-soluble in water. can be extremely effective in lowering styrene emis These and other objects are accomplished with a styrene sions, but equipment cost and maintenance cost is a great 35 reduction agent plus a catalyst that combine to effectively and disadvantage. economically reduce styrene emissions in Cured-In-Place 6. Using a styrene Suppressant is another option. Pipe or other Surface coating curing processes. Generally, the Further to option 6, a number of styrene Suppressant addi invention comprises a calibrated mixture including persulfate tives are currently available to the composite fabricator. They salts (Peroxodisulfates), plus hydrogen peroxide (H2O) as a are most effective when using the open-molding processes 40 catalyst to increase reactivity of the styrene reduction agent. and, when properly used, can reduce Styrene emissions dur A method is also disclosed for incorporating both into the ing the curing stage of the composite. Styrene Suppressant Cured-In-Place Pipe process and then removing them from agents can effectively and economically reduce styrene emis the Cured-In-Place Pipe processes in such a way as to reduce sions when properly used in any open-molding process. Spe styrene emissions by 75% and more. More specifically, the cifically, the advantages of Styrene Reduction in CIPP Cure 45 mixture includes ammonium persulfate (APS) and/or potas Water are: sium persulfate (KPS) and/or sodium persulfate (NPS) with i. No additional equipment needed for as much as a 75% sodium chloride (NaCL) combined in the following preferred reduction concentrations within acceptable ranges: ii. Minor equipment needed for reductions above 75% iii. Mixing not required, simply add required amount in 50 water soluble packaging iv. Non-toxic, Non-Hazardous Product % by weight V. Meets all compliance regulations APS 30 By way of example, StyridTM is an existing Styrene Sup KPS 35 pressant additive manufactured by Specialty Products Com 55 NPS 30 pany to reduce the amount of styrene vapors escaping from NaCL 05 the composites. StyridTM and most other styrene suppressant formulations contain wax and other components that produce The calibrated amounts of the persulfate salt mixture are a film on the top of the laminate, creating a barrier which encapsulated in a water soluble packaging for addition to the prevents styrene, or organic diluents, from leaving the com 60 cure water. Preferably, the packaging comprises capsules for posite in the form of a vapor during the curing stage. StyridTM material handling and product safety. The capsule(s) may be creates a film similar to that provided by paraffin wax. added to the cure water at anytime during the process. For It would be greatly advantageous to preserve all the above example, the capsule(s) may be added prior to starting the identified qualities of existing Styrene Suppressant formula heating equipment, or boiler, for the Cured-In-Place Pipe tions and yet provide an even higher level of effectiveness, 65 process in order to reduce the residual monomer, styrene, and worker and public safety, with an advantage to economi content in either the process or waste streams. The addition of cally reduce HAP and VOC emissions. the capsules is followed by addition of a calibrated amount of US 7,820,069 B2 5 hydrogen peroxide (H2O), which serves as an effective cata lyst to increase reactivity and proceed to full reduction of -continued toxics and pollutants. Optimum Possible Range The capsules in combination with the HO facilitate safe, Preferred Amt Range (+/- % (+/- % by quick and ready deployment. Product (% by weight) by weight) weight) BRIEF DESCRIPTION OF THE DRAWINGS NPS 32.5 25-35 O-1OO NaCL 2.5 <10 O-10 FIG. 1. is a graphical analysis of the calculations for cali brating the amount of the present mixture to be added 10 The ingredients are combined in powder form and, in FIG. 2. is a graphical depiction of the present styrene accordance with the present invention, the mixture is com reduction calculations indicative of the efficacy of the cap pressed into Soluble capsules containing calibrated amounts Sules. of the mixture. The capsules are used in packaging for dis FIG. 3. is a drawing of a StyReduxTM Capture System, persion. The capsules are preferably soluble gel capsules when placed into operation will capture, filter, polymerized 15 (veterinarian grade), size SU-07 (the largest currently avail styrene and non-polymerized styrene. able. Other types of packaging can be easily deployed includ FIG. 4. is a calculation for the amount of styrene in the ing dispensing powder directly, dispensing powder into an Cured-In-Place Pipe process water. FIG. 5 is data series table and a graphical representation of inert liquid and then dispensing. Typical weight of one cap a polymerization rate series analysis. Sule is 30 grams +/-5 grams. FIG. 6 is a block diagram of a suitable filtering system that The styrene reduction agent capsule(s) may be added to the may be deployed in unison with the mentioned styrene reduc cure water prior to starting the boiler equipment for the ing agent capsules. Cured-In-Place Pipe process in order to reduce the residual monomer content in either the process or waste streams. The DETAILED DESCRIPTION OF THE PREFERRED 25 capsules facilitate quick and ready deployment of the mix EMBODIMENT ture. An amount of hydrogen peroxide (H2O) is then added in The present invention is a styrene reduction agent, or “ini solution form to the cure water based likewise on the weight tiator/oxidizer, in combination with a catalyst comprising a of reactive monomer or aromatic hydrocarbon. Specifically, calibrated amount of hydrogen peroxide (H2O), the combi 30 HO may be added within a range of from 0.1-10:1 w/w of nation effectively and economically reducing styrene emis reactive monomer or aromatic hydrocarbon. This is also how sions and effluents in Cured-In-Place Pipe closed molding the styrene reduction agent capsule(s) are added, and so the processes by means of emulsion polymerization. H2O may be added on a 1:1 basis relative to the styrene The styrene reduction agent comprises a calibrated mixture reduction agent weight/weight ratio. In other words, a 6 Pph of peroxodisulfates, also known as Persulfate salts, and the 35 ratio of styrene reduction agent to styrene in the cure water preferred catalyst is a calibrated amount of Hydrogen Perox results in a ratio of 6 Pph of HO. Of course, the styrene off ide Solution. A method of calculating and incorporating the gassing during exotherm and residual monomers in the resin styrene reduction agent and catalyst into the Cured-In-Place composite is difficult to predict or estimate in the challenging Pipe process is also disclosed in Such a way as to reduce applications of CIPP. Future monitoring of percent reduction styrene emissions and effluents by as much as 75% or more. 40 may alter the dosage of styrene reduction agent and/or H2O. More specifically, the styrene reduction agent is preferably Additionally, Styrene Reduction Agent may be used solely or a composite of sodium chloride (NaCl) plus three persulfate H2O may be used solely if extra dosage is required (as salts: ammonium persulfate (APS), potassium persulfate determined by monopersulfate test strips or hydrogen peroX (KPS), and sodium persulfate (NPS). The APS is available as a white crystalline powder which begins to decompose when 45 ide testing strips). The intent is to maintain low concentra heated to 120°C. It is known as a strong oxidant and is widely tions of either/any added chemical to a minimum prior to used in the organic synthetic industry as an initiator for poly release into the environment, but also maintain optimum merization of polymer compounds. The KPS is likewise polymerization of monomer/hydrocarbons. available as a white crystalline powder, soluble in water, and The addition of styrene reduction agent together with decomposes attemperatures of approximately 100°C. It too 50 hydrogen peroxide catalyst will increase reactivity and pro is a strong oxidant and has been traditionally used for chemi ceed to full reduction of toxics and pollutants. Reductions of cal bleaching, and as an accelerator for polymerization of aromatic hydrocarbons can be accomplished at ambient tem vinyl chloride resin emulsion. The NPS is also available as a peratures over a longer cure time which will proceed quickly white, crystalline, odorless salt. NPS is conventionally used from the heat supplied by the exothermic reaction. The heat/ as initiator for the polymerization of monomers and as a 55 energy from the exothermic reaction is determined from the strong oxidizing agent in many applications. The NaCL is resin system, i.e. catalyst, promoters, initiators and the like to conventional salt. In accordance with the present invention, increase conversion rates of the reactive chemical Solution The APS, KPS, NPS and NaCL are combined in the following added. relative concentrations: The hydrogen peroxide (H2O) catalyst may be obtained 60 from FMC Corporation, Philadelphia, Pa. or a variety of other chemical companies. Hydrogen Peroxide is commercially Optimum Possible Range available in many concentrations: 35, 50 and 70% w/w are Preferred Amt Range (+/- % (+/- % by common for industrial applications, while a 3% solution w/w Product (% by weight) by weight) weight) is common for topical Solutions. Transportation regulations APS 32.5 25-35 O-1OO 65 are more Stringent for concentrations over 8%, and so a less KPS 32.5 30-40 O-1OO than 8% solution is preferred, and specifically a Hydrogen Peroxide Solution diluted (DI) to 3% by weight is suggested. US 7,820,069 B2 7 8 While the amount per capsule may vary, the size of the including cooling water is generally 2.5 to 3 times the water capsule or packaging may vary, the composition of the pack used to inflate the liner and hold the liner against the host pipe aging may vary, or the powder may be pre-dispersed in a or Surface to be coated, in this example 5,621 gallons. Treat non-reactive fluid, the specific guidelines for use herein ment of 5,621 gallons is calculated by entering 2,454 feet with described with a stepwise example. 5 one hour process time, the result being 4 capsules. If three Step 1. Calculate amount to be used for the CIPP liner. This is accomplished with the assistance of either a software cal hour cooling from 180 to 100, then 10 capsules and so on. culator or a predetermined “look-up' table. The software is In addition to the styrene reduction agent described above, based on extrapolation from laboratory testing data, and is a calibrated amount of the catalyst is added based on a weight/ essentially a spreadsheet equation based on linear progres 10 weight ratio of the amount of pure H2O per Volume of cure sion from absorption and extraction tests. water. 0.36 ounces of pure H.O. per 5,000 Gal of cure water A. The input variables are as follows: is sufficient to trigger the catalytic reaction and achieve 96% i. Diameter of pipe (inches) reduction. Thus, if a 3% solution of Hydrogen Peroxide is ii. Length of pipe (feet) used, 12 fluid ounces of diluted HO may be used to treat iii. Process time at 180° F (hours) 15 each 5,000 Gal of cure water. B. The outputs from the software are: The HO may be added into the cure water by any of the i. Amount of styrene in process water (ppm, gallons, following methods: pounds, etc.) 1) Direct application into water source . . . . ii. Amount of process water used (gallons) iii. Amount of capsules to add to the water (capsule(s)) a. Directly into down-tube iv. Amount of styrene after treatment (ppm) b. Directly into boiler while filling reservoir V. Percent removal accomplished (%) 2) Pump from premixed tank into manifold or Styrene vi. Amount of hydrogen peroxide (H2O) catalyst to add to Capture System outlet prior to entering surface to be treated the water 25 (preferred if there are concerns about boiler/piping damage vii. Amount of styrene after treatment (pounds) by injection at the input manifold). viii. Percent removal accomplished (%) The software module essentially calculates from the input 3) Spray/brush diluted solution directly onto tube coating. variables the amount of process water used during the Cured The following are test results using a calibrated amount of In-Place Pipe process, and calculates the amount of residual 30 styrene reduction agent capsules and catalyst applied directly styrene present in the process water from collected data. The to a styrene-containing medium, Hexion Specialty Chemical software then calculates the amount of residual styrene that unsaturated vinyl ester resin 780-1115 (30% styrene): 1.7g will be present in the process water, and calculates the reme (0.68 g). dial amount of the present mixture. For example, given input variable as follows: 35 Example 1 Diameter: 8" Length:800 Process Time(a) 180° F.: 5 hours Hydrogen Peroxide Solution diluted (DI) to 3% by weight: The software output will be as follows: 256 g (8.45 g) 40 Styrene Reduction Agent (SRA): 34:33:33 mix ratio: 0.1 g The SRA and HO were mixed to a resin emulsion state Amount of styrene in the process water: 240 ppm and coated onto the medium, which was then temperature Amount of water used for inversion/filling: 1,873.6 gal cured until non tacky with the following parameters. Note: General multiplier for cooling: X3: 5,621 gal Amount of styrene present in the water: 0.5 gallons 45 1) Cured without heat for 18 hrs Amount of styrene present in the water: 3.73 pounds 2) Same ratio: Heat to 90 F. Cured non-tacky: 12 HRS Amount of styrene in the process water after addition: 39 ppm Equal to or lower 3) Same ratio: Heat to 105 F.: Cured non-tacky: 5 HRS Percent Styrene Reduction: 84% 4) Same ratio: Heat to 125 F.: Cured non-tacky: 3 Hrs Styrene reduction agent to add to the process water 4 capsules (1,873.6 gallons) 50 5) Same Ratio: Heat to 180 F.: Cured non-tacky: 3-5 min Amount of styrene present in the water after treatment: 0.61 pounds utes (equal to or lower) Amount of hydrogen peroxide (H2O) to add 0.38 pounds Tested by GC, EPA method 8260-B for volatile organic car to the water Amount of styrene after treatment (pounds) 0.13 pounds bons, Percent removal accomplished (%) 96% 55

FIG. 1 is a spreadsheet analysis of the foregoing calcula Benzene Toluene Ethylbenzene Xylenes Styrene tions for a specific example, which conclude that a total of sample (PPM) (PPM) (PPM) (PPM) (PPM) four (4) capsules of the present mixture (bottom right) should 1 O491 O.O3S O.049 O.O28 117 be added to achieve 84% styrene reduction, given 240 ppm 60 2 O464 O.O34 O.061 O.O22 128 styrene in 1873.6 gallons of process water. Note that cooling 3 O.683 O.066 O.353 O.425 446 water is generally added to reduce the process water below 4 O.S22 O.046 O.324 O413 136 100 degrees F. prior to release. Holes are put in the terminal end to release water while filling with cooling water. Cooling cycles range from one (1) to three (3) hours but vary accord 65 Addition of Styrene reduction Agent: 6 Pph per 100 parts ing to thickness (thicker liners require longer cool-down styrene, +HO 6 Pph per 100 parts styrene: Equal Parts cycles) and type of resin System used. The total Volume H2O2 (StyRedux SP): Styrene reduction Agent (StyRedux) US 7,820,069 B2 9 10 and described will obviously occur to those skilled in the art upon becoming familiar with said underlying concept. It is to be understood, therefore, that the invention may be practiced Percent Styrene otherwise than as specifically set forth in the appended Reduc 5 claims: sam- Benzene Toluene Ethylbenzene Xylenes Styrene tion I claim: ple (PPM) (PPM) (PPM) (PPM) (PPM) (%) 1. A composition for reducing styrene emissions from ther 1 ND ND ND ND ND 100 moset unsaturated resin curing during Cured-In-Place Pipe 2 ND ND ND ND 1.68 99.7 (CIPP) installation in aqueous environments, consisting 3 ND ND ND ND 6.64 99.5 10 essentially of 4 ND ND ND ND ND 100 cure water from said CIPP installation; Ave. 99.8 a persulfate salt mixture including a plurality of different species of peroxodisulfates pre-mixed in calibrated The Styrene Reduction Agent or the HO can be pumped amounts and pre-packaged; and from a reservoir into the “clean water input of the filter 15 hydrogen peroxide that functions as a catalyst; system. The hose from the filter system is attached to a spare/ whereby said pre-packaged persulfate salt mixture is or tied into an existing recirculation hose for dispensing adapted for emulsion polymerization reduction of Sty throughout the curing liner. rene emission when added to said cure water from said CIPP installation, and said hydrogen peroxide catalyst is The Agent and/or HO can be added directly to the cure adapted for catalyzing said emulsion polymerization water by the inversion point access. reduction by said persulfate salt mixture. The Agent and/or HO can be added directly to the make 2. The composition according to claim 1, wherein said up/inversion water through the water Supply feed. persulfate salt mixture includes any one from among the One skilled in the art should expect that increasing concen group including ammonium persulfate (APS), potassium per tration ratios of either the styrene reduction agent and/or 25 sulfate (KPS) and sodium persulfate (NPS). hydrogen peroxide should increase the conversion results. 3. The composition according to claim 2, further compris It must be noted that the best technology or work practices ing sodium chloride (NaCL). are always defined in relation to a specific company. For 4. The composition according to claim 3, wherein said example, what might be the best way to minimize waste at one persulfate salt mixture and NaCL are formed as of com company may be very different from the best methods achiev 30 pressed crystalline powder pre-packaged in water-soluble ing the same objectives at another company. In each case, capsules. what is the “best practice' or “best available technology' will 5. The composition according to claim 2, wherein said depend on the availability of resources, what materials are mixture of persulfate salts consists essentially of 32.5% by processed, how they are processed, what products are made, weight ammonium persulfate (APS), 32.5% by weight potas local community or regulatory requirements, and other fac 35 sium persulfate (KPS), and 32.5% by weight sodium persul tors. However, in all such cases the present invention will fate (NPS). provide a catalyzed styrene reduction agent that effectively 6. The composition according to claim 5, further compris and economically reduces styrene emissions in Cured-In ing approximately 2%-2.5% by weight NaCL. Place Pipe, closed molding processes. 7. The composition according to claim 3, wherein said Having now fully set forth the preferred embodiment and 40 mixture of persulfate salts comprises a range of from 25-35% certain modifications of the concept underlying the present ammonium persulfate (APS), a range of from 25-35% potas invention, Various other embodiments as well as certain varia sium persulfate (KPS), and a range of from 0.1 to 10% NaCL. tions and modifications of the embodiments herein shown k k k k k