RAFAEL A. GARCIA USDA-ARS, WYNDMOOR PA FPRF EMERGING ISSUES AND OPPORTUNITIES SEMINAR TUESDAY, OCTOBER 24TH, 2017 BACARA RESORT, SANTA BARBARA, CA

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1 ANIMAL PROTEINS AS BIO-BASED FLOCCULANTS RAFAEL A. GARCIA USDA-ARS, WYNDMOOR PA FPRF EMERGING ISSUES AND OPPORTUNITIES SEMINAR TUESDAY, OCTOBER 24TH, 2017 BACARA RESORT, SANTA BARBARA, CA

2 AGRICULTURAL RESEARCH SERVICE WITHIN USDA S RESEARCH, EDUCATION, AND ECONOMICS MISSION AREA - NOT DIRECTLY INVOLVED IN REGULATIONS OR INSPECTIONS USDA S PRIMARY IN-HOUSE RESEARCH AGENCY - DON T MAKE GRANTS LOCATIONS ALL OVER THE COUNTRY $1.1B ANNUAL BUDGET 690 PROJECTS, ~2000 SCIENTISTS

3 ANIMAL PROTEIN UTILIZATION GROUP TEAM MEMBERS RAFAEL GARCIA, LEAD SCIENTIST/RESEARCH CHEMICAL ENGINEER GEORGE PIAZZA, RESEARCH CHEMIST VACANT, RESEARCH CHEMIST MATTHEW ESSANDOH, ORISE POST-DOC (CHEMISTRY) LORELIE BUMANLAG, PHYSICAL SCIENCE TECHNICIAN 2 VACANCIES, PHYSICAL SCIENCE TECHNICIAN CHRISTINE NIEMAN AND JULIANNE WAGNER, DREXEL UNIVERSITY COOPS OVERALL GOAL: DEVELOPMENT OF VALUE-ADDED USES FOR SLAUGHTER BYPRODUCTS AND RENDERED PROTEIN SPECIFIC GOAL: DEVELOPMENT OF A COMMERCIALLY-VIABLE FLOCCULANT THAT CAN SERVE AS A BIO-BASED SUBSTITUTE FOR SYNTHETIC FLOCCULANTS

4 CO-WORKERS HIDES, LEATHER, GELATIN/COLLAGEN COMPLETE PILOT-SCALE TANNERY 2 PERMANENT SCIENTISTS, POST DOC, ENGINEER, DREXEL COOP, CHINESE SCIENTIST WOOL 1 PERMANENT SCIENTIST, 1TECH

5 SUSPENSIONS CLAY, CELLS, FIBERS, COAL DUST PARTICLES SCATTER LIGHT STABLE SMALL DON T SINK FAST NEGATIVELY CHARGED REPEL ONE ANOTHER

6 POLYMERIC FLOCCULANTS SYNTHETIC LINEAR VERY HIGH MOLECULAR WEIGHT (LONG) POLY-ELECTROLYTES ALL POSITIVE OR ALL NEGATIVE CHARGES HIGH, UNIFORM CHARGE DENSITY OPEN, FLEXIBLE STRUCTURE

7 POLYMERIC FLOCCULANTS POSITIVELY CHARGED HARMFUL TO AQUATIC ANIMALS NEGATIVELY CHARGED REQUIRE COUNTER ION

8 FLOCCULANTS IN ACTION FLOCCULANTS DESTABILIZE SUSPENSIONS NEUTRALIZE CHARGE, REDUCE REPULSION CONNECT PARTICLES, INCREASE SETTLING RATE

9 FLOCCULANT APPLICATIONS PULP AND PAPER PROCESSING IRRIGATION WASTEWATER TREATMENT BIOENERGY MINERAL PROCESSING COAL REFUSE SLURRY BEVERAGE CLARIFICATION BAUXITE PROCESSING POOL AND POND MAINTENANCE

10 FLOCCULANTS AREN'T JUST FOR SETTLING FLOCCULANTS CAN BENEFIT: DISSOLVED AIR FLOATATION FILTRATION CENTRIFUGATION

11 HOW WE GOT INVOLVED Furrow Erosion From One Pre-Irrigation

12 SOIL-CONTAMINATED IRRIGATION WATER POLLUTES WATERWAYS Snake River Return Flow, ca 1975

13 PAM IS A GREAT SOIL FLOCCULANT PAM CAUSES SUSPENDED PARTICLES TO FLOCCULATE, DRAMATICALLY INCREASING SETTLING RATE PAM IS EFFECTIVE IN SOIL CONSERVATION NOW COMMONLY USED IN SOME AREAS TRENDS ARE AGAINST PAM - A BIO- BASED ALTERNATIVE IS DESIRABLE ATTEMPTS TO USE CARBOHYDRATE BASED FLOCCULANTS HAVE FAILED

14 PROTEIN AS A FLOCCULANT NATURALLY OCCURRING LINEAR POLY-ELECTROLYTE HIGH MOLECULAR WEIGHT BUT MUCH SMALLER THAN SYNTHETIC FLOCCULANTS MIXED CHARGES CHARGE DISTRIBUTED NON-UNIFORMLY AND LOWER DENSITY LESS OPEN STRUCTURE; SOME CHARGED GROUPS NOT EXPOSED

15 SOME PROTEINS WORK, OTHERS DON T WATER EXTRACT OF MBM GELATIN SOME PROTEINS DON T WORK (SOY, MILK) HYDROLYZED PROTEINS CAN WORK, BUT EFFECTIVENESS IS REDUCED HAS DO WITH SIZE AND CHARGE, BUT NOT THE WHOLE PICTURE Hemoglobin vs. no 90 minutes

16 CHICKEN BLOOD POULTRY PLANTS TRY TO KEEP BLOOD OUT OF WASTE WATER COD/BOD AND TKN TYPICALLY PAY RENDERERS FOR REMOVAL NOT TURNED INTO A HIGH VALUE PRODUCT DEGRADES RAPIDLY COAGULATES PUTREFIES CELLS LYSE

17 CHICKEN BLOOD IS A GOOD FLOCCULANT WORKS BETTER AT ph<6 DOESN T ADD RED COLOR CHICKEN BLOOD ISN T NECESSARILY BETTER THAN OTHER BLOOD THERE S A LOT OF IT AND NOBODY WANTS IT PATENTED

18 CHICKEN BLOOD PROTEINS HEMOGLOBIN HAS STRONG FLOCCULANT ACTIVITY A FEW OF THE PLASMA PROTEINS PROMOTE FLOCCULATION, BUT AREN T ABUNDANT ISOLATING HEMOGLOBIN NOT PARTICULARLY EXPENSIVE

19 RATE OF CLARIFICATION PURIFYING HEMOGLOBIN DOESN T IMPROVE RATE KCE IS A LOGARITHMIC SCALE KCE=1 MEANS 90% REDUCTION KCE=2 MEANS 99% REDUCTION Turbidity (NTU) Whole blood Plasma Hemoglobin Settling time (hours) KCE Settling time (hours)

20 WHOLE BLOOD IS LESS SENSITIVE TO OVERDOSING COMMON FOR POLYMERIC FLOCCULANTS TO PERFORM POORLY WHEN OVERDOSED WHOLE BLOOD DOESN T HAVE THIS PROBLEM EVEN AT >4X OPTIMUM DOSE

21 DOESN T LEAVE OTHER POLLUTANTS BEHIND SEWAGE FEES ARE BASED ON LEVELS OF COD AND TKN BLOOD HAS LOTS OF COD 100 Whole blood Hemoglobin 10 8 AND TKN APPROPRIATE DOSES OF BLOOD DON T ADD COD OR TKN TO TREATED WATER COD (mg/l) Flocculant (mg Hb/g kaolin) TKN (mg/l) Flocculant (mg Hb/g kaolin)

22 METHYLATED HEMOGLOBIN ONLY POSITIVE CHARGES 3.5 LESS FOLDED UP 3 Methylation SIMPLE REACTION IMPROVED PERFORMANCE TOLERATES HIGHER PH Mean KCE Hemoglobin Methylated Hemoglobin ph

23 BIGGER BUT NOT LINEAR POLYMERIZED HEMOGLOBIN GREATLY INCREASES PERFORMANCE OF HEMOGLOBIN FLOCCULANT KCE Hemoglobin GTA-crosslinked hemoglobin Flocculant dose (mg/g kaolin)

24 MAGNETIZED HEMOGLOBIN COMPOSITE OF HEMOGLOBIN AND HEMATITE INSOLUBLE HIGHLY ADSORBENT OF DYES CAN BE RECOVERED USING MAGNET RE-USABLE PROBABLY EXTENDABLE TO OTHER ORGANIC CONTAMINANTS PATENT PENDING

25 GETTING MORE PROTEIN OUT OF MBM

26 APPLICATIONS PRIORITIZING APPLICATIONS WHERE PATHOGENS ARE A NOT MAJOR CONCERN USER NEEDS TO AVOID SYNTHETIC FLOCCULANT CURRENT OR RECENT APPLICATIONS ANAEROBIC DIGESTER EFFLUENT ETHANOL THIN STILLAGE LIGNIN RECOVERY

27 Technology transfer TECH TRANSFER WE LIKE TO PARTNER WITH PRIVATE SECTOR COOPERATIVE RESEARCH AND DEVELOPMENT AGREEMENTS (CRADAs) FOR JOINTLY-CREATED INTELLECTUAL PROPERTY NIFA-SBIR GRANTS CAN PAY FOR COLLABORATIVE RESEARCH

28 CURRENT EFFORTS ADDING POSITIVE CHARGES TO PROTEIN COST MODELLING OF PRODUCTION TREATING PULP/PAPER PLANT WASTE STREAMS USING FLOCCULANT IN DAF CROSS LINK/MODIFY HYDROLYZED MBM TO IMPROVE PERFORMANCE

29 THANK YOU! QUESTIONS?

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