Cryogenic grinding of spices- Review.pptx

Cryogenic grinding of spices- Review of the technology

1. Welcome 1

2. PSMA – 691 Doctoral Seminar I “Cryogenic grinding of spices ” Presented by , Ms. Shephali Satish Surve Ph.D (Hort.) Plantation, Spices, Medicinal & Aromatic crops Reg. No. HDPD/22/0022 Seminar In-Charge , Dr. R. C. Gajbhiye Professor (CAS) Department of PSMA College of Horticulture, Dapoli 2

3. ADVISORY COMMITEE Chairman and Research Guide Dr. R. C. Gajbhiye Professor (CAS) Department of PSMA College of Horticulture, Dapoli Members 3

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5. A lso called as “ Cryomilling ” or “ freezer grinding .” It is the process of size reduction of solid materials in the cooling environment created by cryogens to retain quality of ground product . Originated from the Greek words “ Kryos ” ( frost) and “ Genic ” (produce) It deals with low temperatures as low as below −150 °C or 123 K to absolute zero (-273.15 °C ). Cryogenics is the study of low temperatures and behavior of materials under the low temperatures. Cryogenic grinding 5 (Sardar et al., 2024) Introduction

6. (Balasubramanian et al ., 2012) History Sir James Dewar ( 20 Sept 1842 – 27 March 1923) Invented Dewar flask The man who first liquefied hydrogen 6 A Dutch physicist, Kamerlingh Onnes (1894) produced a gas having low boiling temperature, named as cryogen. LH 2 and LO 2 are used in rocket propellant and LN 2 and LCO 2 in liquid or solid form are the major cryogens used for food applications. Though LN 2 has been used for many decades as a refrigerant, in recent years its widespread applications in almost every branch of science, viz. electronics, space technology, biology, medicine, sports and musical instruments, food and agriculture are remarkable.

7. Application of Cryogenics Air separation gas industry As a space simulation F ood industry Electronics Magneto Cardiography Nuclear and high energy physics and metal producers S teel industry Thermoplastics and Thermosets Adhesives and Waxes R ocket propellant 7 (Kumar et al., 2021)

8. Spices Area ( in ‘000 ha ) Production ( in tons) Export (tons) Black pepper 303230 86056 17958 Cardamom (S) 70410 24463 7352 Dry Chilli 844303 2278550 516177 Ginger 188423 2303298 50885 Turmeric 325611 1169864 170085 Coriander seed 711603 973712 54481 Cumin 714188 461998 186509 Nutmeg & Mace 24310 18207 3447 Fenugreek seed 146234 234595 35055 Clove 1990 1257 - (DGCI&S and Spice Board of India, 2022-23) 8 Table 1: Area, production and export of spices from India during 2022-23 India is the world’s largest spice producer. C ontributing 44% share in output and 36% in global spice trade, Out of the 109 spices listed by ISO, India produces about 75 from its different agro climatic regions. Indian scenario in spices p roduction Area and production of spices in Maharashtra 2022-23 Crop Area (ha) Production (tons) Chilli 6127 18991 Ginger 9163 131472 Turmeric 83000 278000

9. 9 (Kumar et al., 2021)

10. The loss of flavoring constituents and volatile oils due to high heat generation inside machinery ( 42-93°C). Sometimes, oil comes out from the material and makes the ground product sticky, gummy which results in chocking of product passage sieves . The color and different properties of the ground product of cryogenic grinding will no longer be changed and their flavor and nutritional value will no longer be lost . This technology has been scientifically proved to be suitable method with less loss of volatile oil content, superior color and grinding operation . Need Spice Loss of volatile oil (%) Nutmeg 37 % Mace 14 % Cinnamon 17 % Coriander 40 % (Singh and Goswami, 1997) 10 (Sharma et al ., 2016)

11. ( Kumar et al ., 2021 ) 11 Fig. 1. Damage to piping system due to cold embrittlement

12. CRYOGENS They produce extremely low temperatures The most common is liquid nitrogen Inert in nature (Durga Prasad et al., 2024) Cryogens are the substances used to produce very low temperature . Liquid nitrogen is the most commonly used in spices. Cryogens are stored in vessels referred to as dewar flask which gives good insulation . 12 Fig. 2: Dewar flask

13. Non toxic in nature Inert or less reactive Non- flammable Low cost Legally purchasable around the world N on-corrosive liquid and extremely cold (boiling point -195.8° C). Why Liquid Nitrogen? Properties of Cryogens LN 2 CO 2 Density (kg/m 3 ) 784 464 Boiling point ( C) -196 -78.5 Thermal conductivity (W/m k) 0.29 0.19 Specific heat capacity liquid (kJ/kg k) 1.04 2.26 Latent heat of evaporation (kJ/kg) 3.58 352 Table 2: Properties of cryogenic fluids used in food systems 13 (Murthy et al ., 2015) Liquid nitrogen in the Cryo-grinding process serves two purposes; To cool the raw material and the mill to operating temperatures To remove the heat liberated during grinding

14. A dvantages of cryogrinding with liquid n itrogen (Murthy et al ., 2015) 14 1. Higher retention of essential oils 2. Prevention of oxidation and rancidity 3. Increased throughput and power saving 4. Fine and uniform particle size 5. Reduction in microbial load 6. F ine grinding of difficult spices Amount of liquid nitrogen required :- 0.6 to 0.8 lit /kg of spices   (Liang and Hao, 2000) Cost of liquid nitrogen:- Rs. 12 /lit (MVS Engineering Ltd)

15. 15 Sr. No. Spice Essential oil Ambient grinding (ml/100g) Cryogenic grinding (ml/100g) % Increase of essential oil in cryogenic grinding over ambient 1 Black pepper 1.40 1.84 31.42 2 Ginger 1.44 1.80 25 4 Coriander 0.26 0.40 53.84 5 Clove 11.50 16.50 43.87 Table 3: Comparison of the essential oil retention by ambient and cryogenic grinding (Sardar et al., 2024)

16. Parameter Traditional grinding Cryogenic grinding Source Energy requirement High Low (Singh and Goswami, 2000) Grinding output Low High (Meghwal and Goswami, 2014) Grinding of soft material Very difficult Possible (Goswami and Singh, 2003) Sieve clogging Frequent No clogging (Singh and Goswami, 2000) Particle size distribution Uneven even (Meghwal and Goswami, 2014) Fire risk High No (Shama et al ., 2016) Colour of ground powder Not original Retain original colour (Godki and Goswami, 2016) Loss of essential oil Higher Minimum (Shama et al ., 2016) Loss of total oil Significant Minimum (Balasubramanian et al ., 2016) Retention of medicinally important compounds Less retention More retention (Balasubramanian et al ., 2016) Control on particle size No control Effective (Gopalkrishnan et al ., 1991) Air pollution Yes No https://spectracryogenic.tradeindia.com Microbial load Possible Does not exist https://spectracryogenic.tradeindia.com Table 4: Comparison of cryogenic grinding over traditional grinding 16

17. Cryogenic grinding process Consists of two main units, 1. Precooling unit and 2. Grinding unit Cleaning of spices Loading in hopper through vacuum conveyor Feeding of material in grinders Grinding of material at low temperature and inert atmosphere Feeding in cryogenic screw conveyor Chilling of spices with liquid nitrogen Extracting low temp from grounded material (Kumar et al ., 2020) 17 Fig. 3. Schematic diagram of cryogenic grinding system

18. Fig. 4 : Cryogenic Apparatus Fig. 5: Lab model of cryogenic grinder at ICAR-CIPHET, Ludhiana (Kumar et al ., 2020) 18 Cost of unit : 5 lakh Capacity : 100 kg/hr Brand : Mechair (Mechair.in)

19. Cryogenic grinding of spices and herbs not only retain the volatiles with no loss as well as maintain the originality in flavor quality, thus has prospective commercial uses. Enhancement of pharmacological properties opens another important avenue for utilization of this technology for herbal grinding in Ayurveda and other traditional system of medicine. Particle size up to 50 μm may be achieved by cryogenic grinding which in turn will be more effective in medicinal or therapeutic use. Less quantity of herbal drugs will be required if ground cryogenically. Practical applications in spice industry Fig. 6: Comparison of cryogenically ground and conventionally ground spices 19 (Sardar et al., 2024)

20. Neetacha Ella Satvam Meera Just half spoon Indian c ompanies that uses cryogenic grinding for their spices 20 Hathi masala

21. 21 No. Spice Price of traditionally grounded spice (Rs/100g) Price of cryogenically grounded spice (Rs/100g) 1 Black pepper 115 134 2 Turmeric 38 49 3 Cumin 50 68 4 Coriander 39 45 5 Fenugreek 58 63 6 Ginger 70 80 7 Chilli 60 70 Source As per local market www.ellafoods.in Table 5: Price difference between traditional and cryogenic grounded spices

22. Table 6: The commonly associated cryogen hazards are presented below Health hazards Effect Safety measures Skin and eye hazard An instantaneous contact between cryogen and exposed skin can produce a painful burn and a splash of cryogenic liquid to eye can cause loss of vision, too. Always wear safety goggles or face shield Appropriate cryogen gloves Cold embrittlement At cryogenic temperatures many materials, such as rubber, plastics and carbon steel can become so brittle that very little stress can break the material Examine the containers and pressure relief valves regularly for signs of defect. Requires skilled labour for operating. Oxygen enrichment Can create potentially explosive condition. 22 (Sardar et al ., 2024)

23. 23 Research findings

24. 1. An experimental study on cryogenic spice grinding system for black pepper grinding (Barnwal et al ., 2019) Sr. No Average particle size (mm) Conveyor screw speed (rpm) Temperature ( C ) 10 C - 50 C 1 5 0.345 ±0.004 0.313 ±0.007 2 10 0.359 ±0.018 0.327 ±0.034 3 15 0.369 ±0.005 0.343 ±0.010 F-values 4.31 NS 0.73 NS CD 0.05 0.04 0.06 Table 7: Effect of conveyor screw speed and temperature on particle size of black pepper powder 24 Material : Black pepper, Cryogenic grinding unit, liquid nitrogen Methods: Temperatures (10°C and -50°C) and C onveyor screw speeds (5, 10 and 15 rpm), the grinding operation of black pepper was carried out in the cryogenic spice grinding system at 6500 rpm of pin mill. The experiments were conducted at ICAR- CIPHET, Ludhiana, India Objective :- To study effect of screw speed and temperature on particle size, colour of parameters of black pepper

25. Temp Conveyor screw speed (rpm) L-value a-value b-value Chroma value Hue angle( ) Browning Index 10 C 5 47.67 ±2.46 2.97 ±0.41 9.78 ±1.11 10.23 ±1.06 72.92 ±3.02 27.31 ±3.89 10 50.61 ±2.27 3.02 ±0.58 8.81 ±2.49 9.40 ±2.17 69.17 ±6.29 23.40 ±5.95 15 50.88 ±3.45 2.50 ±0.60 10.33 ±1.59 10.65 ±1.59 76.26 ±3.28 26.34 ±5.92 F-values 3.29 NS 2.27 NS 1.42 NS 1.14 NS 2.39 NS 1.15 NS CD 0.05 3.89 0.56 1.90 1.74 7.73 5.56 -50 C 5 52.14 ±1.39 3.23 ±0.30 a 10.11 ±0.61 ab 10.61 ±0.62 a 72.24 ±1.52 a 25.77 ±2.32 a 10 53.69 ±2.67 2.19 ±0.44 b 9.41 ±0.94 b 9.67 ±0.96 b 76.92 ±2.31 b 22.01 ±3.16 b 15 50.79 ±2.94 2.34 ±0.56 b 10.49 ±0.80 a 10.76 ±0.81 a 77.41 ±2.95 b 26.29 ±3.73 a F-values 2.82 NS 12.72 3.74 4.25 11.89 4.44 CD 0.05 3.83 0.46 0.83 0.85 2.43 3.25 Table 8: Effect of conveyor screw speed and temperature on colour parameters of black pepper powder NS=Non-significant; Mean values with the same superscript letters within the same column do not differ significantly (p > 0.05) (Barnwal et al ., 2019) 25

26. 2 . Effect of cryogenic grinding on essential oil and oleoresin content of cumin ( Cuminum cyminum L.) genotypes  Cumin Varie ty Essential oil Oleoresin Cryo ground (%) Non cryo ground (%) % increase in cryo over non cryo grinding Cryo ground (%) Non cryo ground (%) % increase in cryo over non cryo grinding GC 4 4.1(± 0.15) 3.0 (± 0.15) 33.9 17.7 (± 0.43) 15.3 (± 0.73) 15.4 RZ 209 3.6 (± 0.09) 2.5 (± 0.15 43.5 14.9 (± 0.13) 11.5 (± 0.49) 29.8 Table 9: Essential oil and oleoresin percentage of cumin genotypes n = 3, value in parenthesis is standard deviation Table 10 : Composition of volatile constituents of cumin genotypes after grinding with cryo and normal grinding Compound Cumin variety GC-4 RZ-209 Cryo (%) Normal (%) Cryo (%) Normal (%) a-Thujene 0.07 (±0.004) 0.1 (±0.019) 0.1 (±0.109) 0.1 (±0.015) Camphene 0.18 (±0.025) 0.03 (±0.001) - - 4-Isopropylanisole 0.24 (±0.009) 0.15 (±0.029) 0.27 (±0.045) - m-Cuminol 0.19 (±0.020) 0.16 (±0.038) 0.87 (±0.049) 0.13 (±0.025) Cuminaldehyde 56.1 (±0.648) 48.2 (±0.474) 71.6 (±1.750) 69.7 (±1.252) p-Cuminol 9.42 (±1.774) 2.07 (±0.304) - - 26 (Sharma et al ., 2016) GC 4 : Gujrat cumin 4, RZ 209 : Rajasthan 209

27. 3 . Study on quality aspects of cryogenic grinding of ginger (Gourav et al ., 2022) Fig 7: Oleoresin recovery of ginger powder at different temperature 27

28. 4 . Biochemical and antioxidant properties of cryogenic and ambient ground turmeric powder (Barnwal et al ., 2014) Table 11:- Effect of grinding conditions on the quality characteristics of turmeric powder N o. Parameter Cryo-ground Ambient ground  1. Volatile oil content, % 5.18±0.05a 4.27±0.11b  2. Curcumin content, % 5.17±0.02a 4.17±0.02b  3. Oleoresin content, % 13.28±0.02a 10.12±0.63b 4. Total phenols (ppm GAE 1000 - 1 ppm) Alcohol extract 2.11±0.01a 1.54±0.06b Water extract 0.70±0.01a 0.57±0.02b Petroleum ether extract 0.31±0.02a 0.24±0.01b  5. DPPH Scavenging % Alcohol extract 84.88±0.03a 63.14±0.47b Water extract 72.38±0.06a 54.16±0.04b Petroleum ether extract 40.28±0.02a 31.14±0.18b 6. Colour values L 54.76±1.17a 52.64±0.78a a 17.39±0.82a 17.70±0.73a b 36.29±0.44a 33.34±0.74b Note : Mean values with the same superscript letters within the same row do not differ significantly ( p > 0.05) 28

29. (Barnwal et al ., 2018) Temp Conveyor screw speed (rpm) Essential oil (%) Total flavonoids (mg QE g -1 ) Total phenolic content (mg GAE g -1 ) Antioxidant content (BHTE g -1 ) 10 °C 5 0.49±0.01 13.35±0.82 54.50±3.12 25.14±0.68 10 0.49±0.01 14.82±1.40 57.32±1.89 26.83±1.08 15 0.49±0.01 16.97±0.97 62.94±0.58 28.73±0.60 F-values 0.76 NS 32.57* 13.24 NS 30.51 NS CD 0.05 0.02 1.43 9.82 4.93 -50 °C 5 0.66±0.01 19.96±2.84 79.32±6.74a 36.13±1.04 10 0.66±0.01 23.45±1.03 82.56±3.23b 37.24±1.44 15 0.66±0.01 24.78±0.88 85.27±7.32c 38.56±1.67 F-values 0.85 NS 23.78 NS 46.32* 36.72 NS CD 0.05 0.03 7.85 1.91 3.87 Table 12 : Effect of screw speed and temperature on essential oil, total flavonoids, total phenolic content and antioxidant content of coriander powder NS=Non-significant; Mean values with the same superscript letters within the same column do not differ significantly (p > 0.05) 5 . Grinding performance of cryogenic spice grinding system for coriander 29

30. 6 . Estimation of oleoresin, total phenolic and flavonoid content of cryo and conventionally ground seeds of coriander ( Coriandrum sativum L.) and fenugreek ( Trigonella foenum-graecum L.) (Saxena et al ., 2012) Table 13 : Effect of cryo grinding on recovery of oleoresin in coriander and fenugreek genotypes Variety Coriander  Variety Fenugreek Cryo Ground (%) Conventional Ground (%) Cryo Ground (%) Conventional Ground (%) Sudha 18.53 9.50 RMt 1 5.63 4.6 RCr 436 18.88 12.80 RMt 305 5.95 4.8 Mean 18.705 11.15 Mean 5.79 4.7 SD (±) 0.247 2.333 SD (±) 0.226 0.141  Variety Coriander Variety Fenugreek Cryo Ground Conventional Ground Cryo Ground Conventional Ground TPC TFC TPC TFC TPC TFC TPC TFC Sudha 63.61 20.22 19.46 13.94 RMt 1 5.63 75.722 4.6 67.377 RCr 436 87.08 16.70 62.39 15.38 RMt 305 5.95 83.544 4.8 71.028 Mean 73.345 18.46 40.925 14.66 Mean 5.79 79.633 4.7 69.202 SD (±) 16.595 2.489 30.356 0.018 SD (±) 0.226 5.530 0.141 2.581 Table 14: Total phenolic content and total flavonoids content in conventional & cryogenically grounded seeds of coriander & fenugreek genotypes. 30 TPC : Total p henolic content (ppm GAE 1000 -1 ppm) , TFC: Total flavonoids content (ppm QE - 11000 ppm)

31. Table 15: Antioxidant content of conventional and cryogenically grounded seeds of coriander and fenugreek genotypes . Variety Coriander Variety Fenugreek Cryo g round Conventional g round Cryo g round Conventional g round Antioxidant c ontent (BHTE g -1 ) Antioxidant c ontent (BHTE g -1 ) Antioxidant c ontent (BHTE g -1 ) Antioxidant c ontent (BHTE g -1 ) Sudha 10.21 4.92 RMt 1 9.32 3.29 RCr 436 8.72 6.47 RMt 305 11.08 8.95 Mean 9.46 5.695 Mean 10.20 6.12 S.D. (±) 1.053 1.096 SD (±) 1.014 4.00 (Saxena et al ., 2012) 31

32. 7. Cryogenic grinding: a physical technique to retain essential oil in coriander genotypes (Saxena et al ., 2013) Table 16 : Effect of cryogenic grinding on recovery of essential oil in coriander genotypes Coriander genotypes Intact s eeds (%) Conventional g rinding (%) Cryo g round (%) Loss during Conventional grinding (%) Loss during Cryo grinding (%) Sudha 0.330 0.240 0.294 0.090 0.036 RCr-436 0.138 0.080 0.100 0.058 0.038 Mean 0.234 0.16 0.197 0.074 0.034 S. D. (±) 0.135 0.113 0.137 0.022 0.001 32

33. (Barnwal et al ., 2018) Temp Conveyor screw speed (rpm) Essential oil (%) Total flavonoids (mg QE g -1 ) Total phenolic content (mg GAE g -1 ) Antioxidant content (BHTE g -1 ) 10 °C 5 2.70±0.80 54.55±0.14 21.23±2.16a 22.38±3.52 10 2.72±0.36 61.23±1.88 24.87±4.51b 24.27±0.59 15 2.69±0.28 67.29±6.16 25.61±1.56b 24.55±0.32 F-values 0.07 NS 0.98 NS 40.87* 0.59 NS CD 0.05 2.61 14.41 3.06 9.28 -50 °C 5 3.61±0.14 56.04±0.79a 31.51±1.44a 27.39±2.78a 10 3.88±0.13 68.29±4.4b 34.44±2.52a 33.19±0.62b 15 3.76±0.52 75.01±0.36b 48.48±3.43b 33.98±1.04b F-values 0.66 NS 24.48* 26.98* 22.86* CD 0.05 1.02 11.15 11.26 4.57 Table 17: Effect of screw speed and temperature on essential oil, total flavonoids, total phenolic content and antioxidant content of Fenugreek powder NS=Non-significant; Mean values with the same superscript letters within the same column do not differ significantly (p > 0.05) 8 . Grinding performance of cryogenic spice grinding system for Fenugreek 33

34. 9 . Effect of cryogenic grinding on essential oil content of fenugreek ( Trigonella foenum-graecum L.) seed extract. (Saxena et al ., 2016) Table 18 : Effect of cryo grinding on recovery of essential oil in fenugreek genotypes Fenugreek genotypes Essential oil content (%) Cryo Normal % Increase AM 1 6.29 3.94 59.6 RMt 1 5.63 4.6 22.4 RMt 305 5.95 4.8 24.0 Mean 5.95 4.44 34 SD (±) 0.33 0.45 - 34 Fig. 8 : Effect of cryo grinding on recovery of essential oil in fenugreek genotypes

35. 10. Effect of milling methods and its temperature on quality parameters of byadagi chilli: with emphasis on cryogenic grinding (Mallappa et al ., 2015) 35 Fig. 9: Quality parameter analysis result of Capsaicin (Traditional method)

36. 11. Effect of cryogenic grinding on oleoresin content of coriander ( Coriandrum sativum L.) genotypes. Fig. 10:- Effect of grinding methods on oleoresin content in coriander genotypes (Saxena et al ., 2013) 36 Cryo ground Non cryo ground S.E.m (±) 0.14 0.16 CD 0.05 0.41 0.47

37. Good quality product Improved colour to the product- black pepper and turmeric Higher essential oil content with negligible loss- Cumin- 4.1% Higher oleoresin content (Cumin- 17.7%, Ginger- 7.67 %, Coriander- 18.88% and Fenugreek- 5.95% Fineness and uniform distribution of particular sized particle of spices can be obtained in black pepper and turmeric Physicochemical compositions and medicinal properties of the spices are preserved in fenugreek and coriander powder. Clogging of sieves can be avoided in cryogenic grinding Hygienically novel technique Conclusion 37

38. It requires research and government initiatives to make the technology feasible for mass-scale production of cryogenic grinder for spices to boost up the domestic and the export market . To demonstrate and promote cryogenic grinding in spice, pilot plants are to be installed considering economical and eco-friendly features to produce higher quality end-product characteristics with lower price tags . A holistic system approach demands optimized cryogrinders to promote the adoption rates in the tune of established traditional grinding systems . Cryogrinding is economically viable , if liquid nitrogen costs are not formidable. Future Thrust 38

39. Barnwal, P. (2014). Effect of grinding conditions on physico-chemical, thermal and antioxidant properties of coriander powder. International J. Seed Spices, 4 (I): 25-32. Barnwal, P. (2014). Effect of cryogenic and ambient grinding on grinding characteristics of cinnamon and turmeric. International J. Seed Spices , 4 (2): 26-31. Barnwal, P. (2018). Influence of pin and hammer mill on grinding characteristics, thermal and antioxidant properties of coriander powder. J Food Sci Technol. DOI 10.1007/s13197-015-1975-0. Barnwal, P. (2018). Grinding performance of cryogenic spice grinding system for coriander. International J . Seed Spices, 8 (1): 1-6. Mallappa, J. (2015). Effect of milling methods and its temperature on quality parameters of byadagi chilli: with emphasis on cryogenic grinding. Research Journal of Engineering Sciences , 4 (3): 1-5. Meghwal, M. and Goswami, T. K. (2013). Evaluation of size reduction and power requirement in ambient and cryogenically ground fenugreek powder. Advanced Powder Technology, 24 : 427–435. Saxena, V. (2018). Improving quality of cumin powder through cryogenic grinding technology . Journal of food processing and preservation , DOI: 10.1111/jfpp.13371. Sharma, L. K. (2014) Cryogenic grinding technology enhances volatile oil, oleoresin and antioxidant activity of cumin ( Cuminum cyminum L.). International J. Seed Spices , 4 (2): 68-72. Sharma, L. K., Rathore, S. S. and Saxena, S. N. (2015). Effect of cryogenic grinding on oil yield, phenolics and antioxidant properties of ajwain ( Trachyspermum ammi L.). International J. Seed Spices, 5 (2): 82-85. Singh, K. K. and Goswami, T. K. (2007). Cryogenic grinding of cloves. Journal of food processing and preservation, 24 (1): 57-71. Singh, S. S. (2018). Effect of grinding methods on powder quality of king chilli. Journal of Food Measurement and Characterization . https://doi.org/10.1007/s11694-018-9784-6. References 39

40. Thank you… 40