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Int. J. Miner. Process. 74S (2004) S425 – S434 www.elsevier.

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Optimised technologies for cryogenic grinding
Michael Wilczek*, Jqrgen Bertling, Damian Hintemann
Fraunhofer Institute for Environmental, Savety and Energy Technology UMSICHT, Oberhausen, Germany

Abstract The production of finest powders of viscoelastic and plastic materials is often very energy consumptive and therefore expensive or even not possible at ambient temperatures. At low temperatures, many materials become brittle so that they can be grinded more effectively. To achieve these temperatures, the materials are presently cooled with liquid nitrogen (lN2), which is followed by high operation costs. At Fraunhofer UMSICHT, a low-temperature fine-grinding plant in technical scale was erected for research. Investigations for optimisation of cooling equipment resulted in the development of an innovative technology based on cooling technology. With this technology, the usage of lN2 could be dramatically reduced. The contribution presents some results of our research in the fields mentioned above. A discussion of the new developments compared to the established techniques will complete the presentation. D 2004 Elsevier B.V. All rights reserved.
Keywords: cryogenic grinding; lN2-consumption; cooling of granulate materials; alternative technology; cooling equipment

1. Introduction Fine grinding or comminution gains increasing importance. This is reflected in the extensive trend towards fine structuring of solid materials and the rapid spreading of research disciplines like micro, nano, and surface technologies. Whereas the state of the art of fine grinding technology for brittle materials is very high, thermoplastic, elastic, or fibrous materials cannot yet be ground as efficiently as brittle materials.

* Corresponding author. 0301-7516/$ - see front matter D 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.minpro.2004.07.032

The production of finest powders of viscoelastic and plastic materials is often very energy consuming and therefore cost-intensive or even not possible at ambient temperatures. At low temperatures, many materials become brittle so that they can be ground more effectively. To achieve these temperatures, the materials are presently cooled with liquid nitrogen (lN2). The use of lN2 has indisputable advantages like easy handling, little additional equipment, and the rendering inert of the grinding plant to avoid dust explosions without additional security equipment. These advantages must be confronted with the

. 1975). In the following.S426 M. Fig. Wilczek et al. the theoretical background of cryogenic grinding and a new technology based on an alternative cooling equipment are presented. experimental results show effects of the variation of different running parameters. disadvantage of high operation costs caused by the use of lN2 (Fig. the operation costs during cold grinding will be drastically reduced. Theory of cryogenic grinding 2. 74S (2004) S425–S434 Fig. 1. 1). With the alternative technology. 2). This work is 10 to hundred times higher for the comminution of plastic than for minerals (see Fig. Advantages and problems of the use of lN2. 2. 2. Process. Miner. / Int. Specific work of comminution W m of different materials depending on the particle size d (Rumpf. Material properties In addition to the target particle size. At the end. J.1. the specific comminution work is substantially affected by the material properties.

This deformation behaviour is largely dependent on temperature and time and is defined with the relaxation module. Whereas in brittle materials. Besides a short stress time. Process. After the beginning of the fracture. flexible chains of molecules. 74S (2004) S425–S434 S427 Differences in the specific work of comminution may be attributed to losses during the deformation of the particle which does not result in a fracture. Wilczek et al. the value of this module is high due to the stress existing in the sample. 3) and is defined by the stress executed on the length modification within the sample Petersen. The first step consists in saving the energy needed for comminution as elastic deformation energy in form of a high elastic strain field in the particle. which are linked up occasionally [Tobo 67]. The energy of the stresses is saved as elastic deformation spreads over a large section of the material. For very short stress impact periods. the necessary strain at break will not be reached and a fracture will not be initiated. major part of plastic materials are being deformed viscoplastically. Rubber materials possess long. At ambient temperatures. This behaviour is attributed to the molecular structure. The cooling further affects the molecule movements so that a plastic deformation by viscous flows is reduced additionally. J. the energy required for proceeding is returned by the degradation of this field. The cooling restricts the molecule flexibility. Characteristic of these materials is the ability of a reversible stretching by more than 100% at ambient temperatures. This module describes the stress relief of a sample of constant expansion by plastic deformation (see Fig.2. hence the stretching is reduced and stress cannot be reduced by stretching any more. At longer impact. Arising stresses will be compensated by the stretching of the tangles. Heat transfer at a particle The heat transfer at particles with a different diameter should be taken into consideration before a calculation of the theoretical lowest demand on lN2 may be performed. This effect is the main reason that the material is not grindable at ambient temperature with impact crushing. / Int. thus the peak of tension is much higher in this area. Miner. particularly of rubber materials. Relaxation of plastics at different temperatures. the imported comminution energy is saved in elastic deformation by high stress fields. These chains form tangles in stressfree condition. due to the multiply stress of particles that is necessary to achieve the desired particle size. Altogether. A high relaxation module is the prerequisite for being able to save sufficient energy in the particle. 2. The energy saved as elastic deformation is concentrated in a smaller area. this leads to an increasing probability of a fracture process. 3. 1983.M. . the increasing of the module may be also achieved by a cooling of the material. these stresses are degraded by viscous flows which lead to plastic deformations. The base of a calculation of a changing temperature field within a particle is the joining of the energy Fig.

density q. Temperature in the center of a particle with different diameters. From Fig. heat capacity c p. 74S (2004) S425–S434 balance with the basic law of heat transfer from Fourier Petersen. it becomes evident that small particles very quickly adopt the ambient temperature. (2) to a dimensionless form with the following dimensionless variables. the Eq. J. 4. (1) is simplified as follows:   B# k B B ¼ r2 ð2Þ Bt qcp r2 Br Br A temperature shift of the ambient temperature from Ta to T l at the time t=0 is designed to be a boundary condition for the calculation. / Int. 1983: À Á l X  sinAi À Ai cosAi  sin Ai r  R Hðr. 1975: ! the observed particle has the shape of a sphere. 4. The results for the particle core temperature are presented in Fig. The Fig. and ! the ambient temperature and the heat transfer coefficient between particle and the surrounding area are well known. Miner. (2) in dimensionless form in standardised temperature function H(r. Wilczek et al. the calculation of the cooling becomes identical to the heating of the standardised distance to the symmetric centre: r nu R dimensionless time (Fourier number): su kt qcp R2 ð4Þ ð5Þ This results with the Eq. ! the particle has a homogeneous temperature Ta at the beginning of the calculation. t Þ ¼ 2 r Ai R Ai À sinAi cosAi i¼1   kt exp À A2 ð6Þ i qcp R2 including the eigenvalues   aA R sinAi Ai ¼ 1 À k cosAi ð7Þ The standardised temperature function for differing diameters was determined according to the example of rrubber granulateT. 1983: B# ¼ rkr# q˙ p c Bt ð1Þ particles: standardised temperature: Hu T À Tl Ta À Tl ð3Þ The temperature compensation of a particle could be calculated by knowing the material values ability of heat transfer k. If the calculation of a one-dimensional radial heat flow in spherical coordinates is examined. . indicating also the average residence time of particles in mills.S428 M. ! the material values are independent on place and temperature.t) Petersen. By transforming the Eq. Process. and the particle start temperature under the following conditions Schfnert. 4.

Considerations including these circumstances and rule out losses merely lead to an increased mass flow by the mill. only three parameters are determined (condensation enthalpy. nearly all drive capacity of a mill is transformed to heat by different processes (particle deformation. heat capacity. and inert atmosphere. the specific grinding work. The idle performance is represented by P 0.). P max indicates the maximum performance of the motor at maximum mass flow. and m feed is the present ˙ mass flow. it is clearly discernible that a consumption of less than 1 kglN2/kgmaterial may be achieved only in few cases as long as the temperature after the mill should lay below the ambient temperature. feed. friction of the particles at processing surfaces. J.feed ðTin À Tout Þ ð9Þ Tin is considered to be the inlet temperature of the material. such as: ! ! ! ! ! ! readily available. the capacity of the mill was assumed to be proportional to the grinding mass flow so that the energy to be discharged may be described by the following relation: ˙ m feed ˙ Q mill ¼ Pmill ¼ P0 þ ðPmax À P0 Þ ˙ m max ð10Þ In Eq. The analysis clearly illustrates the important impact of the grinding material mass flow and of the specific grinding work. Both factors lead to considerable changes/shifts of the specific nitrogen consumption at a 10% change. To simplify. and the plant configuration) and may therefore vary in wide ranges. Calculation of lN2 consumption The heat to be discharged at cryogenic grinding is composed of heat. h i cp. During this operation mode. 5 presents a sensitivity analysis of the free parameters of Eq. On the basis on calculations. Miner. 74S (2004) S425–S434 S429 advantages of cryogenic grinding for particles that are stressed in a impact mill that. low technical input. The performance data are dependent on the mill used. a further grinding of the particles is hampered due to the heating of the fragments. Wilczek et al. easy control. because the refeed grinding air has the same introduction and outlet temperature. 5 were used as starting point for the sensitivity analysis. (12). This is why both the particles and the mill are to be cooled in the process of cryogenic grinding. which has been introduced by the ˙ product (Q feed) and the heat introduced by the drive ˙ capacity of the mill (Q mill). It is necessarily provided that with cryogenic grinding. good heat transition. the theoretical minimum amount of liquid nitrogen required for the cryogenic grinding related to the mass flow of the grinding material is yielded. easy handling. Process. and Tout the temperature at the outlet of the mill. and temperature of the liquid nitrogen). (8)–(11).3.M.4. etc. (12). m max. / Int. Â Ã ˙ ˙ Q lN2 ¼ m lN2 DHV þ cP. The values listed in the table besides Fig. provided that the grinding air flow required for the operation of the mill is met by the condensing nitrogen alone. as described in Section 2. Other parameters are to be set according to the material used (such as P spec. The energy balance however remains unchanged. Economic aspect of cryogenic grinding The utilisation of liquid nitrogen (lN 2 ) has undoubtedly numerous advantages in application.lN2 ðTout À TIN2 Þ ð11Þ . ˙ ˙ ˙ Q total ¼ Q feed þ Q mill ð8Þ As a result of combining the Eqs. internal friction of the particle collective. c p. 2. Fig. those plant configurations are usual that allow a refeeding of part of the grinding air into the mill.feed ðTin À Tout Þ þ mP0 þ Pspec: ˙ feed ˙ m lN2 ð12Þ ¼ ˙ DHV þ cP. The cooling performance of the liquid nitrogen comprises the condensation and the sensible heat.1. may not be made use of in a noncooled mill.lN2 ðTout ÀTlN Þ m feed 2 The calculation of the heat to be discharged from the grinding material is as follows: ˙ ˙ Q feed ¼ m feed cp. 2. In practice.

Optimised process design In addition to increasing the efficient factor by optimising the operation of conventional plants.1. the theoretical consumption of lN2 was calculated. these advantages have to be counterbalanced against the high energy consumption. That shows that there is a demand of optimisation. 3..3. 2001). Process. 74S (2004) S425–S434 Fig. an amount ranging between 0. the efficiency factor g lN2 is defined as glN2 ¼ ˙ m theo 100½%Š ˙ m real ð13Þ At a cryogenic grinding plant in the chemical industry. 3. In-house measurements at various contract grinding companies yielded even consumptions of up to 6 kglN2/ kgsolid material. Wilczek et al. New technology developed by Fraunhofer UMSICHT In Section 2. this efficiency factor varies from 25% to 75%. Miner.10 /kgln2/kg solid material. Fraunhofer UMSICHT has developed an innovative technology which allows to avoid the use of lN2 partially or completely. This technique is based on the employment of a refrigeration plant. thus representing over 40% of the cost of cryogenic grinding (see Fig. and thus investment cost for the supply of the cold agents which considerably affects the operation cost of a cryogenic grinding plant. .S430 M. depending on the material. J. 2000. Measurements at production plants showed that the real consumption is sometimes much higher than the theoretical calculated consumption. 5. / Int. 6.6 and 4 kg liquid nitrogen is required in optimised mills Liang and Hao. To relate the theoretical to the practical consumption. This plant has a cooling power of 40 kWth which is equal to 360 kglN2/h . Sensitivity on IN2 consumption of different parameters. Cost structure of cryogenic grinding with IN2. 6. Provided a nitrogen price of approximately 0. The heat is Fig. Wilczek et al. For the grinding of 1 kg viscoelastic material for example. the cost of nitrogen alone would amount to more than 100 per ton material used (at 1 kgln2/kg solid material). However.

independent of the cooling of the material. the material may be exposed to further cooling in a cryoscrew with lN2 (see Fig.M. so that the results achieved may be readily transferred to largescale plants.2. To be able to compare different cold process to another. The plant has a throughput performance of 300 kg/h (depending on the material). This can be done by the Carnot process. Injection options of nitrogen at different places of the grinding air circulation allow cooling of the mill. this temperature is sufficient to become brittle. Characteristic for a process of cold generation is the performance coefficient e Nesselmann. Wilczek et al. 7). A number of applicable grinding aggregates with different grinding principles may be applied for different milling functions. a pilot plant has been erected at the technical laboratory of Fraunhofer UMSICHT. For many materials. and W the required mechanical capacity. 74S (2004) S425–S434 S431 transported by a cooling medium. Process. including the performance coefficient e c: 1 Wideal T ¼ ¼ À1 ec T0 Qo ð15Þ T here is the absolute temperature at which the exhaust heat may be discharged to the ambience/ environment. J. To allow detailed estimates. This made it possible to test both according to the traditional method and according to the new method. In order to perform the optimisation described. as well as by combining both methods. extensive measuring technology was included. Planning did in particular focus on a high flexibility of the plant. 1957: e¼ Q0 W ð14Þ Q 0 represents the cold quantity. and T 0 the temperature at which the cold is generated. Should this temperature be not sufficient. Miner. 3. 7. . / Int. temperature levels noticeably above À80 8C are sufficient to make plastics brittle. which is still liquid at temperatures below À1008C. Comparison between conventional and alternative cooling technique The supply of cold at a temperature of À196 8C is not necessary for many plastic materials. these processes have to be related to a reference process. Fig. This allows to cool the grinding material and the grinding air separately in special heat exchangers down to a temperature of about À608C. In many cases. Process design of the cryogenic grinding facility at Fhl UMSICHT.

As a consequence. Miner. 9 shows the factor of four different processes (rcold steamT. Fig. 4. By generating the cold with the alternative technology. and subsequently continued to be cooled with lN2 down to the required temperature. rPhilipsT. 11 displays the contrasting operational cost/ running cost of a plant with conventional and a plant with alternative cold as a function of the amount of hours of operation during a year (h/a) under the frame conditions listed in the box. The saving of lN2 may be calculated by a simple energy balance: ˙ DmlN2 cp DT ¼ ˙ cp. the material has to be precooled down to approximately À50 8C. / Int. Efficiency factor g of different process (Nesselmann. Fig. 1957).5 kglN2/kgmaterial is yielded only for cooling the material. J. the conventional technology is more efficient. the cold steam process is the efficient process. Performance coefficient e c at different supply temperature. 8 shows clearly that a cold amount of thermal energy ( Q th) may be generated at a temperature level of À80 8C utilising one-sixth of energy input compared to a temperature level of À196 8C. This efficiency factor depends on the used cold generation process. indicating the threshold for a cost-efficient application of the alternative technology. With respect to the temperature range between À80 and 0 8C. For the case that the temperature at which the cold is generated is not sufficient. First. Wilczek et al. the increased investment input for the acquisition of a cold generation plant comprising the necessary equipment has to be considered on the other hand. 9. . which material properties are listed in the table of Fig. In comparison to the use of lN2. and radiabatic isothermalT). This plant configuration would yield a break-even point of 2676 h/a. Process. a mass flow of 12 kg/h lN2 per kWth can be substituted. 5.S432 M. The example presented refers to a plant in which the entire cold requirement is met by the alternative technology. a plant based on the alternative technology will be costefficient only after a certain operation time. The Fig. For a starting temperature of Tout of the gaseous nitrogen to À100 8C and a precooling temperature of –50 8C. 74S (2004) S425–S434 Fig. and DT the ˙ temperature difference resulting from the precooling.lN2 m material ð16Þ Dm IN2 represents the saved nitrogen. Summary The theoretical consideration showed the demand of optimisation of the cryogenic grinding process. a saving of approximately 0. 1957: g¼ e eC Fig. 10. the reduced energy input of the alternative cold technology is reflected in lower operation cost. Decisive in this context is the temperature at which the cold should be available. a combination of conventional and alternative cold technology may be applied.lN2 ðTout À TlN2 Þ þ DHV. 8. However. For plants with lower operating hours. Plan and cycle in different diagrams of these processes are shown in Fig. rThomson–JouleT. The connection between the performance coefficient of the Carnot process e C and the parameter of the real process e is formed by the efficiency factor g Nesselmann.

74S (2004) S425–S434 S433 Fig. Fig.M. . / Int. Wilczek et al. Plan and cycle in different diagrams of the regarded processes Nesselmann (1957). J. Process. 10. 11. Miner. Specific cost of conventional and alternative cooling technology.

S187 – S197.S434 M.. Hintemann. D. Dqsseldorf. Verfahrenstechnik. A novel cryogenic grinding system for recycling scrap tire peels. S198 – S200. Nqrnberg. 11 (2). Das Verhalten von Kunststoffpartikeln bei Prallund Druckbeanspruchungin: bFeinmahlen und Sichten von KunststoffenQ. Nesselmann.. Process. À) Standardised distance to the symmetric centre (À) References List of Symbols A Eigenvalue (À) cp Heat capacity (kJ/kgK) m Mass flow (kg/h) ˙ P0 Idle performance of the mill (W) P max Maximum performance of the mill motor (W) ˙ Q Transferred heat (W) Q0 Cold quantity (W) r Distance to the symmetric centre of a particle (m) R Particle radius (m) t Time (s) T Temperature (K) W Mechanical capacity (W) DH Enthalpy of evaporation (kJ/kg) # Particle temperature (K) H Standardised temperature (À) Liang. 74S (2004) S425–S434 which was confirmed by some measurements at grinding plants. 1957. 2000. a e g k q s n Heat transfer coefficient (W/m2K) Performance coefficient (À) Efficiency factor (À) Material values ability of heat transfer (W/mK) Density (kg/m3) Dimensionless time (Fourier number.Nqrnberg. Reihe vol. H. K. The real consumption of lN2 at these plants was up to twice the theoretic calculated consumption. Europ7isches Symposium. 27. Powder Technol. .. 1975. M. Wilczek. Kqmmel. S.03. Zerkleinern vol. H. Schfnert. Some grinding tests showed the influence of different parameters on the resulting particle size. J. Wilczek et al. Rumpf.B. Y. Innovative Technologies for Cryogenic Grinding. Petersen..C. 4.. / Int. Kollektive Zerkleinerung von Kunststoffen bei Temperaturen unterhalb 273 KVDI-Fortschrittsberichte.. Bertling.2001. 1975. R. J... VDI-Verlag.. Ways of optimisation developed by Fraunhofer UMSICHT were shown for the reduction of lN2 by using a new process control as well as using a new cooling equipment. Hao. Dqsseldorfe.-29. Partec 2001. Chemieingenieurtechnik 29 (3). Miner. K. Verfahren zur K7lteerzeugung unter À100 8C. 1983. 3. Wirtschaftliche und fkonomische Bedeutung des Zerkleinernsin. Adv.