Sustainable paths for managing solid and liquid waste from distilleries and breweries

Sustainable paths for managing solid and liquid waste from distilleries and breweries

Accepted Manuscript Sustainable paths for managing solid and liquid waste from distilleries and breweries Bernd Weber, Ernst A. Stadlbauer PII: S0959...

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Accepted Manuscript Sustainable paths for managing solid and liquid waste from distilleries and breweries Bernd Weber, Ernst A. Stadlbauer PII:

S0959-6526(17)30268-8

DOI:

10.1016/j.jclepro.2017.02.054

Reference:

JCLP 8980

To appear in:

Journal of Cleaner Production

Received Date: 14 August 2016 Revised Date:

4 February 2017

Accepted Date: 7 February 2017

Please cite this article as: Weber B, Stadlbauer EA, Sustainable paths for managing solid and liquid waste from distilleries and breweries, Journal of Cleaner Production (2017), doi: 10.1016/ j.jclepro.2017.02.054. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT Sustainable Paths for Managing Solid and Liquid Waste from Distilleries and Breweries Bernd Webera, Ernst A. Stadlbauerb a

Bernd Weber, Universidad Autónoma del Estado de México, Toluca, C.P. 03310, [email protected] b Ernst A. Stadlbauer, University of Applied Sciences, THM, Giessen, C.P. 35390, Germany

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Key Words: Spent grain, Vinasse, Hydro-Thermal Carbonization, Anaerobic Digester, Biogas

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Dr. Bernd Weber Facultad de Ingeniería Universidad Autónoma del Estado de México Cerro de Coatepec s/n C.P. 50130 Toluca, Edo. Mex. Mexico Tel. 0052722 2140855 Ext. 1064 FAX: 0052722 2140855 Ext. 1064 E-mail: [email protected]

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Abstract:

Attempts towards a more sustainable food industry focus on reducing the energy intensity of biomass conversion processes and finding better alternatives for the management of the large amounts of agro-industrial waste produced in such industries. While various sustainable practices for managing waste streams have been set forth in recent studies, their integration into established production schemes is lagging due the lack of an assessment of their technical feasibility and economic practicality. This study investigates the use of anaerobic digestion (AD) and

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Corresponding author:

hydrothermal carbonization (HTC) on wastewater and solid waste streams generated by the brewing and distilling industry to be considered for further implementation in a German brewery, which has already implemented AD for treating wastewater generated in brewing and distilling processes. The layout of the HTC reactor is based on previous

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experimental studies, which, when converting 895 kg h

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of wet spent grains, produces 257 kW of excess heat

available to cover energy demands in the brewing process. Exploitation of solid wastes by AD and HTC enables energy conversion in combined heat and power (CHP) systems which can meet more than 40% of electricity demands and more the 23% of thermal energy demands. Moreover, the mass of remaining solids is reduced to 43% of initial mass in the case of AD and 58% in the case of HTC treatment, which reduces energy demand for dehydrating solids significantly.

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1. Introduction:

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Transition to a low carbon economy has put focus both on the use of renewable or nuclear energy as well as the

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While there is a rising interest in further using these by-products, the challenge is in finding value adding processes or

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These valuable industrial techniques show promise for more efficient use of all resources in the food and beverage

increase in energy efficiency and reduction of resource consumption for industrial processes (DDPP, 2015). Basic ecostrategies for breweries include improving insulation and implementing heat recovery measures (Sturm et al., 2013). By-product management is an augmented approach to achieve lower carbon dioxide emissions. Presently, waste, such

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as liquid and solid wastes from breweries and distilleries, plays a variety of important roles in strategies aimed at sustainably managing the technical, economic, ecologic, and social aspects of the alcohol production industry. High strength brewery effluents are traditionally treated on-site in anaerobic sludge blanket reactors, fixed film reactors, and/or completely stirred tank reactors (Pettigrew et al., 2015). The current industry practice is to dispose of distillery molasses and sell brewery grain mash for use as an animal (Cook, 2011; Fillaudeau et al., 2005) or human (Rosa and

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Beloborodko, 2015) nutrition supplement, however, this industrial waste is increasingly being viewed as a useful by-

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product, from a more molecular point of view.

tailored applications for more energy efficient uses of industrial wastes. Some studies have reported on the feasibility of using spent grains from breweries as a nutrient base for actinobacteria or mushroom cultivation (Mussatto et al., 2006; Philippoussis, 2009). Extraction technologies applied to brewery spent grains focus on obtaining protein, in particular zein, which is used as feedstock for the production of coatings, plastics, textiles, and adhesives (Anderson and Lamsal, 2011), or the recovery of polyphenols as a feedstock for the antioxidant industry (Menesses et al., 2013). Alternatively, due to the high remaining lignocellulose in these wastes, other studies have been realized at the laboratory scale for

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alternative processes such as second generation bioethanol production (White et al., 2008), xylose to xylitol bioconversion (Mussato et al. 2005) or lactic acid fermentation to be used in bio-based plastics manufacturing (Shindo and Tachibana, 2004; Mussatto et al. 2008). At the same time, spent grains offer exceptional benefits with respect to decreasing energy dependency within breweries and the brewing process by providing a substrate for on-site anaerobic digestion (AD), combustion, or bio-char formation and thus promoting energy self-sufficiency. As an

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example, small anaerobic digesters are already available and are being used on high strength brewery streams as reported by Cummings (2015). The same trend has been observed for the use of spent grains in industrial incineration systems. Cook reports that more than 100 combinations of mechanical drying and combustion are already being

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implemented worldwide (Cook, 2011). Similarly, spent grains can undergo low temperature conversion at 350 °C to 500 °C to generate bio-oil and bio-char (Sanna et al., 2011) or may be subjected to hydrothermal carbonization (HTC) to produce bio-char with chemical characteristics (C/O) similar to lignite for on-site use (Poerschmann et al., 2014). For most procedures the reaction temperature is between 180 °C to 260 °C with heat released due to exother mic nature of the reaction (Kruse et al., 2012). As such, the process can be driven auto-thermally. The carbonaceous materials obtained in the process show a reduction in mass while at the same time exhibiting an increase in net calorific value (Stengl et al., 2012).

sector. On the one hand, energy demand for processing foods is considerably high, therefore, increasing plant

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efficiencies has the potential to be very beneficial. In developed countries alone, food processing accounts for 6% of

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With the intent of achieving sustainable development of industrial processes, the objective of this study is to evaluate

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Starting with the hypothesis that the energy demand of a facility producing beer and wine could be met by processing

the industrial primary energy demand (IEA, 2016). Meat and dairy production is considered the largest share of the food processing industry by commercial value, however, the production of alcoholic beverages is important as well. For example, in Germany the production of alcoholic beverages is fourth in the industry by market volume, generating 56 billion Euros (Statista, 2016). The production of alcoholic beverages is divided into small, medium, and big facilities, each with a different specific energy demand for processing their products. About 30% of beer production in Germany

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is carried out in medium sized breweries, which have a production rate of 5 000 to 500 000 hL per year (Marx, 2009). On the other hand, running a high efficiency production plant that effectively manages secondary products in a more -1

intelligent way is an on-going challenge. The specific energy intensity of brewing processes is about 150 MJ hL , which is showing a decreasing tendency over time with the ongoing implementation of technical and management improvements (Sturm et al., 2013). The energy recovery from spent grains by anaerobic fermentation can reach 36 MJ hL

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beer produced (Muster-Slawitsch et al., 2011). Decisions on which alternatives are chosen to promote more

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energy efficient production schemes are normally driven by economic considerations.

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the potential of energy recovery by AD of the effluent mixture of a medium sized brewery (90 000 hL y ) and wine -1

distillery (1 000 hL y ) in combination with the use of an HTC unit for conditioning spent grains. To achieve the aim of this study, (1) the design and performance of biogas fermenters in pilot and technical scale are described to ensure operational digester stability, (2) the principal design parameters of the HTC-Reactor are outlined, and (3) changes made to the initial energy management scheme to integrate excess heat are discussed. The assessment is based on a comparison between the existing brewery, which as a first step towards more sustainable production has already implemented AD for treating liquid waste streams (Strategy A), with two treatment alternatives for solid waste streams

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to promote energy recovery management: AD extended to wet spent grains, denominated as Strategy B, and the proposed novel integration of HTC for treating spent grains, termed Strategy C. Finally, conclusions are drawn on the role of AD and HTC as sustainable tools for effective energy use and greenhouse gas reduction.

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2. Methodology:

secondary organic streams in an intelligent manner, different technologies which convert organic matter into usable

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energy resources were evaluated. Fig. 1 shows possible solid waste management strategies for a medium sized brewery. Strategy A, corresponding to the existing brewery, is considered a typical brewery employing state of the art technology, where spent grains are commercialized and processed outside of production facility and wastewater is treated in an anaerobic digester. Strategy B consists of an anaerobic digester for treating liquid waste streams and a second digester for treating spent grains. Strategy C comprises an HTC-Reactor for treating spent grains. The brewery in this study also distills wine, therefore, vinasse management is considered as part of all the above process schemes (Strategies A, B and C).



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Secondary side streams in breweries and distilleries mainly consist of wastewater, vinasse, and spent grains. The energy content of the liquid secondary streams generated was assessed in the course of an investigation conducted on a local brewery in Germany. Over several weeks the wastewater generated and the organic contamination of specific flows, as measured by the chemical oxygen demand (COD), were quantified at selected points in the

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production facility. The volume of vinasse generated was taken from a logbook which registered vinasse transportation by tank vehicles. The organic content of the vinasse was also quantified by the COD. Based on the potential energy recovery from these wastes, AD was proposed as an appropriate process for treating such contaminated wastewater. The choice of treating high concentrations of dissolved organic matter in wastewater with high performance digesters, 3

some of which can reach a production capacity of more than 10 m of biogas per cubic meter of digester volume, is

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supported in the literature (Moletta, 2010).

The main stream of organic solid wastes in breweries is the generation of spent grains. The quantity of spent grains is

 =

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determined using the overall brewhouse yield (OBY):   ∑  

(1)

The waste stream consists of spent grains, which is a wet solid product, and a small amount of wastewater, which is ignored. Under this assumption the yield of spent grains (SGY) is:  = 1 − 

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Evaluation of the potential for energy recovery from wastewater and spent grains

(2)

The chemical energy content of the solid waste streams can be assessed by the organic dry matter content (oDM). AD of spent grains (Strategy B) is a widely applied method that reduces oDM by producing biogas. Kafle and Kim (2013) 3

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reported that when organic matter is digested in co-fermentation, biogas yield (YBiogas) is approximately 0.55 m kg of oDM with a methane concentration of about 59%, which is the biogas generation potential used in energy balances in

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2.1.

this study.

For HTC treatment within the solids treatment process, energy content of the spent grains comprises the process heat released during thermal conversion, the biogas generated from the wastewater using AD, and residual solid product.

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The heat released during HTC treatment is determined by an enthalpy balance of process input and output flows. Because the exact chemical composition of spent grains is unknown, the enthalpy balance is alternatively based on the gross calorific values of its substrates and products as described by the following equation: ∆ℎ =  ∙



+ " ∙

#



#$

(3)

Here, yL is the liquid phase yield of organic matter; yS is the solid phase yield; and HL, HS, and HSP are the gross calorific value of the liquid phase, solid phase and spent grains, respectively.

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produced during the carbonization of cellulosic matter, conceptualized as a dehydration reaction in combination with decarboxylation steps. The composition of the liquid phase has been described previously by the authors and includes acetic acid as the most prevalent compound, making up approximately 30% of the total organic matter found in the reaction water (Weber et al., 2013). The high organic content is well suited for AD and thus the overall biogas potential 3

is increased. For this kind of wastewater, a specific biogas production of 0.55 m kg

oDM was used for energy

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3

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balances, which results in a biogas production potential of 0.099 m of biogas per kg of wet spent grains (fresh mass, FM) processed. The biogas released during the AD process stage in a high performance digester in Strategy C is the sum of the wastewater generated in beer production, the vinasse discharged, and the additional wastewater from the HTC process.

The three process alternatives, Strategies A, B, and C, produce final solid products, each with a different specific

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generation potential and moisture content. A dehydrating step for each of the three alternatives was used as a comparable standard. Mass flow into the dehydrating process is different for each treatment because the mass loss depends on the specific reaction paths (e.g. formation of biogas during AD of spent grains). In the case of AD of spent

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grains, mass loss and solids concentration in the anaerobic effluent is determined with the following equations, taking into account specific biogas potential, elemental analysis of spent grains (C: 45.6%; H: 8.2%; N: 2.5%; S: 0.2% Ash: 4.4% and O: 39.1% - latter by difference), and water needed for hydrolysis of organic matter according to Symons and Buswell (1933):

%&.()(

* &.+,- .&.&++ &.&&*

+ 0.0812

+ 

→ 0.190 %+ + 0.274 %

(

+ 0.022 .

6

Where the water needed for hydrolysis, described by ;8 :,=>?@A>"B" 789 : = 9 ∆;@CD -1

is 0.125 kg kg

+ 0.001

+

(4),

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mashing. The water in the HTC process originates from the initial moisture present in spent grains and the water

oDM of spent grains. From the chemical equation, a methane concentration close to 60% was

determined. The remaining component was assumed to be CO2 since sulfur elimination is required as a plant

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In addition, HTC produces wastewater with mainly organic constituents since inorganics are mostly washed out during

precondition for running CHP systems. With respect to ammonia, the equilibrium is mainly shifted toward the -3

ammonium side due to pH in the range of 7. This corresponds to a biogas density ( ) of 1.21 kg m under standard conditions. The mass balance based on the water needed for hydrolysis must be equal to the produced biogas

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calculated with specific biogas yield. The following equation shows this balance: ∆;#E,CD,FGG? ∙ H1 + 789 : I = ;#E,@CD,FGG? ∙ JB@KL" ∙ MJB@KL"

(5)

Using ∆mSG,oDM,feed = mSG,oDM,feed - mSG,oDM,out, the residual fraction of digestate flowing out of digester is expressed by the following equation: ;NO,OP = ;,QP ∙ (1 − S,

2

) ∙ US#E,V"=

+ H1 − S#E,V"= I ∙ W1 −

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X  ∙ MX  (1 + 7

2

)

YZ

(6)

ACCEPTED MANUSCRIPT Where φSG,H2O and φSG,Ash are the fractions of moisture and ash in SG. The moisture content of anaerobic digestate is SNO,

=

φSG,H2O and φSG,Ash:

1 − (1 − S,

∙ 

X 

∙ MX 

(1 + 7

2

)

YZ

(8)

Finally the fraction of fresh mass in the final product from anaerobic digestion of spent grains is calculated with equation (9): ;NO,OP

1 − SNO,

2

(9)

The reactions occurring during the HTC process can be classified into a dehydration reaction with water as a reaction product and decarboxylation steps with CO2 as a reaction product, which is partially released into the gas phase. Based on the yield of HTC char from spent grains the concentration of solids in suspension leaving the HTC reactor (Fig. 1) is determined with the following equations: ;

^%,OP

S

= ;,QP ∙ \1 − S#E,8 : ] ∙ %ℎ , 9 ^%, 2 

=

1 −  ,

17 ^%,QP

=

^%

^%

− \1 − S#E,8 : ] ∙ %ℎ , 9 1 −  ,

;

^%

^%

^%,OP

1−S

(10)

(11)

(12)

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;

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2

) ∙ H1 − S#E,V"= I ∙ X  ∙ MX 

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2

7

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=

] ∙ US#E,V"= + H1 − S#E,V"= I ∙ W1 + 2

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2

1 − \1 − S,

;NO,QP =

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(7)

and, using this information, the moisture content of the anaerobic digestate is expressed as a function of YBiogas, µH2O ,

SNO,

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;VC,[D − ;VC,CD ;#E,[D − ;JB@KL"

assessed with the following mass balance:

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1 2

^%, 2 

Similar to anaerobic digestion of spent grains (Equations 6, 8, and 9) equations 10, 11, and 12 calculate the fraction of HTC char produced, the moisture content (at the outlet of corresponding treatments), and the fresh mass fraction, which has to be dehydrated. The dehydration of the solid products to a residual moisture content of 12% was realized by subjecting the solid products to a mechanical step which reduced moisture content to 60% followed by a subsequent step in a convection -1

dryer. The specific energy of 40 kWh t of fresh mass needed for mechanical dehydration in a screw press was taken from BMU (2012). Weger et al. (2014) reports similar energy requirements for mechanical dewatering of spent grains.

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spent grains. This study assumes the same specific energy for all three solid streams. The specific energy required for thermal drying of spent grains (2.93 MJ t

-1

of water removed) was taken from Dorset (2016) and also used for the

digestate and carbonized product.

2.2.

Hydrothermal carbonization (HTC) treatment

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HTC of spent grains is considered as an innovative treatment of waste streams and is carried out to obtain a carbonaceous material with an enriched net calorific value and an improved dewatering ability. In this form, the converted waste is viewed as a value added product, which has market potential as an alternative fuel or soil conditioner (Libra et al., 2010; Zhengang et al., 2013). The conversion of spent grains was realized at a laboratory scale under various temperature conditions between 180 °C and 260 °C with a constant reaction time of 3 hours (Weber et al., 2013). It is worth mentioning that longer reaction times on a technical scale are not feasible from an

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economic point of view.

This study outlines the design of a HTC reactor for processing spent grains originating in the local brewery with a reaction temperature of 220 °C and a reaction time of 3 hours. Under these reaction conditions the HTC conversion

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transforms 18% of the organic matter into the liquid phase (Weber et al., 2013). The HTC Process can be realized in batch or continuous operation. A current version of the operation in batch mode is demonstrated in a pilot plant at the Institute of Technology in Karlsruhe, Germany (Kruse et al., 2013). Alternatively, the continuous operation has the advantage of needing only one screw feeder to move the substrate. The reactor dimensions and energy balance for such a configuration are calculated in this study. The screw feeder is divided into three zones: Zone I provides the energy to heat the substrate, Zone II serves as the reaction section, and Zone III acts to cool the carbonaceous

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product (Fig. 2).



A pressureless thermal oil system should be used as an intermediate heat carrier for all heat transfers realized throughout the tube reactor. The principal design parameters of the HTC-Reactor ensure heat transfer through the tube

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There is a lack of information about the specific energy needed for mechanical dehydrating of digested or carbonized

shell (about 20 mm thick) in the different zones and the residence time of the substrate in the reaction zone (3 hours). The convective heat transfer coefficient from the reactor shell to the biomass is calculated with the dimensionless Nusselt number using Equation 13:

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*

. = _` ∙ ab c ∙ d 6 (

7 &.*( ) 7eLAA

(13)

where the Reynolds number is: ab =

 ∙ f ∙ + 7

(14)

In Liepe (1982), values of cNu and m for screw mixers are given as 0.4 and 0.62, respectively. These values result in -2

-1

-2

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total heat transfer coefficients from 100 W m K to 150 W m K as screw diameters vary from 0.325 m to 0.625 m.

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ACCEPTED MANUSCRIPT Such heat transfer coefficients are in accordance with experimental arrangements for applications of screw heat exchangers in sludge drying in the sticky phase with about 30 to 50% solid content (Koellemann, 2016). The specific surface per meter of reactor length can be increased with parallel operation of various screw reactors, which also allows for more flexible production. The authors used a method of trial and error to determine temperatures and the length of the three zones of the reactor acting as heat exchangers which is described as follows. Zones I and III function as counter flow heat exchangers

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while Zone II, with respect to the outer jacket, functions as a parallel flow heat exchanger. For a given length of Zone III the effluent temperature inside the screw was determined under the following conditions: product temperature at the outlet at 80 °C to 90 °C, thermal oil temperature a t the inlet at 80 °C, and thermal oil temperature a t the jacket outlet at 182 °C. For Zone III, the heat capacity rates of th e thermal oil along the screw and through the jacket were determined using the energy balance for the same conditions. The flow inside the screw was set as constant and the temperature between Zone I and II was set at 180°C, the tempera ture at which the speed of the reaction starts increasing rapidly.

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Thus, the temperature at the outlet of the screw in Zone I was selected such that the thermal oil flow inside the screw is equal in Zone I, II and III. Using a chosen outlet temperature for thermal oil in Zone II in the jacket of 214°C, which must be lower than the maximum reaction temperature, the inlet temperature of the thermal oil into the jacket was

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calculated under the condition that heat transferred to the heat carrier medium is equal to the heat of reaction released. With the inlet and outlet temperatures determined for the jacket in Zone II, the heat capacity rate of the flow was determined from the energy balance. The heat capacity rate in the Zone I jacket is higher than in the coupled Zone III because a fraction of the thermal oil at its highest temperature (in Zone II) is combined with that of Zone III before being injected into the jacket of Zone I. Next, the reactor length of Zone I and thermal oil effluent flow in the jacket were adjusted such that heat transferred is set equal to the temperature increment of the product from 50 °C to 180 °C and the mass flow of thermal oil balances with the mass flows of the thermal oil in Zones II and III. Finally, the temperatures

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of the thermal oil must be equal in interconnected sections. The energy available for the consumer at high and low temperature levels was then determined. Thus, the energy available for consumers at high and low temperature levels is a function of the fraction of thermal oil from Zone II combined with that of Zone III before entering into Zone I.

Full scale anaerobic digester

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2.3.

The design of the full scale anaerobic digester for liquid effluents was based on extensive experimental data from 3

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running a 1.5 m pilot plant. At the pilot-scale, an 80% reduction in COD with an organic loading rate of 10 ± 3 kg m d 1

-

was obtained (Stadlbauer et al., 2001). The full scale anaerobic digester was then built as a combination of a

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continuous stirred tank reactor (CSTR) and an up-flow biofilm reactor. The volume of the CSTR reactor was 21 m and the volume of the biofilm reactor for methanization was 14 m3. This configuration was chosen to incorporate sulfate reduction in the hydrolysis reactor. As pretreatment for solids separation, sieves with 4 mm, 1.5 mm, and 1 mm mesh size were installed at the inlet. Between the hydrolysis tank and the methanization tank, a two stage pH titration system was installed. Effluents from the methanization reactor were then passed through a sedimentation tank and a percolation column where FeCl3 was added and biogas was blown counter-current through the wastewater effluent to remove H2S. The biogas was burnt with a Dreizler burner in a Vitola Biferral VB040 boiler from the Viessmann Company, Germany. The thermal energy released was used for the reactor heating and bottle washing stages of the beer production process. Operation of the plant was controlled using analytical measurements throughout the process

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to ensure the stability of the digesters. The pilot plant was operated for 50 weeks to allow sufficient time for the growth

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3.1.

of anaerobic microorganisms on the support material in the anaerobic filter after initial seeding with sludge originating from the anaerobic digester of a neighboring brewery. After 24 weeks, sulfate containing vinasse was fed into the digester and the performance of the digesters was evaluated during a subsequent adaptation phase to assure stabilization. Initializing digesters and substrate changes should be realized slowly due to slow bacterial growth of the

2.4.

Energy demand for beer and distilled wine production

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anaerobic microorganisms (Barber and Stukey, 1999).

Beer production requires high quantities of thermal and electric energy, especially during malt extraction, wort boiling, and fermentation. In the literature there is a wealth of information about specific energy demands of the various stages of beer production (Sattler, 2000; Kubule et al., 2016), which was compiled to estimate the energy demands of the

2.5.

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brewery.

Balance between energy demand of production facility and conversion potential of secondary streams

The overall energy balance of the brewery and distillery was determined by the demands of the different production

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steps and the energy recovery by running CHP units with biogas obtained from anaerobic digestion of the liquid and -3

solid waste streams. The analysis for all scenarios was based on a net calorific value of 6.8 kWh m for the biogas, electric efficiency of 38% for the CHP system, and recovery of 80% for the thermal energy. The internal power demand of the biogas digesters was assumed to be 3% of the electric energy produced for the liquid stream fermenter and 5% for the solid stream fermenter (VDI, 4631). Estimation of energy loss through the fermenter shell was based on an -2

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overall heat transfer coefficient of 0.8 W m K and an average temperature difference between the fermenter and ambient temperature of 26 °C. Because spent grains and most wastewaters are produced at higher temperatures, an

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energy demand for heating up the substrate was not considered in the balance. The operational change as a result of HTC treatment integration (Strategy C) produces thermal energy at a high temperature level which can also be used in production processes.

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3. Results and Discussion:

Energy demand of brewing and wine distillation

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The implementation of more energy efficient production methods requires the identification of possible measures to reduce energy as a first step. A compilation of beer production energy requirements reported in the literature is shown in Table 1 (Sattler, 2000). Table 1 shows that scaling factors play a role in energy requirements, as bigger production facilities are more efficient (Russel et al., 2008). Specific thermal energy demand exhibits a steeper drop from the first category to the second than from the second category to the third. This is because smaller plants with a production -1

lower than 200 000 hL y have to switch to discontinuous production, thus losing more opportunities for heat recovery.

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In general, more than 40% of electric energy is used for refrigeration purposes. About 6% of electric energy is used for air compression, which is necessary for various stages and is normally balanced as a sum of all process stages. Other stages of beer processing consume 13% of the total electric energy required, while the remaining 23% is required for

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ACCEPTED MANUSCRIPT other activities including administration and illumination. Thermal energy is needed for mashing the malt, where different temperature levels are applied and the maximum temperature reached is about 70 °C. After pha se separation and filtration, the hops are added and the wort is cooked at about 100 °C. Before further fermentation , the wort must be cooled rapidly to 6 °C or 20 °C, depending on the t ype of fermentation required. Finally, the beer is refrigerated over longer periods during post fermentation. The temperature changes of the liquid medium are realized by heat exchangers and the potential for heat recovery depends on the plant design. Recent implementations have focused on

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intelligent thermal management, which uses large tanks with various temperature layers for thermal energy storage. These kinds of thermal energy accumulators also provide the opportunity for the integration of thermal solar systems (Vajen, 2014). The maximum vapor temperature required in the brewing process is 140 °C for sterilizati on of the equipment (Esslinger and Narziss, 2003), therefore, special equipment is necessary when CHP systems using biogas are employed. Fortunately, the market already offers heat recovery solutions for both internal combustion engines and gas turbines (Schaumann and Schmitz, 2010). These types of cogeneration systems are suitable for covering thermal

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and electric energy demands in a brewery.

The booming photovoltaic (PV) market continues to be incorporated at breweries and PV implementation projects in breweries can easily be found on the internet. However, cogeneration has the advantage of being able to provide

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thermal energy. Furthermore, when refrigeration systems based on absorption technologies are used, the energy demand is shifted from electric to thermal, requiring less of the former and more of the latter. This alternative is the preferred strategy for energy management with integrated thermal solar systems because the thermal energy demand of absorption chillers increases when outside temperatures are high, as a result of higher solar radiation. The reference brewery in this case study produces 90 000 hL of beer and distills about 1 000 hL of wine annually. Taking into account these data and the information in Table 1, the energy demand for the production of one liter of beer is estimated at 0.15 kWh L

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electric and 0.31 kWh L

-1

thermal. The energy demand of one liter of distilled wine is 6

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6

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estimated at 1.5 kWh, which results in an electricity demand of 1.38 • 10 kWh y and a thermal energy demand of y 3.96 • 10 kWh y for the reference brewery.

3.2

Generation of solid wastes in the brewery process

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Usually, a solubles yield of 78% to 81% is reached during the mashing process (Esslinger and Narziss, 2003). The wort is then adjusted to a solids concentration of 12%. Thus, using the OBY, the calculation yields about 15.8 kg of malt required per 1 hL of beer processed. Using equation (2) the generation of spent grains is 3.84 kg of dry matter of spent grains per 1 hL of beer processed. Wet spent grains have a moisture content of about 70% to 80%. Thus, the

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secondary stream of 1344 tons of wet spent grains (340 t oDM) generated as a result of beer production in the local brewery was investigated. This by-product may be advantageously used as forage under these conditions as long as adequate infrastructure is available nearby, otherwise, they must first be dewatered, which is often difficult and costly. As such, it is important to investigate the feasibility of alternative processing for spent grains to reduce the production facility’s energy footprint. To meet this challenge Strategy C, the integration of HTC treatment, is considered more feasible because the organic content of the reaction liquid is converted into biogas during the anaerobic treatment of the wastewater.

3.3.

Anaerobic Digestion (AD) of liquid waste streams only (Strategy A)

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As mentioned above, one of the objectives was to establish the operational stability of AD in treating wastewater from

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The operation of the pilot plant during 50 weeks with varying wastewater composition showed a stable process with a

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stages is listed in Table 2. The information presented makes clear that, at most of the sampling points, high strength wastewater was found that should be treated in an anaerobic digester. The water demand for beer and wine processing is defined as the sum of the amount of water used in each processing step, expressed as water quantity used per liter of product for both beer production as well as wine distillation. This study determined a demand water of

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5 L of water per liter of beer and 18.9 L of water per liter of wine. The water consumption reported here agrees with other literature values, which suggests that best available technologies are mostly integrated into the process of interest (Fillaudeau et al., 2006; EC, 2006). Wastewater from the distillery consists mainly of vinasses, the bottoms fraction from the distillation process, which is generated at a rate of about 10 to 14 liters per hL of wine for most feedstocks like corn, potato (Kreipe, 1986), grape (Driessen et al., 1994), or agave (Mendez-Acosta and Gonzalez-

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Alvarez, 2014).

specific biogas yield of 0.75 m kg COD eliminated. The methane concentration reached 80%, which is typical for digesters applied in wastewater treatment because a considerable portion of the CO2 produced during fermentation is retained in the liquid phase (Stadlbauer et al., 2001). Similar methane concentrations when treating anaerobically such effluents are also reported by Xiangwen et al. (2008).

The results of the pilot plant verified the suitability of AD treatment for the combined effluents and, subsequently, a full scale plant was built. The wastewater from the beer production process exhibited a COD of 0.2 to 80 g L-1 and from the -1

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distillery showed a COD of 0.3 to 80 g L .

The facility sewage system was modified to conduct the high strength wastewater directly to the anaerobic digester. Initially the waste water infeed for the anaerobic digester was collected manually at different points in the production facility because anaerobic digester operation was started during the sewer modification phase. This strategy allowed for visibility of the wastewater component fraction quantities that were fed into the anaerobic digester. Influent 3

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composition and origin fractions are given in Fig. 3. After plant start-up, the flow rate was increased by about 1 m d

-1

each week with stillage integrated into the waste stream beginning in week 24.

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the brewery and distillery. The quantity of wastewater generated and its organic contamination at the different process

AD was chosen as an anaerobic filter and achieved organic matter removal of 70% to 80% under stable conditions with -3

-1

-3

-1

an organic load of 6 kg COD m d (Fig. 4.). Starting at a low initial loading rate, approximately 1 kg COD m d , space loading was subsequently increased in a stepwise manner. To maintain both reactor stability and volatile fatty acid (VFA) concentrations, the VFAs C2 to C6 were routinely monitored in the hydrolyzing CSTR and methanogenic biofilm reactor. The COD of the wastewater in the processing stage between the hydrolyzing reactor and the anaerobic biofilm reactor was composed of VFA and other non-hydrolyzed organics. Using the theoretical COD of the VFA, the yield of hydrolysis (YHydrolysis) is determined with equation (15):

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=

%OgQN,ℎb b 

(15)

%O

After 12 hours of retention, the brewery wastewater reached a hydrolysis efficiency between 50% and 70% (during the first 24 weeks of operation), an efficiency that was maintained even with the addition of stillage as an input. Thus, the hydrolysis stage was unaffected by sulfate reducing microorganism activity in the same bioreactor, a phenomenon which is confirmed in the literature (Gustavsson et al., 2011). However, the methanogenic reactor performance was affected, increasing the amount of dihydrogen sulfide produced and lowering COD treatment efficiency to 60% - 70%, depending on the loading rate, as seen in Fig. 4.

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Due to adequate isolation, the plant is virtually self-sufficient with respect to thermal energy consumption, with even the bottle washing stage making use of excess heat. In addition, the treatment system is now able to purify about one third

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of its stillage per year. With the brewery's effort to implement its own anaerobic plant, future projects for the management of liquid waste streams may be realized given that the anaerobic treatment makes nutrients such as phosphorus and nitrogen available in the effluent, which can be used for hydroponic crop production (Power and

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Jones, 2016). It is also important to note that the municipal authorities allowed the owner to keep its distilling license as a result of the environmentally friendly measures that were implemented.

3.4.

AD of solid waste streams (Strategy B)

Because spent grains are protein enriched (23 - 28%) (Esslinger and Narziss, 2001), a low C/N relation may cause operational problems for anaerobic digesters. These problems encourage the use of co-digestion of spent grains in German biogas plants, however, biogas digesters for single spent grains treatment are seldom used (Gleixner, 2016).

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Only one biogas plant is known by the authors to use spent grains as the main substrate (Ammich, 2006). In addition, on-site codigestion is a method for increasing the share of energy from residues (Sturm et al., 2012). The estimated 3

340 tons of organic dry matter from spent grains generated (Chapter 3.2) have the potential to produce 187000 m of biogas. It is worth mentioning that according to Fig. 1 a second anaerobic digester for treating the solid stream must

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still be built. Another disadvantage of AD of spent grains is the relatively long residence time of 30 to 100 days, which increases the space required for processing inside the brewing facility.

3.5.

HTC-conversion of spent grains (Strategy C)

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The HTC reactor shown in Fig. 2 runs at a spent grain mass flow into the HTC reactor of almost 895 kg h . The reaction energy is negative and is transferred through the reactor shell in the reaction zone to thermal oil as a heat carrier. Under these conditions the screw heat exchanger functions as a tube reactor. The favorable heat of reaction is -1

4915 kJ kg of spent grains and is released at the highest temperature level (Fig. 2.).

A remaining challenge is intelligent heat management through the use of heat exchangers, which act both to drive the HTC process and produce an energy surplus. Zone I, where substrate is heated up, uses residual heat with a heat -1

capacity rate of 2.18 kW K from the carbonized product to act as a heating zone. An additional heat capacity flow of -1

0.49 kW K enters into Zone I raising the temperature of the heat carrier from 182 °C to 189 °C. The substrate, which

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ACCEPTED MANUSCRIPT was heated up in Zone I from 50 °C, then enters Zon e II, with a temperature of about 180 °C, where exo thermic carbonization reactions heat up the substrate and produce excess heat, which must be transferred through the reactor shell. In Zone III, the carbonized material is cooled to about 90 °C. Zone I and III are thermally cou pled by heat exchangers with the intent of recovering residual heat for heating the substrate.

Excess heat must be integrated into brewery energy management in such a way that other loads can make use of it.

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Since the brewhouse is the most intensive thermal energy consumer in a brewery, both the HTC reactor and wort production should be run in parallel. For a beer production scheme with a capacity of 90 000 hL a year, uptime of 1 500 hours per year is technically reasonable for the HTC reactor (Schmidt, 2016; Blesl et al., 2007).

This study evaluated the parallel operation of four 0.325 m diameter reactors. The screw heat exchangers were 2

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modeled with a heating/cooling screw with a specific surface of 1.78 m m -2

-1

of reactor length and a heat transfer

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coefficient of 130 W m K (the value considered for screw and tube surfaces of all zones). The required hydraulic retention time of 3 hours for hydrothermal conversion resulted in a 10 meter design for Zone II. In this zone, 200 kW of excess heat would be transferred to the carrier medium, which would reach a maximum temperature of 214 °C.

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According to the calculations, about 42 kW of excess heat would be induced to the exterior heat exchanger in Zone I to raise its temperature. The energy balance of Zone I showed an excess heat of 99.6 kW at 130 °C.

The four reactors would contain about 6 tons of biomass, which would need to be heated prior to start-up, after which thermo-chemical reactions would allow for operation with a positive energy balance. The 1500 hours of uptime were made up of about 125 mashing cycles which equates to 125 HTC-reactor start-ups demanding a total of 229 GJ of thermal energy per year. Each start-up phase would be realized in 1 h 40 min, after which excess energy from the

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HTC-reactor, with a capacity of 270 kW, is discharged to the brewhouse for mashing and wort cooking (annual thermal recovery of 1460 GJ). Thermal energy recovery from the HTC-reactor is difficult during system shut-down, because of its transitory state, and, thus, start-up and shut-down energy of the reactor (16%) was considered lost. Nevertheless, it

shut-down.

3.6.

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is possible to use hot water storage tanks with good thermal stratification for energy recovery during the HTC reactor

Dehydration of solid secondary stream

While spent grains were traditionally sold to nearby farmers, more recently the alternatives mentioned above were

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considered to give options with different added values and avoid dependencies. Without a doubt, all secondary solid management strategies to increase the radius of product distribution must also include a dehydrating step which brings residual moisture down to about 12%. In comparison with untreated spent grains the alternatives of HTC-char and digested spent grains show reductions in mass flow and also have better mechanical dehydration characteristics because the composite structure of spent grains is modified (better dehydration characteristics were not considered in the energy balances). Table 3 compares the mass and energy balances of both the mechanical and thermal dehydrating of spent grains, anaerobic digestion of spent grains, and HTC-char from spent grains.

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spent grains, and HTC char of spent grains. The transfer of organic matter during anaerobic digestion or hydrothermal treatment into gaseous or liquid phase result in a mass loss of 17% and 10% respectively. Energy required for mechanical dehydration is listed in column 4 and is highest for dewatering untreated spent grains. Total wastewater generated from the dehydration step is listed in column 5. AD and HTC treatment are characterized by a higher

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concentration of organic matter in the waste water and as a consequence an anaerobic treatment of waste water with energy recovery from biogas is only feasible with these alternatives. Finally, column 6 shows the water that must be removed by thermal drying. The thermal energy for drying for the three alternatives is shown in the last column. Because higher mass reduction is achieved in AD and HTC treatment, the required thermal energy for thermal drying is

3.7.

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also reduced.

Overall energy balances for the production facility

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The electric and thermal energy demand of the production facility is compared with the potential of energy recovery in Table 4 for the 3 scenarios. In order to fulfill current requirements for solid waste streams a dehydration step was included for all scenarios. The additional energy needed for dehydration was 3.8% for electricity and 11.3% for thermal energy in the case of the basic treatment, the anaerobic digestion of liquid waste streams. Using the annual potential given in Table 2 and the specific biogas production value, the recoverable energy from the waste streams in the CHP system was calculated. For the basic process 20% of electric energy and 9% of thermal energy demand at the production facility could be covered by a CHP system running with biogas from the digester. Because the residual solid

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fraction was smaller for Strategies B and C, the additional electricity and heat demand for product dehydration was reduced. Specifically, thermal energy for drying treated spent grains was less than 50% of the energy required for drying spent grains without treatment. When solids were incorporated into energy recovery schemes both electricity and thermal energy available for production purposes was doubled. The energy recovery by anaerobic digestion of solids was higher than that of HTC treatment, which is a result of the enriched net calorific value of the HTC char.

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The second column in Table 3 displays the mass of spent grains generated by beer production, anaerobically digested



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Biogas, which acts as an intermediate energy carrier within the plant, is produced according to the same basic processes in all three strategies, which indicates that uncertainties of the values presented in Table 4 would be similar for all the strategies. Modern biogas technology is a well-established process with many studies related to longtime stability of plants, such as a biogas monitoring program (BMLEV, 2010) and a surveillance project focusing on small biogas plants realized recently by the authors (Hessen Energie, 2015) which both provide reliable data about the performance of such plants. The quantity of liquid wastes generated in the brewing process reported in this investigation is similar to other findings in the literature and as such, data in Tables 2, 3, and 4 as well as the assessment methods used can easily be applied to other breweries. The generation of solid wastes was assessed with the OBY, a balance commonly applied in breweries, but which would exhibit a greater variation when applied to breweries producing specialty beers. Thus,

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variations from the values presented in Table 4 are expected to be low and corrections can be realized using Equations

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4. Conclusions:

2 and 3. While sizeable energy recovery was found in this study, further studies should analyze if the energy recovery flows obtained can feasibly be used in the production facility. While electricity generated on site is captured due to the use of open grid systems, the thermal energy generated must be utilized within a short time or it is lost. As described below, the use of waste heat in the production scheme can be complicated when its contribution increases, as with Strategies

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B and C. For example, the integration of the waste heat produced in Strategy A, about 9% of the total energy demand, into the bottle cleaning process is quite simple because this stage demands around 17% of the total thermal energy and, additionally, has a high capacity factor (Aidonis et al., 2005; Kunze, 2007). However, when larger quantities of waste heat are produced than is required in specific process stages of production, the intelligent use of waste heat must consider the different temperature levels which correspond to various production stages instead of a single use

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water management in such production facilities (Pettigrew et al., 2015).

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(Muster-Slawitsch et al., 2011). Nonetheless, simulation tools have been developed that can help optimize energy and

The anaerobic treatment of liquid waste streams in breweries and vinasse derived from distillery process under stable 3

operation with an organic loading rate of 6 kg COD m d

-1

was demonstrated. The biogas released in the digester

represented 20% of the electricity demand and 9% of the thermal energy demand in the existing brewery. The energy recovery rate from the conversion of solid waste streams was increased by a factor 2 when employing AD of spent grains in a fermenter for solid substrates or the HTC of spent grains. The specific advantages of the HTC treatment is that because AD is already realized for the liquid phase and HTC does not require continuous operation, such a

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system for the conversion of spent grains can be operated in parallel with brewhouse activities, while AD of the spent grains would need to run continuously to maintain an active biology. As a consequence, recovery of excess heat from a CHP system in AD of spent grains is more complicated than for HTC of spent grains. Processing beer and distilled wine under the presented scheme does not create a net-zero energy footprint, but the conversion of liquid and solid wastes has the potential to contribute a share of 41% of electric and 27% of thermal energy needs, which can be

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further increased by using the carbonaceous HTC product as fuel on-site. The reduction of the use of external energy resources for local brewery processes is a small but effective regional contribution to the global transition to a low-

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Figure captions:

3 Fig. 1. Process scheme for three different management strategies (A, B and C) of solid residues in a combined brewery-distillery Fig. 2. Process scheme for the HTC-Reactor treating spent grains during steady state operation conditions with the process parameters: Temperature, Mass flow (;h); Heat transfer rate (ih ); Heat capacity rate (%h )

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Fig. 3: Total wastewater input flow rate and component fractions fed into the anaerobic digester.

Fig. 4: Degradation pattern of wastewater over time in the CSTR-biofilm plant. Week 1- 23: high strength brewery effluents; week 24-48: mixture of alcohol slops and high strength wastewater from beer production

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M AN U

13

19

ACCEPTED MANUSCRIPT

Table 1 Specific energy demands for processing beer (Sattler, 2000) Electric energy Production capacity

-1

Thermal energy -1

(kWh hL )

25

49

15

31

8

24

-1

Up to 50000 hL y

-1

Up to 500000 hL y

-1

AC C

EP

TE D

M AN U

SC

More than 500000 hL y

RI PT

(kWh hL )

ACCEPTED MANUSCRIPT

Table 2 Specific wastewater flows of different processing steps in the brewery/distillery facility and the contamination of these flows expressed as chemical oxygen demand (COD) Specific flow

Organic load

-1

-1

(hL hL )

(g L )

(g COD hL )

Mashing

0.083

3.3 - 33

129

Fermentation

0.011

0.03 - 1.1

Yeast production

0.012

0.3 - 19

Filtration and bottling

1.51

0.5 - 35

Not identified

3.39

2.2

5

2.0

SC

-1

COD

RI PT

Production step

80

151200

Vinasse

18.9

10

M AN U

Total Beer Production

1

85

770

1000

Annual potential for the production of 90000 hL of beer and 1000 hL of distilled wine Annual potential

Volume 3

-1

(m y )

Wine distillation

1890

AC C

EP

Total

45000

COD Total

(g L )

-1

(t COD y )

2

90

80

151

TE D

Beer production

COD

-1

241

ACCEPTED MANUSCRIPT

Table 3 Mass and energy balances for dehydration of spent grains, digested spent grains and HTC char of -1

spent grains (specific energy for mechanical dehydration 40.2 kWh t of FM and specific energy for -1

Mass Flow -1

-1

(t FM y ) 1344

(%) 75.0

(kWh y ) 54144

1117

87.3

44999

1209

83.9

48705

3

-1

(m y ) Anaerobic/Aerobic 504 (Aerobic) 762 (Anaerobic) 721 (Anaerobic)

AC C

EP

TE D

M AN U

Spent Grains Digested Spent Grains HTC Char of Spent Grains

Moisture

Mechanical dehydration Energy Waste Water

SC

Product

RI PT

thermal dehydration 2.93 kWh kg of water removed)

Thermal dehydration

Δm water

Energy

-1

(kg t FM) 460

(GJ y-1) 1808

194

634

222

786

ACCEPTED MANUSCRIPT

Table 4 Overall energy balance for the strategies: without any treatment of spent grains (A), Anaerobic digestion of spent grains (B) and hydrothermal carbonization of spent grains (C)

Process

AD of solid wastes (Strategy B)

Heat

Electricity

(kWh y-1)

(GJ y-1)

(kWh y-1)

Production

1380000

14256

1380000

Dehydration

54144

1808

44999

Biogas Waste Water

286372

1524

HTC Reactor (%) 3.8

Contribution Alternative

20

EP AC C

Heat

(GJ y-1)

(kWh y-1)

(GJ y-1)

14256

1380000

14256

634

48705

786

286372

1524

598421

2869

368057

1903

-18000

1159

(%)

(%)

(%)

(%)

(%)

11.3

3.2

4.3

3.4

5.2

9

46

23

41

27

TE D

Percentage of Dehydration

Electricity

M AN U

Biogas Solid Treatment

Heat

SC

Electricity

HTC of solid wastes (Strategy C)

RI PT

Without Treatment of solid wastes (Strategy A)

ACCEPTED MANUSCRIPT

Vinasse

Spent Grains

Anaerobic Digestion (Solids)

TE D

B

Hydrothermal

Spent Grains

AC C

C

Filtration Bottling

Beer

Waste Water

Strategy A Spent Grains

Strategy B Digestate Biogas

Strategy C HTC - Coal

Conversion

Waste Water

Vinasse

SC

Fermentation

EP

A

Spent Grains

Boiling

M AN U

Mashing

Malt

RI PT

Liquor

Distillery

Beverages

Biogas

Anaerobic Digestion (Liquids)

Treated Waste Water

ACCEPTED MANUSCRIPT

Consumer

121 °C

 = 99.6 

 = 157.1 

130 °C

RI PT

Consumer

214 °C

80 °C

SC

 = 0.49   

M AN U

123 °C 189 °C

182 °C

179 °C 139 °C

EP

 = 0.249    50 °C

TE D

 = 2.18   

ZONE I

AC C

180 °C

 = 0.59   

 = 1.43   

134 °C

88 °C

220 °C

ZONE II

ZONE III

ACCEPTED MANUSCRIPT

M AN U

1.6

0.0

EP

TE D

1.2

0.4

Total input

SC

2.0

0.8

Low Wine Water

4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 Time (Weeks)

20

16

12

8

4

0

Flow Rate (Total Input) (m3 d-1)

Stillage

RI PT

Returned beer

AC C

Flow Rate Fractions (High Strength Waste Water) (m3 d-1)

Last runnings

ACCEPTED MANUSCRIPT

M AN U

SC

RI PT

Degradation Yield Last runnings Returned beerStillage Low Wine Water Total input η [%] [m3 d-1] 96.1553398 0.53125 0.1875 0 0 1.59317212 97.0873786 0.125 0 0 0 1.59317212 96.3106796 0.15 0 0 0 3.04409673 96 0.375 0.28125 0 0 5.60455192 91.961165 0 0 0 0 9.44523471 92.5825243 0.71875 0.40625 0 0 11.0384068 88.3883495 0.34375 0.15625 0 0 11.6358464 90.0970874 0.375 0.15625 0 0 13.7411095 80 0.7125 0 0 0 16.6145092 82.7961165 0.484375 0.278125 0 0 18.7766714 86.2135922 0.234375 0.1875 0.175 0 12.2901849 81.3980583 0.234375 0 0.671875 0 10.9815078 77.3592233 0.15 0 0.771875 0.203125 11.4366999 76.7378641 0.328125 0.1 1.265625 0.103125 14.1394026 77.3592233 0.6625 0 0.940625 0 10.6970128 76.4271845 0.525 0.203125 0.865625 0 14.1394026 65.7087379 0.203125 0 0.359375 0 7.28307255 76.5825243 0.53125 0.296875 0.46875 0 9.64438122 75.4951456 0.375 0.296875 0.640625 0 13.0583215 77.2038835 0.984375 0.59375 0.484375 0 13.6273115 75.8058252 0.765625 0.109375 0.765625 0 14.7937411 71.9223301 0.725 0.19375 0.70625 0 14.1109531 68.038835 0.95625 0 0.975 0 14.0256046

AC C

EP

TE D

4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48

Loading Rate OLR kg m-3 d-1 0.62135922 1.25825243 1.28932039 2.68737864 3.38640777 4.27184466 3.29320388 3.10679612 2.7184466 3.2776699 3.15339806 6.13592233 7.33203883 7.53398058 6.67961165 8.79223301 4.14757282 4.93980583 6.61747573 6.67961165 7.14563107 6.53980583 4.17864078

ACCEPTED MANUSCRIPT

Loading Rate

Degradation Yield

M AN U

SC

8

2

0

EP

4

TE D

6

4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 Time (Weeks)

80

60

40

20

0

Degradation Yield (%)

RI PT

100

AC C

Loading Rate (kg COD m-3 d-1)

10

ACCEPTED MANUSCRIPT Degradation Yield

EP AC C

SC

M AN U

96.2 97.1 96.3 96.0 92.0 92.6 88.4 90.1 80.0 82.8 86.2 81.4 77.4 76.7 77.4 76.4 65.7 76.6 75.5 77.2 75.8 71.9 68.0

RI PT

η [%]

TE D

4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48

Loading Rate OLR kg m-3 d-1 0.62 1.26 1.29 2.69 3.39 4.27 3.29 3.11 2.72 3.28 3.15 6.14 7.33 7.53 6.68 8.79 4.15 4.94 6.62 6.68 7.15 6.54 4.18

ACCEPTED MANUSCRIPT

Highlights

• Hydrothermal carbonization of spent grains must combined with anaerobic digestion.

RI PT

• Brewery wastewater and vinasse can be treated anaerobically at high loading rate. • Excess heat of hydrothermal carbonization can be used in brewhouse processes.

• Hydrothermal carbonization and anaerobic digestion show similar energy recovery.

AC C

EP

TE D

M AN U

SC

• Mass loss in treatments are reducing energy demand for drying of solid wastes.