WO2002051561A2 - Pre hydrolsys system of the organic matter of the rubbish and process for industrialization of the rubbish - Google Patents

Abstract

The present invention relates to the average composition of urban waste, composed of plastics, paper, metal, glass, organic material of Municipal Solid Waste (OMMSW), ashes, batteries and humidity contents. OMMSW has been subjected to acidic prehydrolysis (2.5 % of H2SO4 on the dry matter), a prehydrolysate of 12 % of sugars and cellulignin with 12 % of ashes being obtained. Since the OMMSW contains only 30 % of dry matter, one has concluded that the economicity of the process defined as weight of solid matter by cubic meter of reactor improves with the mixture of 50 % of OMMSW and 50 % of biomass (wood, grass, agricultural residues, etc.). With this technique one has achieved 300kg of dry biomass/m3 (DB) of reactor. This requirement is not limiting, since the biomass may be supplied by planting trees in the urban perimeter or planting 1ha of grass for each 1000 inhabitants in the cities surroundings.

Description

Title: "PRE HYDROLYSYS SYSTEM OF THE ORGANIC MATTER OF THE RUBBISH AND PROCESS FOR INDUSTRIALIZATION OF THE RUBBISH"

FIELD OF INVENTION The present invention relates to a system of prehydrolysis of organic matter from waste, more precisely its industrialization and to a waste industrialization process.

OBJECTIVES OF THE INVENTION

It is an objective of the present invention to use biomass for the purpose of obtaining a renewable source of energy and biomass chemical products.

It is an objective of the present invention to reduce the operational costs of waste industrialization.

It is an objective of the present invention to reduce pollution from waste industrialization.

It is an objective of the present invention to establish organic matter parameters from organic waste (OMMSW = Organic Material of Municipal Solid Waste) processed through prehydrolysis and the resulting cellu- lignin and prehydrolysate characterization. It is a further objective of the present invention the experiments of cellulignin combustion, combustion gases characterization, utilization feasibility analysis of the prehydrolysate from the OMMSW. SUMMARY OF THE INVENTION

The present invention is based on the presentation of average composition of urban waste, composed of plastics, paper, metal, glass, organic matter from organic waste (OMMSW), ashes, batteries and humidity contents. The OMMSW was subjected to acidic prehydrolysis (2.5% of H₂SO on the dry matter), and a prehydrolysate of 12% of sugars and cellulignin with 12% of ashes contents. Considering the OMMSW contains only 30% of dry content, one came to the conclusion that the economicity of the process, defined as solid matter weight per cubic meter of reactor improves with the mixture of 50% of OMMSW and 50% of biomass (wood, grass, agricultural residues, etc.). With this technique one has achieved 300 kg of dry biomass (DB)/m³ of reactor. This requirement is not limiting, since biomass may be supplied by planting trees at the perimeter of the city and plantation of 1 ha of grass for each 1000 inhabitants of the cities surroundings.

The cycle of the process takes 10 min for charging, 25 min for heating, 25 min for prehydrolysis, 10 min for discharging the prehydrolysate, 10 min for recovering the sugar and 10 min for discharging, making a total of 90 min for the complete processing. Due to high humidity contents in the OMMSW, it was necessary to work with liquid/solid ration, L/S=2.8 higher than the IJS=2 of wood ration when used as a Raw material. In this way, the consumption of steam has risen to 1.24 t of steam/t of (OMMSW+Biomass), compared to the consumption of 0.43 t of steam/t of wood, for water entry temperature into the boiler of 20^QC. For water entry temperature into the boiler of 80⁹C there is a reduction of 50% of the steam consumption corresponding to 6.3% of the heat contained in the wood cellulignin and 18% of the heat contained in the OMMSW cellulignin.

The OMMSW cellulignin and the biomass (CLOMMSWB) pre- sented combustion characteristics similar to the wood cellulignin, exhibiting its feasible economical technique as fuel for furnaces, boilers and steam thermoelectric boilers and gas-type turbines.

One defined the effluents treatment (prehydrolysate from the mixture OMMSWB in the beginning, while there is no furfural distillery, and furfural residues, luter at the end, when there is no furfural distillery and washing waters), being constituted of: aeration tank, sludge flotation, water demineralization (sand filter, charcoal filter, cationic, anionic and mixed resin columns). All the process water is recycled through rain water collecting from the neighboring areas into stabilization tanks, it is possible to achieve a com- plete balance in the process without the need for taking water from artesian wells or discharge of liquids into creeks and rivers.

The odors from the selective waste conveyor are suctioned and burned in the boiler. There is no e gases emanation other than C0₂ in the boiler chimney and even this will be purified in the future, liquefied by compression and commercialized.

The only residues are inorganic solids from the OMMSW (cera- mic pieces, stones, sand, clays, etc.) with technology achieving a level of "Zero Pollution" this way.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 shows the resulting products from the biomass processing. Figure 2 shows the annual generation and the forms of managing the residues in the developed countries.

Figure 3 shows the average percentage composition of household waste in some countries.

Figure 4 shows the average percentage composition of hou- sehold waste in some Brazilian cities.

Figure 5 shows a flow diagram of triage of waste and prehydrolysis of the organic portion from the urban waste.

Figure 6 shows the characteristics of solid residues.

Figure 7 shows the microstructure of cellular walls. Figure 8 shows the biomass model of hexagonal cellular structure.

Figure 9 shows the biomass cellular structure (weight %).

Figure 10 shows the chemical composition of the vegetable cellular walls. Figure 11 shows the hemicellulose structure.

Figure 12 shows the cellulose structure.

Figure 13 shows the lignin structure.

Figure 14 shows the hemicellulose reaction mechanism.

Figure 15 shows the micrography cellulignin wood, with crater di- ameters of 90 nm and the distance between the microvulcanoes of (600 nm).

Figure 16 shows the average specific power irradiated in the combustion of a cellulignin particle. Figure 17 shows the side view of the wood combustion cellulignin.

Figure 18 shows the feeding system of catalytic cellulignin to boilers/furnaces or gas-type turbine. Figure 19 shows the skeleton of the furfural reactor and its reactions.

Figure 20 shows the distribution furfural applications.

Figures 21 and 22 show the furfural derivatives.

Figure 23 shows furfural price. Figure 24 shows a comparative table between the furfural art state production, and the advances foreseen in the present invention.

Figure 25 shows the representative schema of the passage of samples weigh parameters definition.

Figure 26 shows the summary of the conventional analytic methods employed the biomass acidic processing.

Figure 27 shows the percentage composition of urban waste.

Figure 28 shows the composition of the organic matter of urban waste.

Figure 29 shows the waste deposit embankment before and after the recovery process.

Figure 30 shows the typical mass balance of the acidic OMMSW prehydrolysis with internal washing.

Figure 31 shows the description of a heat exchanger/acidic solution tank. Figure 32 shows the mass balance of the wood acidic prehydrolysis with internal washing.

Figure 33 shows the acidic solution tank/heat exchanger.

Figure 34 shows the scheme of the Belfano washing tower adapted for condensation tower. Figure 35 shows the flow diagram of batch flow prehydrolysis integrated mass batch flow prehydrolysis (4.5 TDB per reaction).

Figure 36 shows the relationship ETS/WTS/DESMI/integrated stabilization tank (Kg/reaction).

Figure 37 shows the CAF(cavitation air flotation) view and cross- section system.

Figure 38 shows the scheme of Sludge flotation by CAF. Figure 39 shows the demineralization system (DESMI).

Figure 40 shows the integrated mass balance flow diagram of the batch flow prehydrolysis with luter recirculation (4.5 TDB per reaction).

Figure 41 shows the hydric balance with luter recirculation and separation between the ETA and the ETS/DESMI/stabilization tank. Figure 42 shows the general view wood hydrolysis.

Figure 43 shows the combustion of cellulignin combustion OMMSW.

Figure 44 shows the environmental management model system for Rule IS014004. Figure 45 shows the materials life cycle analysis from the waste.

FIGURES DETAILED DESCRIPTION

Waste destination in Brazil is a question of public calamity; at present its destination is: 76% dumped at dumps (open sky); 13% controlled embankment, 10% embankment, 0.9% composted in plants and 0.1% incine- rated. Brazil produces over 242,000 tons waste/day, out of which 90,000 tons

/ day come from homes.

Nearly 90% of what is daily thrown away may be changed into some form of riches. Considering that the household waste grows 5% a year, and that in Brazil very little is done to recycle this material, the volume of what is wasted is reasonable. In the city of Sao Paulo alone, over 900 tons household and industry waste is dumped at dumps every day. Without a significant innovation in the integral utilization of household waste, there will be no solution for this problem. The present-day solutions (embankments, composting, incineration, pyrolysis/gasifying) have not solved the problem in an economical technical way. Figure 2 shows the annual generation and the residues managing forms in developed countries.

The waste is an extremely heterogeneous material, its characte- rization being complex and made according to the desired objectives. Figures 3 and 4 show the waste percentage composition in some countries and of some Brazilian cities from the point of view of selective collection.

Vale do Parafba geology is characterized by crystalline rocks from the mountain ranges Serra da Mantiqueira and Serra do Mar, with the Sedimentary Basin of Taubate, which extends from Jacare to Cruzeiro. The Taubate Basin is subdivided into two types of sediments, one being of lacustrine nature (200 m thick), called Trembembe formation, which crops out on the surface only around the above-mentioned municipality, and a second se- diment of fluvial nature (150 m thick), called Cacapava formation throughout the Taubate Basin, except for the surroundings of Tremembe. The Tremem- be formation is an ion-absorbing clay (decolorizing clay), for which reason that city is used as an "embankment of industrial residues". The Cacapava formation has a permeable clay without any absorbing power. This means that any dump or embankment in this region will contaminate the surface and subterranean water table. Table 3 in particular shows the contamination of the underground aquifers by the city dumps and embankments of the state of Sao Paulo, showing that only Lorena, Guaratingueta and Ibate qualify as Hh (High-high risk of contaminating the underground aquifers). Preliminary stu- dies by INPE - Instituto Nacional de Pesquisas Espaciais (National Institute of Space Researches) (with documentation not published yet) also indicate that there are no available areas in Lorena city where one can install an embankment without contamination of the water tables. It is easy to understand this situation, considering two situations: 1^st) if the embankment is made in the Cagapava formation, it is highly permeable and will contaminate both water tables (the surface and the underground waters).

2^nd) If the embankment is made in the region of the crystalline (mountain zones), it is impermeable and the contamination will go down to the underground aquifer in its feeding zones.

Therefore, one concludes that the waste Integral Processing is the only technical ecological solution for the cities in Vale do Parafba, located in the Cacapava formation.

Table 1 - Types of arrangement or deposition of solid residues and rate of natural vulnerability

φ c

CD CD φ

C c c ^"cδ o !______ ------- CO

^"cc ^"cc CO o CO O ≥^» O CO CO CO CO CO ϋ CO CO

H ϋ ϋ _Q .Ω ϋ

1 U α. -σ z ___: ___: ^■σ _E _c _ _c -σ _c _c c _c T5 3 CO CO _c

_I _l _] _l X Z _ι X _I _ X X _I _l z: _

_l _ι _I _I Έ wz. _> X ≥

•+-» c c c c c

CD φ φ φ φ

E E E

__*_ s. __*_ ε_ __ ε<_ - c c c C c

Q. Q. Q. Q. Q. Q. CO Q. Q. Q. Q. Q. cC CO Q. Q. Q. Q. Q. Q. Q. Q. a. CO α. Q. CO Q. Q. C

E ε E E E E _Q E E E E E _Q _Q ε ε E ε ε ε ε ε E _D

3 3 3 3 E 3 3 3 3 3 E E 3 3 3 ε ε _Q ε ε -

3 3 3 3 3 3 3 3 ε 3 3 ε 3 3

Q Q Q Q Q Q LU Q Q Q Q Q LU LJJ Q Q Q Q Q Q Q Q Q LU Q Q LU Q Q L O

3 o

_Ω

Φ ___ +-» cC c σ φ Q Φ CO

CO

+-- CO -σ CO > O) 3 CO

CO o c _— O

CO ^"5 CO o C -o

3 CO O) 0_ CD Q.

CO o _c C

CO CC O) Q. c CO c Φ CO E 3 Q_

> _Q c 3 "_____. o _Q C c _ cC 3

CO ^"cδ cC φ O 2 Q. CC →— ' > CO Φ __ __ CO CO E CO 3 ϋ C c o CO O ^■o »CC CO

C D ^'c

__O CD C "CO _9 CO CO ^'φ "σ ^'ϋ O 3 φ ^'co Φ ϋ C Q. ^"O) 5 Q. ϋ __ c C __O____ C -O_ ^'~ __ φ

3 cC O C E _—

O CC o o __ O O. c CO CO CO <c

-3 —3 _l _ι _J Έ _> _ b. ϋ Q. 0_ D_ ir ir C

KB

O

I- CO σ> o CM O ^t in O 1^ 00 CΓJ o CM CO * in O CO σj o CM CM M O CO CO CO CO CO CO CO O CO ^ 5- ^ 't ^<sf ^r ^ ^t- ^<* ^< L O

S R^{i dt}ao. ^tro

S R^tanaos^a

Vulnerability rates:

Hh - High high; HI - High low; Mh - Middle high; Ml - Middle low;

Lh - Low high; LI - Low low; Nd - Not defined.

Figure 5 illustrates a waste triage flow diagram, followed by OMMSW prehydrolysis. The triage objective is to collect as much paper/cardboard, plastics, metals and glass as possible, materials with some aggregated value that may be sold or recycled. For the next recycling step it is suitable that electric batteries, stones and large materials should also be triaged, the latter being intended for the shredder.

The prehydrolysis objective is to hydrolyze the hemicellulose, generating the prehydrolysate, opening porosity in the cellulose and glo- bulyzing the lignin (cellulignin). The prehydrolysate is intended for the production of biomass chemicals (alcohol, furfural or xylitol) and the cellulignin is intended as fuel for furnaces and boilers (with average ash contents ) and gas-type turbine (with low ash contents). The technical economical maximization of the waste integrated processing depends upon the following points: 1 ^st) effective selective collection of plastics, metals and glass, so that these products will not occupy too much space in the reactor. Although these products do not make the prehydrolysis in the reactor unfeasible, they are not transformed into saleable products (cellulignin and prehydrolysate) within the reactor.

2^nd) Ashes Minimization (stones, pieces of broken material, earth, sand, clay, etc. ) - In an asphalted city the ash contents in the waste is on the order of 2% (close to the contents of hard wood - 1.2%) and in peripheral districts of Lorena (streets without asphalt and courts without pavement) the ash contents may reach 60%. Waste from a clean city approaches reforestation and waste from dirty cities approaches waste material/ earth. Unfortunately waste material/earth does not generate saleable products and need to be minimized in the waste, in order to maximize the technical and economical profitability. 3^rd) The prehydrolysis technology eliminates the contaminants from the final products (cellulignin and furfural) which are rejected to the liquid effluents. The treatment cost of these residues is minimized, whereby the contents of toxic components (batteries, insecticides, chlorinated products, heavy metals, etc.) in the waste decrease. 4^1h) The waste has high humidity content (66%) and water does not generate a saleable product. One way of maximizing the technical economical result is the mixed processing of waste along with the biomass (grass or wood). It is fundamental to achieve awareness and accomplishment of the urban biomass production increase (planting trees in wasteland, parks, roadsides, etc.)

5^th) The optimization of electric energy in thermoelectric stations is on the order of 2/3 in the gas-type turbine (for burning clean cellulignin from biomass) and 1/3 in the boiler/steam-type turbine (for burning dirty cellulignin from garbage). In this way, the technical and economical maximizati- on of the Waste and Biomass integral Processing is about 1/3 of the mass in OMMSW and 2/3 of the mass in Biomass (wood, grass, etc.). In the initial steps of BEM program in which the gas turbine will operate with cellulignin at lower temperatures that would operate with clean fuels (natural gas, kerosene, oil), the CL of the OMMSW will generate 40% of the energy in the gas type turbine and 60% in the steam turbine.

The technological success of the sure-failure-type reactor of Pro- gram BEM - Biomassa - Energia - Materials (biomass - energy-materials) in the prehydrolysis execution stimulates the extension of the clean biomass technology to the dirty biomasses (organic matter from the waste, agricultural residues, etc.).

One of the characteristics of the sure-failure type reactor is its low water consumption due to the low relationship in the processing of L/S = 2 and in the washing of LS = 6, making a total of L/S = 8. This means that for each 0.75 kg/inhabitant day of waste there is a consumption of 1.44 L of water/inhabitants/ Day. This value is negligible when compared with the water consumption and sewage of 125 LJinhab day. The liquid residues from the prehydrolysis could be disposed off and treated in the sewage network without overcharging it. Another consequence is the possibility of treating the waste in closed buildings or basements with controlled atmosphere, even in the centers of big cities, thus avoiding the costs of waste transportation to long distances. The maximum energetic utilization is achieved when one produces a clean cellulignin that may be burned in a gas-type turbine, which requires total particulate contents < 200 ppm, particulate contents higher than 5 μm <8 ppm and Na+K contents < 5 ppm. These requirements have already been achieved with wood prehydrolysis, and one of the great justifications of the present dissertation is to research the technologies in order to utilize cellulignin from the OMMSW in gas-type turbine. The specifications of ash in the waste from the city of Sao Paulo are very low (2%) and in the municipal waste in general (domestic and industrial waste) are very high (20 - 40% - Figure 6). Even with these high values, Bioten Incorporation, located in Kno- xville, Tennessee, USA, a corporation that has developed the gas-type turbines, operated successfully gas-type turbines (GE LM1500) with sawdust and rice straw with ash contents of up to 20% [PADILHA 2000]. The technology consists in reducing the Na+K contents in such a way, that its melting point (vitrification) will be above the turbine operation temperature. [MARCONDES 2000].

General concepts in the chemical engineering and in a more specific area in the extractive metallurgy and leaning of combustion gases have been used in the present paper, namely:

Hydrometallurgy: Embracing,

1^st) rotary sieving after the waste selection process;

2^nd) acidic digestion in the reactor, where most of the non- organics are converted into soluble sulfates;

3^rd) washing the cellulignin after digestion;

Physical Metallurgy:

4th) cellulignin drying

Combustion: 5^th) scorifying combustor;

6^th) cycloning the combustion gases, and

7^th) hot ceramic filtering (possible).

The various overlapping factors that render the waste integral treatment possible are: a) necessity of the city to have this type of technology; b) necessity for the R.M. Materials Refratarios Ltda to install units for testing biomass prehydrolysis reactors; c) existence of the Polo Urbo-lndustrial Mondesir (Urban-industrial Pole Mondesir) with characteristics for evolving into a level of energetic dis- trict; d) the geographic location (between Sao Paulo and Rio de Janeiro) and plane topography Lorena city have favored its continued growth, and may achieve, within a few decades, conditions of unavailability of the area for embankments (beside being condemned from the ecological point of view), similar to the situations of Sao Paulo, Campinas and Rio de Janeiro cities; e) Lorena city has initiated the process of Waste Selective Collection involving 3 entities (Municipal Government, Recycling Center "Antδnio Frederico Ozanam" CRAFO, of the Sociedade Sao Vicente de Paulo and the program BEM) and the latter is in charge of utilizing the OMMSW.

Sociedade Sao Vicente de Paulo, in a direct and indirect actuation with the population, and with a serious awareness, is now managing to achieve a control and reduction of the amount of waste produced by the population of Lorena, thus enabling a considerable human and social work [CRAFO, 92].

The City Hall and its association with the Sociedade Sao Vicente de Paulo should be responsible for the delivery of the OMMSW to R.M. Mate- riais Refatarios Ltda. with a minimum of recyclable material and ashes (earth, wastes, etc.).

In the beginning, glass, plastics and metals are merely sold to third parties. In the future, they will be changed into products with higher aggregated values. Since the petroleum crisis in the Seventies, the world has been looking for alternative sources of energy, among which the biomass. At present, the use of biomass represents about 15% of the world consumption of energy, most of it being used in the traditional form of firewood or charcoal, in household use and in an ineffective way. Utilization of this source of energy in an effective and sustainable way may bring about many environmental and social benefits, if compared with the use of fossil fuels.

Most sources of biomass available today are in the form of refuse from the paper industry, saw-mill and forest residues (branches, dead leaves, dead trees, which otherwise have initiated a putrefaction process and would again be changed into C0₂).

Another form of biomass utilization would be the creation of farms for cultivating sugar cane, grass and trees. Great emphasis has been placed on the cultivation of hard wood, including the flexibility in cutting throughout the year and not associated to seasonal growth cycle. The ad- vantages of using these hard wood include the flexibility in cutting throughout the year, not associated to the cycle of sugar cane growth, for instance, to the rapid growth and regeneration of forests intended for tree falling. This latter characteristic reduces operational costs of the fuel farm.

Although the utilization of residues from the biomass represents a source for rapidly beginning the production of energy, emphasis should be placed on the formation of cultivation farms, since the production in areas having poor maintenance is quite below 5 TDB/lnhab. Year, while in areas having good maintenance, the production may reach 10 - 15TDB/lnhab. Day in regions of temperate climate and 15 - 25TDB/inhab. Year in the cultivation of eucalyptus in Brazil and in Ethiopia. (At present, productions of 40TDB/lnhab are achieved). It should be pointed out that this production is influenced by variables such as the quality of land and the species to be cultivated.

The biomasses are composed of cellulose, hemicellulose and lignin. The cellular walls are composed of macrofibrils, microfibrils, cellulose micells and molecules, which are arranged especially as illustrated in figure 7.

One should observe that the cellulose fibers are approximately arranged according to a hexagonal symmetry, the diameter of the microfibrills being of -50 nm, containing 13 microfibrills (in practice on the order of 10).

Microfibrills with a diameter of ~10nm contain 12 micells and these with a diameter on the order of 3nm contain 30 - 35 cellulose molecules, (figure 8).

The theoretical specific surface of the cell is on the order of 0.7m²/g, of the macrofibrill on the order of 50m²/g, of the microfribill on the order of 200m²/g, of the micell on the order of 900m²/g and of the molecules on the order of 1300m²/g. According to the equation of the hexagonal structure, wherein:

N = number of cellulose molecules n = number of layers i = index of the sum

N = 1 + 6 ∑rø^' = (1), (1 + 6 = 7), (1 + 6 + 12 = 19), (1 + 6 + 12 +

0 18 = 37),...

Hence:

13 - microfibrills in the macrofibrills 19 - micells in the microbibrills 37 - cellulose molecules in the micells.

In this model we can estimate the specific surface (area per mass unit) of the biomass as follows:

1 - specific surface of the cell:

Geometry with Square cross-section and Length λO b = 10 U.m

(S e M: surface and mass of the cell).

2 - Specific surface of the macrofibrills, microfibrills, micells, and cellulose

Cylindrical geometry.

S = 4bl ;M = 4blep . — = ^U ■ 0,61m²1 g

M Ablep ep 1,0x10-° xl,5xl0⁶ 2. a - Specific surface of the macrofibrill (φ= 50nm; Macropores >

50nm)

S 4

^■ = 53m² /g

M 50xl0-⁹ xl,5xl0⁶ 2.b - Specific surface of the microfibrill (φ = 50÷4 = 12,5nm; Me- sopores 2nm < φ < 50nm)

4

213m²1 g

M 12,5xlO^~9 xl,5xlO^"6 2.c - Specific surface of the micell (φ = (12,5÷4)nm = 3,1 nm; cropores φ < 2,0nm) - = 860m² /g

M 3,lxl0-⁹xl,5xl0⁶ 2.d - Specific surface of the cellulose molecules ((3,1÷6)nm =

0,517nm)

S 1 ,

- = 1290m² Ig

M 0,517xl0^_9 xl,5xl0⁶ Figure 9 shows a photomicrography of the cross-section of a vegetable cell showing the various layers of the cellular wall; figure 10 shows a graphic with the concentration of the vegetable cells walls (cellulose, hemicellulose and lignin). One can see that the average lamella is composed only by lignin, the primary wall has an average concentration of lignin on the order of 65%, an average concentration of hemicellulose on the order of 25% and only 10% cellulose. Cellulose concentration reaches a maximum value on the order of 55% in the central region of the portion (S2) of the secondary wall, decreasing to a concentration on the order of 45% in the tertiary wall, where the lignin reaches a minimum concentration on the order of 15%. Cellulose, hemicellulose and lignin behave as polyalcohols in which the main functional group is OH.

Hemicellulose is an ordinary polysaccharide with a branched chain, in which the main components are 4-0methylglucoroxylanes in hard wood and glucomanes in soft wood. The main functional groups of hemice- llulose are carboxylic, methylic and hydroxylic groups. Hemicellulose is digested in the prehydrolysis and is not present in cellulignin, represented in figure 11.

Cellulose is a linear polysaccharide of anhydroglucose with glu- cosidic links β-1->4; after oxidation, the functional groups are carboxylics, ketones and carboxylics. It is the most abundant organic polymer on earth, representing about 50% of the wood mass and about 38% of the sugar-cane- bagasse mass. It is a three-dimensional polysaccharide in which the basic molecular structure may be represented by figure 12.

Lignin is a three-dimensional skeleton of 4 or more substituted phenylpropane units. The basic constructive blocks are guayaquil alcohols (soft wood) and seringil alcohol (for the two types of wood). The dominant links are β-0-4. It is a natural, three-dimensional, amorphous polymer, responsible for the interconnection of cellulose fibers plants, imparting rigidity to the wood and protecting carbohydrates from oxidative destruction. Its amount in plants ranges from 18% to 38%. The complexity of the lignin macromole- cules results from the statistic nature of the polymer, involving from one to two dozens of different intermonomeric links, represented by figure 13. The cellulose and lignin structures are highly oxygenated (figures 12 and 13) an the location of the functional groups is useful in understanding the mechanisms of pyrolysis and oxidation. One of the most ancient processes of generating energy from biomass is that of direct burning in the form of firewood. Although this method is quite ineffective, it is still widely used in households, mainly in rural zones and in underdeveloped countries.

Prehydrolysis takes place inside a Sure-Failure Type Reactor, where the shredded biomass is slightly compacted, and then an acidic solution is injected. The ion H⁺ (H₃0⁺ Hydroxonium) penetrates the cellular wall, reacts with the hemicellulose (hydrolysis) absorbing the H₂0 molecule, releasing the H⁺ (figure 14), partly forming H₂₎ which increases the internal pressure, exploding the cellular wall in a process similar to a volcanic eruption. Lignin is globulized, bearing in mind that the prehydrolysis temperature is higher than the vitrification temperature. Hemicellulose + H₂O → Xilose

(C₅H₈O₄)n + nH₂O → n C5H10O5

In the prehydrolysis, only ingestion of the hemicellulose (liquid portion) takes place, and the crystalline cellulose and lignin remain intact (so- lid portion), which is called cellulignin; to obtain these products, one should maintain the pressure at 0.67% MPa and the temperature at 160⁹C.

The remaining solid material (cellulignin) is a porous material with a large specific area (4.4m2/g) when compared to the biomass that has originated it (0.7 m²/g for wood). [SOARES, 2000]. Figure 15 shows micro- graphies of wood cellulignin, taken with the help of an electronic scanning microscope. It is not difficult to increase the biomass contents in the OMMSW by increasing the green area in the city (urban forests). At the rate of 0.75 kg/inhab. day of waste we have 66 kg/inhab. year. At the rate of 100 inhab/ha (10.000 inhab/km²) for cities with land residences we will have a production of OMMSW of 6.6TDB/inhab.year. In these cities it is easy to achieve this rate of biomass production in wastelands, grass planted land, and reforestation close to urban zones. From the average of 4 floors on, the cities begin to be the largest "artificial forests" producing organic matter, a production higher than 26 TDB/ha.year, which is on the same order as the reforestation of eu- calyptus from seeds and half the reforestation of cloned eucalyptus. In the case of densely populated cities, the economy in the cost of H₂S0₄ may come from using acidic residues, since the acidic prehydrolysis actuates as a "cleaner" of these acidic residues produced in the region. The consumption rate of acid in prehydrolysis is of 1 ,64 kg/inhab.year. The present consumpti- on of H₂SO₄ in Brazil is of 4x10⁶t/year for a population of 160 million people, resulting in a rate of 25 kg/inhab. year. It is highly probable that the 6,5% of H₂S0 consumed in Brazil is found as residue in the city for integration in the prehydrolysis of OMMSW, showing that this technology does not imply an increase in the consumption of H₂S0 in Brazil. Taking as a basis the knowledge of molecular structure and organization of cellulose and lignin, studies made have indicated that the combustion of cellulignin particles > 500μm emits a low specific thermal power (conventional carbonization), while particles < 250μm emit a thermal power 50 times as high (catalytic combustion) (figure 16). The main characteristic of catalytic cellulignin is the possibility of oxygen access to the internal pores of particles with diameter smaller than 250μm, during combustion, which does not happen in conventional processes in which combustion occurs from the external area. The lower calorific power of wood cellulignin is of 20 MJ/kg.

The reactivity of the catalytic cellulignin is higher than that of bi- omass (absence of water, larger specific surface) and the combustion heat is the double, causing a heat release rate several times as high as that of wood. The particles combustion injected with the help of a haul gas into a combustion chamber and with ignition by means of a pilot flame enables one to control the variables inside the chamber, such as oxygen pressure and concentration (figure 17). The fuel dosage is made with helical threads or rotary valves and the feed of air with the haul gas is in the ratio of air: cellulignin = 3.28 : 1 by weight and 1261.6: 1 in volume. This imparts to the cellulignin a characteristic equal to that of gases and liquids in the dosing and feeding operations, being drastically easier than the conventional dosage and feeding of solid combustibles, especially biomass. The ignition time of catalytic cellulignin is on the order of 11 ms and the combustion time is on the order of 257 ms for particle on the order of 175μm, lower than the time of mineral coal or liquid fuel and tending to the times of gaseous fuels.

Catalytic cellulignin combustors are directly coupled to the boilers and furnaces, since this equipment has devices for ashes removal. For gas- type turbines, the combustors are provided with cooling chambers for the combustion gases and cyclones to reduce the particulate contents (figure 18).

Prehydrolysate is preferably a xylose solution intended for the production of biomass chemicals (furfural, alcohol or xylitol). Furfural and its derivatives are the only large-scale commercial products obtained from hemicellulose.

The project and detailing of the semi-industrial furfural reactor manufacture with capacity of 15 1 of furfural/day (tFF/day) is in development. By means of prehydrolysis with diluted acid, one converts hemicellulose to xylose (160^SC, 0,7 MPa, 1 % H₂S0₄ - 25 min) and by means of distillation one converts xylose to (190 to 220⁹C, 3 MPa, 1 to 2% H₂S0₄ - 3 to 5 min) - figure 19. So far, the whole production of furfural is carried out in one step, with superposition of the two above-listed processes, resulting in a low output of furfural and virtually making the remaining cellulignin useless (a difficult-to-burn product).

The technology of furfural production in two steps by means of a reactor manufactured with refractory metal (Ti and its alloys, NbTi or NbTa) consists of pumping (3MPa) of the xylose solution (10%) to the continuous or batch-type tubular reactor (manufactured in Ti or Nb alloys), heated with direct steam (190-220^QC). The heating period ranges in1 to 5 minutes, depen- ding upon the temperature and the acid contents. After heating, the solution is expanded in a "flash" tank, esteamating the furfural

Furfural is used as a chemical intermediate extractant in the production of Nylon and other fibers, resins, fungicides, proteins, medicaments and a basic compound in the chemistry of the furans. Furfural is a versatile chemical product, from which a number of aliphatic and heterocyclic compounds may be synthesized. On an industrial scale, it is the source of furfuric alcohol, tetrahydrofurfuric alcohol, furans, tetrahydrofuran and polytetra- methylene ether glycol. Nitrofuran compounds derived from furfural are used as bactericides in human therapy, in the treatment of cocidiosis in chicken and enteritis in pigs.[SANDERS, 1955] Selective solvent in refining oils [El- CHWALD, 1925], extractants for unsaturated hydrocarbons C e C₅ [BUELL.1947; PETERS,1968], among several other applications.

The distribution of the furfural use is shown in the proportions shown in figure 20. The applications are determined by its excellent properti- es as a selective solvent and by its high chemical reactivity, due to its aldehyde group, to the double-valence links and to the configuration of its molecular structure.

Figures 21 and 22 show the chemical products obtained from the main chemical furfural intermediaries. Program BEM opens the perspective for lowering the production costs of furfural, increasing the production to a large scale and to have its application as petrochemical products substituting intermediaries. Figure 24 shows a comparison between the present state of the art and the perspectives of the Program BEM for the production of furfural. This product is the best economic alternative of commercializing products from hemicellulose. The second product is ethanol, which technology by means of the engineered bacterium Eche chia coli is not yet stabilized and the maximum value of the product is US 300,00/t (equal to the minimum value of furfural). The third product is xylitol (dietetic sugar) with high economic results, but with a limited market with regarding the production scale foreseen by the Program BEM. Figure 23 shows the historical evolution of furfural prices. Program BEM enables one to reduce the cost of furfural to its historic value of UU$ 500.00 / tFF.

The present invention was made in two processing campaigns, totaling 13.526 kg ~ 13,5 t of OMMSW. In the first campaign, one took objective data such as humidity, amount of acid sufficient for the prehydrolysis and leaving the refinings as an ideal amount of biomass, reaction time for them to be executed in the second campaign, which were executed with the help of two engineers and two equipment-operation technicians from RM - Materials Refratarios Ltda.

Sociedade Sao Vicente de Paulo with the creation of the "Centra de Reciclagem Antonio Frederico Ozanam" - CRAFO (Recycling Center Antonio Frederico Ozaman) has been doing a work with a view to arouse awareness of selective collection in some districts of Lorena city.

However, in order to carry out this work, the selected organic matter was the Lorena dumping ground itself, located at the Rodovia Itajuba- Lorena between the cities of Lorena and Piquete, in the area of former IPT (Instituto de Pesquisas Tecnolόgicas) (Technologic Research Institute). The refuse gatherers themselves helped in the collection along with the cooperation of members of the CRAFO. In order for the collection to be carried out correctly, days of following-up were necessary, except for the collection of plastics, clean paper, metals, glass, since technologies for recycling these products already exist. Stones and sand also could not be collected, because there would be an increase in the ash contents in the final product, with only the organic matter remaining. Taking advantage of this work, a characterization of the composition of the Municipal waste of Lorena was made by way of exploration, for which purpose one chose a truck that collects waste from distant districts and, after discharging, the waste was mixed and quartered, with 1.1 t remaining for selection, with the results shown in figures 27 and 28. After the waste has gone through a sorting station, it was taken to RM - Materials Refratarios to be washed in a sieve with jets of water for the purpose of decreasing the inorganic contents (earth, sand), then following to the feeder. In the final campaigns, the washing was eliminated because the water for washing Crude waste constitutes a very serious problem of liquid effluent. In industrial production, the question of the ashes will be treated as follows:

1^st) rotary sieve following the selective conveyor;

2^nd) cycloning the ashes after combustion, on the basis of the experience of Bioten Incorporation, an American company that burns rice straw with 20% of ash, provided that the K+Na contents are low (from 10 to 40 ppm).

The reactor was feeding carried out by means of an endless screw that compacts the biomass inside the reactor. The feeding was carried out in approximately equal parts between the OMMSW and biomass Wood, with a view to optimizing the humidity contents of the mass (about 50%), since the humidity of the waste is very high, namely 70%. In addition to wood, other biomasses (grass, straws, twigs, etc.) may also be used, which are shredded in the field and taken straight to the feeder. In this case, one used wood, which was shredded in a compact shredder - Krupp Industrie Teckinix Buckanwalter - with wood chips being gathered in "big bags".

There are three justifications for the use of 50% OMMSW + 50% MD: a) the technology of the Program BEM remunerates the biomass residue in US$ 7.50/TDB, thus enabling one to plant trees in streets, squares, parks and wasteland that is often avoided due to the costs. The required amounts are feasible (6.6 TDB/ha.year), according to analysis on page 35; b) there is today low-voltage and middle-voltage (13KV) network insulation technology with costs of only 20% higher than the non-insulated air network [FU- RUKAWA,2000], eliminating the distributors objection of electric energy against urban forestation [TOMICH, 2000]; c) for densely populated cities with buildings, the possibility of urban forestation is reduced, which is compensated by waste generation with lower earth and humidity contents (lower percentage of food cooked at home and higher consumption of packed food).

The feeding is initiated with a wood layer to made a "bed" on the discharge of prehydrolysate. One managed to complete the reactor with 300 kg in Dry Biomass (DB), which is similar to the charge obtained with eu- calyptus chips.

The prehydrolysis process is divided into 6 operations: flooding, heating, pressurization, recovery of sugar, cellulignin discharge and washing. After feeding and closing the reactor, one adds 100 liters (L) of acidic solution in the proportion of 2.5% of residual sulfuric acid in relation to the biomass - dry base. This acidic solution comes from the solution tank, which is at room temperature. The prehydrolysis process also acts as a technology of cleaning the residual sulfuric acids that are disposed into rivers and in which we can use them as Raw material in the process.

After flooding, stirring is started, with the reactor oscillating around its horizontal axle and the passage of the process heating steam. Part of the steam is condensed in the reactor, and there is a fraction that is purged into a serpentine-type condenser, mounted so as to collect data, with 11.5 m x 1" ¹/2 inner diameter of flexible tubes that discharge the condensate into a tank with a known volume, in order to have the control over the volume of steam that is purged. This purge is carried out with a view to maintaining the temperature at 160⁹C and 6.7 atm pressure.

The process is initiated, opening the steam entry totally until the pressure reaches 6.7 atm and starts to control the steam coming out, so that this pressure is maintained and the temperature reaches 160⁹ C; after this heating of about 22 minutes, the reaction time begins with another 28 minutes, making a total of 50 minutes of prehydrolysis. Due to the heterogeneity of the mass, the heating time of the reaction may vary for about 50 minutes.

The sugar contents (Brix) starts at 5.0 and may reach 19.0, without any risk of decreasing, as is the case of the eucalyptus wood. This fall in the sugar contents in the eucalyptus prehydrolysis is due to the partial conversion of xylose into furfural. In the case of waste, the sugars are composed of xylose, glucose, fructose and others, having a smaller fraction of xylose and, therefore, less conversion to furfural.

The pH of the solution starts at 1.0 and, after reaction with the ashes (earth and sand) and pigments, rises to 2.5. After completion of the prehydrolysis reaction, the prehydrolysate is discharged through an exit in the lower part of the rector to the bottom of an underground tank, so that the steam can condense. After pressure foiling, compressed air is injected (5kgf/cm2) for the complete removal of the prehydrolysate.

For this work, a part of the prehydrolysate was reserved for analysis and the remaining part was neutralized and pumped into a stabiliza- tion tank, coated with a plastic blade (polymeric blend) and dug in the ground for tests of effluent treatment test. In the industrial plant the prehydrolysate will be intended for the furfural, alcohol or xylitol manufacture.

After prehydrolysate discharge, the drinkable water is introduced at the proportion of one part of liquid to one part of solid (L/S = 1) for the first internal washing of the cellulignin for 5 minutes under stirring, with a view to recovering sugar and sulfuric acid, which is called sugar recovery. The sugar recovery solution is discharged with pressurized air in a tank of known volume, twice pressurized to make sure that the whole solution has come out.

After sugar recovery, two internal washings of the cellulignin in the reactor are done with drinkable water in the proportion of L/S = 4 for 5 minutes and under stirring at each washing, for the purpose of reducing the acid contents, one reaches the pH = 3.0. The outlet washing water (OWA) is discharged with compressed air into a large tank and, after neutralization, it is pumped into the stabilization pool for treatment. The internal washing takes time of the reactor, which could be working in the next reaction. In this way, in the industrial operation the washing will be carried out externally in the dumping bucket of the reactor.

After discharging the outlet washing waters (OWA) and making sure that there is no pressure in the reactor, one couples a "big-bag" to a funnel and opens the reactor for the cellulignin discharge. Right afterwards, the "big-bag" is weighed. In the industrial reactor the discharge is made in the washing bucket. There are four drying technologies that may be applied to cellulignin:

1^st) solar drying on slowly-moving conveyors, covered by plastic greenhouses. This technology will not be used because the cost of the con- veyor is high and its efficiency on rainy and clouded days is low.

2^nd) drying in stationary grain (rice) dryers. This technology will be briefly tested, with a view to verifying the losses of the cellulignin fines.

3^rd) drying in a cyclone, which meets all the requirements for being applied. It will be developed if the technology described below is not executed.

4^th) drying in a drying mill overlapping the two grinding and drying functions in the same equipment. This is a technology already tested by Bio- ten Incorporation, in the USA, which utilizes 1% of the combustion gases from the gas turbine in the drying mill. After or before drying, the cellulignin is passed through a 3-mesh

(6.68mm) sieve in order to remove some non-organics that may have passed on through the initial selection and to separate the cellulignin into coarse and fine. Then the coarse cellulignin passes through a hammer mill - Brand Tigre No. 9030 Type C7 - with 0.7 mm sieve, because it contains many pieces of hydrolyzed wood. Then it is passed, together with the fine cellulignin, through the 0.3mm sieve. The handling is made in a "big-bag" on the pilot scale and with buckets on the industrial scale. During the grinding there is sufficient recirculation of air to keep the cellulignin cold. This is a fuel that only ignites after having been heated up to 350⁹C, thus being safer than gaseous and liquid fuels, which ignites at room temperature. During the prehydrolysis, the hemicellulose is digested, eliminating the volatile fraction responsible for propagating grass and atraw fire in nature. The cellulignin does not contain hemicellulose and needs to be heated up to 350⁹C in combustors to be burned. In this regard, the cellulignin is an ideal fuel, that is to say, it is not incendiary. Following the sieves, it advisable to install a magnetic separator for collecting metallic parts that might damage the mills.

After the grinding, the cellulignin is stored in a stationary or mo- vable cylindrical tank. At the base of the tank, there is a helical dosing device that controls the rate of feeding cellulignin into the combustor. The cellulignin is hauled in the air proportion: cellulignin ratio of 3.2: 1 in weight. In the combustor the ignition is initiated with micro-blowtorches of liquefied petrol gas LPG, natural gas or diesel oil. The power of the LPG micro-blowtorches ranges from 3 to 5% of the cellulignin power consumed in the rector.

The effluent treatment is composed of the following equipment: aerator, Sludge separator and demineralization (sand filter, activated charcoal filter and columns of cationic, anionic and mixed resins). However, within the concept of zero pollution, the washing water will be totally recycled at two treatment levels:

1^st) after the activated charcoal, when cellulignin is not intended for gas-type turbine.

2^nd) After the demineralizer, when the cellulignin is intended for the gas-type turbine. The water of the boiler for generating steam will always be demineralized.

The hydric balance allows that, by collecting rain water in a stabilization tank, one can virtually avoid taking water out of artesian wells, approaching the concept of null consumption and discharge of water. Only on a few days of a heavy-rain in a year there will be discharge of rain water, and in the period of dry winter (when there is intense esteamation) one would take water out of the artesian well.

The analytic program is described by the following steps:

- humidity contents (HC): An amount of OMMSW is collected at random so that it will be quite heterogeneous. Due to the heterogeneity of the material, humidity is provided in large amount, in order to minimize the error. Samples of about 120 kg of wet biomass are weighed in an industrial balance, taken to the bell- shaped oven and left to dry at a temperature of 120⁹C until the material is completely dried. Due to the delay in drying, a smaller amount of approximately 10 kg was employed, and one noticed that the same proximity of results was maintained. On this smaller scale the drying was carried out in la- boratory ovens until the material was completely dried. It is removed and left to cool in a desiccator. After cooling, one weighs it in a precision balance, and the calculations are made according to the following schema.

- Ashes Measurement (AM)

Since the material has already been dried for measuring the humidity contents, the same sample is weighed on an industrial balance and burned in a bell-shaped oven at 500⁹C until the burning is complete. In a smaller amount, the material is in a muffle at 600⁹C until the burning is complete (ash appearance). It is removed and left to cool in a desiccator. When it is cool, it is weighed in a precision balance, and the calculations are made as shown in the following schema.

- Representative schema (figure 25) of the weighing of samples and definition of parameters:

Humidity Content (0 < HU < 1)

HU(%) = HB-DB "H2Q , _m _ _m f HC BH ^mH20 ~ ^msolιd i-HC ^mH20 ^+msolιd Caption:

HC: humidity contents

Solid Content (0 < SC < 1) : DB: Humidity base

DB: dry base

SC (%) =— = solid → m_H20 = m_solιd

BH m_H20 +m_solιd SC TOrg: organic contents

As: ash

UH+SC =1 iT)H2o: water mass

Organic Contents . m_Solιd solid mass m_org organic mass

OrgC( ) = °3 — y° ITIAS ash mass

DB m_0rg +m_As

AshContents :

Ac AC (%) = — = — "As "As DB m, ^{→ m}As ^{= m}Org

Org ^{+ m}As 1-TAs

TOrg + TAs = l - Analysis of the sugar contents in the Prehydrolysate:

Figure 26 shows the conventional analytic methods employed in following up the acidic processing of biomass, the detailing of which is in the reference.

The main methods are: - Reducing Sugars:

Ebulliometric: using Fehling solution Volumetric: Somogyi using Fehling solution; Somogyi - Reagent 1952

- Potential Furfural: AOAC using HCL 12% (w/w)

There are more modern methods (ultraviolet spectroscopy and high-performance liquid chromatography - HPLC

- Parameters used by the Centra de Tecnologia da Copersucar - CTC - Piracicaba - SP, for analysis of the sugar contents in the prehydrolysate, acids and furfural formed during the prehydrolysis.

For analysis of carbohydrates (sugars), one used: • High performance Liquid Chromatography -HPLC - Rl

SHIMADZU - Refraction Index Detector, model RID-6A.

• High performance Ionic Chromatography - HPIC - PAD " DIONEX - Amperometric Pulse Detector, model ED40. Methodology: Determination of Sugars, Glycerol and Ethanol by Li- quid Chromatography. Worked out by the CTC from ASBC, 1976 and ICU- MSA, 1998.

For analysis of the organic acids, one used:

• High Performance Liquid Chromatography - Ultraviolet - HPLC - UV SHIMADZU - Ultraviolet Detector

Methodology:

• Determination of Organic Acids by Liquid Chromatography Worked out by the CTC from "JOURNAL OF CHOMATOGRAPHY", 1987.

For analysis of anions, one used: • High Performance Ionic Chromatography - HPIC - PAD --

DIONEX - Amperometric Pulse Detector, model ED40. Methodology: - Determination of Anions, Fluoride, Chloride, Nitrite, Nitrate and Sulfate. Worked out by the CTC from "SM - 16th Ed., STANDARD METHODS".

For analysis of the furfural and hydroxymethylfurfural one used:

• High Performance Liquid Chromatography - Infrared HPLC - IR SHIMADZU - Refraction Index Detector, model RID-6A.

Methodology: Determination of Sugars, Glycerol and Ethanol by Liquid Chromatography Worked out by the CTC from ASBC, 1976 and ICU- MSA, 1998. - Environmental Analysis of the Prehydrolysate:

Parameters used by Ambiental Laboratόrio e Equipamentos Ltda, Sao Paulo - SP.

- Analysis of the OMMSW prehydrolysate - 260699-1 (100% OMMSW), and wood washing water. (Table 8.12), - Analysis of the prehydrolysate, washing water, treated effluent,

Crude effluent - (Table 8.14) and Sludge (Table 8.17 - 8.17.5) of the OMMSWW - 210300-1 (50% OMMSW with 50% MD).

Methodology: ("Standard Methods for the examination of water and wastewater" SM - 20th Edition) Metals: Atomic Absorption Spectrophotometry

(Spectrophotometer PERKIN-ELMER Mod. ANALYST 100) DBO: Dilution and Incubation 05 days, 20⁹ C DQO: Open Reflux

Total Phosphor: Colorimetry - Spectrophotometer HACH Mod. DR 2000

Nitrogen: Titrimetry pH: Direct Reading pH meter DIGIMED Solids: Gravimetry

Sulfate, Phosphate, Silica, Chromium, Cyanide and Phenols: Colorimetry (Spectrophotometer HACH Mod. DR 2000). Chloride: Titrimetry.

Ashes: Calcination/Burning (Muffle Oven - Fornitec Mod.1863). Sludge: Leaching Essay (Rule NBR 10005 of the ABNT) and Solubilization Essay (Rule NBR 10006 ABNT). Note: The Sludge is from the pilot treatment, as shown in the industrial flow diagram in figure 36.

- Cellulignin analysis: Analysis of the wood cellulignin were made, combustible constituted by a preliminary analysis (Fixed Carbon, volatile material, ashes and humidity), ultimate analysis (C, H, O, N, S, CI, Ashes, humidity and Inferior Caloric Power IPC), water-soluble alkalis (Na₂θ, K₂0, CaO), elementary composition of the ashes (Si0₂, Al₂0₃, Ti0₂, Fe₂0₃, CaO, MgO, Na₂0, K₂0, SO₃, P2O₃, Cl₂, others, undetermined) and total elementary composition (Ca, K, Na, Mg, P, Al, Si, Mn, Fe, Sn, S,).

- Parameters used by Dr. Rosa Ana Conte for analyses of the inorganic impurities concentration in the Eucaliptous grandis and in the Cellulignin Samples:

Eucalyptus Wood ⁽¹⁾

Normal Cellulignin (Water Artesian Well - WA) ⁽¹⁾

Non-washed Cellulignin (Deionized Water - DW)⁽¹⁾

Washed Cellulignin (DW)⁽²⁾ Equipment:

⁽¹⁾ Quantitative Analysis by Inductive Coupled Plasma _ Absorption Energy Spectroscopy (ICP-AES).

⁽²⁾ Semi-quantitative Analysis by XRF, graft for Na Atomic Absorption Spectroscopy (AAS-flame) and K (ICP), both referring to detection limits. RESULTS OF THE INVENTION:

A town with 70,000 inhab. and that generates 45 tons of wet waste a day (0.64 kg/inhab.day) was considered. The following composition of the waste was measured: 75.5% of OMMSW, including dirty paper and 24.5% of recyclables (11.7% of plastics, 7.8% of clean paper, 2.3% of glass, 0.3% of aluminum and 2.4% of other metals - fig. 27). The fraction of 75.5% of the OMMSW presented the following composition: 88.9% of organic matter, 10.0% of ashes; 0.1% of batteries, and 1% of plastics, glass and metals not collected by the gatherers (figure 28). The final composition will therefore be 67.1% and the ash contents will be 7.6%. Obviously, the above values are only illustrative, because the waste is an extremely heterogeneous material with significant variations from lot to lot. (Only after the CEPIL operation it will be possible to obtain statistic averages). It will be necessary to process 34.01 of humi- dity OMMSW, of which only 30.21 is effectively organic matter.

The dump of Lorena is located at Rodovia (Highway) Itajuba-

Lorena between the cities of Lorena and Piquete in the area of the ancient

IPT (Instituto de Pesquisas Tecnolόgicas). This is a totally contaminated area with a spring of a river that passes in the middle of the whole waste, for which the City Hall has been repeatedly fined by CETESB.

Since May 2000, the Centra de Reciclagem Antonio Frederico Ozanan - CRAFO is responsible for collecting waste from Lorena city and also responsible for recovering the dump area, as shown in figure 29. The banks of the creeks are being cleaned, the collected material and that remaining in the area are being covered with earth in order to continue the reforestation in the beginning of 2001.

In some points of the city selective collection is being carried out, this material being taken to a storage area in the dump, in which it is sold. With the implantation of the CEPIL, sorting and recycling city refuse will reach 100%.

In order to achieve a typical balance of mass of the OMMSW, 13.51 of OMMSW were processed for the process optimization. These data are shown in figure 30 and table 3. The data were taken for the purpose of defining quantitative data for the plant of CEPIL. The following results are pointed out: 1^st) the dry-matter contents of the OMMSW is of 30.1% and humidity is 69.9%. These values show the economical disadvantage of processing only the OMMSW, because this will result in filling a large fraction of the reactor with water. Water is a component that requires a high consumption of energy in heating, without resulting in a saleable product. 2^nd) The OMMSW mixture with dry wood has enabled one to achieve 300 kg of dry biomass in the 1.2m³ reactor, which is the same value achieved by pure wood.

3^rd) The liquid/solid relationship (US) was of 2.8, not much higher than the L/S value used for pure wood. 4^th) The L/S relationship in washing water was of 5.5, very close to the value 6 utilized in processing wood.

5^th) The consumption of acid used in processing OMMSW is of 2.5% due to the ashes contents in the OMMSW of 12%, of which 0.5% is potassium from the earth which consumes the acid, thus being higher than the amount of acid used in processing wood, which is of 1.7%, wherein the potassium contents comes from the nutrients of the plant and the sodium from the common salt. Although the consumption of acid of 2.5% is higher, this does not render the economy of the process unfeasible. In cites with a high index of asphalt covering and paved backyards, the ash contents drop to values on the order of 2%, very close to those of wood. The waste from Sao Paulo and Rio de Janeiro cities are real urban forests. 6^th) Table 4 shows the consumption of energy in the wood prehydrolysis and the calculus memorial 8.3 shows the same calculus in the OMMSW prehydrolysis. One can realize that the energy consumption in the first case with pre-heating of water up to 80^QC (item b.2 - table 8.2), is close to the consumption of energy of the second case, with pre-heating of water up to 120⁹C (item b.3 - table 8.3). The heat-exchanging tank/acidic solution tank for processing wood and OMMSWW are similar as shown in item 8.3

Table 3 - Typical Balance of the OMMSW Prehydrolysis Mass a) GENERAL MASS BALANCE Inlet Outlet 186 wood 605 cellulignin

472 OMMSW

7 acid

100 solution water 280 prehydrolysate(ρ = 1 ,025 x 10³ kg/m³)

372 boiler steam 399 water + solid hauled condense wa- ter (p = 1 ,0 x 10³ kg/m³)

400 water of SR 323 SR (p = 1 ,01 x 10³ kg/m³)

620 water IWW1 580 water OWW1 (p = 1 ,0 x 10³ kg/m³)

620 water IWW2 590 water OWW2(p = 1.0 x 10³ kq/m³)

2777 2777 b) BALANCE OF DRY MASS

158 wood 219 cellulignin

142 OMMSW 35 prehydrolysate 6 solid hauled by the condensed water 20 SR-Sugar Recovery

14 water OWW1 (Outlet washing water) 6 water OWW2 300 Total Biomass (TB) 300 c) HYDRIC MASS BALANCE AND ACID AT THE EXIT

28 wood 386 cellulignin

330 OMMSW

100 solution water 245 prehydrolysate 372 steam from the boiler 393 condensed water

830

830 Process water = = = 2,8

/S 300

400 water of SR 303 SR

620 water IWW1 566 water OWW1

620 water IWW2 584 water OWW2 2470 Total water 2477^**

1240 Inletting Wash Water (IWW ) ___> % = ^mw^ ^SR = ^÷⁴⁰⁰ = 5,5

** This difference is of the entering acid that is not considered in the hydric mass balance. In doctorate graduation the acidic mass balance will be made. IWW - Inlet Washing Water

TB - Total Biomass OWW - Outlet Washing Water SR - Sugar Recovery

Table 4. - Calculation Memorial of the Energy Consumption/ TDB in the Wood Prehydrolysis a) Biomass Heating (35% wetness; Cp= 2,345 MJ/TDB^eC) [CAMARGO,90]

Q = mShΔT =1 x 2,345 x (160-20) = 328,30 MJ/TDB b) Heating of 2t de water (L/S=2 used in processing wood) h^a ₂₀= 83,96 kJ/kg (water) p h^a= specific enthalpy of water h^aso= 334,91 kJ/kg (water) h^v= specific enthalpy of steam

calorific power of cellulignin h^vι 60=2.758,10 kJ/kg (steam) Sh = specific heat

H_CL= 20MJ/kg (combustion of cellulignin)

[CAMARGO.C.A., Preservation of Energy in the Sugar and Alco- hoi Industry - IPT -, 1990]

Note: A wood reaction produces 80% of cellulignin and 20% of prehydrolysate. b.1 ) A From water at 20⁹C

Q = mΔh → Q = m(h^aieo - h^a ₂₀) = 2 x 10³ (675,55 - 83,9)= 1.183,18 MJ/TDB

Percentages on energy contained in the cellulignin 328,20 - 83.18 ₅

10³ x0,8x20 b.2) From water at 80⁹C m(h^a ₁₆₀ - h^a ₈₀) = 2 x 10³ (675,55 - 334,91) = 681 ,28MJ/TDB Percentages on energy contained in the cellulignin

328,20 + 681 ,28

= 0,0631 = 6,31 %

10³ x 0,8 x20 c) Steam required for 80^eC.

(328,30 + 681 , 28) x10³KJ/TDB _cel . ^^_r.

(2.758,10)KJ/kg ^{= 366kg dΘ Va} °^r/TDB d) Efficiency of the boiler = 90% e) Consumption of cellulignin for steam production

(328,30 + 681 ,28)MJ/TDB _{γQ cιmB} 0,9xO,8x 20 MJ/kg f) Consumption of energy by the Tower-type reactor (US = 12 water - conventional processes)

Q= m(h^v ₁₆o - h^a ₈₀) = 12 x 10³ (675,55 - 334,91)= 4.087,68 MJ/TDB

Percentage on energy contained in the cellulignin 328,20 + 4.087,68 _{= =}

10³ x0,8x20 g) Consumption of energy by percolation reactor (US = 12 - steam) Q= m(h^v ₁₆o - h^a ₈o) = 12 x 10³ (2.758,10 - 334,91)= 29.078,28 Percentage on energy contained in the cellulignin 328,20 +29.078,28

= 1 ,840 = 184%

10³ x 0,8x 20

Note: In the COALBRA - wood coke and alcohol, in Uberlandia - MG there was steam recovery in the "flash", lowering the energy consumption to 100% that is, for the processing of 1TDB another TDB was burned in the boiler. > Solution Tank/Heat Exchanger:

• Volume of the Tank (V):

• Volume of

1 ,5 weight of biomass (cellulignin humidity =50%)

• Weight of the Biomass (P) = 4,5 1; V_PH = 1 ,5x4,5=6,75m³ Vi= πr²nL=6,75 m³ (n=19 internal tubes)

Vi= πr² x 19 x 3 = 6,75 r = 0,194 m

. ώ -5x2r 3,0-5x2x0,194 λ= - = — ^! = 0,176m

6 6 • Volume of solution (V_s); Weight of the solution (W_s)

V^V-πr² nL (n=19) V_s=21 ,20 - π(0,194)² x 19 x 3

V_s= 21 ,20 - 6,74 = 14,46 m³

P_s> 2 x P(biomass)= 2 x 4,5 = 9t

Solution Tank/Heat Exchanger Heat Transfer between tubes and tanks q=UAΔT; U= — — _; r — U= global transfer coefficient

— 1 + — A -, —r_β —/r, + — A, — ^~ h, 2πKL h_ΘA_θ hi = he = 890— ^— (HOLMAN.J.P - Heat Transfer-McGrawhill - p. m²²C

13)

A, r_; 0,194

— = - = (thickness 3mm)

A_e r_e 0,197

A_j = 2πriL = 2^(0,194) x3 = 3,657m² K_inox = 16,3W/m°C; K_Ti = 17,2 W/m°C

W

U = - = 415-

(1, 12 + 0,18 + 1, ll)xl0^~3 m^2oC

The significant portion for the obtention of the U is due to the coefficient of heat transfer by convection • Incrustation Factor (R_f):

U = 0,002 (water of the boiler) [HOLMAN, J.P., Heat Transfer - McGraw-Hill - p. 502] R_f = .^*. = R_f +

U dirty U clean IJ dirty u clean

R_f = 0,0002m² °C/W ¹ = 0,0002 + — = 0,0002 + 0,0024 = 0,0026

U^ 415

U_dirty = 383W/m²°C

At first, the incrustations should not influence the heat exchanges. • Central Tube for heating the boiler water (80⁹C) q_t=UAΔT = heat exchange power = U2πrλΔT qt= 385 x 2π x 0,346 x 3 x (80-20)=150,6 KW q_n= power required =— ;t = 60min

steam mass (m) = 33% of the mass of biomass = 1.500 kg (see table 8.2. - Consumption of Energy/TDB - item C) 1500 x 4,18 x 10³(80 - 20) _κw ⁿ 60x 60

There is feasibility in heat exchanging, because this is a batch process.

5 The heat exchange capacity is virtually 50% higher than the heat required for pre-heating the boiler water.

• Heat Exchange prehydrolysate/acidic Solution.

Q_t = Ux2πrLxnxΔT = 385x2πrxO,194x3x19x(l 00-80)

Q_t = 479,9 KW

Q_n = heat neesaaryfor heng the solution (return heat from the reactor)

_{Qn =}i_^ _{= 6}0_min

₌ 9-000*4,18x10³(80-20) ⁿ 60x60 ⁿ '

Thermal balance 10 Heat of the prehydrolysate + heat of washing water > heat for pre-heating the boiler water + solution-heating heat.

6.750 x 4,18 x 10³ (160-80) + 6.750 x 4,18 x 10³ (100-80) > 1.500 x 4,18 x 10³ (80-20) + 9.000 x 4,18 x 10³ (80-20) 2.257,2 MJ + 564,3 MJ > 376,2 MJ + 2.257,2 MJ 15 In addition to the heats on the left, there is the steam return heat from the biomass heating which is small in the case of wood.

• Sequence of Heating:

1. Reactor heating (steam stocked in the boiler)

2. Flooding with acidic solution preheated by the previous reacti- 20 on.

3. The return heat heats the solution for the next reaction. The operations of filling and heating the acidic solution tank with return steam are simultaneous. The volume of tank/heat exchanger should be maximized in order to decrease the simultaneousness.

25 4. Discharge of the prehydrolysate. A greater contribution of heating the solution tank. This heat is consumed for preheating the boiler water and the solution to be created in the next reaction.

• Cost of the Solution Tank/Heat Exchanger. Volume of material (VM); Weight of the Titanium (W-π) and Weight of the lnox (Wj_noχ). v, (e = thickness)

V_M =[τrx3x3 + 4^^- + 19x 2πx0,200 x3]x3x10^~3

V_M = (28,26 + 28,26 + 71 , 60)x3x10^"3 = 0,384m³

W-Π = 0,384m³ x 4.500kg/m = 1.728kg

Wjpox = 2x0,384m³ x7.600kg/m³ = 5.836,8kg - (Fator 2 of overmetal - corrosion) Material cost : {titanium = 1.728 kg x R$ 82,50/kg = R$ 142.560,00 { inox = 5.836,8kg x R$ 8,00/kg = R$ 46.695,00

Obs. : Titanium in the international market costs half the price of Brazil.

Table 5 - Theoretical Calculation Memorial of Energy Con- sumption/TDB in OMMSW Prehydrolysis a) Biomass heating:

Specific Heat Dry Biomass = 1 ,77 KJ/kg⁹C Specific Heat of water = 4,18 KJ/kg⁹C

Specific Heat of the Biomass with 70% H₂0

Cp=0,3 x 1 ,77 + 0,7x 4, 18 = 3,46KJ/kg⁹C

Q = mCpΔT = 1 x 3,46 x (160-20)= 484,40 MJ/TDB b) Heating of 2,81 of water (US = 2,8) h^a ₂₀= 83,96 kJ/kg (water) h^a= water enthalpy h^a ₈₀= 334,91 kJ/kg (water) h^v= steam enthalpy h^ai₂o=503,71 kJ/kg (water) H_CF calorific power of cellulignin h^a ₁₆₀= 675,55 kJ/kg (water) Cp = specific heat I ₆₀=2.758, 10 kJ/kg (steam) H_ci= 20MJ/kg (combustion of cellulignin)

[CAMARGO,C.A., Preservation of Energy in the Sugar-and-

Alcohol Industry - IPT -, 1990] b.1)From water at 20⁹C (US= 2,8) m(h^a ₁₆₀ - h^a ₂₀) = 2,8x10³ (675,55 - 83,96)= 1.656,45 MJ/TDB Percentages on energy contained in the cellulignin

484,40 -. 1656,45 _{= 38 = 1 8%} 10³ x0,8x20 b.2)From water at 80⁹C m(h^a ₁₆₀- h^a ₈₀) = 2,8 x 10m³ (675,55 - 334,91) = 953,79MJ/TDB

Percentages on eenneerrggyy ccoonnttaaiined in the cellulignin 484,40 + 953,79 = 0,090 = 9,0%

10³ x0,8x20 b.3)From water at 120⁹C (Pressurization of the tube for prehea-

5 ting boiler water in the heat exchanger of the acidic solution tank 0,19MPa) m(h^a ₁₆₀- h^ai2o) = 2,8 x 10³ (675,55 - 503,71) = 481 ,15 MJ/TDB

Percentage on energy contained in the cellulignin 48440 + 481 ,15 _{= {}, _0%

10³ x0,8 x20

Note: This value is close to that of item b.2 of Table 8.2 for the

10 energy consumption in wood prehydrolysis with preheating of water at 80⁹C. c) Necessary steam: c.1) From water at 20⁹C

(484,4 + 1656,5)MJ/TDB __{e nI} , . _-.__ — = 776,2kg of steam/TDB

(2.758,10) KJ/kg c.2)From water at 80^eC ι c (⁴⁸⁴'⁴ + 953,8)MJ/TDB _no . , . , __ _

15 ^! — - = 521 ,4 kg of steam/TDB

(2.758,10) KJ/kg c.3)From water at 120⁹C

(484,4 + 481 ,2)MJ TDB _{cn nl} , . ___ — = 350,0kg of steam/TDB

(2.758,10) KJ/kg

7th) However, the consumption of steam measured in the pilot plant was of 1.24 kg of steam/kg of OMMSWW, corresponding to a value

20 1.60 times as high as the calculated value of 0.776 kg of steam/kg of OMMSWW (item c.1 - Table 5). The cause of this discrepancy is that the OMMSW is a more heterogeneous material and offers easier percolation ways for the passage of steam and, consequently, lesser heat exchange. Possibly the OMMSW grinding in a hammer mill without a sieve will improve 5 this heat exchange. Anyway, it is feasible to recover much of the excess steam consumed through the acidic solution Tank /heat exchanger (item 8.3). The steam consumption of 1.24 kg/TDB represents 21.4% of the energy contained in the cellulignin, a value that is still economically acceptable.

8^th) The volume of prehydrolysate generated in the OMMSWW of 0 0.93, which is smaller than the W prehydrolysate of 1.5. Consequently, the cellulignin of the OMMSWW with 63% of humidity is equal to the cellulignin humidity of the W, which is about 64%.

9^th) The behavior of the washing is similar in both cases.

10^th) The cellulignin output of the OMMSWW of 73% is a little lower than the cellulignin output of the W of 80% and, coherently, the Brix in the OMMSWW of 12.5% is higher than that of the W of 9.0%.

11.) The 45 t/day of wet waste from Lorena represent 34 t/day of OMMSW which contains 10.2 t/day of dry biomass. Operating in the proportion of 50% OMMSW + 50% Biomass it will make a total of 20.4 TDS/day; this represents 27.2% of the nominal capacity of 75TDS/Day of an industrial reactor providing two conditions:

1^st) high operational safety in the beginning of the operations;

2^nd) possibility of treating the waste from Lorena (74,970 inhab.) Canas (3,118 inhab.), Cachoeira Paulista (26,813 inhab.), Piquete (15,437 inhab.), Guaratingueta (103,433 inhab.), Aparecida (35.102 inhab.) and Po- tim (13,874 inhab.), making a total of 272.747 inhabitants, which is in a radius of economic transport of the OMMSW to the CEPIL. Lorena city represents 27.5% inhabitants of the cities selected for waste processing.

12^th) This conclusion is a strong indication that the integrated tre- atment of waste may also be an option of lesser investment than embankments, in addition to all the other advantages already presented. The cost for "ditch embankment" (which does not meet the requirements of a "sanitary embankment" completely) ranges from R$ 30 thousand to R$ 60 thousand (US$ 17 thousand to US$ 34 thousand) for small towns of 15 thousand inhabitants. For a population of 272,747 inhabitants the value would range from US$ 309 thousand to US$ 618 thousand, which should be compared with the value of US$ 1 ,000 thousand for investment in the waste integrated processing. With the technology development, it will be possible to process 100% of waste (without Biomass), reducing the investment by a half. In addi- tion, the integrated processing generates profits which sanitary embankments do not generate.

13^th) In figure 31 , one can follow up a typical reaction of OMMSW prehydrolysis in function of the sugar contents - Brix. As the digestion of the hemicellulose takes place, the sugar contents increase. Please note the peak of about 10-20 min; that is when explosion of the cellular wall takes place, according to the description in chapter 6. In the industrial process, 20 minutes of heating and 20 minutes of reaction will be used, making a total of 40 minutes. In this way, after the explosion period (distance of 600 nm between the microvolcanoes) there will be hydrolysis by diffusion of the hemicellulose molecules (74 nm) between the craters of the microvolcanoes. Figure 32 shows the flow diagram of the prehydrolysis mass acidic balance of acidic with internal washing for the case of wood, tables 6 and 7 show the measured and foreseen balance of mass relating to figure 70. In this case, it is feasible to recover the heat of the prehydrolysate, preheating the boiler water and the acidic solution, due to the fact that the steam con- sumption is low (366 kg of steam/TDB - item c table 4). For the case of OMMSW prehydrolysis, it is impossible the complete heat recovery, because of the higher consumption of steam due to the high waste-humidity contents and mainly due to the higher purge of steam, to maintain the rector at 160⁹C during the prehydrolysis. Figure 33 and table 8 illustrate the calculations of an acidic solution tank, to recover the heat of OMMSW prehydrolysis. One concludes that a complete recovery is impossible, because the available heat (11.37 kW) is more than the required heat (1.33 kW).

In this way, the best alternative is to work with two prehydrolysis reactors in series (by the way, as the configuration of prehydrolysis of the program BEM has always been considered), to recover part of the purge heat from a reactor during the prehydrolysis in heating the mass of the second reactor.

Table 9 shows the recovery calculation of a part of the heat from the purge steam by preheating the mass of the second reactor. Admitting the heating of the second reactor up to 100⁹C (atmospheric pressure, without affecting the prehydrolysis conditions of the first reactor) there will be a reduction from 5985 t (6 t) to 4498 t (4,5 t) in the primary steam consumption, because the injection of the latter will take place in an already preheated reactor. From this amount, 1487 kg will be condensed in the second reactor and the remaining 3,377 kg (3.4 m³) to be condensed by the Belfano-type washing Tower (figure 34) will need 28.9 m³/h for condensing the escape steam after the second reactor; if a part of the escape steam is not recovered in the second a washing tower of 49.3 m³/h would be necessary.

It is highly likely that one can pressurize the second reactor during the recovery of the escape steam, achieving a greater reduction in the steam consumption and in the size of the washing tower. Anyway, the washing towers are available at a low cost on the market for capacities involved in both the steam volume to be condensed and the volume of water used in the condensation.

The condensation water from the acidic solution tank/heat exchanger and from the washing tower is clean water, which will be used in recovering sugar, acidic solution and probably in the washing water from the cellulignin, because much of its acidic contents has been absorbed in the second reactor.

Table 6 - Mass Measured Balance from Wood Prehydrolysis. (Measured) a) G GEENNEERRAALL MMASS BALANCE

Inlet Outlet

250 wood 468 cellulignin

3,6 acid

450 solution water 369 prehydrolysate (ρ= 1 ,025x10³ kg/m³)

143 boiler steam 100 water + solid hauled condensed water (p = 1 ,00)

220 water RA 160 RA (p = 1 ,00) 00 water IWW1 390 water OWW1 (p .-- 1 ,00)

400 water IWW2 380 water OWW2 (p = 1.00)

1867 1867 b) BALANCE OF MASS (DRY BASE) 212 wood 168 cellulignin

29 prehydrolysate

0 solid hauled by the condensed water

5 RA

7 water OWW1

3 water OWW2

212 Total Biomass (BT) 212 c) MASS HYDRIC AND ACIDIC BALANCE AT THE EXIT

38 wood 300 cellulignin 450 solution water 340 prehydrolysate

143 boiler steam 100 condensed water

631 Process water ---> / = ⁶³¹ = 2,98 212

220 water of SR 155 SR

400 water IWW1 383 water OWW1

400 water IWW2 377 water OWW2

1651 Total water 1655

1020 Inlet washing water (IWW) _ IWW +SR _ 800 + 220 . _Q

RT 212 ^{= 4}'^{81 **} The difference is of the inlet acid that is not considered in the mass hydric balance. In doctorate graduation the mass acidic balance will be made.

IWW - Inlet Washing Water BT - Total Biomass OWW - Outlet Washing Water SR - Sugar Recovery

Table 7- Foreseen Mass Balance of Wood Prehydrolysis (Prediction)

Reaction a) GENERAL MASS BALANCE MD 200400-1

Inlet outlet 250 wood 468 cellulignin

3.6 acid 250 solution water 269 prehydrolysate (p = 1 ,025 x 10³ kg/m³)

143 boiler water 0 water + solid hauled condensed water (p = 1 ,00)

220 water of SR 160 SR (ρ = 1 ,00)

400 water IWW1 390 water OWW1 (p = 1 ,00)

400 water IWW2 380 water OWW2(p = 1.00)

1667 1667 b) MASS BALAN DRY BASE)

212 wood 168 cellulignin

29 prehydrolysate

0 solid hauled by the condensed water

5 SR

7 water OWW1

3 water OWW2

212 Total Biomass (BT) 212 c) MASS HYDRIC AND ACIDIC BALANCE AT THE EXIT 38 wood 300 cellulignin 250 solution water 240 prehydrolysate 143 boiler water 0 condensed water

431

431 Process water 2,03 212

220 water of SR 155 SR

400 water IWW1 383 water OWW1

400 water IWW2 377 water OWW2

1451 Total water 1451

Inlet Washing Water (IWW)

IWW + SR 800 + 220

= 4.81 = BT 212

Table 8 - Calculation Memorial of the Acidic Solution Tank and Heat Exchanger Heat Transfer

U= Global coefficient of heat transfer

A= average of the internal and external area

Bearing in mind that on each surface r_e~ n

In r_e/n = In 1=0; = = A_{e u} _

W hi - he - 890 m²⁹C

[HOLMAN, J.P - Heat Transfer - McGrawhill- p. 13) Incrustation Factor or Incrustation Resistance (R_f):

R_f = 0,0002m² °C/W [Holman,1983]

¹ = 0,0002 + — = 0,0002 + 0,00225 = 0,00245

U_dirty 445

U_dirty =408,6 W/m²°C

At first the incrustations should not influence the heat exchanges Volume and area Tanks calculation: • Water for the Boiler:

300 kg DB → 372 boiler steam (fig.8.4) (pilot reactor) 4,5 t of DB → x -=> x = 5,58 m³ of steam in the industrial reac- tor

First Water Tank: -(10,24-9,86)x3 = 0,90m^£

S = πDL =» S = πx3,14x3,0 = 29,59m²

- Second Water Tank: = -(5,29 -3,61)x3 = 3,96m³ _v= -,_{st +}

S = πDL =» S = πx2,30x3 = 21 ,67m² 2^nd water Tank = 3,96 + 0,90 = 4,86m³

S= 1 st + 2^nd Water tank = 29,48 + 21 ,67 = 51 ,15 m² Note: The volume of 4,86 m³ is smaller than 5,58 m³, however, as will be seen later, the absorption of escape heat in the 2^nd reactor will reduce the steam consumption.

• Condensate: 300kg de DB → 399 kg condensed steam (fig.8.4)

4,5 t de DB -> y => y = 5,99 m³ condensed steam

- First Condensate Tank

V = -(3,14² -2,30²)x3 = -(9,86 -5,29)x3 = 10,76m³

- Prehydrolysate Tank or Second Condensate Tank

V = -(1 ,9² -0,80²)x3 = -(3,61 -0,64)x3 = 7,0 m³ 4 4

S = πx1 ,9x3,0 = 17,90 m²

• Acidic Solution: (Water 1 ,5 m³ e Acid 112,5kg H₂S0₄ )

Water: 300 kg de DB → 100 kg of water for the acidic solution (pilot reactor - fig.8.4) 4,5 t de DB → t => t =1 ,5 m³ of water for the acidic solution (industrial reactor)

Acid: 300 kg de DB → 7,5 kg of H₂S0₄ (fig. 8.4)

4,5 t de DB → u => u = 112,5 kg of H₂S0₄ (industrial reactor)

- Acidic Solution Tank

V = — xL → V = -(0,8)² x3 = 1 ,51 m³ 4 4 '

S = πxDxL -=> S = πxO,8x3,0 = 7,54 m²

• Heat Available in the Condensate from the Escape Steam.

Without Recoverv of Heat in the 2^nd Reactor m = 4.860 kg of steam (maximum capacity of the boiler) q_c= m(h^v ₁₆₀- h^a ₁₀o) = 4.860(2.758,1 - 419,0) = 11,37 MJ h^v ₁₆o, h^a ₁₀₀ [WYLEN,1994]

Recovery of Real Process Heat m = 4.498 kg of steam (real process capacity) q_c= m(h^v ₁₆₀- h^aιoo) = 4.498 (2.758,1 - 419,0) = 10,52 MJ

With Recoverv of Heat in the 2^nd Reactor (calculations in item d table 8.7) q_c= m (h^v ₁₃o- h^aιoo) = 3.337 (2.720,5 - 419,0) = 7,68 MJ

• Necessary heat for heating the Boiler water + Acidic Solution: q_n = m(h*₀ - h ₀ ) = (4.860 + 1500)(334,9 - 84,0) = 1 , 60 MJ

g_n = ¹ -^60MJ = 1.333KW 20min x60s reactor optimization time: 20 minutes.

• Heat Transfer q_t = UAΔ T = 408,6(29,48 + 21 , 67 + 1

q_t = 408,6 x (82,73)x 40 = 1.352KW

Obs.1 : The thermal coefficient ΔT = is an average be-

tween the hot water of the condensate and the entry of cold water.

Obs.2: There is a balance between the required heat and the capacity of transferring heat by the contact surfaces.

Obs.3: Heat Available in the condensate (6,93MJ) is much more intense than the necessary heat for heating the boiler + acidic solution, a washing tower being necessary with the calculations detailed in item g - table 9.

Obs.4: Enthalpy h₁₃₀ is the temperature average of 160⁹C which came out of the reactor pressure and 100^QC at the atmospheric pressure.

Table 9 - Part of the Purge Heat Recovery of a Reactor in another Reactor a) Heating of the Biomass (Cp= 2,345 MJ/TDB ⁹C) up to 100⁹C: Q = mCpΔT = 4,5 x 2,345 x (100-20) = 844,2 MJ up to 120⁹C: Q = mCpΔT = 4,5 x 2,345 x (120-20) = 1055,3 MJ b)Unit (table 8.1): OMMSW: 472 - 142 = 330 kg Wood: 186 - 158 = 28 kg

Acidic Solution: = 100 kg

Total Water: = 458 kg

300 kg BS → 458 kg H₂0 4500 kg BS → x => x = 6.870 kg H₂0 Heating of the water (Cp = 4,18 kJ/kg C)[HOLMAN,1993] up to 100⁹C :Q = mCpΔT => q = 6870 x 4,18 x 10³ (100 - 20) = 2.297,3 MJ up to 120⁹C :Q = mCpΔT = q = 6870 x 4,18 x 10³ (120 - 20) =

2.871 ,7 MJ

Total of necessary Heat: up to 100⁹C : item (a+b) = 844,2 + 2.297,3 = 3.141 ,5 MJ up to 120^eC : item (a+b) = 1.055,3 + 2.871 ,7 = 3.927,0 MJ c) Energy contained in the escape steam according to table 8.1 :

300 kg BS → 399 kg condensed steam 4500 kg BS → x=»x = 5985 kg m(h^v ₁₆o - h^v ₁₀o) = 5.985 (2.758,1 - 419,1) = 14,0 GJ d) Primary steam consumption reduction 14,0 - 3,1 = 10,9 MJ m (h^v ₁₆o - h^a ₈₀) = m(2.758,1 - 334,9) KJ/kg

10,9MJ m = ■ = 4.498,2 kg of steam

2.423,2 KJ/kg

Steam economy with preheating with escape steam from the other reactor, 5.985,0 kg - 4.498,0 kg = 1.487,0 kg of steam e) Distribution of the preheating times and heating + reaction

Preheating:— — x50min = 12,4min

5.985,0

4 498 0

Heating + Reaction: — — xδOmin = 37,6min

5.985,0 f) Calculation of the total escape steam to be condensed in the Belfano-type washing tower, resulting from the primary steam in the 1^st reactor reduced by the absorbed steam (condensed) by the preheating of the

2^nd reactor qq 4.498 x ^Ξ. _ .487,0 = 3.337 kg of vapor 372

3.337kg x 1 ,673 m³/kg = 5.577m³ of vapor g) Calculation of the condensation capacity in the Washing Tower (Variation of the steam enthalpy equal to the variation of the water enthalpy in the Washing Tower - mass flow)

• Without steam purge through the second reactor: m_v(h₁ ^v ₆₀ -h?₀₀) = m_a(h^₀₀ -h^₀)

5.985(2.758,1 -419,0) = m_a (419,0 - 84) m_a = 41 ,8m³ /reacao

41 ,8x60min ._ _{3 /}. m_a = — = 49,3m³/h

50min • With steam purge through the second reactor: m_v (h'oo - h'oo ) = ma (h^ - \ _2Q ) (3.337 - 654) x (2.676,1 - 419,0) = m_a (419,0 - 84,0)

. -- . ₃ , _ ^* . _{n j} 60min _{Λ 3 /I} m_a = 18,1 m³ /reacao .\ m_a = 18,1x = 28,9 m³/h ^y 37,6min h) Before being sent to the Washing Tower, part of the escape steam is used for preheating the boiler water and acidic solution. The amount of condensed steam is given by: ^mv (^h1^V30 - ^h"θθ ) = (^mc + ^msa ) (^h80 - h2θ ) m_v (2.720,5 - 419,0) = (4.498 + 1.500) x (334,9 - 84) m_v (2.301 ,5) = (5.998) x (250,9) m_v = 654kg

This means that most of the escape steam needs to be condensed by the washing tower.

Figure 35 shows the flow diagram and the prehydrolysis balance mass prehydrolysis of 4.5 TDB/batch with mixture of the effluents in a single flow. Table 10 shows the respective memorial of calculation. The consumption of steam is of 4.5 t corresponding to a total of energy of 12.41 GJ, which will require 620 kg of cellulignin, representing a percentage of 18.9% of combustible cellulignin. One expects a reduction in this value in the industrial plant due to two factors: 1^st) lesser relationship between the surface (thermal loss) and

4πR² 3 the reactor volume.

R

%^πR3

The relationship between the pilot reactor and the industrial one is of ^ = -^- = — = 2,3 wherein (V, = l5m ³ = -πR³ and y R_P 0,66 ' 3 '

e V_p = 1 ,2m² = — π R_p ) . The steam consumption will represent 8,2%.

2^nd) One expects that the grinding of the waste will decrease its permeability and increase the thermal contact with the purge steam. • As a result, of the greater steam consumption, there is a need for cold water in the washing tower for condensation of the purge steam of 18.100 kg, in which cold water is used for condensing the acidic solution, recovering sugar and cellulignin washing. Considering the relationship between cold water mass and steam in the washing tower of 3.37, it is necessary to cut only 1 ,821 kg in the steam consumption. In addition, this value will not result in any economy of water.

• The preheating of the reactor charge (biomass + waterO reduces the steam consumption from 5,985 kg to 4,498 kg (24.8%). Therefore, it is fundamental to work with two reactors. • The preheating of the boiler water up to 80⁹C has not been taken into account in all the calculations effected so far. The energy economy is represented as follows: o m(h^aso - h^a ₂₀) = 4.498 (334,9-84)=1 ,13GJ and an economy of steam of . '- = 466kg

(2758,1 -334,9) kJ/kg The preheating of the acidic solution up to 80⁹ C represents an energy economy of: om(h^a ₈o-h^a ₂o)= 1.500(334,9-84)=0,38GJ. Corresponding to the „ ■ _* -. (0,38)GJ 0,38 . __. . . followmg economy of steam -_i_i_^_ = — ^ _{= 1}57kg , makmg

a total of economy of 466 kg+157kg = 623 kg of steam. • For comparison purpose, the steam production of one boiler ATA

H3N-22 which produces 4.800 kg/h with water at 20⁹C and 5.280kg/h with water at 80^eC for a consumption of 360 kg/h of oil. The difference of 480 kg should be compared with the value 466 kg calculated in the preceding item.

• One expects that the economy of 623 kg of steam from the water preheating, factor of scale of the pilot and industrial reactor and the grinding of the OMMSW will increase this economy.

Figure 36 shows the flow diagram of the ETS - WTS- Deminera- lizer (DESMI) with the respective memorial of calculation (Table 8.9 and Ta- ble 8.10) of hydric balance taking into account the pluviometric precipitation in the industrial area of CEPIL. Figure 8.11 shows a view and section of the CAF (CAF - Cavitation Air Flotation), figure 8.12 shows the Sludge flotation schema and figure 8.13 shows the demineralization plant schema. The following points are: • For the case of consumption of cellulignin in a steam boiler, it is not necessary to demineralize water into cold water in the washing tower (acidic solution, sugar recovery and washing of the cellulignin). In this way, the water will be removed after the activated charcoal, and only the boiler water and washing water from the sand and activated-charcoal filters should be demineralized.

• When it comes to a demonstration plant, the DESMI of CEPIL from Lorena will have the capacity of demineralizing the total 35 m3/reaction equivalent to 46m3/h. (table 8.9 - item 5).

• The feeding water is 32,6 m³ (figure 8.10), a deficit due mainly to the evaporation from the furfural-condensers cooling tower. At first, this deficit will be compensated by taking water out of an artesian well.

• Table 8.10 shows that 88,803 m3 stabilizing tank is enough to store enough rain water for supplying CEPIL, without the need to take water out of artesian wells. The necessary collection area is of 285,320 m²,out of which 25,883 m² are available in the area of CEPIL, and the remaining is available in the Apolomec area, which occupies an area of 400,000m2.

Table 10 - Mass Balance Integrated Calculation Memorial of the Prehydrolysis 4,5TDB/reaction:

Note: Calculation with respect to the pilot plant (figure 8.4) with the industrial plant (figure 8.9).

1 ) Biomass OMMSW 4.500 kg de DBflnd.) _{χ 1} ^ _{Rg Dβ (pj]ot) = 2Λ ∞ kg Qf Dβ (jndustrjal)}

300 kg de DB (pilot) 4.500 kg de DB(ind.) x (472 kg de HB - 142 kg DB) = 4.950 kg of water

300 kg e DB(pilot)

_«/ r,- ■ ■ -j _. •. _. 22..113300 kg of dry OMMSW _Λ „_,„ „-, „„,

• % Biomass in the ind uussttrπill r reeaaccttoorr _ =_ — — = 0,473 = 47,3%

4 -..550000 ooff DDBB

_• % Water coπtaed in the OMMSW = 44..995500 kkgg ooff water _{= g = 6g>g%}

(4.950 kg of water + 2.130 kg DB)

2) Biomass Wood:

4500 kgof DB (ind.) x 158 kg of DB (pilot) = 2.370 kg of DB (industrial)

300 kg of DB (pilot)

4500 kgof DB (ind.) x (186 kg of HB - 158 kg of DB) = 420 kg of water

300 of DB (pilot)

• % Biomass in the industrial reactor = ²-^{370 k}9 ^{of drv w} _{= 0 527} =_ 52,7%

4500 kg of DB

_• % Water contained in the wood = 420 kg of water _{= Q 5Q = 1 %}

420 kg of water + 2.370 kg of DB

3) Boiler (ATA H3N - 6,5 t/h of steam) Relationship between the calorific power:

•488 kg/h of combustible oil — > 976 kg/h of Celulignina

• Actual consumption of cellulignin = — x 976 kg/h = 675 kg/reaction

6.500 kg/h

• Actual consumption of oil = — x 488 kg/h = 338 kg/reaction

6.500 kg/h ^~

4) Combustion Gas:

Calculated by the Program NASA SP273. [VIEIRA,2000] For Natural Gas (Consumption of pilot flame): => Approximately: 14 kg/h of natural gas with 30% excess air, T=

1 .800⁹C

Fuel ) ₌ (C ) ₌ o,1186 v /oxidant weight V θ'_p mτoτ = mcEL+ ΠIGN => mτoτ = 675 + 14 =-> mτoτ = 689kg/h πiTOT = fuel mass flow, as (C/O)_p = 0,1186

Concentration on the combustion producs (by mass) : de CO₂ : 24,32%^* → Flow of : (5.809 + 689) kg/h 24,32% = 1.580 kg/hx0,75h

=> Flow of 1.185 kg of CO₂/reaction de N₂ : 68,45%^* => Flow of : (5.809 + 689)kg/h x 68,45% =4.448 kg/hx0,75h

=> Flow of 3.336 kg de N₂ /reaction

For Combustible Oil (consumption of pilot flame): (C/O)_p = 0,0635

1 m_όieo = 338kg/h => mar = xm_όι_eo = 5.322kg/hx0,75h = 3.992 kg/reacton

0,0635 with 20% of excess air, T = 2.048° C mco₂ = 17,07%^* of the total =. Flow of : 5.322 kg/h x 17,07% =908 kg/h x 0,75 h

=> Flow of 681 kg de CO₂/reaction mm = 71,99%^* do total = Flow of : 5.322 kg/h x 71,99% =3.831 kg/h x 0,75 h

= Flow of 2.873 kg de N₂/reaction

* datum taken from the simulation of the cellulignin combustion. [VIEI- RA.2000]

5) Steams from the Industrial Reactor of 4.500 kg of Biomass/ reaction:

•Escape steam from the 1 st to the 2nd ractor :

399 kg of exit steam (pilot)

4.498 kg entry steam (ind.) x-

372 kg of entry steam (pilot) => escape steam to the 2nd rector is of 4.824 kg.

• Steam condensed from the escape steam of the previous reactor 1.487kg

(Theoretical Calculation - table 8.7 - item d.)

• Escape Steam for acidic solution tank heat exchanger 4.824-1.487=3.337kg

• H₂0 contained in the 1^st reactor: + 4.498 kg of entry steam

- 4.824 kg of steam came out to 2^nd reactor + 1.487 kg of condensed water with the preheating + 5.370 kg of water contained in the biomass + 1.500 kg of the acidic solution = 8.031 kg of water in the reactor.

Relation US:

8.031 kg of water in the reactor + 3.337 kg of steam to/ heat exchanger _

4.500 kg deBS '

L/S (industrial) = 2,53 < IJS(pilot) = 2,8 because the temperature of the industrial reactor begins at 100⁹ C and that of the pilot reactor at 20⁹C.

6) Acidic Solution Tank / Heat Exchanger and Washing Tower.

• Total Water of the Washing Tower: escape steam + Cold Water = 3.337 kg+18.100 kg = 21.437 kg of water

• Water for Acidic solution: 100 kg (pilot) => 1.500 kg (industrial)

Sugar recovery

400 kg entry water (pilot) x 4.500 de DB (industrial)

300 kg exit water (pilot) = 6.000 kg of entry water in the industrial reactor

• Cellulignin Wash Water:

2x 620 kgof water (pilot) , ,_„„ . _nn ,. . _.. . ,_>

= - — — -x 4.500 kg DB (industrial)

300 kg DB (piloto)

= 18.600kg Wash water in thindustrial reactor • Reposition of Water after Washing Tower:

21.437 kg of water from the washing tower

- 1.500 kg of water from the acidic solution - 6.000 kg of water from the sugar recovery -18.600 kg of water from the ALE - 4.663 kg of missing water.

=>Enter with water reposition of 4.663 kg.

• Grinding the waste in a hammer mill without sieve will decrease the permeability of the purge steam, permitting its reduction, achieving a total balance. It is enough to cut 709kg in the purge steam (21%) to achieve the balance.

7) Cellulignin:

• Dry Mass

= 2 9 kg of dryCL(pilot) _{χ 4500 Dβ = CL}

300 kgof DB(pilot) (industrial) % of cellulignin on biomass 3.285 kg of dry CL (industrial)

: 0,73 = 73%

4.500 kg DB (industrial)

• Humidity

_ (605 kg of humidity CL (pilot) - 219 kg of dry CL (pilot)) x 4.500 kg of DB

300 kg de DB (industrial) = 5.790 kg of water in the cellulignin

% of humidity 5.790 kg of water in the CL

: 0,638 = 63,8%

5.790 kg of water in te CL + 3.285 kg of dry CL

8) Prehydrolysate:

In the industrial reactor the contents are of L/S = 2,53 = 8.031 kg of water in the reactor In which the cellulignin comes out with 5790 kg of water contained in its mass and the prehydrolysate with 2.241 kg

9) Sugar recovery:

Since the cellulignin is saturated and with the injection of compressed air for removing water, the amount that enters is the same amount that comes out.

SR = 6.000 kg of SR

10) Outlet Washing Water:

Since the cellulignin is saturated and with the injection of compressed air for removing water, the amount that enters is the same amount that comes out.

IWW1 = 9.300 kg of OWW1 e OWW2 = 9.300 kg of OWW2

11) Mass balance:

• Solids:

=3.285+2.241 x(0, 125)+6.000x(0,060)+9.300x(0,02)+9.300(0,008 )+ Residues =

=3.285+280,1+360+186+74,4+314,5= 4.500 kg

• Liquids:

Entry = 4.950+420+4.498+1.487+1.500+6.000+18.600+112,5=37.567 kg Exit = 4.824+5.790+2.241 + 6.000 + 9.300 + 9.300 + 112,5 = 37.567,5 kg Table 11 - Mass balance Memorial Calculation of the ETS / WTS / DESMI and Stabilization Tank with mixture of the Effluents (kg/reaction).

1) Natural evaporation (20%). Calculated considering all the entries in the aeration tank of fig.8.10.

20% x [5,8 m³ + 4,5 m³ + 34 m³ +1 m³]= 9,1 m³

2) Machine Washing water

Calculated in the entry waters (lutter and washing water) 20% [7.791 m³+18.600 m³] = 5.272,4 - 5.278 kg

3) Slurries:

Lutter : only 20% of the BS is hydrolyzed and out of these 20%, 10% is changed into furfural and 10% into Sludge 450,0 kg

Machine Washing water 20% x 5.278 kg 1.056,0 kg Cellulignin washing water 9.300 kg x 0,020 186,0 kg

9.300 kg x 0,008 74.4 kα

Total 1.766,4 kg

4) Water volume to be demineralized from the Cationic, Anionic and Mixed Columns. • Considering the washing tower water:

63,4 m³ - 34 m³ = 29,4 m³ p/reaction = 39,2 m³/h. • If the washing tower does not need demineralize water, then:

63,4 m³ - 34 m³-18,1 m³ = 11 ,3 m³p/reaction => 15,1 m³/h The larger capacity will be installed of 39,2 m³/h. 5) Volume for the sand retro-washing and activated charcoal filters:

In the pilot plant of 1 m³/h the manufacturer recommends 170 L per cycle.

170 L → 24.000 (24m³) x → 63,4 m³ x = 449 L x 2 = 898 m³ 1 m³ for the industrial plant. 6) Water volume and reactants in the regeneration of the co- lumns:

* Data from the pilot plant recommended by the demineralizer manufacturer.

• Cationic resin column H₂0: 100 L → 24.000 kg * x → 29.400 kg => x = 123 kg

HCl at 30%: 20 L → 24.000 kg *

Y → 29.400 kg => y= 24,5 - 25 L at 30% • Anionic resin column:

H₂0: 260 L → 24.000 kg * x → 29.400 kg => x = 319 L NaOH a 50%: 13 kg → 24.000* y → 29.400

=> y = 16 kg a 50%

• Calculation of the anionic and cationic columns salt excess

HCl + NaOH => NaCI + H₂0 36 40 => 59 36 40

0,3 x 25,0 → x X = 8,3 kg; excess 16,0 - 8,3 = 7,7 « 8,0 kg de NaOH

Calculation of NaCI 36 → 58 0,3 x 25,1 → y = y= 12,1 kg de NaCI

Excess: NaCI + NaOH = (12,1 + 8) kg

• Regeneration of the mixed resin column:

Cationic:

H₂0: 5 L → 24.000 kg Y → 29.400 kg y = 6,2 L DH₂0 => 7,0 LDH₂0.

HCl a 30%: 15 L → 24.000 kg x → 29.400 kg x = 18,4 L → 19 LDHCI Anionic:

H₂0: 20 L H₂0 → 24.000 kg t → 29.400 kg t = 24,5 L=» 25 LDH₂0. NaOH at 50%: 13 L → 24.000 kg z → 29.400 kg z = 15,9 L =» 16 LDH₂0 • Salt excess in the mixed column:

HCl + NaOH => NaCI + H₂0 36 40 → 59 36 → 40 0,3 x 19 → x => x = 6,3 kg; excess 16,0 - 6,3 = 9,7 10 kg of NaOH Calculation of NaCI

36 → 59 0,3 x 19 → y y= 9,18 kg of NaCI Excess: NaCI + NaOH = (9,18+10) kg • Water spending for washing the columns and equalizing the water:

4,2 m³ → 24.000 L * x → 29.400 x = 5,3 m³ Making a total in 5,8m³ of water for the processes of the ion- exchange columns:

Water for preparing the solutions 0,5 m³ retro-washings, washings and equalization of the water 5,3 m³. Spending by batch in the industrial plant 5,8 m³

7) Deficit/Reaction = 32,6 m³ practically due to the condensers of the furfural plant refrigeration (Evaporation from the refrigeration tower)

8) Daily deficit: 32,6 m³/reaction x 16 reaction/day = 521 ,6 πrVdia

9) Monthly Deficit: 521 ,6 m³/day x 320 days/12 months = 13.910 m³/month.

Table 12- Hydric Deficit supply by Pluviometric precipitation in the Industrial Area

1) Pluviometric Precipitation throughout the year.

2) The annual net precipitation is of 585 mm needing the following area for supplying the hydric deficit: 0,585 m x A = 32,6 m³/reaction x 16 reaction/day x 320 days/year

A = 285.320 m² = 28,5 ha

3) Monthly Consumption: 32,6 m³/reaction x 16 reaction/day x

320days/year

=13.910 m mes.

12months

4) Determination of the stabilization Tank for pluviometric collection to eliminate the hydric deficit.

Flow Diagram of the Mass Hydric Balance and Hydric Balance with Recirculation of the Luter and Separation between the WTS and the ETS / DESMI / Stabilization Tank.

A second study is being developed in the RM - Materials Refrata- rios, according to figure 40 and 41 , with luter recirculation in the prehydrolysis reaction, since Luter has high solid contents, wherein any economic possibility of treating this effluent is eliminated, suggesting separation between the STW and the STE / DESMI / Stabilization Tank, facilitating and reducing the treatment cost. This paper will be more detailed at doctorate level.

With luter recirculation, one meets the following technical requirements: a) sulfuric acid recirculation, making possible the total elimination of catalyst pollution, reducing its cost and facilitating the use of the prehydro- lysis technology in remote regions (Amazon region); b) acetic acid and formic acid recirculation enables the contribution of autohydrolysis, so that the concentration of these acids will not increase continuously, the furfural plant will have measures for their separation, purification and commercialization.

Table 13 shows the analysis made by COEPRSUCAR- Piracicaba of the carbohydrates (sugars) from prehydrolysate of the organic acids formed during the prehydrolysis, the furfural contents, hydroxymethyl- furfural and anion (S0₄) of the samples OMMSW - 210300-1 with Brix = 12.5% and of Wood W - 200400-1 with Brix = 8.0%; compared with a sample of hydrolyzed sugar-cane bagasse from COPERSUCAR. Table 13 - Carbohydrates, Organic Acids and Anions analysis

WD = without data

* = percentage in relation to the dry sugar mass

For the results analysis, see figure 42, about the Wood hydrolysis. The sample OMMSWW 210300-1 exhibited higher hydroxymethylfurfural contents, which is the product of the hexoses degradation that is present in larger quantity, wherein in the sample W 200400-1 the hydroxymethylfurfural contents is lower. The amount of furfural analyzed is of free furfural, that is, that which formed during the prehydrolysis reaction. Pentose will be converted into furfural, in which a small amount of the latter will be degraded.

The xylose contents were very low and those of acids very above from what was expected. It should be noted that, by interpreting the total of solute as BRIX, there is a reasonable agreement with the value of figure 8.7 (8.0%) for wood and 50% of error in relation to the OMMSWW of the figure (12.5%). A more systematic study of green wood (35 days of drying in the field) will be made for identifying the causes of the low xylose contents in the prehydrolysate. In the tests, old and dry wood were used, probably with partially decomposed hemicelluloses. Table 14 shows the characterization chemical analysis of the prehydrolysate from the OMMSW 260699-1 and of the cellulignin from the OMMSW 260699-1 without washing (the reaction was processed with 100% of OMMSW, made in the beginning of the master paper), and of the cellu- lignin washing water of MD 180699-1.

• Table 15 shows the characterization chemical analysis of the concentration of inorganic impurities in the Eucalipto grandis and in the wood cellulignin. • Table 16 shows the characterization chemical analysis of all the products and effluent of the reaction of the OMMSWW 210900-1 (50% OMMSW with 50% Wood), washed with drinkable water.

• Table 17 characterizes the concentration of inorganic impurities in the cellulignin OMMSW 260699-1 and OMMSWW 210300-1 reactions. • Table 18 shows the melting temperature of potential minerals having a low melting point found in biomass.

• Tables 19 - 19.5 show the chemical analysis of the Sludge characterization and classification produced in the treatment of effluents from the OMMSWW 210300-1 , washed with drinkable water. The analyses of table 14 show that: a-1) the cellulignin is extremely clean, even without washings with the level of inorganic impurities (heavy metals) lower than those foreseen for the extract obtained in the leaching test Attachment G - List No. 7 - concentration - maximum limit in the extract obtained in the leaching test of NBR 10.004 - (Solid Residues). If they are already lower in the solid, they will be even lower in their leaching and lower after the washing. a-2) Since the cellulignin from the OMMSW is intended for boiler due to its high ash contents (7.8%) washing will be made only with the water treated in the ETS. If one wishes the burning in gas-type turbines, the latter should be washed with demineralized water for reducing the contents of sodium, potassium and calcium, thus avoiding corrosion on the turbine blades. a-3) The contents of 180 mg/kg of S04 in the cellulignin from the OMMSW is low when compared with the cellulignin OMMSWW of 4,700 mg/kg, because it has been consumed by the high inorganic contents pre- sent in the reaction 100% OMMSW, reaching the pH of 6.20.

Table 14 - Products and Effluents characterization made by Ambiental Laboratόrios e Equipamentos Ltda. Client: RM - Materials Refratarios Ltda

Address: Av. Dr. Leo de Affonseca Netto, 750, Lorena, SP

Dates: 30/06/99 (collection); 02/07/99 (entry); 09/08/99 (delivery).

ND: Not Detected; - Not Found

* OMMSW - 260699-1→ 100% -OMMSW without washing Table 15 - Concentration of inorganic impurities in the Eucalyptus grandis and in the Wood Cellulign (μg/g).

Concentration of inorganic impurities in the Eucalyptus

Table 16 - Characterization Chemical Analysis of the products from Prehydrolysis OMMSWW 210300-1.(50% OMMSW + 50% W - washed with drinkable water)

(^**) Gross Effluent Composed of 1/3 of prehydrolysate + 2/3 washing water w/ drinkable water

The analyses of table 16 show that: b.1) The values for most elements of the prehydrolysate OMMSWW 210300-1 are smaller in relation to OMMSW 260699-1 due to the mixture with wood, which has lower inorganic contents, thus consuming little acid. b.2) The washing water will be treated as shown in figure 36 and recirculated for the process. The gross effluent is a mixture of 1/3 of prehydrolysate with 2/3 of washing water, simulating the situation in which the prehydrolysate is discarded as an effluent until the furfural plant is ready. This is the most critical situation in the process. Thus, when mixing the wood washing water, which is cleaner, with the washing waters from the biomass courtyard, this gross effluent will be less concentrated, further facilitating the treatment. b.3) In the cellulignin analysis, one made the conversion into oxides, observing that the ashes difference is due to the carbonates present in the ash, which have a melting point higher than the temperature used for burning the ashes at 600^QC shown in table 19. When the cellulignin is burned in the combustor at the temperature of 1300²C this ash will be reduced.

Table 17 - Concentration of inorganic impurities in the OMMSW cellulignin

ND = Not Detected

OMMSW - 260699-1 - 100% OMMSW without washing; OMMSWW - 210300-1 - 50% OMMSW +50% W with washing

It is necessary to make a more intensive washing of the cellulignin of the OMMSW and OMMSWW, in order to make a comparative analysis. However, one can note some significant differences with respect to the cellulignin of wood, namely: c-1) the contents of Alkali/Earth Alkali are significantly higher, showing that there will always be formation of eutectic of the type SiOx/K20 with melting at 760^SC, causing incrustation (formation of glass) above this temperature. c-2) The refractory contents are on the same order as the cellulignin of wood. c-3) The earth contents are significantly higher than the cellulignin from wood, combining with the high chlorine contents one foresees the formation of low-melting-point chlorides and chlorates (table 18). c-4) The important factor of the anionics is the high CI content resulting from the use of common salt in human food. These high contents may require the washing of the OMMSW cellulignin , in order to avoid formation of low-melting-point chlorides during combustion.

Table 18 - Melting temperature of potential low-melting-point minerals found in biomass.

Table 18 (cont.) Melting temperature of potential low-melting-point minerals found in biomass.

Tables 19, 19.1 , 19.2 show the results achieved in the analyses processed in the sample Crude Mass, with the respective maximum limits permitted in the NBR 10004 - Attachment I - List 9 and PN 1 :603.06-008.

Table 19 - Characterization of the Sludge Crude Mass of the OMMSWW 210300-1

- Not required by the rule.

Table 19.1 - Crude Mass Characterization of the Sludge Volatile Organic Compounds of the OMMSWW 210300-1.

Table 19.1 (cont.)

Crude Mass Characterization - Sludge Volatile Organic Compounds of the

OMMSW 210300-1.

ND: Below Detection Limit

Table 19. 2 - Characterization -Crude Mass -Sludge Semi- volatile Organic Compounds of the OMMSWW 210300-1.

ND: Below Detection Limit

Table 20 shows the results in the analyses processed in the extract from the Leaching essay with the respective maximum limits permitted in the NBR 10004 and PN 1 :603.06-008.

Table 20 - Characterization of the Sludge Leached Extract of the OMMSWW 210300-1.

ND: Below Detection Limit

Table 21 shows the results achieved in the analyses processed in the Extract from the Solubilization essay with the respective maximum limits permitted in the NBR 10004 e PN 1 :603.06-008

Table 21 - Characterization of the Sludge Solubilized Extract of the OMMSWW 210300-1.

(*): Result not obtained due to the presence of interfering factor. ND: Below Detection Level

Table 22 shows the Solid Residue Classification generated in the effluent treatment of the OMMSWW 210300 -1.

Table 22 - Solid Residue classification

Parameters at Variance with the Legislation

IdentificatiCruLeached Solubilized Ex- Classification accoron of the de Extract tract ding to NBR 10004 Sample mass and PN 1.603.06-008 ABNT

Industrial Total Aluminum, Class II - Non-Inert Sludge Lead, Chloride, Total Hardness, Total Iron, Total Manganese, Sodium and Sulfate

Class II Residues - Non-Inert - Are those that do not fall into the classification of class I residues - dangerous or class III - inert, in the terms of Rule 10004 - Solid Residues. Class II residues - Non-inert - may have properties such as: combustibility, biodegradability or water-solubility. Finally, the Sludge generated in the effluents treatment being a class-ll residue - not inert (Attachment G, List 7 - Concentration - maximum limit in the extract obtained in the leaching test - NBR 10.004 - Solid Residues - Classification), have three destinations, and may be carried to industrial sanitary dumps (Attachment 8.1), additions to red ceramics, in which it would be stabilized by vitrification (red ceramics produced by Sedimentary and primary clays one from the Taubate basin of the Vale do Parafba river with and without addition of ashes and solid residues from the Program BEM) [SANTOS - 2000], fertilizers, considering the very low contents of heavy metals (table 8.17). The volatile organic compounds have indicated values only in Chloroform and Methylene Chloride (table 8.17.1) due to the fact that the waste contains chlorinated products (common salt and cleaning products). The semi-volatile organic compounds (table 8.17.2) indicate the presence of 1-chloronaphthalene for the same reasons. Norm 10.004 - Solid Residues - does not specify limits for volatile and semi-volatile organic compounds, and it is enough to indicate their presence for the residue not classified as inert. The analysis of the leached extract (table 8.18) did not indicate the presence of any heavy metal. The analysis of the solubilized extract indicated the presence of aluminum, lead, chlorides, iron, manganese, sodium, sulfate and total hardness above the limits permitted for an inert material, classifying the Sludge as non-inert. The studies of the utilization of this Sludge as a fertilizer are under way.

Figure 43 shows the gases analysis from combustion of the OMMSW cellulignin.

The tests were carried out with the help of a combustion-test kit, brend DWYER, model 1.200 B, to measure the soot in gases, compared with the Reinmam scale and to measure concentrations of CO, C0 , O₂ e HC in gases, by using an equipment, ALFATESTE, model 488 (Analisador Digital Multigas por Radiacao Infravermelha = Infrared-Radiation Multigas Digital Analyzer).

The effected with 50% of OMMSW and 50% of W was burned in the test table for combustion and comparison with the result measured in the chimney of an ATA boiler, for the production of 1 ,000 kg/h of steam, manufactured in 1973 and burning BPF oil, with 1% of sulfur. The results are shown in Table 23, indicating null contents of CO, HC and low soot contents.

Table 23 - Comparative table of gases emissions and soot in the combustion

HC*: Hydrocarbons

The Environment Management Program is composed of the following rules: • NBR ISO 14001 - Sistema de Gestao Ambiental (SGA = Environmental Management System ) - Specifications and Guidelines for use.

• NBR ISO 14004 - Sistema de Gestao Ambiental (Environmental Management System) - General guidelines on principles, systems and su- pport

• NBR ISO 14010 - Guidelines for Environmental audit - general Principles

• NBR ISO 14011 - Guidelines for environmental audit - Audit procedures - Environmental Management Audit Systems • NBR ISO 14012 - Guidelines for Environmental Audit - Criteria of qualification for environmental auditors

Figure 44 shows the model of SGA for Rule ISO14004. Figure 45 shows an application exercise of the five principles of the SGA to CEPIL (Program BEM) about the materials life cycle from waste. The following points are stressed:

• The rules ISO 14000 were worked out for a time when the world was walking towards a high-pollution situation and aims at identifying sequential principles that aimed at reducing pollution in a continuous way.

• In the case of the Program BEM, one achieves a level of "zero pollution", immediately emptying the practice of application of the sequential principles.

Below, we give the list of the five kinds of pollution eliminated by the Program BEM:

• Solid: The waste and any kind of biomass are processed and generate two commercial products, cellulignin fuel and furfural, having in a first instance only three residues, earth, sands in the rotary sieve, Sludge from the ETS and ashes from the cellulignin burning. The Sludge from the ETS will be converted into oil (additive to fossil combustibles) and activated charcoal. [SOARES, 2000]. The latter, after having been used, will be bur- ned, generating ashes. Given the small volume of ashes (earth and sand), it is possible to stabilize them by adding them to ceramics (ceramic vitrificati- , on), achieving the level of "zero pollution" [SANTOS, 2000]. As long as the development of the stabilization of the heavy metals contained in the ashes is not completed by ceramic vitrification, the residue will be sent to small-size embankments. Lorena produces 3.0 t/day of OMMSW, equivalent to 90m3/ by volume, resulting in 1.1 t/day of ashes. Taking the density of 2.300 kg/m3 for the ashes, we have 0.5m3/day, which represents 0.5% of the initial volume of waste. Please note that, by adding 10% of the ashes to the clay to produce solid bricks (20x10x5cm3), we will have a production of 5,000

• Bricks a day for stabilizing the ashes from the waste processing. Making the population aware of the problem might reduce the ash contents from the present-day 12% to 2%, reducing the above value to 1 ,000 bricks/day.

• Liquid: the effluents are treated and the water is recirculated. The volumes involved are so small that it is possible to establish the CEPIL with rain water from the neighboring industries, thereby eliminating the need to take water out of artesian wells, discharge into any stream (rivers, creeks or underground tubes intended for rainwater). This will contribute to the reduction of floods. It should be noted that the technology of the STE / STW / DESMI of Program BEM may be applied to any branch of industry or residential district, enabling one to recycle water, thus contributing to decrease the need for water supply.

• Gaseous: At the level of CEPIL, there is only emission of gas in the boiler chimney. By burning cellulignin in the boiler, one achieves a level of null pollution in CO and HC. The C02 may be separated in the N2 by means of a PSA - Pressure swing Absorption - [SOARES,2000], compressed, liquefied, and distributed to the industry, (bottling of water, soft-drinks, production of Crystalline Calcium Carbonate (CCC) and Sodium Carbonate for the Paint Industry, etc.)

• Thermal: Table 24 shows the Emission Potential avoided by Program BEM in carbon equivalent to a plant operating with 50% OMMSW and 50% wood. Calculated by the IVIG-2000, according to the criteria approved by the CDM - Clean Development Mechanism [IPCC, 1995]. The following comments are made: 1) The environmental criteria would be sufficient to pay the whole investment of US$13,879,500,00.

2) It is necessary to implant 3.825ha of forest (table 9.3) in order to sequester the same amount of carbon as a plant of 150 TDB/day of Program BEM operating with 50% OMMSW and 50% Wood. The investment made is close to the cost of the land plus implantation of the forest (US$ 4.000,00/ha), justifying the value paid US$ 10,00/ton of equivalent Carbon (tC eq), which is lower on the carbon-sequester market. The international contracts are being signed at values close to US$20, 00/tC eq. 3) Program BEM further has the possibility of sequestering carbon by using C0₂ from the chimney of the thermoelectric station through the production of Crystalline Calcium Carbonate - CCC (a hydrothermal process) utilizing it as substitute for Ti0₂ in paints.

4) Without this latter application, it would take 39,200 plants of Program BEM to sequester the whole excess carbon that is going to the greenhouse effect of 3 billion tC/year. Considering that each plant can generate 15MW of power, this would result in the production of 588 GW, which represents only 6% of the installed world capacity. (10TW). • Unemployment: The population of Brazil generates 25.58 x 10³ TDB/day; with capacity of the plant of 150 TDB/day (50% OMMSW+50% biomass), 340 plants will be necessary. Each complete plant (refuse selection, prehydrolysis, furfural and thermoelectric station) generates 120 direct jobs, making a total of 20.460 jobs. Considering the forest biomass with 400 plants and the biomass from sugar with 1200 plants, we will have a total of 1770 plants, making a total of 212,460 direct jobs. This number is equal to the number of direct jobs generated by the automobile industry. Therefore, the Program BEM has an enormous technical and economical capacity of generating jobs.

Table 24 - Potential of Emissions Avoided by Program BEM in carbon equivalent to 150 TDB/day for reactions with 50% OMMSW and 50% Wood. 1. Methane 20.880 tC eq/year

2. Generation of Electric Energy from Biomass 47.200 tC eq/year (replacing the fossil fuel).

3. Presentation with Recycling 8.420 tC eq/year ⁽¹⁾ (Plastics, Paper, Metal, waste)

4. Annual Total 76.500 tC eq/year

5. Total in 20 years 1.530.000 tC eq ⁽²⁾

6. Environmental Credits at the Value of US$ 15,300,000 ⁽³⁾ US$10,00/tC eq.

7. Equivalent Forest to sequester the same 3.825 ha ^{( )} amount of carbon 40 TDB/ha.year sequesters 20 tC/ha.year

8. Equivalent Value of a hectare of land by the value of the environmental credits. US$ 4.000,00/ha

9. Industrial Utilization of C0₂ from the chimney of the thermoelectric station

150 TDB/day x 80% de CL per reaction = 120 tCL/day

120 TCL/day x (66% C contained in the CLØ-INATTI, 99]) = 79 tC/day 120 tCL/day

79 tC/day x 320 days/year = 25.280 tC eq/year 79 tCL/day

25.280 tC eq/year

⁽¹⁾ (20.880 + 47.200 + 8.420)tC eq/year = 76.500 tC eq/year

⁽²⁾ US$10,00 x 1.530.00 tC eq in 20 years = US$ 15.300.000,00

⁽³⁾ 76.500 tC eq./year ÷20 tC/ha.year = 3.825 ha

⁽⁴⁾ US$ 15.300.000,00 environmental credits ÷ 3.825 ha = US$ 4.000,00/ha

In a short term, one intends to achieve the following developments:

• Taking measures for the industrial reactor to operate with pressure 8.0 MPa, 170²C, aiming at the start of digestion of cellulose (pressure of 10 MPa - 180^SC should be avoided because of the significant digestion of cellulose)

• Multiple-effect evaporation of the Prehydrolysate for producing the xylose syrup (40 - 65% of Brix). • Appraisal of the Potential of alcohol production from prehydrolysate from the refuse by fermentation with Pichia stipitis. At the price of the alcohol of US$ 0,33/L = US$ 0,41 / kg = US$ 410 / 1, a production of 70 L / 1 (50% of the production potential, if it is fermented engineered Eche chia coli ) to render the alcohol production economically feasible.

• Utilization of green eucalyptus (up to 30 day of cutting) for a real appraisal of the potential of furfural production.

• Appraisal of the potential of furfural production from the sugarcane bagasse and straw. • Appraisal of the poter -.; furfural production from Napier grass.

• Real Cavitated-Air-Flotation (CAF) test of the washing waters from the production of OMMSW cellulignin. Therefore, it should be understood that the system and method of the present invention and their component parts described above are only a few of the embodiments and examples of situations that may occur, the real scope of the invention being defined in the accompanying claims.

Claims

1. A system for making prehydrolysis of organic matter from waste, characterized by comprising:

- a selective conveyor; - a Safe-Failure-type reactor;

- a reactor of furfural from the prehydrolysate;

- a reactor for converting sludge into oil and activated charcoal.

2. A system according to claim 1 , characterized in that it may be used for industrializing waste in an integral way.

3. A system according to claim 1, characterized by comprising a conveyor screw for compacting the biomass inside the reactor.

4. A process of industrializing the waste characterized by comprising the steps of:

- separating the matter to be used; - washing the selected matter;

- screening the selected material;

- feeding it into a reactor;

- prehydrolysis of the selected material.

5. A process according to claim 4, characterized in that the sepa- ration of the material to be used in is carried out on a rotary conveyor.

6. A process according to claim 4, characterized in that the washing of the selected material is carried out by means of jets of water.

7. A process according to claim 4, characterized in that the feeding of the reactor is carried out by means of a conveyor screw that com- pacts the biomass inside the reactor

8. A process according to claim 4, characterized in that the feeding is carried out in equal parts between OMMSW and the biomass Wood.

9. A process according to claim 4, characterized in that the prehydrolysis is divided into the following steps: - flooding;

- reactor stirring;

- heating; - pressurization;

- discharge of the prehydrolysate;

- sugar recovery;

- discharge of cellulignin; and - washing the cellulignin.

10. A process according to claim 9, characterized in that after discharging the prehydrolysate, drinkable water is introduced in the proportion of one part of liquid to one part of solid for the first internal washing of the cellulignin.

11. A Process according to claim 4, characterized in that, after sugar recovery, two internal washings of the cellulignin are carried out inside the reactor with drinkable water.

12. A process according to claim 3, characterized in that the drying of the drying of the cellulignin may be solar drying on a slowly moving conveyor, drying in stationary-grain dryers, cyclone drying and drying in a drying mill.

13. A process according to claim 3, characterized in that, after or before the drying, the cellulignin is passed through a 3-mesh sieve for removal of any residue of organic material that may have passed through the initi- al selection.