Conversion oils

of halophilic

algae into extractable

Yosef Goldman,

Nissim Garti, Yoel !&won,

Ben-Zion

Ginzburg

and M. R. Blocht

The Casali Institute of Applied Chemistry, School of Applied Science and Technology, *The Department of Botany, Institute of Life Sciences, and the tGround Water Research Center, The Hebrew University of Jerusalem, Jerusalem, Israel (Received 11 June 1979)

A salt water slurry of Dunaliella Parva, an halophilic alga, was treated in order to convert it into benzene-soluble material, as rich as possible in carbon and hydrogen. Several features have been brought to light during the course of this work: (1) 25% of the combined carbon can be extracted under mild conditions of pressure (atmospheric) and temperature; (2) the presence of CO as well as transition metals salts, had only minor effect on the conversion and the composition of the product; and (3) up to 75% of the combined carbon is converted by in-situ presence of benzene during the pyrolysis of the alga-salt water slurry.

Various sources of organic materials have been studied as possible feedstocks for production of liquid fuels. Most popular are cellulose*, wood*, peat3, coal, bituminous shale@, and organic wastes>s. Recently, biomass as a renewable potential feedstock has been mentioned by some authors as a promising starting material for conversion into oi19>. In comparison with other feedstocks, some particular types of algae can grow in saline water, with a minimal supply of nutrients and CO2 rl. Those algae can therefore be grown even in arid areas. A thorough research has been carried out in this university on the growth of Dunaliella Parva, which can grow even in 4 M saline water. Optimal and economical conditions for supply of nutrients and carbon dioxide, as well as for harvesting and concentrating have been developed. In solar basins it has been found that D. Parva can be grown in quantities of 12-20 g of organic material per m* per day. Economical studies have shown that although the obvious use of algae is for production of proteins, one should not exclude the feasibility of converting algae into fuel. This report describes a series of experiments in which attempts were made to treat algae in saline water under various conditions in order to convert the slurry into benzene-soluble material, as rich as possible in carbon and hydrogen. EXPERIMENTAL Dunaliella Parva was obtained as a 0.1% slurry from the growing pools. Centrifugation in a sharpless centrifuge at approximately 20.000 g yielded a slurry of 30% dry material in sodium chloride solution. The material was homogenized and divided into samples of 18 cm3 volume each. Samples from different batches were analysed for proteins (Kjeldahl method) and glycerol (periodate method). After

drying and washing, the material was subjected to elementary analysis. A sample of 18 cm3 of the salt water slurry was extracted in a Soxhlet extraction thimble with boiling benzene for 24 h. The benzene was evaporated and the residue was weighed and analysed. In a similar way, samples which were previously dried (at 60C for 24 h) and refluxed for 12 h with 10% hydrochloric acid (or 10% potassium hydroxide) and filtered, were extracted with benzene. High-temperature processes were carried out in a 70 cm3 Parr autoclave. An 18 cm3 sample (as a slurry or dried) was charged into the autoclave together with benzene and other reagents. After heating with shaking, the vessel was cooled and the mixture was transferred to an extraction thimble and extracted with benzene for 24 h as previously described. RESULTS A typical analysis of a batch of alga is as follows: proteins, 60 wt %; glycerol, 20-30 wt %; and lipids, 7-10 wt %. Negligible amounts of carbohydroates were detected (mainly in the form of starch), which varied in quantity according to the growing conditions. After drying, the slurry of 30 wt % solids resulting from centrifugation yielded a mixture of organic materials and inorganic solids. Upon separation by acid treatment, the dry organic material was found to contain 55-65 wt % carbon, 8-10 wt % hydrogen and 7-8 wt % nitrogen. The inorganic material was found to contain mainly sodium chloride and only traces of phosphates, nitrates and sulphates. In an initial set of experiments, we attempted to treat the algal lipids by use of a Soxhlet apparatus and with benzene as the extraction solvent. This extraction was carried out on a 30 wt % slurry, as well as on dry material, and on previously acid- or base-treated slurry. The results of these

0016-2361/80/030181-04 0 1980 IPC Business Press

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Conversion of halophilic algae into extractable oils: Y. Goldman et al.

Table 1 Extraction of lipids from crude algaea Product Composition Yield of Product Source Wet slurry Dry material Acid washed slurry d Base washed slurry e (wt%)b 12 8.5 12 6 with Conversion (wt %) c 25 14.1 1.9 14.2 C 88.4 72.7 65.1 79.3 algae H 8.4 10.0 9.6 11.1 N 0.3 0.8 1.3 2.7 fwt %)

a The results are average of several experiments b Based on dry organic material Based on carbon dRefluxed 12 h with 10% HCI and filtered e Refluaed 12 h with 10% KOH and filtered

five different batches of

Tab/e 2

High-temperature

treatment

of algaee Product Composition Yield of Product (wt %) N 5.8 7.8 5.3 7.8

Source Wet Dry Wet Dry sfurry material slurry + benzene material + benzene

fwt%)b 31.2 25.8 40.0 25.8 with five different

Conversion fwt %I c 55.6 43.5 72.1 43.5 batches of algae

C 78.9 74.1 80.2 74.1

H 9.2 8.5 8.3 8.5

a Average results of several experiments b Based on dry organic material c Based on carbon

Tab/e 3

Effects of catalysts and CO on the process Product Composition (wt %I N 3.6 4.2 3.1 4.6 4.7 4.7 4.9 4.7 4.7 5.1 5.4 by addition of CaC03

Catalyst

Yield of Products fwt%)b 16.5 17.5 19.0 19.5 20.0 20.3 21.2 22.2 22.2 22.8 26.6

Conversion fwt %I c 32.4 33.1 33.9 35.4 37.9 38.5 40.3 41.4 41.8 42.7 50.6

C 74.3 75.7 71.1 73.0 75.8 75.8 76.1 74.6 75.4 74.9 76.2

H 11.1 10.7 10.8 10.2 10.9 10.8 10.6 10.8 10.7 10.5 10.6 [pH 9 was obtained

Cr,fSD& CuBrg ZnAq AgAc PdClz FeClz MnCl2 COCI, FeAq NiS04

a Reaction conditions and reagents: 18 cm3 of slurry, 10 cm3 of 10% aqueous sodium and Na2C03] , 1 .128 x 1 O-3 mol of catalyst, 70 at CO, temp 300C. time of reaction: b Based on dry organic materials c Based on carbon

chloride,
2 h

experiments

are summarized in Table 1. More drastic conditions were then applied on the algae slurry. Both dry and wet material were heated in an autoclave to 350C for 2 h. The mixture obtained was extracted with benzene as described earlier. In a second step, benzene was added into the pressure vessel and the extraction was carried out in-situ. The results are given in Table 2. The roles of various additives were studied; several transition metal salts were added as catalysts, and carbon monoxide was examined as reducing agent. Results of these experiments are given in TabZe3. It was found that presence of carbon monoxide in the reacting system did not affect the yield, the conversion nor the composition of the

product. Experiments in which pressures of 6, 10,15,30, 50,70 atm* carbon monoxide were applied gave practically the same results (Ca 25 wt % yield based on total dry organic material, at 50 wt % conversion based on combined carbon and the product composition C, 71.0; H, 10.8; N, 4.5). These data are similar to results obtained in the absence of carbon monoxide. Finally, the effect of adding benzene to systems containing both catalysts and carbon monoxide as well as additives was studied. The results are summarized in Tuble 4.

*l atm =O.l MPa

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Table 4 The effect of various conditions (time, additives, CO pressure, and benzene) Yield of Products (wt %I 25.5 30.5 25.5 25.8 28.9 40.0 31.2 33.7 39.6 37.1 39.5 39.8 39.6 39.7 indicated on the processa Product Conversion c (wt %) 44.9 45.8 53.6 43.5 49.9 72.1 55.6 60.4 70.8 60.1 70.4 70.7 70.9 70.5 C 73.8 73.6 75.2 74.1 76.6 80.2 78.9 79.5 79.1 71.9 79.1 78.7 79.2 78.9 H 10.4 10.3 9.5 a.5 9.2 8.3 9.2 8.8 8.6 8.6 9.2 8.8 9.1 8.8 N 6.2 6.2 5.7 7.8 a.0 5.3 5.8 6.7 6.2 6.4 6.3 5.2 6.2 6.1 Composition (wt %)

Experiment 1e.f ,: 4d 5d 6 7 8 9 10 11 12 13 14 a Reaction

Catalyst NiS04 NiS04

A203

Time (h) 2 2 2 2 2 2 2 2 l/4 1 I2 2 4 ia

Benzene (cm31 20 20 20 20 20 5 10 20 20 20 20 20

conditions as previously

described unless otherwise

b Based on organic material c Based on carbon d Reaction carried out on dry algae e 6.8 MPa CO pressure f Adjusted to pH 9 with CaCO3 and Na+O,

Tab/e 5 Experiments

on other raw materialsa Product Composition (wt %) Conversion (wt%)b 4.1 9.8 13.1 6.6 13.5 36.5 c 70.7 73.2 73.1 72.3 70.6 71.0 H 6.4 6.5 7.2 6.9 6.8 7.8 N 6.8

Source Sugar Paper Cotton Starch Glycerol Protein (albumin)

Yield of Product (wt %) 2.4 5.5 7.2 3.6 7.5 24.7

a 20 ml benzene, 350C, b Based on carbon

2 h

Low temperature extraction

I Water,
T = 35oc Thermal reaction

salt,

glycerol

t = 12 h
initial pressure: 0.1013 MPa

Figure I A proposed process for the most economical of algae into fuel

conversion

DISCUSSION It is obvious that significant percentages of the combined carbon can be extracted by very simple means. This allows the formation of high quality liquid fuel containing practically no nitrogen or sulphur. Up to 25 wt % of the combined carbon can be extracted in this way. An additional special advantage was the fact that after the benzene extraction, the residue could easily be filtered, unlike the original slurry, and therefore excess water as well as salts can be removed providing a more concentrated material for further processing. This residue contains mainly proteins and glycerol with traces of starch and some inorganic salts. As shown in Table 5, glycerol and carbohydrates are practically not affected by the described thermal process. Proteins, however, are more quantitatively converted into benzenesoluble material by the above treatment. Since the efficiency of the process is practically unaffected by carbon monoxide pressure, or by added transition metal salts, one may assume that the main reaction taking place in the thermal process is a pyrolysis of the algal proteins. This was supported by the fact that albumin and other proteins, when treated under similar conditions, behave in the same manner. Thus, the overall process may be carried out in two ways: a one-step process, in which the slurry is heated to 35OC in presence of benzene, or a twostep process in which the algal lipids are extracted by means of benzene under mild conditions, the residue is filtered and in the second step the concentrated organic material is heated as described previously. The same overall conversion and yields of products are obtained by the two processes, but the latter appears more economical, since the thermal reaction is carried out on material free from salts and water, thus saving energy. In addition, the fraction extracted with benzene in the first step is almost free from nitrogen and sulphur, and does not need further treatment. A process can therefore be proposed as shown in Figure I. The fact that the best results are obtained when benzene is present in-situ in the thermal reaction, leads to the possibility of recycling the obtained liquid fuel itself as extracting solvent in the two steps. Another advantage is found

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Conversion of halophilic algae in to extractable oils: Y. Goldman et al.

Tab/e 6 Comparison of algae with other potential conversion feedstocks

Reaction and results Temperature Feedstock Peats2 (C) 350 Pressure fatm) a 550 (H,/CO) Cellulosic wastes12 380 100-330 (H21CO) Reagents Water K&03 (12) Ca(OH)2 Water Na2C03 Alcohol Organic Solvent Water NitOH) CafOH)2 Organic Solvent Benzene 1 40-50 Time (h) 2 Yield (wt %J 45

Conversion as carbon (wt%)

Productcomposition C H N

75

11

Solid wastett carbohydrates

400-455

1500

(H2)

314

30

85

14

Halophilic

Algae

350

l/2-3/4

40

72.1

80

a 1 atm = 0.1 MPa

in the fact that the combustion of the final residue (17 300 J g-r) may provide the energy required for the thermal reaction. It is interesting to compare (Table 6) the results obtained in this work with data given by other authors for different potential feedstocks. One can see that algae form a better starting material since higher conversion is achieved under more moderated conditions. Further studies for optimization and improvement of the process, as well as for elucidation of reaction mechanisms are now in progress. REFERENCES
1
Israeli Patent Pending, No. 57712, July 3, 1979

1 8 9

10 11 12

Appell, H. R., Fu, Y. C., Illig, E. G., Staffgen, F. W. and Miller, R. D. BuMines RI, 1975,8013 Cavalier, J. C. and Chormet, E. Fuel 1977,56,57 Cochran, N. P. Sci. Am. 1976,234(S), 24 Appell, H. R. and Wender, I. Div. Fuel Chem. Preprints. Am. Chem. Sot. 1968,12(3), 220 Work in progress at the Hebrew University of Jerusalem, Israel Anderson, L. L. B&fines IC 1972,8549,16 Appell, H. R., Fu, Y. C., Friedman, S., Yavorsky, P. M. and Wender, I. BuMines RI 1971,7560,20 Calvin, M. Green Factories C.E.N., March 29, 1978 Felbeck, G. T. Jr, Soil Sci. Sot. Am. Proc. 1965,48 Bloch, M. R. and Ginzburg, B. Z. unpublished results Kaufman, J. A., Gupta, D. U., Szatkowsky, T. S. and Weiss, A. H. Chem. Eng. World a(u), 1974,55

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