Project No. R5-7 COMPREHENSIVE RESEARCH ON RICE ‘UAL REPORT January 1, 1981 - Decenber 31, 1981 PROJECT TITLE: Analysis of Rice Straw as Papermaking, and Dissolving Pulp Grades PROJECT LEADER AND PRINCIPAL UC INVESTIGATORS: S. Hl, Zeronian and D. L. Brink (Project Leaders) D. L. Brink and S. H. Zeronian (Principal Investigators) LEVEL OF 1981 FUNDING: $47,400 oayecrives: 1, To establish pulping conditions that can be used to prepare Dleachable grade pulps from rice straw using modified soda pulping techniques and to establish the properties of the pulp for papermaking. Experiments conducted under the supervision of Or. D. L. brink, ULE. Forest Products Laboratory. 2, To prepare and to establish the properties of dissolving-grade or ‘chemical" grade celluloses made fron rice straw pulp. Experinents conducted under the supervision of Dr. 8. Hl. Zeronian, Division of Textiles and Clothing, UC Davis Caspus. 5. To develop commercial uses for rice straw. Experiments conducted under the supervision of Dr. S. H. Zeronian and Dr. D. L. Brink. EXPERIMENTS CONDUCTED BY LOCATION TO ACCOMPLISH OBJECTIVES: Objective 1 (Or. D. L. Brink): a) Optimize the conditions of soda pulping. fan contents OF aTt pulps prepared darine TBio were run to add to data required to select a process for preparing a bleachable-grade pulp, b) Evaluate modified soda processes, particularly the nitric oxide-onygent soda (W0S) process, 182Five NOS pulping reactions, two NOSC, i.e., NO pretreatment and sodiua carbonate pulping reactions and one kraft (k) pulping’ reaction were carried out. Evaluation of the zesults included screening the pulp to provide fan 8-cut (Pulp passes through slot 0.008 inch wide) accepts and rejects fraction, ‘The kappa nunber, chlorine demands and ash contents of the accepts pulp and residual sodium hydroxide in the spent (black) liquors Mere determined, Beater runs were made on six of the pulps to determine basic physical strengths including tensile (breaking length), burst (burst factor) and internal tear (tear factor). Also, Canadian Standard Freeness, refining rates, and densities of all samples in a beater run for each’ pulp wore attained. ©) Bleaching conditions using CEM and CBIEH sequences. Eleven bleaching experiments were carried out during 1981. Ten of these were run using NOS pulps and included one CENEI and six CEH Sequences and three single stages. The brightness of all bleached pulps, ash contents of selected pulps, and residual active chlorine in the bleach Liquor were determined. 4) Rice straw cleaning to rexove high silica-containing fractions. ico Stra was Obteinelenith the cooperation oF MF. George MiTTer, Cooperative Extension, UC Davis. ‘Thee different amples vere prepared. Whole rive stray was’ cue in approximately 3-inch Lengths using a band saw at UC FPL. 2, hole rice straw was refined using the W.H.O. tub grinder evaluated by Agricultural Engineering, UC Davis. This equipment was fitted with a screen having 3-inch openings. ‘The product was classified using an 18-inch Sweco Iaboratory sereen Into +20 and 20 mesh material. The 420-mesh material was used in pulping. 5. Whole rice stray vas refined at the Agricultural Engineering Departaent, UC Davis, using an Allis-Chalners Shear-Rar Forage Chopper, Nodel 782, Fitted with a screen having I-inch openings. ‘This product yas then classified fas described in 2 and the +20 mesh material was used in pulping. ‘Yields and ash contents of the various fractions collected were determined. Bulk density of the material prepared under ten 3 was determined. ©) Alternative spent-Liquor treatments. Work as been initiated to adapt analytical procedures for the deteraination of silica in rice stray, unbleached and bleached pulps land spent Liquors for use in establishing material balances on silica introduced with rice straw. 183Objective 2 (Or. 8. H. Zeronian): Rice strav analysis. Anslysis was conducted with an energy disporsive x-ray fluorescence spectrometer, Conparison of modo1 cellulose prepared fron rice stray and east dissolving grade pulp ‘The model cellulose vas an alpha cellulose prepared from rice straw holocellulose using standard techniques and its composition compared to that of a commercial pulp used in cellulose acetate manufacture using established analytical methods. indus Potential extraction procedures to be used for production of dissolving ‘grade pulps from rice straw pulps. ‘The process studied involved treating rice straw holocel lulose with 4 solution containing 128 sodium hydroxide and Gt borax (both weight per Yolume) at 30°C for 1 hour. To terminate the treatment the solution was Filtered off using suction and the sample washed to remove all traces of alkali before drying. Direct acetylation of rice straw. Acetylations were done with an acetic anhydride/acctic acid/sulfuric acid reagent solution. The acetylations were conducted on rice straw extracted with ethanoi/benzone and then hot water followed by various pretreatnents to activate the rice strav. Acetylation was conducted at temperatures up to 50°C. Objective 5 (Dr. $, H. Zeronian) a) Formaldehyde-treated rice stray. Finely cut rice strav was treated with 354 fornsldchyde solution in the presence of sulfuric acid of various strengths at S0"C for 2 hr. b) Rice straw sulfonation, Finely cut rice straw was treated with sodium bisulfite solution of various strengths at different plls and temperatures. Absorption of metal ions. 1 g of substrate was agitated at room temperature with 100 EL of solution containing a known concentration of metal ions for 18 hr. The suspension was then filtered. Part of the filtrate was used to determine the pl of the solution. The rest was used to analyse the concentration of the metal ions in the solution using a Perkin-Elner Atomic Absorption Spectrophotoneter. 184criterion of low ash content for a dissolving-grade pulp appears to be achievable. Relatively high brightness of NOS pulps have been obtained by bleaching with a simple CEH sequence (Run no. 18) and even by a single H stage (run nos. 17 and 17A), Also, a rerun of brightness obtained using chlorine dioxide in CED and CEDED sequences has shown that high bright~ esses were achieved, This is contrary to the results reported in 1980 land has been attributed to a malfunction of the brightness meter. Further work is required to correlate conditions of rice straw pulp bleaching With results obtained in order to establish feasibility in the prepara- tion of a dissolving-grade pulp. 4) Rice straw cleaning to renove silica-containing fractions. Rice Straw" cleaning to Fenove high silice-containing fractions contributing Little or no fiber has involved the use of equipment described under ‘experiments conducted by Location to accomplish objectives; objective 1, item d. Samples of rice straw prepared by procedures 2 and 5 were classified using an 18-inch Sweco vibratory Screen. Results are given in Table IV. Ash content of the two straw sanples tested were 13.4% and about 198. "A minor portion of this ash is due to admixed inorganic hatter clinging to the strax; a major portion is due to the deposition Of inorganie matter within the plant tissues and especially in the Jeaves, The mechanical pretreatnents used, based on the summations of tho ash in the -20 fractions yielded a fines fraction containing about 3:2 to 1,58 of the total inorganic ash per percent of the total weight of the straw in the fines fraction. Thus, dry screening provides a System for renoval of fines but does not strongly beneticiate The accepts portion of the straw. ©) Alternative spent-Liquor treatments, Analytical procedures for deteraination of the silica content of straw, unbleached pulp, bleached pulp, and spent pulping and bleaching ‘agents have been initiated, A process to eliminate silica is being dosigned. 1) Dissolving-grade pulp for evaluation by Dr. Zeronian under et Cnty smal samples of pulp have been submitted pending selection of the pulping process to be used and selection of a satisfactory bleaching sequence to provide a low ash content bleached pulp. RESULTS UNDER ORJECTIVE 2: Rice straw analysis ‘The inorganic matter (ash) present in the rice straw used in this study was examined by x-ray fluorescence to complete the analysis jnitiated in the last report, It was found to be rich in silicon, -186-calcium and potassium, Traces of such elenents as zinc, manganese and iron were also present. warison of model cellulose prepared from rice strax and an industrial dissolving grade pulp (Table V) ‘The Lignin content (0.38%) of the model cellulose, is comparable to that of the commercial pulp (0.208). The ash content is markedly high in the nodal cellulose indicating that inorganic materials will have to be eliminated prior to or during the pulping process. These naterials appear to be tenaciously held by the pulp since they are not being resoved in the caustic treatnents given to the holocel lulose to extract the non-cellulosic polysaccharides (henicelluloses). The U.c. Forest Products Laboratory have been able to establish procedures to Femove inorganic matter during processing. Thus it is not antici- pated that inorganic residues will be a problem during the refining Of their pulps to produce dissolving grade pulps from rice straw ‘The degree of polymerization (DP) of the model cellulose (1490) is significantly lover than that of the commercial pulp (2370), but higher than values reported in the Literature for rice straw pulps, which range from 580 to 1252. A broad range is found in the DP of Commercial pulps used for acotate production from about 1200 to 3000, In terms of suitability for conversion to textile fibers, then the data Wwe have obtained from our model cellulose indicates. that ‘the chain Tength of rice straw cellulose is adequate, In fact, a lover OP aay be acceptable since the DP of the ultinate cellulose acetate fiber is approximately 250 to 400. It can be concluded from a comparison of the suger analyses of the nodel cellulose and the holocellulose (Table VI) that the removal of hemiceLluloses has been successfully accomplished by the alkali extraction used in the preparation of our model cellulose. An even greater portion of henicelluloses could probably be renoved by other nethods or additional extractions. To facilitate analysis of the changes in composition which occurred during processing, average data Yalues obtained for holocellulose and model cellulose have heen con- verted to percentages based on rice straw in Table VI. Thus data in this table are not dizectly comparable to data given in Table VII of this report. ith the exception of a relatively high xylose content, sugar analyses indicated that the composition of our nodel cellulose from rice straw is comparable to the comsercial pulp, and the mannose content is lover (Table VII). For successful acetate production, the xylose content must be further reduced to avoid excessive haze and -187-acetylation of the rice straw was attempted utilizing an acetic anhydride/acetic acid/sulfuric acid reagent solution. in prelininary experinents we obtained only small yields of cellulose acetate (about 34 based on weight of rice straw). Yields have bean improved markedly, by Increasing the reactivity of the rice straw to the acetylating Teagent. One of the attempts included refluxing the rice straw with 12% NaOii for 30 minutes under nitrogen, After this treatment the rice straw was washed with vater; the water displaced by glacial acetic acid and then the acetylating reagent was added. ‘The yield was 42.4%, The product did not contain any inorganic residue. This cellulose acetate is now being characterized Most of the rice straw, which dissolved in the reaction solution in the earlier experiments, ‘renained in the solution after the cellulose acetate had been precipitated out and removed. We are now attempting to extract the renaining solute. The solute will then be characterized to determine whether it has any comercial potential. Results undor objective ‘The purpose of this part of the study was to investigate the effectiveness of rice straw for removing toxic heavy metal ions from polluted water. There is water soluble coloring matter in rice stray However, it ean be insolubilized by treatnent with fornaldchyde in the presence of acid. We determined that this insolubilization required « hnuch lower concentration of formaldehyde and sulfuric acid than had been used hitherto for similar products (Table VIII). In Table VIII the success in preventing dissolution of the coloring matter can be seen from the absorbance colunn which gives the absorbance to ultraviolet Light at 191.4 nm of the distilled water used to extract rice stray for 8 hr. in'a soxhlet. We also observed that increasing the concen- tration of these reagents increased the copper binding capacity of the rice straw, (Table 1X). In studies to enhance the ion exchange properties of rice straw we partially sulfonated it. The ion-exchange properties of partially Sulfonated rice straw were the most promising of commercial utility of ‘the products we prepared. In this modified rice straw we have sulfonic 45 well as carboxyl. groups and they appear to complement each other in the removal of metal’ ions from solutions. Thus metal ions of much wider range of ionic size can be renoved fron industrial and mining waste waters by the partially sulfonated rice straw. For exanple, the sulfonated rice straw renoves more manganese ions from a solution of manganese acetate than tho fornaldehyde-treated rice straw (Table X) but it extracts less copper ions from a copper sulfate solution than the latter material (Table IX). -169-PUBLICATIONS OR REPORTS: McGee, Kaye, M. Utilization of rice straw for production of cellulose acetate. MIS. Thesis, University of California, Davis, 1980, Zeronian, S. H., D. L. Brink and K. M. McGee. Rice straw for paper~ taking and dissolving pulp grades. Agricultural Residue Managenont. ‘A focus on rice straw. A Report of the Residue Management Task Force, University of California, 120-131, August, 1981 CONCISE GENERAL SUMMARY OF CURRENT YEAR'S RESULTS Rice straw pulps prepared by the soda process, which is conven- tionally used, were shown to have ash contents that, after bleaching and preparation of a dissolving-grade pulp would probably be higher than could be tolerated. Also, the bleach requirements of these pulps were high. Accordingly, further work on soda pulping was deferred in order to screen the modified soda process using nitric oxide-oxygen pretreatuent. Following bleaching NOS pulps ash contents below IS have been achieved and bleach requirenents are low. The Physical properties of the pulps prepared are equivalent to those of kraft pulps and’ better than those prepared by other processes. The NOS pulps have been bieached to relatively high brightness for a papermaking grade pulp using ‘Sequences with either hypochlorite or chlorine dioxide. Chopping the straw followed by dry screening has elininated 2 portion of inorganic material that could comprise a part of tiie sit ti un unbleached pulp. ‘The pulping and bleaching results indicated that preparation of & dissolving-grade pulp using a NOS process and a conventional bleaching process may be technically feasible. Further work is required to strengthen this conclusion. A model cellulose was prepared from rice straw to provide a comparison for dissolving grade celluloses prepared fron rice straw pulps manufactured by the U.c. Forest Products Laboratory, The Properties of the model rice straw cellulose were compared with a Comercial dissolving grade cellulose pulp which had been manufactured from wood for the purpose of making acetate rayon fibers. A technique was developed for obtaining dissolving grade cellulose from impure rice straw pulps. A study is being made to determine the feasibility of obtaining cellulose acetate by dizect acetylation of the rice straw and ‘thus eliminating the need to initially make @ purified pulp from the rice straw for acetylation. A yield of 42.4% cellulose acetate based fon weight of rice straw has been achieved so far. The properties of this acetate are being determined. A study has been made to determine the suitability of rice straw as san ion-exchange material for the removal of heavy metal ions fron -190-industrial and mining waste waters. The rice straw was chemically modi- fied with either formaldehyde oF by partial sulfonation. Sulfonated rice straw behaved like a strong as well as weak polyelectrolyte. The results obtained so far indicate that sulfonated rice straw could be a useful polyelectrolyte. Table I. Ash Content of Soda and Soda Anthraquinone Pulp Reaction Nunber Accepts Pulp H Factor Ash Content Keppa ogee: Mabe srs 1-0 12.3 10.9 568 RS 2-0 no na 245 srs 3-0 12 10.9 170 srs 4-0 64 ne ne SaQRS 1-0 5.5 no 10. "percentage based on oven dried straw -191-es 6s vs so este seta eet, - wut wre = ove sgee yo 3 157 ve vo re ci ee wet ° ro vo se i coe al sate ca ns er nz nat wot wth ora, SHEL mao “ant “atanO wes se besser ESE ESR se oe mas-oomN te of : : : : : ef 36050 Fagg rm : = on ° on on 380s He a za 2x01 o we aot * © o 5 t 2 t oO * a om “uyw *um-2n-30L ut out out ot om on tate ay aameaaay - o a o oo uu fea, : 6 6 06 6s be faunas : eo 201 bol aL at ofnes munseosenoi : ore roe vor eo : 2 # @ ® 2 Row : 2 2 2 2 2 2 o@ : ot ot we oe oe oe oe t t t t z 2 . 2 __soeasaat tojue4 Er oa oH a Te oz Er oa cr ison st5ON St ry mesg 2 “TE BUReL 192own a ay ware we om oa wen ore wt ote woe ote wc ow ve 25 ‘oe sete vo wo we woe wo 2 2 eee wg 0 ‘SERS THORTS st “eae ng wesas 2318 Joy suns put Fy oy sins Ly oar seas Heuanbes 960155 Hy -atonoyous, seorzns F096 wus © nds wHADeUAL 5, sea dine a0 3 wo st ses wo se se su oro set uso 5S ot Su a508 ee ve ost pee et susan ze eet uso re re at son ony se sm st sow sus o1ysoug ay ey oy woira007 ———S 1 sae, @ a ut a a tenor -193-voor oon ra 194TABLE ¥ COMPOSITION OF MODI CELLULOSE AND COMMERCIAL PULP Moisture 5.63 6.31 Ash 9.3 0.10 Lignin 0.38 0.20 Degree of Polymerization so 2370 NOTE: AIL values except Degree of Polymerization expressed as percentage of oven-dry weight. Athe moisture values are not directly comparable since the noisture uptake of alpha cellulose was determined as absorption fnoisture regain, while that of Commercial Pulp was desorption regain. ~195-‘TABLE. VI COMPOSITION OP RICE STRAM, HOLOCELLULOSE AND ‘MODEL CELLULOSE EXPRESSED AS PERCENTAGE (OF OVEN-DRY RICE STRAW Rice Stray Holocellulose Model Cellulose Ash 15.86 12.20 3.47 Lignin 97 1.65 0.14 Raamnose 0.03 v.02 0.00 Fucose 0.02 0.02 0.00 Arabinose 2.41 247 0.03 ylose 1.1 1.69 0.46 Mannose 0.42 0.20 0.02 Galactose 0.78 0.82 0.01 Glucose 2.40 1.90 24s Uronic acids 0.09 0.12 0.02 7196TABLE VIL SUGAR ANALYSIS OF MODEL CELLULOSE AND COMMERCIAL PULP Se So Nodel Cellulose Commercial Pulp average Range Average Range Rhamnose | 0.00 = 0.00 — Fucose 0.00 aoa 0.00 o pesbinose | 0.07 0.05-0.11 0.04 0,00-0.08, xylose 1az1,10-1.39 0.48 0.35-0.53 Mannose 0.08 0,00-0.09 0.28 0.17-0.27 Giactose | 0.01 0.00-0.05 0.00 Glucose 6.50 5.89-7.38, 3.78 3.02-4.51 Uronic acids| 0.05 S 0.07 ot nore: ‘A11 values expressed as percentage of oven-dry weight. Neutral sugars are averages of 2 injections each of 2 samples; uronic acids are the average of duplicate determinations. -197-TABLE. VET (COMPARISON OF THE ABSORBANCE OF WATER EXTRACT FROM ‘MODIFIED AND UNMODIFIED RICE STRAW Absorbance ® Moditication condtttons pe iota na Substrate Rice straw Formldehyde Sulfuric code parte pacte Sit os contro 4.06 orms 1010 oa ox | 0.700 6.65 crs 110011 oa or | ors es orms 0 02s on | 0.650 na orms 101 ors on | 0.655 nat orms 110 oso oa | Ouest 7.05 orms zor to om | ces 102 ors 1110 1.0 on | 0.66 2.08 GSBSTRS XI Partiatty sutfonated 0.680 6.83 GRS = Ground rice straw; GFTRS = Ground formaldehyde treated rice straw; GSBSTRS = Ground sodium bisulfite treated rice straw Kbsorbance of hodiFied Fice straw extract — -198-TABLE 1X UPTAKE OF COPPER FROM COPPER ACETATE SOLUTION: INITIAL pH 5.95 a a Substrate® Initial concentration Final Concentration Final pil Pr pa rs 30.4 9 7.18 GPTRS 1401, 39.4 16.7 ars eres 1210 39.4 9.2 4.40 crres 1110, 48.4 28 4.50 (osBSTRS XI 48.4 7.08 5.25 ae 4 See footnote in TABLE VIIT TABLE [UPTAKE OF MANGANESE FROM MANGANESE ACETATE SOLUTION: INITIAL pH 5.72 eee a Substrate” Initial concentration Final concentration Final pH cas 49.85 28.28 6.78 GrrRS 1401, 49.85 28.60 5.01 rres 1210 49.85 30.25 5.00 Gems 1110 49.85 27.40 4.82 GsasTRS X1 49.85, 14.25 5.61 ® see footnote in TABLE VIII -199-