Journal of Cleaner Production 17 (2009) 16031606

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Journal of Cleaner Production

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A salt-free pickling regime for hides and skins using oxazolidine

Kai Li a, b, Hui Chen a, Yajuan Wang a, Zhihua Shan a, *, Jeff Yang c, Patrick Brutto c
a

The Key Laboratory of Leather Chemistry and Engineering of the Ministry of Education, Sichuan University, Chengdu 610065, P.R. China Hunan Entry-Exit Inspection and Quarantine Bureau, P.R. China c The Dow Chemical Company Dow Biocides, Midland, MI 48674, USA
b

a r t i c l e i n f o
Article history: Received 12 July 2008 Received in revised form 10 June 2009 Accepted 12 June 2009 Available online 21 June 2009 Keywords: Salt-free pickling Swelling Chrome uptake Oxazolidine

a b s t r a c t
During the last few decades new materials and technologies have being studied and applied in order to reduce the ecological impact of leather production. Severe restrictions imposed by the pollution control authorities on the disposal of chromium, total dissolved solids and chlorides in tannery efuents have forced the tanners and researchers to look for eco-benign pickling and tanning processes. In this study, we would focus on the novel process development of pickling with the presence of oxazolidine based product. Investigations indicated that oxazolidine is a potential material to replace neutral salts in pickling and, realize high chrome exhaustion in the subsequential chrome tanning. 2009 Elsevier Ltd. All rights reserved.

1. Introduction In the conversion of hides and skins to chromium tanned leather, an intermediate pickling process is normally performed before tanning, which brings the entire collagen matrix to uniform chemical and physical conditions to prevent the rapid combination of the skin substrate with chromium compound [1], therefore enables the even penetration (without precipitation) of chromium into the collagen matrix. Salt, usually sodium chloride or sometimes sodium sulphate and the salts of the organic acids such as sodium formate and sodium acetate, are previously added to restrict the swelling of the collagen in the acidic medium [2]. The acidic treatment minimizes the negative charge of the carboxyl groups and maximizes the positive charge of the amino groups of the collagen peptides thus making the pelt positively charged. The repellent effect of like charge widens the spacing of the collagen peptides resulting in collagen swelling. Whats more, the conglutination and crosslinking of the collagen bres is partially destroyed and the stability of the collagen weakened. Such swelling and disruption of crosslinking can probably be avoided with the presence of neutral salt. The prior addition of neutral salt into the pickling bath increases the ion concentration resulting in high osmotic pressure. This enhances the migration of water from the inside of the collagen to the outside, resulting in a decrease of the

* Corresponding author. E-mail address: likai152142@163.com (Z. Shan). 0959-6526/$ see front matter 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.jclepro.2009.06.004

ion concentration in the pickling bath. The ionization of the acid and the salt is thereby increased. The ions then penetrate the collagen under osmotic pressure, passivating the carboxyl groups and making the amino groups exist as amine salts. The swelling of the collagen is avoided [3]. Although it is effective and inexpensive, the traditional process described above suffers in that high salt concentrations in the tannery efuent can be a serious environmental problem: contributes to about 35% total dissolved solids (TDS) in the efuents [1]. The TDS load in the waste water is high due to the great application of salt in preservation and tanning stages of life cycle of leather [4]. Salinity and TDS in tannery efuents is a major environmental concern where the efuents are used for irrigation. High salinity in irrigation water causes high osmotic pressure, resulting in dehydration and retarded growth of salt-intolerant crops. In addition, high concentrations of sodium ions in irrigation water can adversely affect soil structure by causing dispersion of clay [5]. Whats more, in the conventional pickling process the temperature is usually maintained at or below 28  C because raw skins have a low shrinkage temperature, usually below 40  C at this stage. Higher temperatures would lead to loose grain and shrinkage of the skin. As a result, the pickling process usually takes a long time and often requires workers to add ice to control the temperature. So the process is labor intensive and higher cost. To overcome the environmental problems of TDS related to neutral salts in the efuent, recycle/reuse of pickle liquor for the subsequent batches as well as resorting to pickle free alum-chrome combination tanning systems have been studied [6]. Salt free

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pickling using naphthalene sulfonic acid is well known and extensively studied [7]. Pickle-less tanning system using chrome syntan and modied basic chromium sulfate (BCS) has been established [1,8]. Pickle and basication free tanning system using commercial BCS has also been developed for cowhides [9]. An enzyme-driven three-step tanning process applicable to hides and skins [10,1114] has been developed that involves enzymatic dehairing, enzyme-based ber opening, and pickle-free chrome tanning at pH 4.08.0. An approach of pickle-less enzymatic vegetable tanning was developed by Kurian Joseph and N. Nithya to decrease TDS and chlorides using pickle-less vegetable tanning by avoiding the use of salt in the pickling process [15]. An integrated chemo-enzymatic methodology has been explored by R. Aravindhan and his colleagues resulted in decreasing of COD and TS (total solids) loads by 67 and 78% [16]. The purpose of our research and paper is to develop a novel pickling process to reduce or eliminate the use of neutral salts thereby avoiding the shortcomings of the traditional pickling process. Research completed during the past few decades has shown that salt-free pickling processes should allow blocking of collagen amino groups at relatively low pH (around 3.0 or lower). This prevents protonation of the amino groups thereby avoiding likecharge repulsion and swelling of the collagen. 2. Experiments and results 2.1. Aims of experiments Experiments in this study were focus on developing a novel pickling method with the presence of oxazolidine based product to reduce the environmental impact from neutral salts in pickling step. The novel regime should be practicable and economical. 2.2. Methods and procedures Oxazolidine chemistry was rst introduced to the leather industry by Samir DasGupta and patented in the 1970s [17]. The main utilization of oxazolidines in the leather industry has been in tanning, retanning and nishing processes. Leathers obtained from processes using oxazolidines are soft and light in color. Oxazolidines can rapidly raise the shrinkage temperature of skin over 60  C, often in less than 30 min, and tend to give higher shrinkage temperatures at higher pH. Addition of oxazolidine into the delimed pelt allows higher temperatures during pickling than the conventional processes. That is to say, there is not as much concern about skin shrinkage and loose grain when oxazolidine is used prior to pickling. In this novel pickling process oxazolidine was introduced starting from delimed pelt using the following steps (offers are on delimed weight): Acetic acid (1:10 v/v aqueous solution) until pH 5.06.0; ZOLDINE ZE 14% (based on the weight of pelt) to desired time; Formic acid sulphuric acid (1:10 v/v aqueous solution) until pH 3.0 0.1; Stand overnight, chrome tanning, dyeing/fatliquoring. In order to have a comparative study, normal pickling to pH 3.0 0.1 was conducted using 8% (wt) sodium chloride. Subsequent tanning with 6% (wt) chrome salt allowed us observe the exhaustion of chromium. The chrome-tanned crust was then subjected to standard dyeing/fatliquoring processes. The shrinkage temperature of the ZE-treated skin and chrome-tanned

crust were measured, and the data were reported as the mean of two determinations. The delimed pelt, pickled pelt and chrome tanned crust were weighed to determine the degree of swelling. The Cr2O3 content of the tanned crust was also determined and the uptake of chrome salt calculated. The data were reported as the mean of two determinations. A nephelometer was used to measure progress of the fatliquoring step. The initial turbidity of the fatliquoring bath was measured on a dilution of 1 mL fatliquor bath in 50 mL; this was repeated every 15 min. The fatliquoring agent was a blend of several kinds of common commercially available fatliquoring agents, added at 16% on the weight of tanned crust. The dyeing speed was investigated using a spectrometer to measure initial dye absorption and absorption at 15 min intervals thereafter. Exactly 1 mL of dyeing liquor was diluted to 100 mL for these measurements. The dye was a common commercially available black dye, added at 2% based on the weight of tanned crust. 2.3. Materials and reagents Oxazolidine. ZOLDINE ZE, a bisoxazolidine from ANGUS Chemical Company, is supplied at approximately 95% actives. The pH of this material (0.1 M aqueous at 20  C) is 10.2. Basic chrome sulfate. Common commercially available material containing 28.33% (wt)Cr2O3; Hide and skin substrates. Delimed and pickled sheepskin pelts were purchased from local tanneries. The delimed pelts were received at pH 7.8 and the pickled pelts were received at pH 3.0; Ts of delimed pelt: 58.7  C; Ts of pickled pelt: 61.8  C; Drums. Laboratory scale trials were conducted on pieces measuring 20 25 cm, with average weight 100 g. The pieces were processed in cylindrical stainless steel drums (40 cm diameter, 20 cm length) which were rotating in a temperature controlled water bath. 2.4. Results The results obtained are presented in Tables 1 and 2, Figs. 1 and 2. As expected, treatment of the delimed pelt with ZE controlled swelling during the pickling process with the absence of neutral salts. Table 1 shows that 1% ZE is not enough to prevent swelling during pickling, there was still nearly 10% increase in weight. However there was a decrease of swelling after chrome tanning

Table 1 Percent increase in substrate weight as a measure of swelling. Pickling regime Acid only (no salt) 8% Salt acid (standard pickling) 1% ZE acid 2% ZE acid 3% ZE acid 4% ZE acid Increase in weighta (%) 7090 35 to 40 8.3 1.6 2.7 6.7 Ts1 ( C) 61.8 76.0 78.8 81.1 83.7 Increase in weightb (%) 30 6.4 5.9 2.3 0.4 Ts2 ( C) 102.0 103.8 106.7 106.9 107.5

Ts1 (  C): Ts of skin after pickling (with & without oxazolidine); Ts2(  C): Ts of skin after chrome tanning. a Percent weight gain (loss) before/after pickling. b Percent weight gain (loss) before/after tanning.

K. Li et al. / Journal of Cleaner Production 17 (2009) 16031606 Table 2 Effects of different pickling regimes on chrome uptake. Pickling regime 8% 1% 2% 3% 4% Salt (standard pickle) acid ZE acid ZE acid ZE acid ZE acid Cr2O3 (%) 4.21 4.78 5.27 5.37 5.42 Uptake (%) 71.9 80.4 88.5 90.3 91.1

1605

Cr2O3%: Cr2O3 content of completely dried chrome-tanned crust.

100

Fig. 3. Assumed mechanism of oxazolidinecollagen combination. (P-NH2 presents the amino group of the collagen side-chain.)

80

60

40

20

8 2

salt + acid ZE + acid

15

30

45

60

75

90

105

Time, min
Fig. 1. The uptake of fatliquor under different pickling processes.

indicating that even 1% ZE has a positive effect. With a ZE dosage of 2% or more the pelt does not swell at all during pickling. The Cr2O3 content and shrinkage temperature of crust increase with increasing offer of ZE. Considering the cost and application effect, 2% ZE is enough to carry out the novel pickling process to replace the neutral salts. The results of subsequent dyeing and fatliquoring process are presented in Figs. 1 and 2. Figs. 1 and 2 indicate that the pickling process with ZOLDINE ZE did not adversely affect the subsequent dyeing and fatliquoring processes. Chrome tanned crust treated with ZOLDINE ZE before pickling exhibited the same afnity to fatliquor and dye as traditional pickled crust did. As reported in the literature [18,19], we can explain the results as follows. The covalent bonding of oxazolidine and the amino

groups of collagen is favored by relatively high pH relative to the isoelectric point of the collagen (close to pH 5.0), according to following mechanism (Fig. 3): hydrolysis ring-open binding. The reaction of oxazolidine with amino groups of the collagen side-chains prevents them from combining with hydrogen ions. Swelling of the pickling pelt is therefore prevented. And the combining of collagen with chromium during the subsequent chrome tanning step increases because of the previously exposed carboxyl groups, resulting in relatively higher chrome uptake. Further investigations were launched into the physicalmechanical properties of the leather obtained from this new pickling process. The ZE pickled leather was treated with traditional tanning/dyeing/fatliquoring processes, and the tensile strength, elongation and tear strength of the nished leather were measured; the results are reported below in Table 3. As indicated in Table 3, the novel pickling method with ZE provides leather with identical tensile strength to that produced with traditional pickling. The leather produced with ZE has superior elongation, and although there is a signicant difference in the tear strength the value is far above the National Standard. All things considered, leather obtained from our novel pickling regime with ZE complies with the main Chinese standard requirements and ISO standard for garment leather.

Uptake,

3. Industrial application Oxazolidine based product has being widely used in the tanneries both in the north and south of China. About 1 ton of such product is consumed every day in the processes of salt-free pickling and chrome-free combination tannages. The above mentioned salt-free pickling regime was conducted in Ningbo Feifan Leather Production Company and Wenzhou Weishuo Leather Production Company since May of 2006, 3000 sheep skins every day for each company. The main differences between the traditional and the novel regime are displayed in Table 4 below.

100

80

60

Uptake,

40

Table 3 Effects of different pickling regimes on the physical-mechanical properties. Pickling regimesa Tensile strength (MPa) Elongation (%) Tear strength (N/mm) 22.934 22.727 !6.5 82.710 72.565 2060 71.242 94.317 !18 !20

20

8 2 0 15 30 45 60

salt + acid ZE + acid 75 90

Pickling with ZE Pickling with salt National standardb ISOc

a b c

Time, min
Fig. 2. The uptake of dye under different pickling processes.

Goat skin, tanned with 6% basic chrome sulfate. China Light Industry Standard Collection Garment Leather (QB 18721993). ISO/FDIS 14931: 2003 Leather Guide to the selection of leather for apparel (excluding furs).

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Table 4 The main differences between the two pickling regimes. Items Neutral salt Oxazolidine ZE Ice (control the temperature) Chromium (tanning and retanning) Dosage Uptake Glutaraldehyde (retanning) Water (washing off the neutral salt) COD (before treatment) BOD (before treatment) Total dissolved chlorides Total dissolved solids Undegradable pollutants Volume of efuent (Comparatively) Erodibility to equipment Ts Traditional regime 8% 0 20% 10% 7075% 2% 400% 15002000 4001000 10,00015,000 35,00055,000 Neutral salt and chromium 1 Serious >90  C Novel regime 0 2% 0 7% >90% 0 100% 12001800 8001200 500010,000 20,00035,000 Chromium 0.8 Slight 48  C higher

Financial support from the Dow Chemical Company, Jeff Yang and Patrick Brutto from the Dow Chemical Company are gracefully acknowledged.

References
[1] Suresh V, Kanthimathi M, Thanikaivelan P, Raghava Rao J, Unni Nair B. An improved product-process for cleaner chrome tanning in leather processing. Journal of Cleaner Production 2001;9:48391. [2] Pojer Peter M, Huynh Chi P. A salt-free pickling regime for hides and skins. In: Proceedings of the XXV IULTCS Congress; 1999. Madras (India). [3] Money Catherine A. Clean technology challenges part 1. In: Proceedings of the XXV IULTCS Congress; 1999. Madras (India). [4] Joseph Kurian, Nithya N. Material ows in the life cycle of leather. Journal of Cleaner Production 2009;17:67682. [5] Manzo G, Maffei G. Elimination of the sodium chloride from the pickling. In: Proceedings of XXVII IULTCS; 2003. Mexico. [6] Sivakumar V, Sundar V John, Rangasamy T, Muralidharan C, Swaminathan G. Management of total dissolved solids in tanning process through improved techniques. Journal of Cleaner Production 2005;13:699703. [7] Palop R, Marsal A. Auxiliary agents with non-swelling capacity used in pickling/tanning processes. Journal of the Society of Leather Technologists and Chemists 2002;86:13942. [8] Thanikaivelan P, Kanthimathi M, Rao JR, Nair BU. A novel formaldehyde free synthetic chrome tanning agent for pickle less chrome tanning: comparative study on syntan versus modied basic chromium sulfate. Journal of the American Leather Chemists Association 2002;97:12736. [9] Legesse W, Thanikaivelan P, Rao JR, Nair BU. Underlying principles in chrome tanning: part 1. Conceptual designing of pickle-less tanning. Journal of the American Leather Chemists Association 2002;97:47586. [10] Aravindhan R, et al. A biodriven lime and pickle free tanning paves way for greener garment leather production. The Journal of the American Leather Chemists Association 2004;99:5366. [11] Saravanabhavan S, et al. Green solution for tannery pollution: effect of enzyme based lime-free unhairing and bre opening in combination with pickle-free chrome tanning. Green Chem 2003;5:70714. [12] Thanikaivelan P, et al. Biointervention makes leather processing greener: an integrated cleansing and tanning system. Environ Sci Technol 2003;37: 260917. [13] Thanikaivelan P, et al. A novel three step bioprocess in leather processing. Patent Facilitating Centre; 2002. [14] Saravanabhavan S, et al. Natural leathers from natural materials: progressing towards a new arena in leather processing. Environ Sci Technol 2004;38: 8719. [15] Kanth Swarna V, Venba R, Madhan B, Chandrababu NK, Sadulla S. Cleaner tanning practices for tannery pollution abatement: role of enzymes in eco-friendly vegetable tanning. Journal of Cleaner Production 2009;17:50715. [16] Aravindhan R, Saravanabhavan S, Thanikaivelan P, Raghava Rao J, Unni Nair B. A chemo-enzymatic pathway leads towards zero discharge tanning. Journal of Cleaner Production 2007;15:121727. [17] DasGupta S. Oxazolidine tannage [P]. British Patent, 1481508; 1973. [18] DAquino A, Barbani N, DElia G, Lupinacci D, Naviglio B, Seggiani M, et al. Combined organic tanning based on mimosa and oxazolidine: development of a simi-industrial scale process for high-quality bovine leather. Journal of the Society of Leather Technologists and Chemists 2004;88:4755. [19] Deb Choudhury Santanu, DasGupta Samir, Norris Gillian E. Unravelling the mechanism of the interactions of oxazolidine A and E with collagens in ovine skin. International Journal of Biological Macromolecules 2007;40: 35161.

In the industrial production, no neutral salt is needed to control the swelling when Oxazolidine ZE is introduced and it doesnt affect the following processes. It is obvious that the cost of Oxazolidine is higher than neutral salt, but when neutral salt is replaced by Oxazolidine, it means lower cost on ice, water, tanning and retanning agent, equipment, labor and efuent management. So the total cost of the novel pickling is not necessarily higher than traditional regime. Since Oxazolidine and its derivatives have being widely used in medicine, agriculture and biochemistry, no literature about its toxicity is published till today, so there is no evidence of the harm on the human health if Oxazolidine treated leather is used. 4. Conclusions 1. Pretreatment with 2% ZOLDINE ZE before pickling controls swelling of pelt in the picking process with the absence of neutral salts, it doesnt adversely affect the subsequent dyeing or fatliquoring process and furthermore improves chrome absorption and the hydrothermal stability of resulting crust. 2. The physical properties of the resulting crust are well within the requirements of the Chinese and ISO standards for garment leather. 3. According to the information from the tanneries, the cost of the salt-free pickling regime would be slightly lower than the traditional one. Acknowledgements Cooperative research program between the Dow Chemical Company through its Biocide Business and Sichuan University.