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SUMMARY OF Smith 1986 Pad Batch Dyeing 2.b.ii Electro1ytes:Smith 1986 Pad Batch Dyeing:HE STATES THAT Same as section 3.2 from Identification and Reduction... Smith 1986 on pad/batch fiber reactive dyeing of fiber reactives on cotton. It covers the same technical area (pad-batch) as Stone 1979, but this review focuses mainly on P2 aspects. The pad batch system addresses several of the major problems for cotton dyers in the future. They are covered in other parts of the outline, ie 4. j Dyeing, 2.a.v Water Conservation, and 2.b.i Color Residues in Textile Dyeing/Printing Wastewater. This information is also very appropriate for 3.j Process alternatives. This section should be substantially included in the document. Same information under all headings noted above. 2.a.v Water Conservation:Smith 1986 Pad Batch Dyeing:HE STATES THAT Same as section 3.2 from Identification and... Reduction Smith 1986 on pad/batch fiber reactive dyeing of fiber reactives on cotton. It covers the same technical area (pad-batch) as Stone 1939, but this review focuses mainly on P2 aspects. The pad batch system addresses several of the major problems for cotton dyers in the future. They are covered in other parts of the outline, ie 2.b.ii Electrolytes, 4.j Dyeing, and 2.b.i Color Residues in Textile Dyeing/Printing Wastewater. This information is also very appropriate for 3.j Process alternatives. This section should be substantially included in the document. Same information under all headings noted above. 2.b.i Color Residues in Textile Dyeing/Printing Wastewater:Smith 1986 Pad Batch Dyeing:HE STATES THAT Same as section 3.2 from Identification and Reduction... Smith 1986 on pad/batch fiber reactive dyeing of fiber reactives on cotton. It covers the same technical area (pad-batch) as Stone 1979, but this review focuses mainly on P2 aspects. The pad batch system addresses several of the major problems for cotton dyers in the future. They are cove in other parts of the outline, ie 2.b. ii Electrolytes, 2. a.v Water Conservation, and 4.j Dyeing. This information is also very appropriate for 3.j Process alternatives. This section should be substantially included in the document. Same information under all headings noted above. 4.j Dyeing:Smith 1986 Pad Batch Dyeing:HE STATES THAT Same as section 3.2 from Identification and Reduction... Smith 1986 on pad/batch fiber reactive dyeing of fiber reactives on cotton. It covers the same technical area (pad-batch) as 1979, Stone but this review focuses mainly on P2 aspects. The pad batch system addresses several of the major problems for cotton dyers in the future. They are covered in other parts of the outline, ie 2.b.ii Electrolytes, 2.a.v Water Conservation, and 2.b.i Color Residues in Textile Dyeing/Printing Wastewater. This information is also veryappropriatefor 3.j Processalternatives.Thissection should be substantially included in the document. Same information under all headings noted above.

3.j Process a1ternatives:smith 1986 Pad Batch Dyeing:HE STATES THAT Same as section 3.2 from Identification and Reduction... Smith 1986 on pad/batch fiber reactive dyeing of fiber reactives on cotton. It covers the same technical area (pad-batch) as Stone 1979, but this review focuses mainly on P2 aspects. The pad batch system addresses several of the major problems for cotton in dyers the future. They are covered in other parts of the outline, ie 2.b.ii Electrolytes, 2.a.v Water Conservation, and 2.b.i Color Residues in Textile Dyeing/Printing Wastewater. This information is also very appropriate for 4.j Dyeing. This section should be substantially included in the document. Same information under all headings noted above.

SMITH/B-TC.0 5-33586.0 CHAP-3.0 18/08/86 08.23.56 PAGE 6 3.2 Pad Batch Dyeing of Cellulosic Fibers The pad batch (cold) method of dyeing cellulosics is hardly a new concept [26-301. It has been used quite successfully in a wide variety of applications. In many ways, it is one of the most reliable and easiest-to- control methods available today for certain applications. Strangely enough, however, it has not caught on in this country to the extent that it is used in A" Continental Europe or in England, where it was first developed by Imperial Chemical Industries. To quickly summarize the pad batch method, prepared fabric is impregnated with liquor containing premixed fiber reactive dyestuff and alkali; excess liquid is squeezed out on the mangle; the fabric is batched onto rolls or in boxes, and covered with plastic film to prevent absorption of C02 from air or evaporation of water, then stored for two to twelve hours (see Figure 3.2-1 1. The goods can be washed off in any of several conventional ways, depending on equipment available in the mill. The method is interesting because it offers several significant advantages, primarily in its simplicity and speed. Production of between 75 and 150 yards a minute, depending on the construction and weight of the goods involved, is commonly reported. In fact, this kind of speed can make the limiting factor the wash-off facilities, which may not be able to keep up. Other benefits include essentially eliminating the need for salt or chemical specialties from the dyebath, with associated reduction in cost and pollution source reduction. Another factor that has generated enthusiasm for pad batch is its flexibility, compared to a continuous range. Either wovens or knits can be done, and in many constructions. Frequent changes of shade are no problem,

. I,- PAD/ BATCH - BEAM STORAGE AND WASH-OFF UNIT Figure 3.2-1. Pad/batch - beam storage and wash off unit

I " SMITH/B-TC.0 5-33586.0 CHAP-3.0 18/08/86 08.23.56 PAGE 8 because reactives remain water soluble, making cleanup easy. This fits many situations well, especially when versatility is required. The pad batch system can run the same cold dyeing fiber reactive combinations that are usually run on package dye, jigs, beams, becks, jets and other equipment. Washing-off can be done with becks, beams, continuous equipment or other available machines. Studies [301 have shown that pad batch dyeing for cotton, rayon and blends conserves energy, water, dyes and chemicals, labor and floor space. Water consumption for pad batch dyeing with beam wash-off is typically under two.gallons per pound of dyed fabric, compared to typically 20 or more on atmospheric becks for the same fiber reactive dyed shades. Energy consumption is similarly reduced from about 9000 BTU's per pound of dyed fabric for becks to under 2000 BTU's per pound for pad batch with beam washing. Chemical use, and associated BOD and COD loadings for waste streams, can be reduced up to 80% compared to atmospheric becks. Labor costs are also reduced. For example, two workers per shift can dye 200,000 pounds of fabric per five-day week. In general, the quality of pad batch dyeings is much better than other dyeing systems. Specifics of cost savings are shown in Tables 3.'?.-I, 3. I.--I1, and 3.%III. Pad batch dyeings require highly reactive "cold dyeing" fiber reactive colors. Examples of brand names of such colors are: Atlafix CX (Atlantic) Cibacron F (Ciba Geigy ). Intracron C (C&K). Levafix E(A) (Mobay 1

f Comparison of Annual Operation Cost Production ( 1 20 hr. wk/ 50 wks./annum Labor Costs Fuel Costs (Extra Drying) ia ter COS ts Dye Costs (Varies, see Table 111) Cold Dyeing Reactives on Cotton Pad/Batch/2 Bern. Wash-of f Stands 193,050 lbs./week or 9, 652,500 lbs./annum $79,560 $ 8,700 Conventional Exhaust Dyeing 100% Cotton (19 becks) 193,050 lbs./week or 9,652,500 lbs./annum $256,360 $272,000 - $ 98,500 Chemical Costs, Salt Alkali 0 $19,112 $337,840 $ 82,820 $207,672 $1,047,520

Table 3.'I -I I r Capital Investment [ 30 1 Cost cost Comparison Conmarison of of Pad-Batch with Becks Pad Batch Dyeing System: Dye Pad for Knits 2 Beam Wash-off Stands Installation estimated to be 30% (includes pad entry, padder, 2 beam wash-off stands, dye/alkali pump, 10 beams, rotation stand, cradle let-off scray $ 160,000 $ 48,000 $ 208,000 Exliaust Dyeing 100% Cotton Only: 19 Atmospheric Becks 1 000 pounds capacity each Cost - $30,000 each Installation estimated to be 30% $570, 000 $171,000 $741,000

77 1 Table 3.l-III Typical Dye Cost for Pad-Batch vs the Same Dyes on Becks [+/pound1 Color Powder Blue Dark Red Bright Yellow Bright Red Bright Blue Light Blue Dark Green Navy Pad-Batch 30 50 35 48 55 37 46 30 Beck-Dyed 40 63 50 75 70 58 70 53 All the above costs are for dyeing only (for 100% cotton), not including preparation. All of the.beck-dyed costs are cold reactive. In cases where the beck dye would be direct, pad-batch would probably cost more. Beck dyeing will probably cost less.

SMITH/B-TC.0 5-33586.0 CHAP-3.0 18/08/86 08.23.56 PAGE 9 Drimarine K (Sandoz 1. Procion M ( IC1 1. Remazol ( Hoechs t One key to successful use.of the system by the dyer is ph control. While all respective dyes are not all equally sensitive, a ph of 10.5 to 1 1.5 will be ideal in most cases for 12 hour batching. An increase in ph may be necessary to increase reaction rate for short batch times (2 to 4 hours). Extensive work in developing the pad batch system of dyeing cellulose has been done by Cotton Incorporated [27-301. Some of the following information was 'developed by them in actual plant experience. Equipment for the pad batch dyeing consists of: 1. Padding unit The padding unit should have the necessary controls for handling the type of fabric that is to be dyed on the unit. In case of knit fabrics, the padder must have adquate guiding, decurling and spreading equipment to handle the knit in open width form. This is especially important on single knit and warp knit fabrics which tend to curl when lengthwise tension is applied. The padder should also have suitable pressure controls to allow the nip to be controlled consistently. A deflection roll padder may be advantageous. Another desirable feature is a small dye trough. This is important to achieve good dye liquor turnover, to minimize the amount of "tailing", and also to avoid reactive dye hydrolysis which might produce shading from beginning to

SMITH/B-TC.0 5-33586.0 CHAP- 3.0 18/08/86 08.23.56 PAGE 10 end of the fabric run. A dye trough of ten gallon capacity or less is usually recommended. Adequate speed controls which control the padder and synchronize the batcher unit are absolutely necessary., In order to obtain a quality dyeing, uniform from side to side and end to end, the fabric must be uniformly prepared. The fabric should be scoured and/or bleached with a residual ph of 7 or slightly less. It should contain no residual alkali, starch, knitting oils or any other foreign substance which will interfere with the evenness of absorbency or the subsequent colorfastness of the fabric. The fabrics must wet out rapidly and uniformly and must be uniformly prepared and dried. It is advantageous to make up dye lots of fabrics which were prepared together to avoid possible shade variation within the dye lot. Pad batch dyeing gives much lower defect levels than rope dyeing on many styles. For example, fabrics of varying thickness such as 100% rayon jacquard tablecloths are difficult to process in rope form without streaking if dyed by exhaust methods on becks using direct dyes. The beauty of the pad batch system using the high reactivity dyes is that a great deal of the dye fixes in 30 minutes, and the difference in depth between one hour and eight hours is negligible in many shades. This is one reason for the unusual degree of shade reliability and is important because the fabric near the core of the take-up roll is obviously first on and last off, and has actually batched longer than the outer layers. Because of the low physical affinity of these cold dyeing reactives, they work extremely well for all continuous operations that include a padding sequence. Color yield (exhaustion and fixation) tend to be lower when dyeing in a long liquor, compared with high affinity dyestuffs such as vat dyes. A

SMITH/B-TC.0 5-33586.0 CHAP-3.0 18/08/86 08.23.56 PAGE 11 worthwhile increase in fixation can be accomplished in a shorter liquor, as the table below illustrates using a typical dye of the low substantivity group--in this case, CI Reactive Yellow 22. Liquor-to-goods ratio 30:l 20:l 1O:l 5:l 2:l 1 :1 0.6: 1 % Dye fully fixed 20% 27% 40% 53% 68% 73% 75% color Increased 265% value using 1 : ratio 170% 82% 38% 7% " " The advantages of this rapid fixation and stability of shade are obvious when compared to other methods. In jig and beck dyeing, for example, the normal routine is to continue dyeing, shading if necessary, until the correct color is obtained. Dyehouse operators are seen constantly cutting swatches off the goods for inspection. Even when the dyer is satisfied with the color, it may be that all fixable color has not reacted with the cloth, so that each batch must be treated individually, and shade variations are inevitable. With pad batch, however, experience has shown that if padding and batching temperatures are properly controlled, reproducibility of shade is outs tanding. There is still another benefit of this rapid fixation. It is a minor point perhaps, and easily overlooked, but there is almost 100% reproducibility from lab to production shades. The pad batch system may be home design, but it must feature accurate in mixing and metering. Two tanks hold dyestuff and alkali solutions which are fed to a mix and dispensing mechanism with a proportioning device. The mix is then fed via a pump to the pad unit. By employing a hollow dispenser, it is possible to keep the passage through which the fabric passes less than one inch wide. This keeps the volume of liquor

I SMITH/B-TC.0 5-33586. o CHAP-3.0 18/08/86 08.23.56 PAGE 12 very low, about eight gallons or less and insures the rapid turnover of liquor so that dye decomposition is kept to a minimum. This is, of course, important because adding the alkali to increase reactivity also affects the stability of the liquor. (See Figure 3.1-2.) In working with plant production pad batch units, the following four point checklist has been helpful in avoiding problems: 1. Keep good alkali control metering techniques. by insuring adequate mixing and/or 2. Adjust exhaust dye recipes for pad batch by keeping accurate data on liquor ratios. Keep the immersion long, the liquor ratio short, and the volume low in the pad. 3. Have good preparation. Actually, pad batch reliability has reached the point where it can be used as a check on the preparation. If something doesn't look right, most often it can be traced to mistakes in preparation. 4. Keep good temperature control, esprcially avoid dyeing hot fabric fresh from preparation. Feed cold fabric to the pad or else the temperature will rise. During very hot weather, keep the mix cool with a cooling water jacket or use ice in the mix. Since many mills that have agreements with municipal sewage systems pay on some formula based on the content of BOD, COD or other undesirable contents of the effluent, the pad batch method employing cold reactives is also attractive from the pollution source abatement standpoint. Reactives do not require reducing or oxidizing agents, as do vats or sulfurs. Reactive dyes require use of massive amounts of salt when employed in becks, but in the pad batch method, cold reactives require no salt at all. "

SMITH/B-TC.0 5-33586.0 CHAP-3.0 18/08/86 08.23.56 PAGE 13 The use of chemical specialties such as lubricants, leveling agents, antimigrants, fixatives, defoamers and other specialties by the pad ba,tch dyeing is usually not required. Small amounts of detergent are used in washing-off. In summary, excellent results have been obtained with the pad batch (cold) system utilizing high reactivity dyes. Dyers hav experienced many benefits : 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. Low capital outlay Low energy requirements High production speed Reduced labor requirement High color yield Outstanding reproducibility Excellent penetration, and leveling characteristics Rapid fixation Substantial overall cost savings (dyes, chemicals, labor, water, etc. 1 Reduction in BOD, COD and ph problems in effluent. At their inception in 1956, fiber reactives were noted for their exceptionally bright shades. However, the range has increased dramatically. The shade range now includes new dyes of muted tones aimed at shades that previously were considered the domain of direct, sulfur and vat dyes. Reactives have given a good account of themselves in terms of fastness and economy against traditional classes of dyes, and future prospects appear very bright indeed.