Bioprocessing for Sustainable production of COLoured textiles

WP3 WP3 Synthesis of bioSynthesis of bio‐‐dyesdyes

BISCOLBISCOLECO/09/256112ECO/09/256112

Siena January 25th, 2013

The precursor of new biodyes produced by UNISIName of precursor Number of identification 

of biodye

4,5‐diidrossibenzensulfonic acid 1

2

3

4

5

6

7

553

543

525

567

422

516

Wool and Cotton

MBTH + 5‐amino‐1‐naphthalensulfonic acid Wool and Cotton

MBTH + aniline‐2‐sulfonic acid Wool and Cotton

2,5‐DABS + 3‐aminobenzensulfonic acid Wool and Cotton

ABTS +4‐amino‐1‐naphthalensulfonic acid Wool and Cotton

MBTH + 6‐amino‐4‐hydroxynaphthalensulfonic acid Wool and Cotton

MBTH + 4‐amino‐5‐idrossinaftalen‐2,7‐disulfonic acid Wool and Cotton

3‐Methyl‐2‐benzothiazolinone hydrazone hydrochloride hydrate + Aniline hydrochloride 

Wool and Cotton

phenylendiamine + aniline + 3‐aminobenzensulfonic acid  Wool and Cotton

benzidine + N‐(1‐naphthyl)ethylenediamine Wool and Cotton

phenylendiamine + 5‐amino‐1‐naphthalenesulfonic acid  Wool and Cotton

4‐nitro‐1‐naphthylamine + 4‐amino‐5‐hydroxynaphthalene‐2,7‐disulfonic acid  Wool and Cotton

3‐Methyl‐2‐benzothiazolinone hydrazone hydrochloride hydrate + 4‐4'diaminostilbene

Wool and Cotton

Wool/Cotton

Biodyes for WOOL

We performed tests dyeing at 45°C and 90°C for the biodyes from 1 to 7

From the considerations on the upgrade of the dyestuff and from the considerations on the exhaustion of the bath we can say that: 

‐ Biodye 1  DiscardedDiscarded; the dyestuff upgrade on fiber is low 

‐ Biodye 3  DiscardedDiscarded; the resulting dyestuff is tenuous and remains a lot of dyestuff in the dye bath

Dyeing uptake on wool

The best biodyes are  2, 4, 5, 6 and 7 on which were made dyeing uptake 

Everyone has problems of dispersion  add dispersant ACHILAN NEW and SULPHATE

Dyeing uptake at 40°C – 60°C – 80°C – 96°C

Dyestuff content Auxiliary Acid

0.5 %2% ACHILAN NEW10% Sulphate 2 cc/L Formic acid

Dyeing uptake on woolConsiderations:

Biodye 2  DiscardedDiscarded; all the dyestuff upgrade only at  high temperature (doesn’t upgrade until boiling temperature). This dyestuff is hardly samplable, so we can not consider it in the set of three dyestuff.

Biodye 4  GoodGood;; it upgrade in tone with the temperature. We can also dye at low temperature (80°C).

Biodye 5  GoodGood; it upgrade in tone with the temperature. We can also dye at low temperature (80°C).

Biodye 6  DiscardedDiscarded; it is very affected of the reducing power of the wool.

Biodye 7  GoodGood;; it upgrade in tone with the temperature. We can also dye at low temperature (80°C), has no problems of reduction.

Dye at  low temperature (80°C)Dyestuff content Auxiliary Acid Temperature and time

80°C, 40 minutes0,5% 2 g/L 80CF4 g/L Protective protein NP (antireduction)

2cc/L Aceticacid

As said before, the biodyes 4 ‐ 5 ‐ 7 give good dye also at low temperature (80°C)

Additional tests of dyeingWe've tried other dyeing varying some parameters of the previous recipe:

• Dyeing at 96°C: 

we have dye at 96 ° C with biodyes 1,3 and 6 but the results have not been good.

Dyeing at 96°C  Dyeing with Formic Acid 

•Dyeing with Formic Acid:

we have dye with Formic Acid with the biodye 3,4 and 6 with Formic Acid worse performance than dyes with acetic acid.

Biodyes for WOOL

• Biodye 525 ‐ 516  Discarded.Discarded.

• Biodyes 543‐567‐422  GoodGood; containing sulfonic groups.

• Biodye 553  GoodGood; even if it doesn’t contain sulfonic groups.

Dyestuff content Auxiliary Acid Temperature and time

5% 10% Sulphate 2cc/L Formic acid 96°C, 40 minutes

Biodyes for WOOL

Tests of dyeing with Acetic Acid  the dyes with Formic Acid are better.

Dyestuff content Auxiliary Acid Temperature and time

5% ‐ 1 g/L Acetic acid 96°C, 40 minutes

Dye at  low temperature (80 and 85°C)Dyestuff content Auxiliary Acid Temperature and time

0.5% 2 g/L 80CF 2 cc/L Formic acid 80°C, 40 minutes

0.5% 2 g/L 80CF 2 cc/L Formic acid 85°C, 40 minutes

Good even at low temperatures with addition of auxiliary 80CF (Aux 2)

Dyeing uptake of 567It upgrade in tone with the temperature may be mixed, obtaining more or less dark brown.

In the image: dyeing uptake and the exhaustion of the bath

Dyestuff content Auxiliary Acid Temperature and time

0.2 % 0.5 g/L ACHILAN NEW 1 cc/L Formic acid 50, 60, 70, 80, 96°C and 96°C  after 40 minutes

Set of three primary biodyes selected for WOOL

5: ABTS +4‐amino‐1‐naphthalensulfonic acid

7: MBTH + 4‐amino‐5‐idrossinaftalen‐2,7‐disulfonic acid

422: 4‐nitro‐1‐naphthylamine + 4‐amino‐5‐hydroxynaphthalene‐2,7‐disulfonic acid 

Biodyes for COTTONWe tested all biodyes discussed for wool also for cotton

Dyestuff content Auxiliary Acid Temperature and time

Formic acid 96°C, 40 minutes0.5 %1 g/L DEX SUPER1 g/L Sulphate2 g/L Carbonate

1

Dyestuff content Auxiliary Acid Temperature and time

Formic acid 96°C, 40 minutes1.5 %

1 g/L DEX SUPER10 g/L Sulphate (+ 10 g/L 

after 20’ at 96°C)2 g/L Carbonate

1 g/L PROTECAL300

2

Dyestuff content Auxiliary Acid Temperature and time

Formic acid 96°C, 40 minutes0.5 %

1 g/L DEX SUPER10 % Sulphate1 g/L Carbonate

2 g/L PROTECAL300

3

Biodyes for COTTON

1

Of all dyestuffs tested the one that deserves furtherstudy is the 553.

Study has just begun.

2 3 553      543      525       567     422     516

Conclusion

Continue to work on dyes for cotton for:

‐ studying the red dyestuff found

‐ have the set of three primary dyestuffs for cotton

• Dyeing woollen items of clothing and fabrics with the set of primary dyestuffs.

Dyeing items of clothing and fabrics of WOOL

ACHIMO has the possibility to dye pullovers. 

Dyestuff required: 300 grams

LANIFICIO LUIGI RICCERI can dyes ribbon, yarn and fabric.

Dyestuff required for laboratory scale dyes: 50 gramsDyestuff required for pilot scale dyes: 2 kilograms