Manufacturing and Mass Balance of Copper Phthalocyanine (CPC) Blue

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Journal of Drug Discovery and Development Volume 2, Issue 1 - 2018, Pg. No. 18-23 Peer Reviewed & Open Access Journal Research Article Manufacturing and Mass Balance of Copper Phthalocyanine (CPC) Blue and Green Pigments Ashok K Rathoure1, Savita Goyal Aggarwal2 1Eco Group of Companies, New Civil Road, Surat (GJ) India. 2Dept. of Chemistry, GRD Institute of Management and Technology, 12, Rajpur Road, Dehradun, Uttarakhand, India.

Abstract Organic pigments are cost-effective, non-toxic, and possess good color strength, which makes them good choice for their use across various end-use sectors. Copper phthalocyanine (CPC) blue is the copper (II) complex of tetra aza tetra benzoporphine (CPC) whereas phthalocyanine green is its chlorinated derivative. The brominated derivatives of CPC provide a yellowish green shade. The specific crystal modification decides the hue of the product as in Alpha Blue-red shade copper phthalocyanine (Pigment Blue 15) and in Beta Blue-green shade blue (Pigment Blue 15:3). CPC Blue is an upstream product and is a raw material used for the manufacture of our Pigment Blue and Pigment Green products. CPC Blue is also sold to other manufacturers of pigments including a related party for the manufacture of textile dyestuffs. Here we have presented the manufacturing process of two organic pigments – CPC Green and Blue.

Keywords: CPC Green, Beta Blue, Ink, Manufacturing, Textile, Tint

Introduction phthalocyanine (Pigment Blue 15), and in Beta Blue – green shade blue (Pigment Blue 15:3). The alpha modification is Manufacture of organic pigments with good light fastness phase stabilized by partial chlorination called solvent stable property is gaining traction among global manufacturers. Alpha Blue or Pigment Blue 15:1. The alpha modification Besides, developing countries such as China and India are which is stabilized towards flocculation and the phase shifting towards becoming the center of global organic change is registered as Pigment Blue 15:2. These pigments pigments market, both from the demand and supply side. find use in paints. Pigment Blue is a cyclic product of copper The manufacturing of organic pigment is in a cautious and reaction between phthalic anhydride and urea. Alpha phase as API bulk drug.3 The information sheet for organic Blue and Beta Blue are variations of Phthlocyanine Blues. pigments is listed in Table 1. Alpha Blue is redder in shade and of smaller particle size and is available as crystallizing type and non-crystallizing Copper Phthalocyanine (CPC) Blue is the copper (II) non-flocculating type. Beta Blue yields bright greenish complex of tetra aza tetra benzoporphine (CPC) whereas blue shades with slightly lower tintorial strength. Beta Phthalocyanine Green is its chlorinated derivative. The Blue is of a more stable crystal formulation than Alpha brominated derivatives of CPC provide a yellowish green Blue and is available as the non-crystallizing type and the shade. The specific crystal modification decides the non-crystallizing non-flocculating type. hue of the product as in Alpha Blue – red shade copper

Corresponding Author: Ashok K Rathoure, Eco Group of Companies, New Civil Road, Surat (GJ) India. E-mail Id: [email protected] Orcid Id: https://orcid.org/0000-0001-9131-1346 How to cite this article: Rathoure AK, Aggarwal SG. Manufacturing and Mass Balance of Copper Phthalocyanine (CPC) Blue and Green Pigments. J Durg Dis Dev 2018; 2(1): 18-23.

Table 1.Information Sheet for Organic Pigments Particular Copper Phthalocyanine (CPC) Green CPC Beta Blue Physical state Solid Solid CAS No. 1328-53-6 147-14-8

Formula C32Cl16CuN8 CuC32H16N8 MW (g/mol) 1127.154 576.0690 Uses Inks, coatings and many plastics, in manufacturing of other pigments in the category Toxicity Serious birth defects in developing embryos; non-bio-degradable LD50 >3 g per kg body weight >5 g per kg body weight LC50 >250 mg/L for 48 h >100 mg/L for 48 h Reference Sandor et al.1 OECD SIDS, 1990

Raw Material

The list of raw material required for the manufacturing of two organic pigments is shown in Table 2. Table 2.Raw Material Consumption (per ton of product) Organic Pigments Raw Material Physical State Raw Material Consumption (per ton of product) CPC Green Aluminum Chloride Solid 1.928 Salt Solid 0.3 CPC Blue Solid 0.571 Cupric Chloride Solid 0.085 Chlorine Gas Liquid/Gas 1.265 MCB (Recovered) Liquid 2.97 MCB (Fresh) Liquid 0.03 Caustic lye Liquid 0.16 Emulsifier Liquid 0.02 Oleic Acid Liquid 0.02 Beta Blue CPC Blue Solid 1.02 Salt Solid 0.15 Xylene (Recovered) Liquid 2.940 Xylene (Fresh) Liquid 0.06 Emulsifier Liquid 0.025 Caustic Liquid 0.05

Manufacturing Process for Copper Phthalocyanine green crude wet cake. Green • Pigmentation: In a reactor, monochlorobenzene, water and caustic soda lye are mixed. Now dispersing agents • Chlorination: In a glass-lined reactor, eutectic mixture are added to it and an emulsion is prepared. The of aluminum chloride and sodium chloride is prepared wet cake from above stage is taken to it and stirring and is melted. Now CPC AD blue and cupric chloride are is continued. The mass is then refluxed. Solvent charged. The chlorine gas is purged till the drawdown monochlorobenzene is then recovered by distillation is found O.K. The mass is then drowned. and the mass is filtered. • Drowning: In a vessel, water is taken. The chlorinated • Filtration: The suspended slurry is then filtered and is mass is then received slowly. The mass is stirred and washed to make it free of alkali. filtered. • Drying: The wet cake from above filtration is dried in • Filtration: Drowned mass is filtered and is then washed a spin flash dryer. to make it free of chloride or aluminum. This gives CPC

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CHEMICAL REACTION COPER PHTHALO CYANINE GREEN

Figure 1.Structure of CPC Green

N C C N

N C C Cl Cl

+ 16 Cl2 N Cu N (1136) Cl Cl C N C

N N N C C C C N Cl Cl N Cl C C Cl N Cu N

Cl C Cl N C Cl Cl CuC32H15N8 N C C Copper Phthalo Cyanine Blue N (575.5) + 16 HCl CuC Cl N 32 15 8 (584) Cl Copper Phthalo Cyanine Green Cl (1127.5) Cl Cl Figure 2.Chemical Reaction CPC Green

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MASS BALANCE OF CPC GREEN Water: 583 kgs AlCl3: 1928 kgs Salt: 300 kgs CPC Blue: 571 kgs CHLORINATION Unreacted Chlorine gas: 250 kgs Three stage Scrubber CuCl2: 85 kgs Cl gas: 1265 kgs 2 HCl (30%): 833 kgs DROWNING Water: 12000 kgs

Water: 22500 kgs FILTERATION & WASHING AlCl3 Soln. (10-12%): 12000 kgs Effluent to ETP: 22000 Kgs

MCB: 3000 kgs Water: 1200 kgs PIGMENTATION Caustic: 160 kgs MCB recovered: 2970 kgs Oleic Acid: 20 kgs MCB loss: 30 kgs Emulsifer: 20 kgs

FILTERATION Effluent to ETP: 23299 kgs Water: 20000 kgs & WASHING

SPIN FLASH Evaporation loss: 1500 kgs DRYER

CPC GREEN: 1000 kgs

Figure 3.Mass Balance of CPC Green

Figure 4.Hazardous Waste Management during Manufacturing of CPC Green

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Manufacturing of CPC Beta Blue with solvent at 90ºC. • Filtration and Washing: The mass is filtered off in filter • Ball Milling: Copper Phthalocyanine Blue is milled press, and washed up to neutral pH. along with vacuum salt below 70ºC. It is unloaded and • Drying: The wet cake is dried in a spin flash drier and transferredPROCESS for FLOW pigmentation. DIAGRAM WITH MASS BALANCEfinally OF BETApacked. BLUE PIGMENT 15.3 & 15.4 • Solvent Pigmentation: The milled powder is treated

CPC Blue (98.5%): 1020 kgs Salt: 150 kgs BALL MILLING

Water: 5000 kgs Xylene: 3000 kgs Solvent recovered: 2940 kgs Emulsifier : 25 Kgs PIGMENTATION Additives : 25 Kgs Solvent loss: 60 kgs Caustic : 50 kgs

FILTERATION Water : 25000 kgs & WASHING Effluent to ETP: 28470 kgs

SPIN FLASH Water Evaporation loss: 1800 kgs DRYER

PRODUCT : BETA BLUE: 1000 kgs

Figure 5.Process Flow Diagram of Beta Blue Pigment

Figure 6.Hazardous Waste Management during Manufacturing of CPC Blue There is no chemical reaction taking place, only rearrangement of molecules of Phthalocyanine Blue and Beta Blue are formed which is stable and has greener blue tone.

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(CuC32H16N8) Figure 7.Chemical Reaction of Copper Phthalocyanine Beta Blue Pigment

Figure 8.Conversion of Organic Pigments Conclusion References

The CPC green and blue pigments are used widely in 1. Sandor S, Prelipceanu O, Checiu I. Sulphonated textile units to color the yarn and used in printing. The phthalocyanine induced caudal malformative syndrome CPC pigments are broad-spectrum organic pigments. Beta in the chick embryo. Morphol Embryol (Bucur) 1985; Blue is of a more stable crystal formulation than Alpha Blue 31(3): 173-81. and is available as the non-crystallizing type and the non- 2. OECD SIDS. Copper Phthalocyanine. CAS N°:147-14- crystallizing non-flocculating type. During manufacturing 8. 1990. Available online at http://www.inchem.org/ of organic pigments, major issue is hazardous water; it documents/sids/sids/147148.pdf. should be properly handled. The life cycle analysis should 3. Rathoure AK, Aggarwal SG. Manufacturing process be done before use of organic pigments. with chemical reactions and mass balance for 6 pharmaceutical drugs.J Durg Dis Dev 2017; 1(1): 54-64. Conflict of Interest: None Date of Submission: 2018-04-02 Date of Acceptance: 2018-04-16

ISSN: 2581-6861