Industrial Chemicals

Monochloroacetic Acid

MCAMonochloroacetic Acid

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AkzoNobel Industrial Chemicals produces and markets high purity salt, chlorine, caustic lye, hydrochloric acid, chloromethanes and monochloroacetic acid (MCA). These products are essential in daily life and are for example used in the manufacture of vehicles, glass, performance plastics, pharmaceuticals, feed and foodstuffs (e.g. Jozo, Nezo, OneGrain and KNZ), textiles and disinfectants for swimming pools.

ContentMCA characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

MCA Pillar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

Properties of MCA and SMCA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

Product range and modes of supply . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

MCA transport . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

Safety and Handling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

Protecting the environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

Sustainability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

Storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

Sampling of MCA liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

General precautions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

Emergency response . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

AkzoNobel Monochloroacetic Acid

AkzoNobel Industrial Chemicals has approximately 1,900 employees based in the Netherlands (Rotterdam, Hengelo, Delfzijl, Arnhem and Amsterdam), Germany (Ibbenbüren, Frankfurt and Bitterfeld), Denmark (Mariager), Sweden (Gothenburg), USA (LeMoyne, Chicago) and China (Taixing, Shanghai). Major joint ventures are Delamine (Delfzijl, the Netherlands) and Denak (Ohmi, Japan).

MCA essential in daily life

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As the world’s largest producer, AkzoNobel supplies a complete range of high quality MCA products. Physical forms include solids, aqueous solutions, molten, and solutions in ethanol. Sodium salts are available as granules and powder. Granules have better flowing char-acteristics and reduced caking, making them easier to use.

You can choose from a wide range of packaging.AkzoNobel is perfectly positioned to serve the global market, with production sites in The Netherlands, China, USA, a 50/50 joint venture with Denak in Japan and a sales network span-ning the globe. Transportation can be arranged by rail, road or sea. We also offer extensivetechnical service and advice.

MCA is a toxic and corrosive organic acid that must be treated with great caution.Training and instruction are indispensable to guarantee safe handling. As an expert in the field of MCA for over 50 years, AkzoNobel has established safety procedures for handling and storage of the products. A summary of the infor-mation is contained in the Safety Data Sheet (SDS), and on the safety website; www.mca.akzonobel.com

CharacteristicsMonochloroacetic acid (MCA) is a chlorine derivative of acetic acid. The chlorine atom in MCA is very reactive: therefore MCA has found increasing use as an intermediate in the prepa-ration of a great variety of chemicals. It is highly soluble in water and freely soluble in methanol or ethanol.

At room temperature, MCA solids have the appearance of a hygroscopic crystalline substance with a characteristic acidic odor. MCA 80% solution in water is a clear liquid with an acidic odor. MCA molten (above 62°C) is a clear liquid with a characteristic acidic odor.

Depending on the temperature, aqueous solu-tions are subject to gradual hydrolysis, ultimately resulting in the formation of glycolic acid and hydrochloric acid.

Sodium monochloroacetate (SMCA) is obtained by mixing MCA with soda-ash (neutralizing).At room temperature SMCA is a white hygro-scopic solid (in powder or granule form). Hydrolysis of aqueous solutions of SMCA leads very rapidly to the formation of sodium glyco-late and hydrochloric acid, depending on the temperature and time.

Monochloroacetic acid, or MCA, is an essential raw material for a variety of products, such as carboxymethyl cellulose, adhesives, pharmaceuticals and crop protection chemicals. MCA is also used in the production of PVC stabilizers and permanent wave formulations for hair.

MCA – an essential raw material for production of crop protection chemicals

AkzoNobel Monochloroacetic Acid

MCA characteristics

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CMC is used in:• oil drilling• mining industry• food additives• personal care products• detergents

MCA or SMCA are applied in the manufacture of crop-protection chemicals such as phenoxy-acetic acids. The most commonly used are:• 4-chloro-2-methylphenoxyacetic acid

(MCPA)• 2,4-dichlorophenoxyacetic acid (2,4-D)

MCA is used in the production of amphoteric surfactants such as betaines and imidazolines. Betaines are becoming increasingly important in the manufacture of mild shampoos, liquid soap and metal cleaning agents.Imidazolines are used as shampoos and indus-trial cleaners. MCA is also used for making ether carboxylic acids.

MCA is also a raw material in the production of thioglycolates, used as the salt, ester or other derivative of thioglycolic acid in a wide range ofapplications such as:• hair cosmetics• thermo stabilizers for PVC

Other applications of MCA include:• cyanoacetic ester, a raw material for purines,

cyanoacrylate adhesives and vitamin B6.• malonic esters, synthesized from SMCA and

used in the preparation of barbituric acid, the basis of a wide range of barbiturate drugs.

• phenoxyacetic acid, raw material for penicillin.

• chloroacetylchloride, e.g. used in the produc-tion of pharmaceuticals and agrochemicals.

• purines. The caffeine type purines are made from urea or its N-methyl derivatives and ethyl cyanoacetate.

• glycines, used in the production of: pet food, flavoring agents, and pharmaceuticals (i.e. soluble aspirin).

• dyestuffs such as indigo.• dimethoate, an important insecticide that

is mainly used in tropical and subtropical climates.

• ibuprofen, produced via the IPA-ester of MCA.

• chloroacetamide, industrial preserva-tive (biocide).

Applications

Acetic Acid

Chlorine

Soda Ash (only SMCA)

Others 1)

MCA Liquids

MCA Flakes

SMCA

CMC

Crop protection

Surfactants

TGA

Other

Agro chemicals

Personal Care

Pharmaceuticals

Paper

Food

Mining

Adhesives

PVC stabilizers

Raw MaterialsShare in

variable costs

MCA (forms)Share in AN sales

ApplicationVolume share in

MCA market

SegmentVolume share in

MCA market

The greater part of monochloroacetic acid production is intended for the manufacture of carboxymethyl cellulose (CMC), a water-soluble cellulose ether, with a wide range of applications as a thickening agent in aqueous systems. CMC can be produced either with monochloroacetic acid (MCA) or the sodium salt of monochloroacetic acid (SMCA). MCA pillar

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Properties MCA solids/molten SMCA MCA 80% solution in water

Molecular weight (g/mol) 94.5 116.5 -

Boiling point at 101.3 kPa(°C) 190 - 138

Density (kg/m3) 1424 at 25°C 1351 at 80°C

1850 at 25°C 1333 at 25°C

Bulk Density (kg/m3) 750 - 850 850 - 900 -

Vapor pressure (hPa) 0.14 at 25°C - 16 at 20°C 38 at 40°C

Viscosity (liquid) mPa.s 1.7 at 80°C - 5.2 at 20°C

Solubility in water g/100g 421 at 20°C 987 at 40°C

820 g/l at 20°C 1100 g/l at 80°C

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pH value in water at 20°C - 6 – 9 (50 g/l) < 1

Flash point (closed cup, °C) 126 ca. 270 >118

Melting point (°C) 62 150 18

AkzoNobel’s MCA products are available in packaging as indicated below. More details can be found in our product specification sheets, or email to mca@akzonobel.com

MCA solids• in 25 kg net weight paper bags on pallet

with shrink film• polypropylene woven FIBCs (big bags)

on pallets

SMCA powder or granules• in paper bags, 25 kg net weight,

on pallets with shrink film• polyethylene woven FIBCs (big bags),

standard 1,000 kg net weight, on pallets

MCA liquidsMCA liquids (such as MCA molten, solutions in water and ethanol) are shipped in bulk containers. Transport takes place in insulated containers.

Containers for MCA molten and MCA 80% solution in water should be heatable to avoid crystallization and MCA resistant. Transportation by road, rail or sea.

Properties of MCA and SMCAMCA – an essential raw material for PVC window frames

Product range and modes of supply

MCA in building

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Even solutions diluted to 1% contacting the skin may cause painful red spots and swellings. Inhalation of MCA vapors has an irritating effect on the respiratory system. Molten MCA and MCA in solution are rapidly absorbed through the skin, even at low concentrations and if the acid has not caused any visible skin lesions. If more than 5% of the surface of the skin has been in contact with MCA, general (“systemic”) poisoning can occur. This includes vomiting and/or symptoms resembling shock (agitation and/or confusion, later unconsciousness, pale clammy skin, rapid pulse). Ultimately, this very serious condition may even end fatally, if immediate and adequate action is not taken.

Exposure time is an important factor. If the treat-ment of MCA skin contamination is delayed, systemic poisoning may occur even when less than 5% of the skin surface has been exposed.

SMCA is NOT corrosive. As far as known, it does not penetrate the skin but it is absorbed after ingestion, causing systemic poisoning. Prolonged contact should be avoided since SMCA is hygroscopic and hydrolysis may occur on wet skin or eyes.

Long-term animal studies have indicated that monochloroacetic acid and SMCA donot cause cancer.

Safety and Handling

1 Easy discharge hose coupling TW80 (Elaflex)

2 Bottom outlet assembly with one internal (with remote control) and one external valve

3 Insulation4 Heating system (electr. or steam)

(between tank and insulation) Inlet pipe: Threaded and capped 1” Outlet pipe: Threaded 1” fitted with steam trap

5 End frame6 Pres./vac. relief valve7 Thermometer8 Small ladder9 Airline/vapour return DN 50 connection

An example of a stainless steel 20 ft ISO container for shipping MCA 80% solution in water

End FrameHeight: max. 2591 mm Width: max. 2500 mm Length: max. 6058 mm Volume: max. 24 m3 total, gross Commercial load: ± 25.5 ton MCA 80% (19.2 m3 at 30o C) Height discharge: 900-1500 mm

1 Height discharge 600 mm -1200 mm2 Easy discharge hose coupling TW 80

(Elaflex)3 Internal bottom valve (remote) and

one external butterfly valve4 Insulation5 Steam heating system (between tank

an insulation) 1” conncection6 Pres./vac. relief valve

An example of stainless steel tanker for shipping MCA 80% solution in water

Height: max. 4150 mm Width: max. 2600 mm Length: max. 11,500 mm (incl. truck 4000 mm extra) Volume: max. 36 m3 Commercial load: ± 25 ton MCA 80% (18.8 m2 at 30o C) (only two compartments are used)

Airline/vapour DN 50 connection in return: spill box

Example 20 ft ISO tank for MCA intermodal transport

Example tank trailer for MCA road transport

MCA transport

MCA is a hazardous substance and is classified as “Toxic”, “Corrosive” and “Dangerous for the environment”. Any contact with skin and eyes may cause severe chemical burns, with possible permanent damage (scarring).

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Past experience has shown that no problems are caused in waste-water treatment plants that have been adapted to take MCA, provided that the concentration in the waste water is not too high and that it has been neutralized.

Since municipal waste-water treatment plants are not normally adapted to deal with the product, MCA products must not be discharged into sewers. Spillages of chlorinated acetic acids and their derivatives should be controlled by damming up the spills with inert materials (sand or soil) and collected in drums for safe disposal after neutralization with agents such as soda ash(Na2CO3) or bicarbonate (NaHCO3).

Waste material should be taken to an approved disposal facility (special landfill disposal, inciner-ator or waste-water treatment plant). Uncleansed empty bags should also be considered as chem-ical waste.

MCA is classified as ‘Dangerous for the envi-ronment’ as it presents a hazard to unicel-lular algae. Fire-fighting water should be collected and disposed of in accordance with local requirements.

Protecting the environment

MCA/SMCA products are readily biodegradable in the aquatic environment and are highly mobile in soil and sediment. These products are therefore not considered to be persistent in the environment.

AkzoNobel Monochloroacetic Acid

Sustainability is at the heart of everything we do at AkzoNobel. It’s vital for the future success of our company, our society and our planet.

MCA in life

The current portfolio consists of steam based on natural gas, household waste as well as biomass. On the Delfzijl site there is strong integration between different plants in order to increase energy efficiency. At the same time we partially use renewable power. We are also looking for renewable or low carbon raw materials.

In Taixing, China, we are the first to supply MCA solution in addition to MCA flakes, currently the market standard. Moving to solution helps to increase safety of employees and contractors, reduce waste significantly and reduce costs. AkzoNobel MCA fully supports customers in this transition.

Our portfolio of MCA product forms allow you as customer to select the product form that best fits with your production process, allowing you to increase the efficiency of your produc-tion process, eliminate unnecessary costs and optimize your carbon footprint. We at AkzoNobel MCA think with you on how to further improve this.

Sustainability

Sustainability is a core principle at AkzoNobel and so it is for AkzoNobel MCA. We continuously revise our MCA value chain to see how we can do more with less. In Delfzijl, where MCA is produced as part of the salt-chlorine chain, we have diversified our steam supply, in order to reduce our carbon footprint.

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SolidsBecause MCA and SMCA solids are hygro-scopic, they should be stored in a dry warehouse in their original packing to minimize absorption of moisture. Storage outdoors of FIBC’s should be avoided. Keep in mind that sun radiation can degrade packaging which may create high risks during handling.

Stocks should be kept as small as possible, pref-erably in sequence of arrival (first in – first out system). If they are to be stored for an extended period, it is advised to take measures to keep the atmosphere dry and at a constant temperature.SMCA powder tends to cake after the product has been stored for some time. We recommend that pallets should not be stacked more than two layers high for either MCA or SMCA. Racks are advised for efficient storage.

The caking of SMCA, however, has no adverse effect on its chemical quality. If caking does present you with significant problems, SMCA granules may be a better option, since they are prone to far less caking and they have better flowing properties. MCA solids can be stored longer without causing any serious lumping. For bulk storage, stainless steel (i.e. AISI 316L), PVC, polyethylene, glass or PTFE-lined equipment are recommended.

Solution in waterMCA 80% solution in water should be kept at a temperature of about 25-35°C, for example by heating or cooling a non-stop circulating flow. The temperature should be kept within this range to avoid crystallization (below 18°C), decomposi-tion and too much corrosion (above 40°C). Very slow hydrolysis is accompanied by formation of glycolic and hydrochloric acid. This hydrochloric acid together with MCA Acid may cause pit-cor-rosion at stainless steel.

Solutions in water are highly corrosive with most common construction metals. The storage tank is normally installed in a pit made of an insulating material such as concrete with an MCA proof coating or liner. AkzoNobel stores MCA solution in water in a glass-fiber reinforced polyester tank with a PVC liner. Glass-lined steel, titanium, PP/polyester and stainless steel (e.g. AISI 317 LN) can also be used. Titanium (commercial pure grade 1or 2) and graphite are effective materials for heat exchangers.

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MCA storage

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Sampling of MCA liquids

Unloading: In view of the hazardous properties of MCA products, the precautions specified in the Safety and Handling chapter should be taken before sampling and unloading are commenced.

The safe way to take a sample from the discharge pipe is via a special sample device. For safety reasons we strongly advise not to take samples from tank trailers via the man hole.

TankersTransport tankers with MCA liquids should be discharged according to clear procedures on site. The tanker and the pump are connected by a flexible discharge hose or rigid unloading arm with a suitable and safe connection. The spec-ification and condition of the hose is of major importance. Periodic checking of hoses is there-fore mandatory.

For more information from our Market Support/Technical Service Department, mail to mca@akzonobel.com

BagsA discharge installation for (S)MCA solids may consist of: A hoist to lift FIBC’s, a unit to discharge the bags dust free, a breaker and a screw feeder for transport to the reactor. The unit has to be extracted by which the air is filtered.

Technical serviceOur Technical Service department will advise you on unloading procedures and installations.

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General precautions

Personal protectionTo avoid all possible contact with MCA/SMCA, the following precautions must be observed when handling the product: Acid resistant gloves and safety goggles should be worn at all times. Dust should be avoided. To protect personnel against inhaling SMCA dust, a dust mask with an effective protection rate (P2 dust mask) should be worn.An “airstream” safety helmet or full face gas mask is recommended as protection againstinhaling MCA (no contact with the skin permitted; complete face protection).If there is a chance of a spillage of MCA solu-tion in water, it is advised to provide additional acid-resistant protective clothing (for example GORE-TEX®), acid resistant boots and a face shield.

ClothingContaminated clothing should be removed immediately, preferably under a safety shower or in an emergency tub (for MCA products only). Contaminated shoes should be disposed of after neutralization in a solution of sodium bicarbonate.

SkinWe advise to install thermostat controlled (30°C) emergency baths with a saturated (7-9%) sodium bicarbonate solution wherever liquid MCA (molten or in solution) is handled. Contaminated workers should submerge themselves as quickly as possible and remove contaminated clothing, shoes and any jewellery while in the bath. To ensure effective neutralization, the worker should remain in the bathtub containing satu-rated sodium bicarbonate solution for at least 30 minutes. Minor skin contaminations (e.g. drops or small splashes) can be treated with a wet slurry of bicarbonate crystals. If no bicar-bonate bath is available, immediate washing with luke-warm (30°C) water is advised for at least 15 minutes. Arrange immediate transport to the hospital. As opposed to MCA, SMCA is not toxic upon skin contact nor damaging to the skin, although redness has been observed after prolonged contact. Contamination of the working area or its surroundings should be prevented, as the product may adhere to and penetrate through footwear.

EyesEyes that have been in contact with MCA prod-ucts should be washed for at least 15 minutes with lukewarm (ca 30°C) water or a physiological salt solution. The patient should be examined by an ophthalmologist.

InhalationInhalation of MCA vapors has an irritant effect on the respiratory tract. The patient must be taken out into the fresh air and remain seated in a semi-upright position.

IngestionMCA/SMCA products are toxic when swallowed. Make the victim rinse his mouth with water as soon as possible. Then preferably give the victim milk to drink (water can also be used) in order to dilute the ingested MCA/SMCA. Vomiting should not be induced. For details see Safety Data Sheet. The patient should be hospital-ized immediately.

First aidExpert medical attention should be obtained immediately for anyone who has been in contact with MCA or ingested SMCA. A sample of MCA/SMCA and/or Safety Data Sheet and/or Transport Emergency Card should be provided to ensure quick diagnosis by the doctors at the medical post/hospital.

Medical TreatmentThere is substantial evidence from animal experiments, that the timely administration of sodium dichloroacetate (SDCA) may be life-saving in serious (S)MCA intoxications. SDCA has also been used succesfully in humans for the treatment of other conditions with a similar biochemical mechanism of action. A protocol for the treatment of (S)MCA intoxications can be obtained through the nearest Poison Information Center with access to the IPCS INCHEM system or from AkzoNobel. Via the AkzoNobel Emergency Response center, in the Netherlands (+31 570 67 921), for general information about IPCS INCHEM, see www.inchem.org.

Fire hazardsMonochloroacetic acid is flammable at higher temperatures and is explosive at high tempera-tures when mixed with air (flash point 126°C). SMCA on the other hand is not susceptible to dust explosions in air. In the case of a fire, MCA/SMCA products generate hydrogen chloride. Acid-resistant fire-fighting equipment (respira-tors, protective clothing) should therefore be used. To fight an MCA or SMCA fire, use water, foam, carbon dioxide or dry powder.

A solid knowledge of MCA/SMCA is the key to safe handling of this product. Companies using MCA/SMCA in manufacturing processes should therefore ensure their employees are trained and instructed to guarantee safe handling.

Eating, drinking or smoking while handling MCA/SMCA products is prohibited. The site or plant emergency plan describes all necessary precautionary measures and steps to be taken after an accident involving MCA/SMCA. Immediate treatment of MCA exposed victims with bicarbonate solution (emergency bath) or water (emergency shower) is vitally important to prevent poisoning symptoms and limit skin damage. Therefore, sites handling MCA products should have at least warm showers (approx. 30°C).

Emergency responseIf advice is needed about disposal, spillage, leakage, fire, explosion or any other accident involving MCA, do not hesitate to call one of the emergency 24/7 telephone numbers:

For North American customers for medical/handling: +1 914 693 69 46and for transport emergencies; CHEMTREC: +1 800 424 93 00) for China: +86 532 388 9090for all other regions: the AkzoNobel Emergency Response telephone number: +31 570 679 21

www.akzonobel.com

AkzoNobel creates everyday essentials to make people’s lives more liveable and inspiring. As a leading global paints and coatings company and a major producer of specialty chemicals, we supply essential ingredients, essential protection and essential color to industries and consumers worldwide. Backed by a pioneering heritage, our innovative products and sustainable technologies are designed to meet the growing demands of our fast-changing planet, while making life easier. Headquartered in Amsterdam, the Netherlands, we have approximately 45,000 people in around 80 countries, while our portfolio includes well-known brands such as Dulux, Sikkens, International, Interpon and Eka. Consistently ranked as a leader in sustainability, we are dedicated to energizing cities and communities while creating a protected, colorful world where life is improved by what we do.

© 2016 Akzo Nobel N.V. All rights reserved. AN

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Contact:AkzoNobel MCA E mca@akzonobel.com T +31 88 969 6921

AkzoNobel China E mca.asia@akzonobel.com T +86 21 2220 5566

AkzoNobel USA E mca@akzonobel.com T + 1 312 544 7083

For more information visit www.akzonobel.com/mca