Alternatives to hydrazine in anticorrosion treatment for boilers

Number

142-EN

Section

General Section

Use

Sector

Electricity, steam, gas water supply and sewage treatment

Function

Aerating and dearating agents
Corrosion inhibitor
Deodorizer
Reducing agent

Process

Other hot work operations with metals

Product category

Metal surface treatment products
Waster treatment chemicals

Application

Heating systems

Abstract

Hydrazine is used to protect boilers form corrosion by reducing the concentration of dissolved oxygen in the water and by contributing to the passivation of the metal surface of the installation. Hydrazine is a hazardous substance and alternatives have been found that give acceptable results.

Substituted substances

Hydrazine

CAS No. 302-01-2 EC No. 206-114-9 Index No. 007-008-00-3

Chemical group

Hydrazine and hydrazinium salts

Classification: hazard statements

H226 Flammable liquid and vapour
H350 May cause cancer
H331 Toxic if inhaled
H311 Toxic in contact with skin
H301 Toxic if swallowed
H314 Causes severe skin burns and eye damage
H317 May cause an allergic skin reaction
H400 Very toxic to aquatic life
H410 Very toxic to aquatic life with long lasting effects

Other adverse effects

The substance is: 2B carcinogen (IARC) as listed in the Substance Database according to SUBSPORT Screening Criteria (SDSC).

Alternative Substances

Diethylhydroxylamine

CAS No. 3710-84-7 EC No. 223-055-4 Index No.

Chemical group

Hydroxylamine derivatives

Ascorbic acid

CAS No. 50-81-7 EC No. 200-066-2 Index No.

Chemical group

Lactones

Carbonohydrazide

CAS No. 497-18-7 EC No. 207-837-2 Index No.

Chemical group

Hydrazine derivatives; urea derivatives

Sodium bisulphite

CAS No. 7631-90-5 EC No. 231-548-0 Index No. 016-064-00-8

Chemical group

Sodium compounds; sulfites

Classification: hazard statements

H302 Harmful if swallowed

Sodium sulphite

CAS No. 7757-83-7 EC No. 231-821-4 Index No.

Chemical group

Sodium compounds; sulfites

Potassium hydroxide

CAS No. 1310-58-3 EC No. 215-181-3 Index No. 019-002-00-8

Chemical group

Potassium compounds; hydroxides

Classification: hazard statements

H302 Harmful if swallowed
H314 Causes severe skin burns and eye damage

Sodium hydroxide

CAS No. 1310-73-2 EC No. 215-185-5 Index No. 011-002-00-6

Chemical group

Sodium compounds; hydroxides

Classification: hazard statements

H314 Causes severe skin burns and eye damage

Reliability of information

Internet information: data are from an internet document and only a basic and partial evaluation could be performed

Reason substitution

CMR
skin/respiratory sensitizing

Other type of alternative

Physical degasification of water.

Hazard Assessment

Substance to be substituted: Hydrazine is: a 2A carcinogen (IARC), 1A or 1B carcinogen (CLP Regulation), a sensitiser (H317, H334; CLP Regulation) as listed in the Substance Database according to SUBSPORTplus Screening Criteria (SDSC). Alternative substance: Unlike hydrazine none of the alternatives is classified as carcinogen. Sodium bisulphite is registered by as harmful if swallowed. Potassium hydroxide causes severe skin burns and eye damage and is harmful if swallowed. Sodium hydroxide causes severe skin burns and eye damage.

Description of Substitution

The use of hydrazine in steam and heating systems is due to its efficacy in reducing the oxygen levels in waters (which favours oxidation and builds up rust) and in creating a passivation layer on the metal surface. Alternatives to hydrazine are already in use. Some of them are presented in a short document, available in French. The organic alternatives include diethylhydroxylamine (DEHA) or ascorbic acid that is also safe to use in the food industry steam system, but is more expensive. The use of carbohydrazide is not a good alternative because is a skin sensitiser and generates hydrazine and formaldehyde in the system. Inorganic alternatives like sodium sulphite or bisulphite as well as sodium or potassium hydroxides may be used instead of hydrazine, but they increase the mineral content of the water. Substitution of hydrazine may be also achieved by implementing other processes like the physical degasification of water. Other alternatives mentioned by the document are hydroxypropyl hydroxylamine (HPHA), or polyamine additives. Adding substances like polyamines creates a protective film for the metal surface limiting oxygen diffusion and therefore the corrosion. Information on the safe use of these alternatives and on HPHA is not easily available from independent sources. Users have to rely mostly on producer information.

Case/substitution evaluation

DEHA is already largely used as alternative to hydrazine. It has technical advantages and is suited to a variety of operational conditions and types of boilers. DEHA is not a carcinogen or sensitiser. HPHA (CAS 97173-34-7) is not registered in the C&L inventory nor is it classified by the CLP regulation annex VI; hazards may be identified according to MSDS. New products containing polyamines (and amines) have in general proprietary formulations that are not disclosed, so users have to rely on the information included by the producer in the MSDS. Physical processes for water degasification may not reach the desired concentration for dissolved oxygen and chemicals might still be needed to further lower its level. TRGS 608 (1991) names possible substitutes for hydrazine in water and steam systems. Most of these are also mentioned in the case study 142-EN from 2008. The case study is therefore state of the art.

State of implementation

In use

Date and place of implementation

France

Availability ofAlternative

Alternatives available on the market

Type of information supplier

Research

Further information

- DEHA http://www.sigmaaldrich.com/MSDS/MSDS/DisplayMSDSPage.do?country=DE&language=EN-generic&productNumber=471593&brand=ALDRICH&PageToGoToURL=http%3A%2F%2Fwww.sigmaaldrich.com%2Fcatalog%2Fsearch%3Finterface%3DAll%26term%3D3710-84-7%26lan

Type of publication and availability

Fact sheet, in French

Publication source: author, company, institute, year

The Fact sheet was developed by CNAMTS and INRS, France and published by INRS on its website in 2008.

Publication source

Type of publication and availability

http://www.inrs.fr/accueil/produits/mediatheque/doc/publications.html?refINRS=FAS%2016

Date, reviewed

December 11, 2020