Eu risk assessment Primary Alkyl Amines title




НазваниеEu risk assessment Primary Alkyl Amines title
страница14/30
Дата01.10.2012
Размер2.51 Mb.
ТипДокументы
1   ...   10   11   12   13   14   15   16   17   ...   30

Exposure assessment

  1. General discussion


The starting materials for manufacturing long-chain, primary alkyl amines are natural fats and oils or synthetic products of the petrochemical industry (Kirk Othmer, 1994).

The discussed five primary alkyl amines are mixtures of primary straight chain alkyl amines partially with one or more double bonds.




Tallow alkyl amine

(Z)-Octadec-9-enylamine

Octadecyl amine

Hydrogenated tallow alkyl amine

Coco alkyl amine

CAS-No.

61790-33-8

112-90-3

124-30-1

61788-45-2

61788-46-3

m.p.

32 – 40 °C

15 - 30 °C

49 – 52 °C

48 – 56 °C

12 – 17 °C

vp.

< 1 Pa

< 1 Pa

< 1 Pa

< 1 Pa

< 1 Pa

form

paste

liquid

solid
(flake, prill)

solid
(flake, prill)

liquid

C & L

R 35

R 35

R 38

R 38

R 35



The five primary alkyl amines are produced by several manufactures in the EU and the total European consumption amounts 29.330 t/year.

In 2001, about 80 % of the primary fatty amine consumption was accounted for their use as intermediates in the production of ethoxylates fatty amines, diamine derivates, sulphosuccinic amides, other intermediates and particularly products with amide structure. The remaining approx. 20 % of primary fatty amine consumption was accounted for their direct use or in the form of their salts (chlorides, acetates, stearates, oleates), mainly as anticacking agents for fertilizers (14 %), as flotation agents (3 %), as lubricant and fuel additives (2 %) and, to a lesser content, as corrosion inhibitors, as dispersing agents for pigments, rubber additive and in textile formulations (1 %).

In the literature there is often no distinction between the use of primary alkyl amines in general, primary alkyl amine salts or products on basis of primary alkyl amines (ethoxylates, fatty amine, diamine derivate, amide).

The detailed production process is described in chapter 2.1.

For workers the inhalation and dermal exposure routes are the most likely.

A new request at the Swedish ( KEMI, personal communication, 2008) and the Swiss product registers (Swiss Federal Office of Public Health, personal communication, 2008) demonstrated that primary alkyl amines are used as ingredients of consumer products (detailed information see chapter 4.1.1.3). The information from the Swiss product register had included exposure information until the end of year 2005 latest.


Occupational exposure

Industrial activities using primary alkyl amines present opportunities for exposure. Exposure ranges depend on the particular operation and the risk reduction measures in use.

OELs (Occupational exposure limit) are not established in the EU (ARIEL, 2006).

The exposure assessment generally aims at assessing exposure levels representing the reasonable worst case situation. The reasonable worst case is regarded as the level of exposure which is exceeded in a small percentage of cases over the whole spectrum of likely circumstances of use for a specific scenario.

The assessment of inhalation exposure is mainly based on measured exposure levels from which – if possible – 90 percentiles are derived as representing reasonable worst case situations. Scenarios are clustered as far as possible to make the description transparent. If quantitative exposure data are not available, model estimates are used.

Beside inhalation exposure, dermal exposure is assessed for each scenario. Two terms can be used to describe dermal exposure:

Potential dermal exposure is an estimate of the amount of a substance landing on the outside of work wear and on the exposed skin.

Actual dermal exposure is an estimate of the amount of a substance actually reaching the skin.

Within the framework of existing substances there is an agreement between the EU member states, to assess – as a rule – dermal exposure as exposure to hands and parts of the forearms. In this, the main difference between both terms – potential and actual - is the protection of hands and forearms by work wear and – more important – the protection by gloves. Within this exposure assessment, the exposure-reducing effect achievable by gloves is only considered if information is provided indicating that, for a certain scenario, gloves are a widely accepted protective measure and that the gloves are fundamentally suitable for protection against the substance under consideration. As a measure for the latter, tests according to DIN EN 374 are taken as a criterion. For most downstream uses it is commonly known that gloves are not generally worn. In these cases, dermal exposure is assessed as actual dermal exposure for the unprotected worker. Since quantitative information on dermal exposure is often not available, the EASE model is mostly used for assessing dermal exposure.

Relevant occupational exposure scenarios are to be expected in the following areas:

Scenario 1: Occupational exposure from production and further processing (4.1.1.2.1)

Scenario 2: Further processing of primary alkyl amines (4.1.1.2.2)

Scenario 3: Use of primary alkyl amines in floatation process (4.1.1.2.3)

Scenario 4: Formulation of products containing primary alkyl amines (4.1.1.2.4)

In the literature further uses as corrosion inhibitors, as photochemical, as fertilisers, as fungicides, as limestone removers, as carpet cleaners, as human medicines or as preservatives in paints, leather and cosmetics are mentioned. The possible exposure during the use of this kind of preparations is not described in this exposure assessment, because it is not known, whether the uses of primary alkyl amines in the mentioned formulations really exist, and, if they do, the concentration of primary alkyl amines is considered to be low.

On account of the low concentration of primary alkyl amines in fertilisers (< 0.2 %), exposure scenarios in the context of handling of fertilisers are regarded to be of minor relevance. Therefore they are not discussed within the framework of this exposure assessment.

Occupational exposure from production (scenario 1)

Starting materials in the manufacture of long-chain, primary alkyl amines are natural fats and oils, or synthetic products of the petrochemical industry. The primary alkyl amines are manufactured by catalytic hydrogenation of nitriles obtained from fatty acids at high temperatures (80 – 180 °C) and pressures (1 – 10 MPa). After separation from the catalyst, the reaction products are purified by distillation under reduced pressure. The production takes place continuously or partially batchwise in closed systems.

All of these products are predominanly handled as molten liquids at temperatures typically up to 80°C. The end products are conveyed in a system of closed pipes and filled into tank trucks or drums via closed pipelines (BUA, 1996). The products are stored in tanks as liquids with nitrogen as protective gas (Hoechst, 1996; Akzo Nobel, 1997). Exposure is therefore effectively limited to sampling or loading activities.

An exception exists for hydrogenated tallow alkyl amine and octadecylamine which are processed in a solid form either as prills or flakes (APAG, 2003).

Inhalation exposure

On account of the melting points the primary alkyl amines are transferred in a molten state via heated pipelines and tanks to the next processing stage. Octadecylamine and hydrogenated tallow amine are produced as solids (flakes, prills). During the handling of the liquid octadecenylamine and coco alkyl amine as well as during handling of the pasty tallow alkyl amine, on account low vapour pressure (< 1 Pa), inhalation exposure to vapour is expected to be low. Inhalation exposure to dust is possible if solid octadecylamine and hydrogenated tallow amine are handled.

Measured data

Tab. 4.1.: Exposure at workplaces during production of hydrogenated tallow alkyl amine (provided by four producers) (APAG, 2003).

Job category

Activities

Year of measurment

Number of samples

Inhalable dust

[mg/m3]

Respirable dust

[mg/m3]

Total primary amines

[mg/m3]

TWA

Bagging operator

2003

1 (pers)

4 (stat)

< 0.38

< 0.21 – 0.85

-

-

0.1

0.16 – 0.57

Filling section

Flaking section

2003

1

1

0.46

0.71

0.07

0.125

-

-

Bag filling

Pellet machine

2003

2 (stat)

2 (stat)

< 0.09

< 0.08

-

< 0.009

0.04

Hydrogenated tallow amine production

2003

1 (stat)

-

0.51

-

pers = personal sampling , stat = stationary sampling

Exposure concentration of dust were determined by a gravimetric method (inhalable: BIA 7552, NIOSH 500; respirable: BIA 7284). The quantity of amines on the dust filter was determined by gas chromatography coupled to mass spectrometry. Due to the measurement method and the sampling strategy applied, the results are regard as valid.

During manufacturing of liquid primary alkyl amine products (distilled C12- amine and coco amine) the concentration of total amine in air have been determined (Akzo, 2008). Sampling was performed with stationary pumps inside the reactor hall and pumps carried by operators during drumm filling in the packing hall. The air was drawn through a gas bubble flask filled with a solution that captures the amines and analysed with a liquid chromatography method. The portable samples (sampling time one hour) show a total amine concentration of 0.04 mg/mth3.

On account of the low number of measurement values (primary alkyl amine specifically) for handling of solids the highest value of 0.57 mg/m3 (see Tab. 4.1) is taken.

Summary of the exposure level

Inhalation exposure has to be assessed for the production of solid primary alkyl amines (C18-amine) in large-scale chemical industry. Normally the primary alkyl amines are handled in melted form. Due to the low vapour pressure inhalation exposure is expected to be low. Octadecylamine and hydrogenated tallow alkyl amine are solids (prills or flakes).

For the assessment of the risks of daily inhalation exposure to octadecylamine and hydrogenated tallow alkyl amines an 8-h time weighed average concentration (8-h TWA) of 0.6 mg/m3 (highest measurement value, round off) should be taken. The level represents the reasonable worst case situation. It is to be assumed that the substances are processed daily. Consequently, the duration and the frequency of exposure are assumed to be daily and for the entire length of the shift.

Dermal exposure

For assessing actual dermal exposure levels, it has to be considered that the substances are produced and further processed primarily in closed systems. Due to the melting temperature of maximal 56°C, the molten primary alkyl amines are transferred and filled at elevated temperatures (T 80°C). As a consequence worker would avoid any direct dermal contact to the hot primary alkyl amines.

Another point of avoiding of dermal contact is the corrosive effect of tallow alkyl amine, coco alkyl amine and octadecenylamine (labelled with R 35). For the handling of corrosive substances, immediate dermal contacts occur only occasionally. It can be assumed that, as a rule, daily repeated immediate skin contact is avoided to a large extent by using suitable personal protective equipment (PPE, here: gloves and eye protection).

Dermal exposure is not assessed for corrosive substances.

Octadecylamine and hydrogenated tallow alkyl amine are labelled with R 38 and sold as flakes or prills. For the handling of the solid substances, as a rule, the suitability of the gloves can be assumed and low levels of daily dermal exposure are to be expected. However, in spite of this, dermal exposure may occur due to e.g.

- unintended contamination during the handling of used gloves

- limited protection of suitable gloves at real working conditions (e.g. mechanical stress)

Since no measurement results are available, an attempt is made to quantify dermal exposure for the above mentioned situations (solid primary alkyl amines, R 38) in application of the EASE model.

During activities like bagging, filling, cleaning and maintenance dermal exposure could occur.

Modelled data

According to the EASE model, potential dermal exposure is assessed as follows:

Input parameters: Non dispersive use, direct handling, intermittent

Level of exposure: 0 - 1 mg/cm2/day.

The consideration of an exposed area of 420 cm² (equivalent of one hand) leads to exposure levels of 42 - 420 mg/person/day.

It is assumed that the use of PPE (here gloves) is highly accepted in the large scale chemical industry. The protection of gloves is considered in a default value of 90 %.

Summary of the exposure level

For assessing the health risks from daily dermal exposure in the area of production of solid octadecylamine and hydrogenated tallow alkyl amine (prills, flakes) is considered.

For handling the solid primary alkyl amine, dermal exposure is assessed to 42 – 420 mg/person/day. The use of suitable gloves reduces dermal exposure to 10% leading to exposure of 4.2 – 42 mg/person/day. The upper value is regarded to represent the reasonable worst case.

Dermal exposure is not assessed for corrosive substances tallow alkyl amine, coco alkyl amine and octadecenylamine.

Exposure to the eyes is largely avoided by using eye protection.

1   ...   10   11   12   13   14   15   16   17   ...   30

Похожие:

Eu risk assessment Primary Alkyl Amines title iconDir 111 Risk Assessment and Risk Management Plan (February 2012) Office of the Gene Technology Regulator

Eu risk assessment Primary Alkyl Amines title iconRisk Assessment and Risk Management Plan Application for licence for dealings involving an intentional release into the environment dir 005/2001

Eu risk assessment Primary Alkyl Amines title iconRisk Assessment and Risk Management Plan

Eu risk assessment Primary Alkyl Amines title iconAn evaluation of risk to u. S. Consumers from methylmercury in commercial fish products, including a quantitative assessment of risk and beneficial health effects from fish

Eu risk assessment Primary Alkyl Amines title iconRisk Assessment

Eu risk assessment Primary Alkyl Amines title iconRisk assessment 4

Eu risk assessment Primary Alkyl Amines title iconRisk modeling, assessment and management

Eu risk assessment Primary Alkyl Amines title iconEuropean union risk assessment report

Eu risk assessment Primary Alkyl Amines title iconRisk Assessment Considerations in the Donetsk Basin

Eu risk assessment Primary Alkyl Amines title iconEu risk assessment chloroform cas 67-66-3 cover

Разместите кнопку на своём сайте:
Библиотека


База данных защищена авторским правом ©lib.znate.ru 2014
обратиться к администрации
Библиотека
Главная страница