1,4-Dioxane A Current Topic for Household Detergent and Personal Care Formulators

L. Matheson and G. Russell - SASOL N.A. B. MacArthur and W. B. Sheats - Chemithon 100th AOCS Annual Meeting, May 6, 2009

1,4-Dioxane: What Are The Issues?

Recent reports suggest that 1,4-Dioxane has been detected at measurable levels (1 to 100ppm) in some personal care products. 1,4-Dioxane is recognized as a toxic substance that should be controlled. The source of 1,4-Dioxane has been inaccurately reported. The reality is:
1,4-Dioxane is not a significant by-product of the base-catalyzed ethoxylation of fatty alcohols. 1,4-Dioxane is a controllable by-product of the highly acidic sulfation process to make AES.

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What is 1,4-Dioxane?

1,4-Dioxane

Not to Be Confused with Dioxin

Dioxin 1,4-Dioxane is not the same as dioxin.

Risk from 1,4-Dioxane Exposure in Household and Personal Care Products

The focus of this presentation is on how and where 1,4Dioxane is created and what can be done to control its formation. However, it should be noted that thorough risk assessments of 1,4-Dioxane exposure from cleaning products have been conducted. Good examples can be found at: www.heraproject.com HERA (Human and Environmental Risk Assessment) is a voluntary industry program to carry out risk assessements on household cleaning product ingredients.
Alcohol Ethoxylates Version 1.0. (2007, May) Alcohol Ethoxysulphates Human Health Risk Assessment Draft. (2003, January)

Where Does 1,4-Dioxane Come From?

Recent publications suggest 1,4-Dioxane is formed through ethoxylation of fatty alcohols. However, in-house evaluation of alcohol ethoxylates produced by Sasol North America shows <5ppm of 1,4-Dioxane in the ethoxylates used in household and personal care products.

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Where Does 1,4-Dioxane Come From?

RO H + M+OHFeedstock Catalyst RO- + M+ + H2O
EO RO CH2 CH2O-

EO

RO CH2 CH2 O CH2 CH2 OEO etc.

RO

(CH2CH2O)nH Ethoxylate

H+

1,4-Dioxane is not easily formed under conditions of alkaline catalyzed ethoxylation of fatty alcohols.

Where Does 1,4-Dioxane Come From?

Most 1,4-Dioxane is produced during the sulfation of ethoxylated alcohols to make AES. The thin film sulfation reaction with SO3 occurs under highly acidic conditions. This has been recognized for some time, and control methods are practiced in the Industry. Assuming that active levels of any one ingredient in personal care products are about 10%, then the 1,4Dioxane in the final product would be diluted by a factor of 10 from that of the starting ingredient.

SO3 Sulfation of Alcohol Ethoxylates (AE)

R-(EO)n-OH + SO3 R-(EO)n-OSO3H

Reaction occurs under strongly acidic conditions.

O O OSO3
-

ROSO3H + NaOH

ROSO3Na

Neutralization of the AES acid should occur promptly after sulfation to minimize decomposition and to reduce by-product formation.

Formation of 1,4-Dioxane by Excess SO3

1,4-Dioxane can be formed from ethoxymers with >1 mole of EO when excess SO3 is used.

Factors Influencing the Level of 1,4-Dioxane During the Sulfation of AE to Make AES
Process and Equipment Factors
SO3 : AE feed mole ratio Reactor loading %SO3 concentration in air Residence time of AES acid prior to neutralization De-aeration and stripping of AES paste

Feedstock Compositional Factors

Average degree of ethoxylation PEG and moisture content EO adduct distribution

1,4-Dioxane Study by Chemithon and Sasol

Objective: Sulfate an alcohol ethoxylate and generate response surfaces showing dependence of 1,4-Dioxane on process conditions for making AES. Experimental Design: Three Factorial Design - Central Composite
SO3 : AE feed mole ratio %SO3 concentration in air Reactor loading (kg/hr-cm of wetted reactor surface)

Response Measurements
1,4-Dioxane (ppm in 100% active product) Klett Color (5% active basis, 40mm path) Free Oil (wt% in 100% active product) Sodium Sulfate (wt% in 100% active product)

AE Feedstock for Experimental Design Study

Feedstock Analysis: C1412-3 Ethoxylate KOH catalyzed linear, primary C12 and C14 alcohol ethoxylated to approximately 3 moles Ave Moles EO: Ave MW: Wt.% Free Alcohol: Wt.% PEG: ppm 1,4-Dioxane: ppm Moisture: 2.8 329 12.1 0.8 0.1 260

1,4-Dioxane vs. Loading & Mole Ratio at 3% SO3

Constant Factor: 3% SO3 in air
ing oad L
Mole Ratio

------Then------

1,4-Dioxane

M ol e

Ra t

io

g in d oa L

1,4-Dio xane

Mole Ratio & Reactor Loading

e ioxan 1,4-D

1,4-Dioxane vs. Loading & Mole Ratio at 4% SO3

Constant Factor: 4% SO3 in air
atio ole R M

Load

ing

Reactor Loading

Mole Ratio
xane 1,4-Dio

------Then-----1,4-Dioxane

Lo ad in g

e ol M

io at R

1,4-Dio xane

1,4-Dioxane vs. SO3 Concentration & Mole Ratio

Constant Factor: 0.92 Reactor Loading
onc SO 3 C
Mole Ratio

------Then------

1,4-Dioxane

M ol e

Ra

tio

3 SO

c on C

1,4-Dio xane

Mole Ratio & SO3 Concentration

e ioxan 1,4-D

1,4-Dioxane vs. SO3 Concentration & Reactor Loading

Constant Factor: 0.99 Mole Ratio
(Slight excess of AE)
ing Load
SO 3 Con c

Reactor Loading
Concentration

SO3

------Then------

1,4-Dioxane

SO

Co nc

g in ad Lo

1,4-Dio xane

o 1,4-Di xane

Color vs. SO3 Concentration and Mole Ratio

Constant Factor: 0.92 Reactor Loading
tio le Ra Mo
SO 3 Con c

SO3 Concentration
Klett C olor
SO
3

------Then------

Klett Color Low color is a very important quality parameter for AES for personal care formulations.
Co nc

e ol M

t Ra

io

Klett C

olor

Color vs. SO3 Concentration and Reactor Loading

SO3 Concentration Then 1,4-Dioxane & Klett Color

Conditions which yield low color (i.e. low SO3 concentration), will generally yield low levels of 1,4Dioxane.
ing Load
SO 3 Con c

0.99 g oadin L

Mole Ratio SO
3

Conc

1,4-Dio xane

SO

Co nc

g in d oa L

SO

Co nc

g in d oa L

Klett C

o 1,4-Di xane

olor Klett C

olor

Free Oil vs. SO3 Concentration and Mole Ratio

Constant Factor: 0.92 Reactor Loading
tio le Ra Mo
SO 3 Con c

Mole Ratio

Free Oil
SO

Conditions which give lower 1,4-Dioxane generally yield high free oil levels.

Co nc

e ol M

t Ra

io

Free O il

------Then------

Free O il

How to Minimize 1,4-Dioxane in AES

1. Proper Conditions for Thin Film SO3 Sulfation SO3 to AE mole ratio of 1.0 or lower SO3 concentration in air at 3% Reactor loading at ~1 kg/hr - cm

2. Properly Designed Thin Film Sulfation Equipment

1,4-Dioxane Reduction by Stripping AES Paste

Reduction of 1,4-Dioxane content in neutral 70% AES paste can be accomplished by stripping. The reduction factor (Inlet 1,4-Dioxane/Outlet 1,4-Dioxane) in a single stripping stage depends on the weight ratio of stripping steam to AES paste employed. Reduction ratios from 2 to 10 can be achieved economically. De-aeration of 70 wt% active AES paste occurs simultaneously upon stripping.

AES Stripping System for 1,4-Dioxane Removal

AES Paste
Steam Steam

Stripper

Cond

Product AES 1,4-Dioxane Destruction

1,4-Dioxane Removal in Stripper

Stripper Outlet 1,4-Dioxane (ppm wt 100% Act. Basis)

72% Active AES with 100ppm Inlet

How to Minimize 1,4-Dioxane in AES

1. Proper Conditions for Thin Film SO3 Sulfation SO3 to AE mole ratio of 1.0 or lower SO3 concentration in air at 3% Reactor loading at ~1 kg/hr - cm 2. Properly Designed Thin Film Sulfation Equipment Sulfation reactor and subsequent neutralization De-aeration and stripping of neutralized 70% active AES paste 3. Appropriate Choice of AE Feedstock

Laboratory Studies on 1,4-Dioxane Formation

Sulfation with excess SO3 Ethoxylate Feedstock Characteristics Degree of Ethoxylation Content of High Mole PEG By-Product Content of High Mole EO Adducts

The Effect of SO3 / AE Mole Ratio

400

300

1,4-Dioxane (ppm)

200

100

0 0 0.2 0.4 0.6 0.8 1 1.2

Mole Ratio of SO3/ETO

1,4-Dioxane vs. EO Adduct Length in AES

ppm 1,4-Dioxane (100% active basis)
2,500 2,000 1,500 1,000 500
`

2093 1858 1285 812 1782

408 0 0
1 2

212

0 0 3 4 5 6 7 8

C12 EO Adduct Chain Length

Ethoxylate comparisons are on equimolar basis, sulfated at 1.03 mole ratio.

Formation of 1,4-Dioxane by Excess SO3

Excess SO3 finds few unreacted hydroxyl groups and attacks ether oxygens instead. Higher EO adducts have more sites to attack.

1214GC (70:30) Alcohol EO Adduct Distributions

45 40
1 EO 2 EO 3 EO

Weight %

35 30 25 20 15 10 5 0 0 2 4 6 8 10 12
1214GC-1 1214GC-2 1214GC-3

10 Wt% 5 EO 25 Wt% 5 EO 39 Wt% 5EO

14

EO Mole Adducts

EO Adduct Distributions for 1214GC-2 Mole Ethoxylates, NRE vs. BRE

30
BRE

25

NRE

Weight %

20 15 10 5 0 0 2 4 6 8 10 12 14 16
BRE NRE 25 Wt% 5 EO 11 Wt% 5 EO

EO Mole Adducts

Effect of By-Product PEG in AE

PEG comes from residual water present during ethoxylation. H2O + EO HO CH2 CH2 O H
Ethylene Glycol
O HO O O O O O O O O O

+ more EO
O O O OH

Typical PEG by-product in 1412-3 ethoxylate Less than 0.8 weight % PEG in AE Ave. MW of 750 for PEG (17 EO units) compared to 435 for alcohol ethoxylate (3 EO units)

Effect of Moisture in Sulfation Feed

H2O +

SO3

(gas)

H2SO4

(liquid)

H2O combines with SO3 and forms H2SO4 H2SO4 condenses as liquid droplets and forms localized excess of sulfating agent. Over-sulfation and heat of reaction can lead to increased formation of 1,4-Dioxane.

How to Minimize 1,4-Dioxane in AES

1. Proper Conditions for Thin Film SO3 Sulfation Mole ratio of 1.0 or lower SO3 concentration in air at 3% Reactor Loading at ~1 kg/hr - cm 2. Properly Designed Thin Film Sulfation Equipment Sulfation reactor and subsequent neutralization Stripping of neutralized 70% active AES paste 3. Appropriate choice of AE feedstock Minimize high mole EO adducts Low PEG and low moisture levels in AE

Conclusions
The main source of the 1,4-Dioxane reported in household and personal care products is from the sulfation of AE to produce alcohol ether sulfates (AES). Our data shows only 5ppm or less 1,4-Dioxane can be attributed to the original alcohol ethoxylate feedstock. The use of proper sulfation equipment, optimum process conditions, and good quality AE feed should produce AES containing less than 100ppm of 1,4-Dioxane on 100% active basis. Stripping of the 70% AES paste can reduce the 1,4-Dioxane levels even further.