Paper presented at the IFEAT International Conference in Lisbon, Portugal, October 2004.

Pages 202211 in the printed Conference Proceedings.

VANILLIN: THE ONCB ROUTE A SUSTAINABLE OPTION?

Dominique Giannotta
Rhodia Perfumery, Performance & Agro,
190 Avenue Thiers, 69457 Lyon, Cedex 06, France
[ dominique.giannotta@eu.rhodia.com ]

This presentation examines vanillin, one of the major aroma chemicals under a strong competitive
pressure from Chinese producers. In China, all vanillin producers are starting from
orthonitrochlorobenzene (ONCB) to make vanillin and the industry has been under the scrutiny of the
local authorities following the introduction of stringent environmental and safety regulations.
My aim is to try to answer the question: Is vanillin ex ONCB route a sustainable option?
The discussion is based on Rhodia's vanillin knowledge (catechol route) and on the experience gained
since our acquisition in 2000 of a Chinese vanillin player operating an ex-ONCB process.
Before embarking on the specifics of vanillin, an outline will be provided of HSE issues in China
today.
The HSE situation in China
Water pollution
Water pollution in China

A critical water pollution situation has arisen

from the rapid and to a certain extent uncontrolled
industrial development.

Polluted rivers in China

100
90

100 times less in China

than in Western countries.

80
70

The majority of urban river sections are polluted

by chemicals and toxic compounds, such as
petroleum, volatile phenol, permanganate,
mercury.
90% of the Northern Rivers and 60% of the
Southern rivers are considered unsuitable for
direct human contact.

Waste water
treatment plants

60
50

Industrial & population

growth > infrastructures

40
30
20
10
0

Northern rivers

Southern
rivers

Suitable for human contact

Unsuitable for human contact

[ Source: Clear Water, Blue Skies:

China's Environment in the New
Century
(The
World
Bank,
Washington, D.C., 1997), p. 14 ]

In addition, it is estimated that there are 100 times less waste-water treatment plants than in Western
countries and, of course, the general infrastructure cannot face the population and industrial growth.
Last year, Mr Xie Zhenhua the Minister of the State
Environmental Protection Administration, said
water pollution controls are a top priority.
Chinese authorities now are reinforcing all controls
and environmental protection departments, which
have been instructed to strictly execute the antipollution laws and regulations. Also, a system is set
up to monitor enterprises practices.

Results of the Implementation of

Water Pollution Controls
Authorities fined 12,000 polluting enterprises *

for serious violation of environmental protection laws

more than 60% of these enterprises

had to shut down
or suspend production
* as of Jan. 2004, mostly chemical and metallurgical industries

202

Today, controls are a reality in China. The authorities have fined 12 thousand polluting chemical and
metallurgical enterprises and due to serious violation of environmental protection laws, more than
60% of these enterprises had to shut down or suspend their productions.
Air pollution:
Water pollution is critical but air is also highly
polluted in China.

Air Pollution in China

7 out of the 10 most

polluted cities in the
world are located in
China

The major source of energy in China to cover the

rapid development of the country is coal burning.
Alternative energy supply, such as nuclear,
represents only 4%.

2 major air pollutants

caused by coal
combustion:
Sulfur dioxide
Soot

The coal combustion is the major source of air

pollution generating sulphur dioxide and soot. All
of this without including a bank of cars that will
compound the negative effect of acid rain which
already is falling on 30% of Chinas total land
area.

ACID RAIN falls

on 30% of
Chinas total
land area

Report released in 1998 by the World Health Organization (WHO)

[ Source: Clear Water, Blue Skies: China's Environment in the New Century
(The World Bank, Washington, D.C., 1997), Figure 1.1, p. 6. ]

The Chinese Governments response to this problem has been similar to some of ours in the Western
countries. For example:
Establishment in 1998 of the State Environmental Protection administration.
Air pollution control policies.
Green pricing.
Pollution levy system (PLS).
Concentration emission standards.
Emission trading. [If an enterprise emits below the cap pollution, it may accumulate
credits or permits towards future emissions (like the US cap and trade system model).]
However, the main challenge lies in implementation and we have seen that the authorities are
becoming more and more committed about strict implementation of HSE regulations.
OHS issues
China was until fairly recently a rigidly planned
economy. Now, after a move to a decentralized
economy and the rapid modernization, Chinese
workers are suffering from decentralized and
deregulated occupational health and safety
conditions and from unsafe workplace
It was recently estimated that 30% of the
industrial workforce in China were engaged in
hazardous occupations.

Occupational Health & Safety (OHS) issues

Rigidly Planned
Economy
Decentralized
Economy
Decentralized &
deregulated
OHS conditions

Rapid Modernization
Explosive growth of
hazardous industries
& unsafe workplace

30% of the industrial workforce in China engaged in hazardous

occupations

National law on preventing occupational illness effective in China (May

2002 )
Workers, exposed to dangerous environment, can seek legal
redress if their employer violates their rights

Since May 2002, the National law on preventing

occupational illness is effective. Thus workers

203

exposed to dangerous environment, can seek legal redress if their employees violates their rights.
The consequences on the manufacture of vanillin in China
In the last 4 years, 3 out of the 5 vanillin ex
ONCB Chinese players were forced to stop,
mostly due to environmental and economical
pressures.

Vanillin Restructuring
In the last 4 years, 3 players out of 5 were forced to stop
Jilin - Flying Deer / SIKA

Jahwa - Polar Bear

These companies were:

Jawha - closed its vanillin plant in 2000;
Tianjin exited vanillin production; and
Xuebao was threatened with closure of its
new plant plant because of noncompliance
with
environmental
standards.

Tianjin - Ying Hai

Xue Bao

Jiaxing - Eternal Pearl

The major chemical processes to manufacture vanillin

There are 2 main nature identical vanillins available on the market:
from the ex-guaiacol route, which is by far the most important, and
from the ex-lignin route.

OH
HO

Rhodia route
OH

OH

Glyoxilic acid
OCH3

CATECHOL
OCH3

Dimethyl aniline

GUAACOL
CHO

VANILLIN

LIGNIN

Chinese
route

NO2
Cl

o-NitroChloroBenzene
(ONCB)

Vanillin ex-guaiacol can be obtained from 2 different processes:

via catechol / glyoxilic acid, which represents the largest installed industrial capacity
and the o-nitrochlorobenzene + dimethylaniline route.

204

As noted earlier, the ONCB / DMA process is only operated in China and the strict measures against
pollution taken by the Chinese authorities has contributed to the shut down of some the Chinese
vanillin producers.
Rhodias experience with an ex ONCB vanillin unit in China
With manufacturing facilities in EU and North of America, Rhodia wanted to be present in the fast
growing country of China. Consequently, in 2000, Rhodia acquired Xuebao, the most recently built
Chinese vanillin unit at that time. This new subsidiary of Rhodia was called the Ruohai Fine
Chemicals Co. Ltd.
Efficiency and pollution assessment
The plant was designed to operate by the ex-ONCB process for the production of vanillin. Our initial
investigation of this process revealed that it was inefficient.
The ex-ONCB and ex-catechol processes both start from benzene but they lead to vanillin via two
different chemical routes:
The major steps of the ex ONCB route are shown on the right hand side of the diagram below.
Benzene, chlorobenzene, ONCB, ortho-anisidine, guaiacol and then dimethylaniline are used
to produce vanillin and PADMA, a toxic by-product.
The ex-catechol process (shown on the left) follows the steps: benzene, phenol, catechol and
guaiacol and finally condensation of glyoxylic acid on guaiacol to produce vanillin.

Our initial findings : an inefficient process

Benzene

ex-ONCB route

ex-Catechol route

Chlorobenzene

Phenol

ONCB

CATECHOL

O-anisidine

Gaiacol
Glyoxilic acid

Dimethyl aniline
PADMA

Vanillin
To produce 1kg vanillin:
ONCB route requires ~2.8 times more benzene than catechol route, and
generates 0.8 kg of various toxic wastes [including p-aminodimethylaniline
(PADMA)]

The eco-balance of ONCB route is unfavourable compared to that for ex-catechol:

The ONCB chemical route requires about twice the amount of raw materials, generates more
salts and consumes more energy to produce the same quantity of vanillin.

205

In addition, the route is more polluting than that of ex-catechol, producing 3 to 5 times more
- COD (chemical oxygen demand),
- tars, and
- VOC ( volatile organic compounds) amongst which 1/3 is due to benzene.

Unfavourable ecobalance of ONCB vs Catechol route

Atoms balance
4

3,5

Electricity

Salts

2,5
2

Catechol Process

1,5
1
0,5

Steam

Process
water

VOC

Ex ONCB process
vs ex Catechol process

COD

1/3 of VOC is due to

benzene

Tars

VOC : volatile organic compound

COD : chemical oxygen demand

Comparison of Raw Materials Toxicity

90
80
70
60
50
40
30
20
10
0

ONCB route
Catechol route

Cumulative toxicity index of the raw

materials involved
hyper-toxic products in ONCB route
NH3, Benzene, DMA, PNCB, CL2

ONCB route

Catechol
route

900
800
700
600
500
400
300
200
100
0

Toxicity index relative to exposure level

and quantity of handled products
ONCB route
Catechol route

ONCB route

Catechol
route

206

Based on the experience of both processes, a comparison was made of the toxicity of the raw materials
involved in both routes. Calculation of a cumulative toxicity index based only on the level of toxicity
of the raw materials used, starting from benzene; and in a second step, integration of the level of
exposure of the workers for the same quantity of vanillin produced.
The cumulative toxicity index is higher for the ex-ONCB route and, when the level of exposure is
added, the result is clearly in favour of the catechol process.
Assessment of HSE practices
The results of an HSE assessment were appalling for a brand new vanillin manufacturing plant:
Non-compliance with environmental regulations.
Xuebao was under a strong pressure from the Chinese authorities.
High health and safety risks.
Unacceptable standards for flavour ingredient production.
With regard to non-compliance with environmental standards:
There was no effluents treatment and direct discharge into the river.
Tars were not treated and were directly stockpiled in unmonitored landfills.
There are 2 types of tars produced during the production of vanillin.
o non toxic tars from the vanillin separation, and
o toxic tars coming from the PADMA (the by product) separation.
Concerning non-compliance with hygiene standards, 1/3 of the VOC in the ONCB process is due to
benzene used in 3 different process steps:
Extraction of guaiacol during the manufacture of guaiacol
Extraction of vanillin
Extraction of PADMA
Due to its high toxicity:
Benzene is classified as carcinogen R45.
The Benzene Convention, 1971 (n 136) requires ratifying states to take measure to substitute,
prohibit or control the use of benzene in the work place.
Benzene has been banned as a solvent in USA since early 1980s.
Some other striking examples of
non-compliance with hygiene
standards are illustrated in these
photographs. Operators are:
in contact with toxic
material (nitrosation step),
exposed to high levels of
methanol vapours, and
in the neutralization zone
for PADMA, there is a
strong
atmosphere
of
ammonia, plus operators
manually handle toxic mud.

Non compliance with hygiene standards

- Operators in contact with toxic material (nitrosation )
- Strong NH3 atmosphere in the PADMA neutralization zone
- Operators manually handling toxic mud (PADMA neutralization)
- High exposure to methanol vapors

207

This combination of hazardous chemicals and poor hygiene is dangerous.

A Chinese study of occupational contact dermatitis in the manufacture of vanillin in China revealed a
50.5 % incidence amongst the 105 employees examined. The results of the survey and of patch tests
on human showed that:
two key chemical intermediates, the p-nitro-dimethylaniline hydrochloride (p-NDMAH) and
the sodium nitrite, were the attributable factors for the dermatitis,
but vanillin was neither irritant nor sensitizing.
Improvements made since 2000
Facing the inefficiency of the process and the disastrous HSE practices, we had to quickly tackle
several problems starting from the removal of the very polluting ONCB part of the process, as well as
benzene used as an extraction solvent.
We changed to supplying the Ruohai plant with guaiacol made from catechol and improved the
guaiacol / dimethylaniline step that leads to vanillin.

Process change: move to ex-catechol guaiacol

Benzene

ex-ONCB route

ex-Catechol route

Chlorobenzene

Phenol

ONCB

CATECHOL

O-anisidine

Benzene used
as a solvent

Gaiacol
Dimethyl aniline

PADMA

Vanillin

HSE management simply did not exist before the company take-over. Therefore. an HSE management
was implemented in Ruohai with a strict training plan for personnel.
We improved the aqueous effluents treatments in two main steps:
Installing a physico-chemical treatment step.
Investment in a biological treatment unit.
The total COD was divided by 20 in order to be able to send the effluents to an external waste water
treatment unit. After final purification, the effluents could be discharged into the river with a COD of

208

below 100ppm, in line with local regulations.

Environmental improvements:
aqueous effluents

Synthesis
of VA

Aqueous
effluents
PADMA

Physicochemical
treatment

Biological
treatment

External
WWTU

RIVER

Aqueous effluents

VA

< 100 ppm

COD
(local regulation)

COD divided by 20
BEFORE
ACQUISITION

SECOND
FIRST
IMPROVEMENT IMPROVEMENT

The other main improvement made at the plant

was the investment in site of a brand new
incinerator to burn solid wastes instead of having
tars stockpiled in unmonitored landfills.

Environmental improvements:
solid waste disposal
An incinerator was built and commissioned in
October 2001 to burn waste solid on-site
(tars and mud)

We made these improvements not only for our

employees and for the protection of environment
but also because vanillin is not only a chemical
product but the most used flavour ingredient in
the world.
The quality of the vanillin and the way it is manufactured to avoid contamination are key for the
consumer safety. It is important to recognize that:
If benzene is used as an extraction solvent, the derived vanillin cannot be used in Food
applications in Europe (88/344 EC) or the USA.
If benzene is used as an extraction solvent, the derived vanillin cannot be used in
pharmaceutical applications in the USA, Europe, Japan and Australia
The EU Directive 93/43/ requires HACCP methodology for the manufacturing of food ingredients and
there are four obligations:
general hygiene principles;
risk management according to HACCP methodology;
staff training in hygiene; and
health compliance of the products

209

Therefore, the application of HACCP methodology is mandatory for the international trade of
foodstuffs. Since 2002, flavours are considered as food ingredients and therefore vanillin must be
manufactured according to HACCP principles.
Rhodia started to implement HACCP practices in the mid-1990s at our plants in Saint-Fons (France)
and in Baton-Rouge (USA). However when we acquired the Ruohai site in 2000 and due to a lack of a
prior HACCP policy, there were potential risks of contamination:
an open crystallization area;
an open dryer, without protection against possible
contamination;
glass risks;
a non-conforming packaging area; and
pest risks.

Subsequently, we have made

many major improvements to
achieve
compliance
with
HACCP, including:

enclosed equipment for the

crystallisation
the
and
centrifugation steps,
improvements
to
the
packaging room and to
procedures, and
thorough
training
of
operators.

HACCP improvements after 2000

Before

Enclosed equipment to avoid external

contamination at crystallisation and
centrifugation steps

Before

Packaging room, procedures

remodeled.
Operating training done

After
After

Conclusion on the ONCB process as a sustainable option

HSE regulatory constraints are increasing in China and we believe that the ex ONCB process can only
be partially upgraded.
Phasing out ONCB-guaiacol and replacing it by catechol-guaiacol was a significant HSE and quality
step change.
However, despite all of the improvements made Ruohai cannot reach the level of excellence of our
vanillin plants in Saint-Fons and Baton-Rouge.
Mid-term, China will be forced by environmental and economical reasons and by Western food
regulations to migrate from the new plant ONCB / DMA old process to the catechol / glyoxilic acid
route.

210

Dominique Giannotta is an organic chemistry graduate and during his

career he has specialized in the fields of formulation, marketing and project
management. He joined the Rhodia Group in 1997 as Product Manager for
the F&F business and later became the Technical Service & Development
Manager for F&F and Polymerization Inhibitors at the Lyon Research
Center. Mr. Giannotta was appointed Global Marketing & Innovation
Manager for the Flavours & Fragrances business of Rhodia in October
2003. Among other achievements, he was at the origin of the Rhovanil
Natural Project (natural vanillin by fermentation) and he remains Project
Leader to drive Rhodia biotech efforts in that field.

Acknowledgements
Many thanks are due to the team that helped in the preparation of this presentation: Marilyne Martinez,
Aline Corbet, Sebastien Meric and Claude Mathieu.

Bibliographic references
(1) The World Bank(1997) Clear Water, Blue Skies: China's Environment in the New Century The
World Bank, Washington, D.C., USA.
(2) Xie Zhenhua, PRC Minister of the State Environmental Protection Administration; speech if July
2003.
(3) Meei-Shia Chen (2003) Workers participation & health & safety protection PhD, Dec.2003
(4) Regulations on Labor Protection in Workplace Where Toxic Substances Are Used (Adopted at the
57th Executive; meeting of the State Council on April 30, 2002, promulgated by Decree n 352 of
the State Council of the People of Republic of China on May 12, 2002, and effective as of the
date of promulgation).
(5) Wang Xia-sheng et al. (1987) Occupational dermatitis in the manufacture of vanillin. Chinese
Medical Journal, 100 (3), 250-254.

211