Feasibility study on

Chinas mercury-free
catalyst R&D

Dr Sun Yangzhao

FECO/ MEP/China
October, 2011
 Content
1. PVC industry developments and mercury
management status in China

2. Project background and progress

3. Mercury pollution control policies

4. Difficulties and challenges

5. Next steps
 1.PVC production and mercury
management in China
PVC plastic is widely used in industry, agriculture, national defense and
chemical construction materials, etc in China.
Chinese PVC production can be divided in two categories: carbide
method and ethylene method.
For the carbide route, CaC2 is used as raw material, and activated carbon
with HgCl 2 serves as catalyst for the production of VCM which will be
further used to make PVC.
Table 1: PVC Data for China 2009 (Source MIIT, 2010)
Type of Production # of PVC production % of total
Facilities (million tonnes) production
Carbide-based 94 5.8 63.4
Ethylene 10 3.35 36.6

Total 104 9.15

 Mercury in carbide based process

Currently for one ton PVC produced in China:

1.2 kg of HgCl 2 catalyst consumed on average (as 11% of HgCl
2 content).

For 5.8 million tons of PVC produced in 2009, around 7000

tons of mercury catalyst used, comprising:
770 tons of HgCl 2 and 570 tons of mercury were used (MIIT,
2010)

Carbide-based PVC production consumes around 60 of

Chinas total annual mercury use.
 Mercury flow chart in carbide PVC
production
HCl

HCl composition

VC Hg Compound Compression Monomer tank

composition remover absorption distillation

acetylene process

C2H2

Hg
absorbed Hg bearing
worn catalyst
activated waste acid
carbon

potential mercury
pollution source
 Catalyst Effectiveness

Sublimation and intoxication causes reduction of catalyst

effectiveness.
When it decreases to certain level, catalyst need to be replaced
and inactivated catalyst becomes worn catalyst.
Usually waste catalyst contains 3-4.5% mercury.
After Hg remover, part of the sublimated HgCl2 will enter the
worn acid and alkali and get emitted.
 Necessity of carbide process

Carbide PVC production uses lots of mercury, but it remains

necessary

Chinese energy structure characterized as "lack oil, poor in

gas and rich in coal"
Ethylene method can hardly meet the need of PVC industry
alone
Carbide PVC industry pays high attention to mercury pollution
administration.
 Emission reduction measures for carbide
PVC production
The industry has adopted the following measures to reduce
mercury use and emissions:
low mercury subsititute for high mercury one
activated carbon in mercury remover to absorb mercury in gas
phase
waste acid recycled by desorption device, a few of which are
used to neutralize worn alkali
waste alkali used to neutralize waste acid, and collected
together with other waste liquid for central treatment;
waste catalyst, activated carbon and other waste sludge are sent
to certified orgnization for central treatment.
One Carbide-based PVC Producer
 2. Project background and progress

UNEP has provided funds for China to carry out PVC

project through small grants program. The project is now
on its second phase.

Phase I Communication and Deliberation of the Practice

of Mercury Use and Emission Reduction during PVC
production agreement was signed in January of 2009.

Phase II Feasibility study on Chinas mercury-free

catalyst R&D agreement was signed in April of 2011.
 Target and Research Results of Phase I

Phase 1 - Overall Target To reduce mercury use in Chinese

PVC industry

Duration From Jan. 2009 to Sep. 2009

Activities and results
Organization of Workshop on Mercury Reduction in Carbide
PVC Production
Investigation and study on mercury use and reduction status in
Chinese PVC production by acetylene
Analysis of administrative and policy needs mercury use in
this industry.
 Target and Progress of Phase II

Phase 2 Overall Target - To promote mercury free catalyst

development and use in VCM production.

Implementation duration April 2011-December 2011

Main activities
Organization of Project workshop on Mercury free catalyst
development feasibility;
Develop a feasibility study report on mercury-free catalyst
research and development, including identification of near-term
and long-term activities.
 Project workshop on Mercury free catalyst
development feasibility, 19-20 September 2011
Approximately 40 participants from Chinese government and
industry, representatives from the international community

Agenda
International mercury convention negotiation process
China PVC industry update
Updates of mercury-free catalyst R&D home and abroad

Outcomes:
Exchange of ideas on demands for and challenges to develop
mercury-free catalyst technology.
Expert team proposed draft criteria for a peer review process.
 Wide-spread use of low Hg catalyst
time target
2012 50% use of low Hg catalyst per VCM production
25% less use of HgCl per ton of PVC at average
whole industry realizes sound collection of worn Hg
catalyst
industrialization of efficient collection technology
of VC composing gas phase
50% use of HCl deep desorption technology
2015 whole industry uses low Hg catalyst
50% less use of HgCl per ton of PVC at average
100% recycling of worn low Hg catalyst
High efficient Hg recycling technology penetration rate
of 50%
over 90% penetration rate of HCl deep desorption
By adoption oftechnology
low Hg catalyst, mercury removal and centralized
treatment of waste,
100%producers aretreatment
use of NaHS able to meet thebearing
for Hg nationalwast
emission
water
limit requirements.
 Mercury free catalyst R&D progress

Currently, carbide PVC producers are working with research

institutes on following research:
to carry out acetylene VCM fluidized bed technology, i.e.
mercury-free catalyst, supportive process, reactor.
catalytic system of hydrogen chloride of acetylene to produce
VCM; R&D of gas-liquid mercury-free catalyst.
enterprise-based mercury-free catalyst R&D and engineering
pilot platform is taking initial shape.
 3. Relevant industry mercury pollution
2007 control
Industry restructuring directory list (2007) specifiespolicy
HgCl2 catalyst
under restricted category.
Encourages oxychlorination of ethylene to replace carbide method
For new, modified or expanded PVC installation must reach the scale
of over 300,000 tons a year.

2009 MEP released clean production standards for chloralkali industry

(carbide PVC), which specifies technological requirements to produce
VCM in a clean manner.

April 2011 12th Five Year Plan for Comprehensive prevention and
control of heavy metal pollution was approved and promulgated by the
State Council (applies to lead, mercury, cadmium, chromium and arsenic).
 2009 MEP Clean Production Standards for
Chloralkali Industry (carbide PVC)
Indicator Class 1 Class 2 Class 3
I. process and equipment requirement
1. For HCl desorption device use HCl deep use HCl regular
desorption desorption
technoogy technology
2. For mercury catalyst use low Hg and use low Hg catalyst
waste acid water technology
treatment technology

3.VC mercury recycling requirements VC mercury recycling treatment

II. resource and energy use indicators

Hg catalyst consumption per unit of 1.2 1.3 1.4
product(kg/t
III. Pollutant generation indicator (before end treatment)
waste water generation per unit of 12 35 40
product
THg per unit waste water(g/t) 1.5 1.8 2.0

Clean Production Auditing Standard

 Notification on Enhancing Hg Pollution Prevention
and Control in Carbide PVC industry.
Issued by MEP - January 19 2011
Purpose was to enhance pollution prevention and control
management framework in carbide PVC production, Hg catalyst
production and treatment of worn catalyst.
Notification requires
i. Increased awareness of the importance of pollution control in
carbide PVC production
ii. Promotion of low Hg catalyst and effective reduction of Hg
emissions
iii. Tighter environmental management and strengthened monitoring
measures
iv. Strengthened policy support and supportive measures
v. Increased role of industry association in education and training.
 Hg bearing waste management

Hg and Hg compound bearing waste or polluted waste are

already listed into State Hazardous Waste List

MEP is formulating Hg bearing pollutant prevention and

control technical policy, which includes worn Hg catalyst.
 Difficulties and Challenges Ahead
(1 Legislation and Enforcement
inadequate force in industry restructuring as well as in
promoting and applying new reduction technology and new
material
administrative weakness in mercury and HgCl2 catalyst
production and supply
production operation needs to be standardized.

(2) Capacity
basic situation and understanding is not clear
lack of monitoring/surveillance of mercury discharge.
 Difficulties and Challenges Ahead

3 Technology
Application of low-mercury technology needs to be further
improved and researched
Need of alternative techology:
mercury-free catalyst is still under research and
development
economic and other effects of application need to be taken
into consideration before wide-scale adoption.
HCl desorption is only partly applied among enterprises.
 Difficulties and Challenges Ahead

4 Financing

involves a wide range and large number of enterprises

most enterprises are small-scale with limited profit margins
alternative technologies are highly specialized and expensive.

As a developing country, China is facing huge shortage of

labor-power, material and financial power.
 Next steps for Carbide based PVC Production

Phase1 (Jan 2010~Jan 2012)

Activity 1 Raise understanding of mercury pollution risks amongst
local environmental protection bodies and industry.
Activity 2 Develop emission inventory.
Activity 3 Study the evaluation and application standards of low-
mercury and non-mercury catalyst.
Activity 4 Set up reduction plan and targets across PVC industry.

Phase 2 Jan. 2012~Dec.2013

Activity 5: Research mercury alternative technology and pilot
application, apply mercury reduction measures and standardize
administration.
Activity 6: Initiate assessment and operation guidance for above.
 Conclusion
Although the Chinese central government has paid a lot
of attention to mercury pollution prevention and
control in the VCM sector, it is still facing a lot of
difficulties and uncertainties with spreading
information on the low-mercury catalyst and the
researching & development of free-mercury catalyst.

We hope for more support, including finance and

technologies from developed countries!
 Acknowledge
Special thanks extended to the
following:
Chemicals Branch, DTIE of UNEP
Department of International Cooperation, MEP
Department of Pollution Prevention and Control,
MEP
Chemical Registration Center, MEP
China Petroleum and Chemical
Industry Association
Thank you for your kind attention !

Email: sun.yangzhao@mepfeco.org.cn