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Feasibility study on China‘s
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
Facilities
PVC production
(million tonnes)
Carbide-based
94
5.8
63.4
Ethylene
10
3.35
36.6
104
9.15
Total
% of total
production
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
China’s total annual mercury use.
Mercury flow chart in carbide PVC production
HCl
HCl composition
VC
composition
Hg
remover
Compound
absorption
Compression
distillation
Monomer tank
acetylene process
C2H2
worn catalyst
Hg
absorbed
activated
carbon
Hg bearing
waste acid
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 China‘s 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 technology
100% use of NaHS treatment for Hg bearing wast water
By adoption of low Hg catalyst, mercury removal and centralized
treatment of waste, producers are able to meet the national
emission 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
control policy
 2007 – Industry restructuring directory list (2007) specifies 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
I. process and equipment requirement
1. For HCl desorption device
2. For mercury catalyst
3.VC mercury recycling requirements
II. resource and energy use indicators
Hg catalyst consumption per unit of
product(kg/t)
Class 1
Class 2
use HCl deep
desorption
technoogy
use low Hg and
waste acid water
treatment technology
use HCl regular
desorption
technology
use low Hg catalyst
technology
Class 3
VC mercury recycling treatment
1.2
III. Pollutant generation indicator (before end treatment)
waste water generation per unit of
12
product
THg per unit waste water(g/t)
1.5
Clean Production Auditing Standard
1.3
1.4
35
40
1.8
2.0
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 lowmercury 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: [email protected]