Feasibility study on China

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Feasibility study on Chinas mercury-free
catalyst RD
Dr Sun Yangzhao

• FECO/ MEP/China
• October, 2011

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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

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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) of total production
Carbide-based 94 5.8 63.4
Ethylene 10 3.35 36.6
Total 104 9.15
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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.

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Mercury flow chart in carbide PVC production
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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.

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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.

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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.

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One Carbide-based PVC Producer
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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 RD agreement was signed
  in April of 2011.

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Target and Research Results of Phase I

• Phase 1 - Overall TargetTo reduce mercury use in
  Chinese PVC industry
• DurationFrom 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.

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Target and Progress of Phase II

• Phase 2 Overall Target - To promote mercury free
  catalyst development and use in VCM production.
• Implementation durationApril 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.

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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 RD 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.

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Wide-spread use of low Hg catalyst
time target
2012 50 use of low Hg catalyst per VCM production
2012 25 less use of HgCl per ton of PVC at average
2012 whole industry realizes sound collection of worn Hg catalyst
2012 industrialization of efficient collection technology of VC composing gas phase
2012 50 use of HCl deep desorption technology
2015 whole industry uses low Hg catalyst
2015 50 less use of HgCl per ton of PVC at average
2015 100 recycling of worn low Hg catalyst
2015 High efficient Hg recycling technology penetration rate of 50
2015 over 90 penetration rate of HCl deep desorption technology
2015 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.

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Mercury free catalyst RD 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 RD of gas-liquid
  mercury-free catalyst.
• enterprise-based mercury-free catalyst RD and
  engineering pilot platform is taking initial
  shape.

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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).

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2009 MEP Clean Production Standards for
Chloralkali Industry (carbide PVC)
Indicator Class 1 Class 2 Class 2 Class 3
I. process and equipment requirement I. process and equipment requirement I. process and equipment requirement I. process and equipment requirement I. process and equipment requirement
1. For HCl desorption device use HCl deep desorption technoogy use HCl deep desorption technoogy use HCl regular desorption technology  
2. For mercury catalyst use low Hg and waste acid water treatment technology use low Hg and waste acid water treatment technology use low Hg catalyst technology  
3.VC mercury recycling requirements VC mercury recycling treatment VC mercury recycling treatment VC mercury recycling treatment VC mercury recycling treatment
II. resource and energy use indicators II. resource and energy use indicators II. resource and energy use indicators II. resource and energy use indicators II. resource and energy use indicators
Hg catalyst consumption per unit of product(kg/t) ?1.2 ?1.3 ?1.3 ?1.4
III. Pollutant generation indicator (before end treatment) III. Pollutant generation indicator (before end treatment) III. Pollutant generation indicator (before end treatment) III. Pollutant generation indicator (before end treatment) III. Pollutant generation indicator (before end treatment)
waste water generation per unit of product 12 35 35 40
THg per unit waste water(g/t) 1.5 1.8 1.8 2.0
Clean Production Auditing Standard
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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
• Increased awareness of the importance of
  pollution control in carbide PVC production
• Promotion of low Hg catalyst and effective
  reduction of Hg emissions
• Tighter environmental management and strengthened
  monitoring measures
• Strengthened policy support and supportive
  measures
• Increased role of industry association in
  education and training.

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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.

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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.

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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.

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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.

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Next steps for Carbide based PVC Production

• Phase1 (Jan 2010Jan 2012)
• Activity 1Raise understanding of mercury
  pollution risks amongst local environmental
  protection bodies and industry.
• Activity 2Develop emission inventory.
• Activity 3Study the evaluation and application
  standards of low-mercury and non-mercury
  catalyst.
• Activity 4Set up reduction plan and targets
  across PVC industry.
• Phase 2(Jan. 2012Dec.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.

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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!
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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

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• Thank you for your kind attention !
• Email sun.yangzhao_at_mepfeco.org.cn