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The answer to this question will most likely keep changing, but it will be interesting to know the current statistics.
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The following create the most greenhouse gas emissions globally

1    China (Coal)    14.32%
2    Saudi Arabian Oil Company (Aramco)    4.50%
3    Gazprom OAO    3.91%
4    National Iranian Oil Co    2.28%
5    ExxonMobil Corp    1.98%
6    Coal India    1.87%
7    Petroleos Mexicanos (Pemex)    1.87%
8    Russia (Coal)    1.86%
9    Royal Dutch Shell PLC    1.67%
10    China National Petroleum Corp (CNPC)    1.56%
11    BP PLC    1.53%
12    Chevron Corp    1.31%
13    Petroleos de Venezuela SA (PDVSA)    1.23%
14    Abu Dhabi National Oil Co    1.20%
15    Poland Coal    1.16%
16    Peabody Energy Corp    1.15%
17    Sonatrach SPA    1.00%
18    Kuwait Petroleum Corp    1.00%
19    Total SA                                    0.95%
20    BHP Billiton Ltd                    0.91%

Source: https://www.theguardian.com/sustainable-business/2017/jul/10/100-fossil-fuel-companies-investors-responsible-71-global-emissions-cdp-study-climate-change
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