Potash Fertilizers, September 1966

Report No. 14

POTASH

FERTILIZERS

by GEORGE

E. HADDELAND

September

1966

A private report by the

PROCESS

ECONOMICS

PROGRAM I

STANFORD

RESEARCH

INSTITUTE

MENLO I

PARK,

CALIFORNIA

Potash Fertilizers, September 1966

0-

CONTENTS

0 I II

INTRODUCTION......................... SUMMARY

.

........

1

.............. Reserves, Markets, and Production ....................... Potash Refining ...................... Potash Fertilizers ..................... Potassium Sulphate ..................... Potassium Nitrate .................. Potassium Metaphosphate

III

0

INDUSTRY

STATUS

00 IV

9

.......................

THE CHEMISTRY

OF POTASH

SALTS

AND THEIR

CONCENTRATION

....................... Atomic Structure ........................ Salt Solutions Reactions of Salts ...................... Double Salts ......................... .................... Potassium Fertilizers Separation and Concentration Methods ............. .......................... Flotation ....................... Crystallization

0

v

POTASH

CONCENTRATION

BY FLOTATION

0

..............

..................... Review of Processes ..................... Process Description ...................... Process Discussion

iii

-

3 3 5 5 6 7

9 9

...................... Potash Terminology Potash Sources ........................ Minerals .......................... Brines ........................... ....................... Potash Reserves ...................... Potash Production ....................... Potash Producers ...................... Potash Consumption ..................... Future Requirements Prices ............................ ........................ Transportation .................. Uses Other Than Fertilizer

0-

-

3

..................

9 11 13 21 23 34 36 36 37 37 ....

41 41 43 45 45 46 47~ 51' 52 57 57 57 71

Potash Fertilizers, September 1966

CONTENTS

Capital Costs Production Discussion

VI

POTASH

77

CONCENTRATION

BY CRYSTALLIZATION

POTASSIUM SULPHATE

77 . . . . . . . . . . .

................... ................... ................... ................... ................... ................... ................... .......... Ammonia Solutions ...................

POTASSIUM NITRATE

-

101

.....

......................

..................... Review of Processes .......... Decomposition and Ion-Exchange Processes Direct Reaction of Potassium Chloride and Nitric Acid ..................... Process Description ...................... Process Discussion ........................ Cost Estimates ....................... Capital Costs Production Costs ...................... .................... Discussion of Costs

iv

85 85 86 86 90 90 91 91 98 98

......................

..................... Review of Processes Recovery from Double Salts ................. Reaction of Sulphuric Acid with Potassium Chloride ..................... Process Description ...................... Process Discussion Cost Estimates ........................ ....................... Capital Costs Production Costs ...................... .................... Discussion of Costs VIII

73

.......................

Costs ...................... .................... of Costs

Review of Processes . . Process Description . . Process Discussion . . . Cost Estimates . . . . . Capital Investment . . Production Costs . . . Discussion of Costs . Crystallization from Solution Mining . . VII

73

........................

Cost Estimates

101 101 103 104 105 105 105 112 112 117

...

117 117 118 120 127 128 128 131 131

0000-

a

Potash Fertilizers, September 1966

CONTENTS

IX

POTASIUM METAPHOSPHATE

...................

Review of Processes ..................... Tennessee Valley Authority Research ............ Scottish Agricultural Industries .............. Other Developments ..................... Process Description ..................... Process Discussion ...................... Cost Estimates ........................ Capital Costs ....................... Production Costs ...................... Comparative Costs ..................... Discussion of Costs ....................

0

APPENDIX

A

DESIGN

APPENDIX

B

PHYSICAL

DATA

APPENDIX

C

ANALYSIS

AND

SPECIFICATIONS

APPENDIX

D

HANDLING

AND

SAFETY.

CITEDREFERENCES. SUPPLEMENTARY

AND COST

BASIS

.................

..................... ..............

.................

.........................

REFERENCES

......................

V

137 137 137 138 138 139 140 146 146 146 150 150 155 161 165 169 173 187

Potash Fertilizers, September 1966

-

ILLUSTRATIONS

0 1

Location

of Potash

Relation

to the Depth

Leases

and Mines

of the Deposit

2

Production

3

World

Consumption

4

Price

History

5

Electrovalent

Bonding

6

Ion Hydration

by Ion-Dipole

7

Processing

8

Joint

9

Potash

of Potassium

of Several

Potash

of Sodium

Circulation

35

Salts

.......

44

...........

and Potassium

Chlorides

.....

..................

11

Influence of Mining Costs and Ore Grade on the Recovery of Muriate of Potash (60% K2O) ................ Concentration

13

Effect

of Cooling

14

Potassium Sulphate from Sulphuric Acid Chloride ...........................

15

16

Potassium

Nitrate

Effect

18

Potassium

19

Process

20

Effect of Plant Production Cost

B-2

of Plant

by Nitric

Size

on Capital

Metaphosphate

Heat

Acid

on Production

Distribution

83

Rate

....

107 Credit 115

...........

and Production Process

Costs

121 .....

........

..................

Capacity and By-Product .......................

97

and Potassium

Process

by Nodulizing

Cost

87

Influence of Raw Material Cost and By-Product Chlorine ......... on the Production Cost of Potassium Sulphate

17

B-l

Temperature

HCl

135 141 145

Value

on 153

Solubilities of KC1 and NaCl between 0' and llO°C in Saturated Brines Containing Various Amounts of MgCl, .....

162

Boiling Temperatures Atmospheric Pressure

163

of Aqueous Salt Solutions .....................

vi

0

72

...........

by Crystallization

54 65

Brine

Potash

0-

49

..............

12

-

42

10

Water

39

..............

Ores

by Flotation

Systems

22

................

Interaction

Solubilities Concentration

Fertilizer

of Atoms

for Potash

19

...........

Fertilizers

Routes

in

................

Salts

of Potash

in Saskatchewan .............

at

0

Potash Fertilizers, September 1966

-

TABLES

00-

a0a-

Major

Potash

Typical

Minerals

Analysis

Representative

of Potash Brine

World

Potash

World

Production

Ores

Analysis

Reserves

................

11

.................

12 15

.....................

of Potash

Fertilizer,

1963/64

........

23

Potash Producers North America ......................... 7

Potash

0-

8

Impending

9

U.S.

0

10

North

11

Properties

12

Comparative

13

A Summary

14

Potash Concentration by Flotation Major Process Equipment and Utilities

a

10

.....................

15

16

17

18

Producers

Outside

Increase

North

in World

America

Potash

of Potassium

Sulphates

American

and European

Potash

Potash Stream

Potassium of Recent

Salts

Flotation

.............

Prices

...........

Properties

Patents

34 40

..........

47 59

Summary

65

.........

69

.............

75

Potash Concentration by Flotation Total Capital Investment ...................

78

Potash Concentration by Flotation Production Costs .......................

79

Total

20

Potash Concentration by Crystallization Major Process Equipment and Utilities Summary

22

33

43

Concentration by Flotation Flows .........................

Potash Concentration by Flotation Process Unit and Utilities Investment

....

.............

19

21

Capacity

.................

Fertilizer

29

............

Production

Producers

of Chloride

25

Potash Stream

Potash

Mining

and Processing

Investments

........

.........

Concentration by Crystallization Flows .........................

Potash Concentration by Crystallization Process Unit and Utilities Investment .............

vii

81

87

89 92

Potash Fertilizers, September 1966

TABLES

23

24

25

26

27

28

29

30

31

32

33

34

35

36

37

38

Potash Concentration by Crystallization Total Capital Investment . . . . . . . . . . . . . . . . . . ,

93

-

Potash Concentration by Crystallization Production Costs . . . . . . . . . . . . . . . . . . . . . . .

95

0

Potassium Sulphate from Sulphuric Acid and Potassium Chloride Major Process Equipment and Utilities Summary . . . . . . . . .

106

Potassium Sulphate from Sulphuric Acid and Potassium Chloride Stream Flows . . . . . . . . . . . . . . . . . . . . . . . . .

109

Potassium Sulphate from Sulphuric Acid and Potassium Chloride Process Unit and Utilities Investment . . . . . . . . . . . . .

110

Potassium Sulphate from Sulphuric Acid and Potassium Chloride Total Capital Investment . . . . . . , . . . . . . . . . . . .

111

Potassium Sulphate from Sulphuric Acid and Potassium Chloride Production Costs . . . . . . . . . . . . . . . . . . . . . . .

114

Potassium Nitrate by Nitric Acid Process Major Process Equipment and Utilities Summary

0 . . . . . . . .

121

Potassium Nitrate by Nitric Acid Process Stream Flows . . . . . . . . . . . . . . . . . . . . . . . . .

125

Potassium Nitrate by Nitric Acid Process Process Unit and Utilities Investment . . . . . . . . . . . . .

129

Potassium Nitrate by Nitric Acid Process Total Capital Investment e . . . . . . . . . . . . . . . . . .

130

Potassium Nitrate Production Costs

133

by Nitric Acid Process . e . . . . . . . . . . . . . . . . . . . . .

Potassium Metaphosphate Major Process Equipment

by Nodulizing and Utilities

Process Summary

. . . . . . . . .

141

Potassium Metaphosphate by Nodulizing Process Stream Flows . . . . . . . . . . . . . . . . . . . . . . . . .

143

Potassium Metaphosphate by Nodulizing Process Unit and Utilities Investment

Process . . . . . . . . . . , . .

147

Potassium Metaphosphate by Nodulizing Process Total Capital Investment . . . . . . . . . . . . . . . . . . .

148

viii

0 0

a0-

0

Potash Fertilizers, September 1966

0

TABLES

39

Potassium Production

Metaphosphate by Nodulizing Process Costs .......................

40

Metaphosphate

Process

B-l

Heats

C-l

Typical

Muriate

c-2

Typical

Sulphate

of Potash

c-3

Typical

Chemical

Grade

of Formation

Cost Comparison

of NaCl

of Potash

............

and KC1 Solutions Analysis Analysis

Potassium

ix

151

at 25OC

.....

..............

Analysis

164 165

.............

Chloride

a

149

166 ......

167