PREVENTING FOULING IN THE DEGASSING TOWER

By: Patrick Lucas Mike Hong GE Water & Process Technologies

Typical NMP Process

P red i lati n stil o (F ro nt E nd D e- P ro p ynei zer) R ecti er fi D eg assi ng To w er B utad i ene C ol n um
C 3 /C 4 R affi nate

C 4 A cetyl ene

B utad i ene

C 4 /C 5

C rud e C 4

W aste W ater

M ai n W asher

A fter W ash

A cetyl ene W asher Sol vent R eg enerati n o

R esi ue d

BASF NMP Process

Fouling Mechanisms
Free Radical Polymerization initiated by: -- Alkyl Free Radicals usually heat and metals induced -- Peroxy Free Radicals originate from peroxide decomposition Aldol Condensation: -- Acetaldehyde, most common carbonyl -- BD copolymer formation Diels Alder Reaction: VCH Inorganics deposition (Sodium/Silicons/Corrosion products)

Fouling Mechanisms Free Radical Generation

O2 R-H
Mn+ O2 ,

RH

R OO

R-O + OH

R-OOH

R-H

Factors Influencing Fouling

Feedstock Quality (diolefin concentration) Extraction Solvent Quality Operating Temperature Residence time Oxygen / Peroxides Catalytic Metals Polymer Seeds Design (high dead spaces/stagnant areas,) Inhibitor system employed -- kinetics -- concentration required

Butadiene BASF Design FOULING TEST/INHIBITION TEST ON NMP TO DEGASSING COLUMN

Objectives

Evaluate the ability of the NMP to polymerize (foul) at different temperatures 150/170 & 190C using the High Temperature Corrosion test apparatus. Evaluate efficiency of GE W&PT antifoulants

Fouling Test Protocol

Sample: N-methyl-2-pyrrolidone (NMP) Transfer to the Vessel Tester 3 mild steel coupons passivated with Sodium nitrite during 24 hours Coupons introduction to the test vessel, 2 in the liquid and 1 in the vapour/head space Stirring (60rpm) and Nitrogen purge to adjust oxygen level at 10ppm Nitrogen Pressurisation to 200 psi Heat at different temperatures: 150/170/190C After 7 days test, check fouling and/or corrosion. If no Corrosion/Fouling, 14 days more test Evaluation of GE W&PT antifoulants

Results
Test 1 Blank - 150 0C.
Coupon Number Starting weight (g) Fouling on coupon (mg) 1.2 Coupon weight loss (mg) Corrosion rate (mpy)

1 (liquid)

6.8950

0.3

<0.1

2 (liquid)

6.7046

0.9

<0.1

3 (vapour)

6.7712

<0.1

Total filterable solids (ppm)

As received

10

21 days at 150 0C

83

Results
Test 2 Blank - 170 0C.
Coupon Number Starting weight (g) Fouling on coupon (mg) 1.3 Coupon weight loss (mg) 0.7 Corrosion rate (mpy)

1 (liquid)

6.6092

<0.1

2 (liquid)

6.7033

1.1

0.7

<0.1

3 (vapour)

6.8278

2.5

2.7

<0.1

Total filterable solids (ppm)

As received

10

14 days at 170 0C

122

Results
Test 3 Blank - 190 0C.
Coupon Number Starting weight (g) Fouling on coupon (mg) 10.6 Coupon weight loss (mg) Corrosion rate (mpy)

1 (liquid)

6.7341

0.9

<0.1

2 (liquid)

6.7905

11.8

0.7

<0.1

3 (vapour)

6.8666

3.5

<0.1

Total filterable solids (ppm)

As received

10

7 days at 190 0C

478

Results
Test 4 190 0C with 100ppm Petroflo 20Y14 added.
Coupon Number Starting weight (g) Fouling on coupon (mg) 2.1 % Inhibition Coupon weight loss (mg) 0.7 Corrosion rate (mpy)

1 (liquid)

6.7164

80.2

<0.1

2 (liquid)

6.3358

1.9

83.9

0.4

<0.1

3 (vapour)

6.7820

2.3

34.2

<0.1

Total filterable % Total (ppm) solidsfilterable % Inhibition solids (ppm) Inhibition As received 10

7 days at 190 0C

92

80.8

Results
Test 5 190 0C with 50ppm Petroflo 20Y14 added.
Coupon Number Starting weight (g) Fouling on coupon (mg) 4.9 % Inhibition Coupon weight loss (mg) 0.6 Corrosion rate (mpy)

1 (liquid)

3.2195

53.8

<0.1

2 (liquid)

3.1853

4.5

61.9

1.1

<0.1

3 (vapour)

3.2264

2.5

28.8

<0.1

Total filterable % Total (ppm) solidsfilterable % Inhibition solids (ppm) Inhibition As received 10

7 days at 190 0C

246

48.5

Results
Test 6 190 0C with 100ppm Petroflo 20Y3151 added.
Coupon Number Starting weight (g) Fouling on coupon (mg) 0.2 % Inhibition Coupon weight loss (mg) 0.3 Corrosion rate (mpy)

1 (liquid)

3.2121

98.1

<0.1

2 (liquid)

3.2037

0.2

98.3

0.2

<0.1

3 (vapour)

3.2254

1.4

60

1.4

<0.1

Total filterable % Total (ppm) solidsfilterable % Inhibition solids (ppm) Inhibition As received 10

7 days at 190 0C

80

83.3

Results
Test 7 190 0C with 50ppm Petroflo 20Y3151 added.
Coupon Number Starting weight (g) Fouling on coupon m(g) 0.4 % Inhibition Coupon weight loss (mg) 0.5 Corrosion rate (mpy)

1 (liquid)

3.2427

96.2

<0.1

2 (liquid)

3.1929

0.4

96.6

0.5

<0.1

3 (vapour)

3.1243

1.9

45.7

1.5

<0.1

Total filterable % Total (ppm) solidsfilterable % Inhibition solids (ppm) Inhibition As received 10

7 days at 190 0C

82

82.8

Butadiene Inhibitor for Extractive Distillation Section (BASF Design)

Best Product
Petroflo 20Y3151: Antioxidants + Antipolymerant, NMP based Features NMP based No risk of solvent contamination - Minimize foaming

Benefits
Prevent both polybutadiene and popcorn formation in the EDS Increase equipment runlength and production Reduce foaming and maintenance cost

GE W&PT Best Practices

Minimize oxygen and peroxides NaNO2 Wash (Oxygen scavenger) Control operating temperatures Minimize C5+ contamination Reduce dead space Passivate before start-up Minimize corrosion by-products Use an adapted treatment program

PREVENTING FOULING IN THE DEGASSING TOWER

By: Patrick Lucas Mike Hong GE Water & Process Technologies