Team Project in Reaction With Separation

Problem Solving Project:
Reaction with Separation
Objective:
To overcome the PX equilibrium
limited reaction
1
Aromatic Complex: p-Xylene Production
Heterogeneous Catalysis
Reforming – Bifunctional Catalysis:
1) It is a catalytic process to convert nephtha to high octane number

gasoline.
2) It is a bifunctional surface catalysis. The catalysts consist of:
 Metal: Re and/or Pt 3
 Metal Oxides: transition alumina functions as “Acidic” catalyst
Reforming – Bifunctional Catalysis (Cont.):
3) The metal oxide support must not be too strongly or too weakly acidic:
chlorinated Al2O3 is optimal.
4) Dehydrocyclization reaction requires both metal and the acid.
 Metal alones does not catalyze the branching reaction; they require
an acidic function to generate carbenium ions, which undergo the
desired isomerization.
 The acidic function alone is not sufficient to generate the carbenium

ions because it is too weakly acidic to protonate paraffins; metal
catalyzes dehydrogenation of paraffins to give olefins, which are
easily protonated and thereby converted by carbenium ion routes.
4
Reforming – Bifunctional Catalysis (Cont.):
5) The presence of excess hydrogen is required:

 minimize catalyst deactivation
6) Catalytic reforming is first developed by UOP in mid-1940 (World War II)

 The UOP Platforming Process
5
Aromatic Complex: p-Xylene Production
Isomar Flowscheme
Reactor Light Ends

Net Gas
Product
Separator
Net
Charge Liquid
Heater
Deheptanizer
Combined Feed
Exchanger Clay
Treater
Product
Condenser
To Aromatic
Compressor Fractionation Unit
Feed from Makeup H2

Parex Unit
Isomar Process
Metal
• Main demand is for pX
+ H2 to make polyester
EB
resin
mX
• EB, mX oX and pX can
oX be brought back to
equilibrium over a
Acid
suitable catalyst
• EB is harder to
Metal isomerize so two types
of Isomar
+ paraffins due to cracking – EB dealkylation (to
pX
Bz)
– EB isom (to C8 mix)
~24 mol% pX eqbm yield
C8-Aromatic Reaction is
Equilibrium Controlled
: Limited to 22-24% PX
•Goal: How to over come the PX equilibrium limited
reaction of 22-24% by combining “reaction with
separation”
Para Xylene Meta Xylene Ortho Xylene Ethyl Benzene
22% 48% 22% 8%

9
Specific Properties
for the Separation of C8 Aromatics
+ 13.3
The UOP “Parex”

20
UOP’s 1st generation process

1
The UOP “Ebex”
10
Chapter 3: Separation Technology in General
Reactive Separation Processes
 Principle
Reactive separation processes are unique in that
they combine the unit operations of reaction and
separation into a single, simultaneous operation.
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
Adsorption
27
Adsorption
28
Adsorption
29
Adsorption
30
Adsorption
Schematic Pulse Test
(2 Aromatic Components and Paraffin Tracer)
RB
RA Net retention volume of A = RA
Net retention volume of A = RB
Concentration
Selectivity (B/A) = ฿ = RB/RA

Tracer Envelope half-width tracer = Wt
A B Envelope half-width, B = WB
Rate parameter = WB-Wt = DW

Wt WB
Volume, time
The net retention volume of any component is ideally proportional

to its distribution coefficient, i.e., its concentration in the
adsorbed phase, divided by its concentration in the unadsorbed
phase 31
Adsorption
Batch Adsorption
Feed, A + B
Desorbent, D Liquid Composition

0 100
A
B
Fixed D
Bed
Extract, A + D
Raffinate, B + D
32
Adsorption
Adsorptive Separation
with Moving Bed
Desorbent D
III Desorption D
Extract A&D of A
Flow of Solid
Flow of Liquid
Desorption
II of B
Feed A&B
Adsorption B
I of A
Raffinate B&D
Partial
IV Desorption
of D
0 100%
Liquid
Composition
33
Adsorption
Sorbex - Simulated Moving Bed
for Adsorptive Separation
1
Adsorbent Desorbent
Rotary
Chamber
2 Valve D
3
4 Extract
5 A
6
7
8
9 Feed
10 B
11
12
Raffinate
0 100%
Pumparound Liquid
Pump Composition
34
Adsorption
Illustration of Changing Pumparound Flow
Rates with Changing Rotary Valve Positions
T=0 T = 90 Seconds T = 180 Seconds

1 1 1
Raffinate
IV 2 2 I 2
Desorbent IV Raffinate
3 3 3
Desorbent
III AC 4 AC 4 AC 4
IV Desorbent
FRC
FRC
FRC
Zone I Flow
Zone I Flow
Zone IV Flow
5 Extract III 5 5
6 6 Extract 6
II III
7 7 7 Extract
8 II 8 8
9 9 9
Feed
10 10 II 10
Feed
I 11 11 11
Feed
12 I 12 I 12
IV Raffinate
T = 270 Seconds T = 360 Seconds T = 450 Seconds

1 1 1
Feed
I 2 2 II 2
Feed
3 I 3 3
Raffinate
AC 4 AC 4 I AC 4
Raffinate
FRC
FRC
FRC
IV 5
Zone II Flow
Zone II Flow
Zone I Flow
Desorbent 5 5 Raffinate
IV 6
6 Desorbent 6
IV 7
III 7 7 Desorbent
8 Extract 8 III 8
III
9 9 Extract 9
10 10 10
Extract
II 11 11
AC = Adsorbent
11
II
12 12 12
Column I Feed II
35
Adsorption
Moving Bed for Adsorptive Separation
Adsorbent Section Desorbent Recovery Section
1 Extract
Rotary Column
Adsorbent
Chamber 2 Valve
3
4 Extract
5
6 Desorbent
7
8
9
10 Raffinate
11 Column
12
Feed Raffinate
36
Adsorption
Sorbex -
Simulated
Moving Bed
Moving Bed for
Adsorptive
Separation
37
Adsorption
A 24-port Rotary Sorbex Valve
(Pilot Plant)
38
Adsorption
A 24-port Rotary
Sorbex Valve
with Adsorbent
(Pilot Plant)
From I&EC Process Design & Development, Vol. 15, Page 261, April 1976
39
Adsorption
Rotary
Valve
(Commercial)
40
Adsorption
41
Adsorption
Reactive Distillation
Target properties of reaction system :
1) Reaction and distillation must occur at the same conditions
2) Equilibrium limited
3) Catalyst stability problem
4) Poor selectivity
Distillation 42
Example :
Reactive Distillation Process by Eastman Kodak (US Pat

4,435,595) for production of Methyl Acetate
H+
CH3COOH + CH3OH CH3COOCH3 + H2O
Note: Acetic acid functions as reactant and extractive agent for

azeotropes methyl acetate / water and methyl acetate / methanol
Distillation 43
Production of Methyl Acetate by
Distillation 44
Benzene Alkylation by
Distillation 45
Distillation 46
Distillation 47
Extraction 48
Extraction 49
Extraction 50
Extraction 51
Non-polar
phase
Polar
phase
Extraction 52
Membrane Reactor
Concept
Advantages
Examples
Membranes 53
Membrane Reactor Concepts
1. Membrane as part of catalytyst or catalytic-support
Catalyst Ceramic membrane
A+B C
D
2. Membrane as part of Reactor

Ceramic membrane
A+B Catalyst C
Membranes 54
Advantages of Catalytic Membrane Reactor
1. Integration of reaction and partial separation

into one process
2. Enhancement of thermodynamically limited or

Product-inhibited reactions
3. Controlled reaction rates for selective reactions
4. Lower temperature and less severe pressure
5. Reduced catalyst fouling
6. Better product with reduce cost
Membranes 55
Representative Reactions for Catalytic
Membrane Reactors
1. Dehydrogenation – paraffin to olefin
2. Hydrogenation – olefin to paraffin
3. Hydrations – C3= + H2O to IPA + DIPE
4. Hydroformylation – olefin + CO to aldehyde or alcohol
5. Selective Oxidation – CH4 O2 to methanol
6. Alkylation
Membranes 56
EX: Membrane as part of catalyst or catalyst support
Ref: T.T. Tsotsis, et al, Chen Eng Sci Vol 45,

No 8, 2,423-2429 (1990)
• Ethane dehydrogenation using 40A alumina membrane
• Impregnated 5 wt% Pt on membrane (in side)
• Obtained 45% conversion (20% at equilibrium) at 600’C

Without sweep gas
• With sweep gas at the permeate side, obtained 78%

conversion
Membranes 57
EX: Membrane as Part of Reactor
Ref: Shell Int., UK Patent 2,201,159 (1988)
1. Propane dehydrpgenation using Cr2O3/alumina catalyst

and 100 A alumina membrane
• At 575°C obtained 59% conversion (40% without membrane)
2. 2M2-butene to isoprene dehydrogenation using

Zn/Pt/Sn/alumina catalyst and 100 A alumina membrane
3. Ethylbenzene dehydrogenation using V/Li/Fe/Cr/K/alumina catalyst

and 100 A alumina membrane

Membranes 58
Problem solving Project: To develop a reaction with
separation process to over come the 22% PX
equilibrium limited reaction
1) Divide students into 4 teams. Select one leader in

each team.
2) Team A: Reaction with Adsorption
3) Team B: Reaction with Distillation
4) Team C: Reaction with Extraction
5) Team D: Reaction with Membrane 59

Recommendations:
1) Select your P-xylene production reaction either:

a) Naphtha to C8-aromatics – Reforming or
b) Equilibrium conversion of OX, MX and EB to PX
- C8-aromatic isomerization process
2) Team A: Read to understand adsorption process – Sorbex technology.

Some background information: PX can be separated
From OX, MX and EB using adsorbent either BaX (with PDEB desorbent) or
KY (with toluene desorbent)
3) Team B: PX is difficult to distill from OX, MX, and EB because of their

close boiling points. Can you separate PX using extractive
distillation or other means? Understand more on distillation
4) Team C: Try to find a high soluble solvent for PX than OX, MX and EB. Or,
catalyst soluble in aqueous phase. Understand more on extraction
technology
60
5) Team D: Read to understand membrane for PX separation from OX, MX
and EB. Silicalite (or ZSM-5) membrane can separate PX and EB from OX,
MX, PX and EB
6) Each team after understand the PX reaction (select from 1a

or 1b – preferred 1b) and separation (selected from 2, 3, 4 or 5), match the
operation conditions (reaction and separation)
7) Keep in mind, since reaction and separation are in one unit.

Operating temperature and pressure should be comparable.
8) Each team can consult your professor. However, you can also email me
for consultation. I plan to ask UOP experts to help each team.
9) Reports:
a) 5 pages report
b) 20 min presentation from the team
61

Team Project in Reaction With Separation

Caricato da

Informazioni sul documento

Titolo originale

Copyright

Formati disponibili

Condividi questo documento

Condividi o incorpora il documento

Opzioni di condivisione

Hai trovato utile questo documento?

Questo contenuto è inappropriato?

Copyright:

Formati disponibili

Team Project in Reaction With Separation

Caricato da

Copyright:

Formati disponibili

Problem Solving Project:

Reaction with Separation

1) It is a catalytic process to convert nephtha to high octane number

4) Dehydrocyclization reaction requires both metal and the acid.

 The acidic function alone is not sufficient to generate the carbenium

5) The presence of excess hydrogen is required:

6) Catalytic reforming is first developed by UOP in mid-1940 (World War II)

Reactor Light Ends

Feed from Makeup H2

22% 48% 22% 8%

The UOP “Parex”

UOP’s 1st generation process

The UOP “Ebex”

Selectivity (B/A) = ฿ = RB/RA

Rate parameter = WB-Wt = DW

The net retention volume of any component is ideally proportional

Desorbent, D Liquid Composition

T=0 T = 90 Seconds T = 180 Seconds

T = 270 Seconds T = 360 Seconds T = 450 Seconds

Adsorbent Section Desorbent Recovery Section

Target properties of reaction system :

1) Reaction and distillation must occur at the same conditions

3) Catalyst stability problem

Reactive Distillation Process by Eastman Kodak (US Pat

Note: Acetic acid functions as reactant and extractive agent for

1. Membrane as part of catalytyst or catalytic-support

Catalyst Ceramic membrane

2. Membrane as part of Reactor

1. Integration of reaction and partial separation

2. Enhancement of thermodynamically limited or

3. Controlled reaction rates for selective reactions

4. Lower temperature and less severe pressure

5. Reduced catalyst fouling

6. Better product with reduce cost

1. Dehydrogenation – paraffin to olefin

2. Hydrogenation – olefin to paraffin

3. Hydrations – C3= + H2O to IPA + DIPE

4. Hydroformylation – olefin + CO to aldehyde or alcohol

5. Selective Oxidation – CH4 O2 to methanol

Ref: T.T. Tsotsis, et al, Chen Eng Sci Vol 45,

• Ethane dehydrogenation using 40A alumina membrane

• Impregnated 5 wt% Pt on membrane (in side)

• Obtained 45% conversion (20% at equilibrium) at 600’C

• With sweep gas at the permeate side, obtained 78%

Ref: Shell Int., UK Patent 2,201,159 (1988)

1. Propane dehydrpgenation using Cr2O3/alumina catalyst

• At 575°C obtained 59% conversion (40% without membrane)

2. 2M2-butene to isoprene dehydrogenation using

• At 550°C obtained 37% conversion (27% without membrane)

3. Ethylbenzene dehydrogenation using V/Li/Fe/Cr/K/alumina catalyst

• At 625°C obtained 65% conversion (51% without membrane)

1) Divide students into 4 teams. Select one leader in

2) Team A: Reaction with Adsorption

3) Team B: Reaction with Distillation

4) Team C: Reaction with Extraction

5) Team D: Reaction with Membrane 59

1) Select your P-xylene production reaction either:

2) Team A: Read to understand adsorption process – Sorbex technology.

3) Team B: PX is difficult to distill from OX, MX, and EB because of their

6) Each team after understand the PX reaction (select from 1a

7) Keep in mind, since reaction and separation are in one unit.

Potrebbero piacerti anche