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SWEETENING TECHNOLOGIES – A LOOK AT THE WHOLE PICTURE

Marco Bergel 1 , Ignacio Tierno 1

1. TECNA Estudios y Proyectos de Ingeniería S.A.

Keywords: 1. Sweetening; 2. Carbon dioxide; 3. Acid gas; 4. Amines; 5. Membranes.

1 Background

Nowadays, a wide variety of gas sweetening technologies is commercially available: different chemical and physical solvents, membranes, regenerable adsorbents, among others . Many have their own niche, but there are still cases where different technologies compete for a same application. Combining processes can even produce better results.

To answer the question: “which method fits the project requirements best?”, one should also consider the whole gas processing scheme and site conditions, and not only the sweetening technology itself.

The present paper analyses sweetening technologies available to treat natural gas with a high

carbon dioxide (CO 2 ) content, considering the integration of sweetening facilities with different gas processing schemes and under different site conditions:

- downstream processing of sweet gas: cryogenic processes, NGL recovery, power generation or injection into pipeline

- acid gas disposal method: venting or reinjection

- energy costs

- inlet gas pressure and CO 2 content

- CO 2 specification

- power availability, remoteness of location

Most selection guidelines focus on the sweetening process and consider it as an isolated facility. However, this paper shows the best choice should arise from a thorough analysis of the complete gas processing scheme. Throughout the following pages the factors that influence sweetening technology selection will be addressed.

2 Introduction

Design of an efficient and competitive processing scheme is a crucial stage in the development of gas fields. In that context, the sweetening unit plays a leading role due to the wide variety of technologies for CO 2 removal currently available. Amongst them, chemical and physical solvents, membranes and regenerable adsorbents stand out. The process engineer faces then the challenge of selecting the technology that best fits the project needs.

This work proposes a critical analysis of the traditional selection tools for removal of acid gases, suggesting an alternative approach that contemplates the project as a whole together with external factors, besides the characteristics of the gas to be treated. Additionally, the flexibility of the main technologies to deal with gradual changes in CO 2 content specifications is analyzed.

3 Sweetening technologies

There are several technologies commercially available to treat acid gases. Some of them are based upon the absorption of CO 2 by means of a chemical or physical solvent and its subsequent desorption, others use the difference in permeability through a material of natural gas components. These differences in the removal mechanism determine the main advantages and disadvantages thereof.

For the purpose of briefly describing each of them, sweetening technologies can be classified according to the following table:

Table 1 – Classification of sweetening technologies

CO2 removal

     

mechanism

Process type

Technology

Commercial name

   

Amines

MEA, DEA, MDEA, DIPA, DGA, formulated solvents

Chemical absorption

Regenerative, continuous

Potassium carbonate

Benfield, Catacarb, Giammarco-Vetrocoke, etc.

Non regenerative, continuos (usual arrangement: lead/lag)

Sodium hydroxide

-

Physical absorption

Regenerative, continuous

Physical solvents

Selexol, Rectisol, Purisol, Fluor Solvent, IFPexol, etc.

Physical-chemical

   

Sulfinol, Ucarsol LE 701, 702 & 703, Flexsorb PS, etc.

absorption

Regenerative, continuous

Physical-chemical solvents

Physical adsorption

Regenerative, continuous (adsorption/desorption sequence)

Molecular sieves

Z5A (Zeochem), LNG-3 (UOP), etc.

Permeation

Continuous

Membranes

Separex, Cynara, Z-top, Medal, etc.

Note: distillation processes (typical of enhanced oil recovery projects, w ere CO 2 is recovered from the gas to re-inject it) are not included in this list; their range of application is beyond the typical cases of natural gas processing.

a. Particular characteristics

A detailed description of each technology can be found in References 1 to 3. It will become useful to remember some particular characteristics:

- Absorption with amines is one of the most widespread processes in the industry. Even though there are several amines, for the treatment of natural gas mostly MDEA or formulated solvents based on MDEA are employed.

- CO 2 absorption with potassium carbonate takes place at high temperatures. The process shows similarities with that of amines in that it consists of absorption and reaction in the contactor column.

- Physical solvents can be regenerated by means of successive depressurizations, without heat input. However, there is a wide variety of process schemes, and thermal regeneration or stripping may be required. Physical solvents absorb heavy hydrocarbons and water, and in certain cases they allow to reach all gas specifications in one same unit.

- Absorption with mixed solvents keeps many similarities with absorption with amines, and has some of the advantages associated to physical solvents (lower heat requirements for regeneration).

- Adsorption becomes efficient for CO 2 contents below 2% and makes it possible to achieve very low specifications (< 50 ppm). In addition, water, H 2 S, mercaptans, and other sulfur compounds are removed, thus its use is usual in gas liquefaction trains (for LNG production).

- Gas pretreatment is very important to ensure membranes lifespan, and it can be classified as follows:

o

Gas heating.

o

Heavy hydrocarbons separation by cooling (by mechanical refrigeration or Joule-Thomson effect).

o

Heavy hydrocarbons and water adsorption by means of a regenerable adsorbents system.

Additionally, all of them include filtering. The pretreatment choice depends on CO 2 removal ratio, the heavy hydrocarbons content and on the uncertainty associated to gas composition. In membranes methane is lost, thus “enriching” the residual gas in heavy hydrocarbons.

- Removal of small amounts of acid gases is usually carried out with non-regenerative chemical scavengers. A possible arrangement consists in making the gas flow through a vessel containing the scavenger.

b. Summary table

Table 2 summarizes the main characteristics of the above mentioned sweetening technologies.It may become useful for a first pre-selection, to discard technologies with application ranges that do not fit the project requirements.

Table 2 – Main characteristics of sweetening technologies

   

PROCESS

 

ITEM

AMINES

 

MEMBRANES

HOT POTASSIUM CARBONATE

PHYSICAL SOLVENTS

MIXED SOLVENTS

PHYSICAL ADSORPTION

NON REGENERATIVE SOLVENTS

Acid Gas Content at Inlet

Up to 70% V

 

Up to 90% V

5% V to 50% V

P CO2 > 3.5 bara

P CO2 > 7.6 bara

0.1% V to 2% V

< 0.1% V

Typical Acid Gas Content at Outlet

From 2% V down to deep removal

 

1% V

1.5% V (single stage scheme) 0.1% V (two stage scheme)

1% V

< 0.5 % V

50 ppmV

5 to 300 ppmV

Typical Gas Flow Rate (MMSCMD)

From low to more than 10

From very low to more than 10

From low to 7

From 3 to 11

From low to more than 10

From low to 3

Low

   

Absorber: 5 to 120 bara Regenerator: 1.5 bara

 

Absorber: 69 bara

 

Absorber: 69 bara Regenerator: 3 bara or lower

   

Typical Operating

Pressure

27

bara to 100 bara

Regenerator: 1.5 bara

Absorber: 69 bara

Adsorption: 14 to 69 bara

As required

Conditions

Temperature

30 to 60ºC (absorption)

 

< 60ºC

110 to 120ºC

-18ºC to Ambient

Ambient to 60ºC (absorption)

Adsorption: 30 to 60ºC Regeneration: 350ºC

Ambient

Typical Hydrocarbon Losses

Less than 1%

1 stage: 8 - 15%

Very low

Absorbs heavy hydrocarbons & aromatics

Absorbs heavy hydrocarbons & aromatics

None

None

 

2

stages: 2%

Process Turndown

Gas Flow Rate

30%

 

20%

30%

Approximately 30%

Approximately 30%

Low (Note 4)

No limitation

Main Equipment (Note 3)

_Contactor _Regeneration System (Note 1) _Flash Drum _Lean/Rich Amine Heat Exchanger _Lean Amine Cooler _Circulation Pumps

_Inlet Pre-Treatment (Note 2) _Membrane Skid _Recycle Compressor and Coolers (for 2 stages systems)

_Contactor _Regeneration System (Note 1) _Gas/Gas Heat Exchanger _Circulation Pumps _Lean Solution Cooler (for 2 stage process scheme)

_Contactor _CO 2 Recycle Flash Drum _Flash Drums at different pressures _Lean Solvent Pumps _Rich Solvent Pumps _Vacuum Pump _Recycle Compressor (Optional) _Chiller (Optional)

_Contactor _Regeneration System (Note 1) _Flash Drum _Lean/Rich Solvent Heat Exchanger _Lean Solvent Cooler _Circulation Pumps _Reclaimer (Optional)

_Molecular Sieve Vessels _Regeneration Gas Heater

_Liquid Scavenger Towers

Materials Requirements

SS for certain parts (Lean/Rich Heat Exchanger, Reboiler tubes, Regeneration System overhead)

Pre-treatment: CS or SS (high acid gas content) Membrane Skid: CS

Stainless Steel for certain parts

Carbon Steel

SS for certain parts (Lean/Rich Heat Exchanger)

Carbon Steel

Carbon Steel

Lay Out Requirements

High

 

Low

High

High

High

Medium

Low

Services Requirements

_Heating Medium _Power _Chemicals (e.g. antifoam)

_Pre-treatment requirements (e.g. Power, Refrigeration) _For 2 stages: Power (for Compression)

_Heating Medium _Power _Chemicals (e.g. antifoam)

_Power _Chemicals (e.g. antifoam) _Refrigeration (Optional) _Heating Medium or Stripping Gas (Optional)

_Heating Medium _Power _Chemicals (e.g. antifoam)

_Heating Medium

 

Ease of operation

High complexity

Low complexity (Note 6)

Very High complexity

High complexity

High complexity

Medium complexity

Low complexity

Contaminants

Oxygen, Heavy HC (liquid state), Solid particles, Organic acids

Heavy HC, BTEX, Glycols, Amines, Liquid water

Solid particles, Heavy HC (liquid state)

Solid particles, Heavy HC (liquid state)

Solid particles, Heavy HC (liquid state), Oxygen

Heavy HC (liquid state), Glycols, Amines, Liquid water

Heavy HC (liquid state)

 

Investment

High

 

Medium

High

Medium

High

Medium

Low

Cost Composition

Operation

Medium

 

1

stage: Low

Low

Low

Medium

Low

High

2

stages: Medium

Notes

Outlet gas saturated with water.

Gas is dehydrated.

Outlet gas saturated with water. Solution can precipitate.

Gas is dehydrated.

Sulfinol solvent is relatively expensive. Outlet gas almost saturated with water.

Gas is dehydrated.

Outlet gas saturated with water. The spent caustic is a hazardous waste.

Notes:

1.- Regeneration System includes: Regeneration Column (Still), Condenser, Accumulator, Reflux Pumps and Reboiler. 2.- Inlet pre-treatment depends on gas composition. Simple pre-treatment includes: coalescing filter, non-regenerable adsorbent (activated carbon) guard bed, dust filter and heater. Enhanced pre-treatment could include a LTS Unit (mechanical refrigeration), a Joule-Thompson Expansion Unit or a Regenerable Adsorption System. 3.- Inlet and Outlet Scrubbers, Filters not indicated. 4.- Adsorption/cooling cycles must be lengthened. 5.- CS: Carbon Steel. SS: Stainless Steel. 6.- Membrane unit only. Complexity increases with recycle compression (two stage membrane process) and enhanced pre-treatment schemes.

4

The traditional approach

Facing the vast range of applicable technologies, the process designer’s challenge lies in selecting the optimal technology for the project at issue. A first approach to the problem consists in referring to the “traditional” selection guidelines.

As starting point, the content of acid gases in the gas to be treated could be an adequate parameter to find guidance in the selection. As it is observed in Figure 1, some technologies can be easily discarded. However, most of them present a quite broad application range. In addition, this criterion seems to be insufficient since it fails to contemplate the treated gas specification that must be reached.

Figure 1 – Example of gas sweetening technologies selection chart [Ref. 1]

100 90 80 70 60 50 40 30 20 10 0 SOLID BED AND SCAVENGER
100
90
80
70
60
50
40
30
20
10
0
SOLID BED AND
SCAVENGER
PRIM ARY AND
SECONDARY
AM INES
TERTIARY AM INES
HOT POTASSIUM
PHYSICAL
M EM BRANES
CARBONATE
SOLVENTS
Acid Gas Content, CO2+H2S Vol%

Incorporating this second parameter in the selection chart, we obtain Figure 2. This allows us to restrict even more the possible alternatives. But again, it turns out to be incomplete since it fails to contemplate a crucial parameter as the pressure of the gas to be treated, and consequently, the partial pressure of the CO 2 to be removed.

Figure 2 – Example of gas sweetening technologies selection chart [Ref. 3]

Guide to selection of gas sweetening processes

100%

Membranes followed by Amines Membranes Physical Solvents, Mixed Solvents, Amines Physical Solvents, Membranes,
Membranes
followed by Amines
Membranes
Physical Solvents, Mixed Solvents, Amines
Physical Solvents,
Membranes,
Potassium Carbonate
Physical
Solvents
10%
Physical Solvents,
Mixed Solvents,
Amines
Amines, Mixed Solvents, Physical
Solvents, Potassium Carbonate
1%
Amines, Mixed Solvents
1000 ppm
Amines,
Mol Sieves,
Batch Processes
Batch Processes, Mol Sieves
100 ppm
1 ppm
10 ppm
100 ppm
1000 ppm
1%
10%
Acid Gas Concentration in Feed

Acid Gas Concentration in Outlet Gas

100%

10%

1%

1000 ppm

100 ppm

Figure 3 is a selection chart that incorporates this consideration.

Figure 3 – Example of gas sweetening technologies selection chart [Ref. 2]

1000 Amines (high loading) or Physical solvents Physical solvents 100 Physical solvents or Amines Potassium
1000
Amines (high
loading)
or
Physical
solvents
Physical solvents
100
Physical solvents or Amines
Potassium carbonate,
Mixed
solvents
or
Amines
10
Amines or
Mixed solvents
1
0,1
1
10
100
Partial Pressure of acid gas in Feed (psi)

Partial Pressure of acid gas in Product (psi)

After a quick visual inspection of the 3 figures, some “rules of thumb” become almost evident, allowing us to discard some of the processes:

- For low quantities of CO 2 to be removed, non-regenerative processes become the recommended alternative due to the low installation cost of this technology, while for large quantities, the operating cost of the solvent that cannot be regenerated makes its application prohibitive.

- Physical adsorption becomes economically convenient for low concentrations of inlet CO 2 , and it is generally applied for gas “polishing”, when H 2 S and mercaptans or other sulfur compounds must also be removed. Its use to remove exclusively CO 2 is not usual.

- Physical solvents present a certain disadvantage for low partial pressures of CO 2 in the inlet gas. For partial pressures above 50 to 150 psi, this technology can become attractive over chemical solvents.

- Processes based upon amines make it possible to achieve ‘restrictive’ specifications of acid gas (for example, lower than 2%), and they present a broad application range.

- Membranes do not seem to be adequate to reach restrictive CO 2 specifications (for example, lower than 2%). This assertion extracted from the figures analysis is not completely valid. Membranes lose competitiveness for high removal ratios of carbon dioxide (for example, an 85% removal: from 14% to 2% CO 2 ), that are generally associated to reaching restrictive specifications. But they become more competitive for low removal ratios of carbon dioxide, even when they are associated to restrictive specifications (for example, a 9% removal: from 1.1% to 1% CO 2 ).

- Some process combinations become attractive, e.g.: membranes followed by amines, also called “hybrid systems”. The preferential use of these systems seems to be high CO 2 partial pressures in the feed gas and low CO 2 contents in the treated gas.

To this point, we have discarded a certain amount of technologies after sketching a quick selection of the applicable ones. However, this traditional approach has shown to be insufficient for a final selection. It is important to incorporate additional criteria that take into account the project restrictions and the conditions of the environment, in addition to the characteristics of the gas to be treated and of course, to carry out an economic analysis of the pre-selected alternatives. The optimum selection may be even different to that arising from using the above mentioned charts.

5 The proposed approach

So far, the technologies have been analyzed isolated from the remaining processing units, even though it is usual to find a strong interaction among them. The proposed approach consists in not losing sight of the impact of the sweetening unit in the remaining facilities, also considering the external factors in the evaluation.

a. Project restrictions

Units located upstream of the sweetening unit

Compression:

Due to the corrosive nature of acid gases, sweetening generally constitutes the first stage of gas processing, afterwards followed by dehydration and hydrocarbon dew point conditioning. But depending on the pressure at which the gas is available and the delivery pressure, it may be necessary to compress it, in such case compressors may be placed upstream of the sweetening unit.

In general, all technologies profit from a higher inlet gas pressure, due to the increase in CO 2 partial pressure (greater driving force). The saving in the cost of the sweetening unit must be compared to the cost increment in compression (since a larger gas flow rate is being compressed) plus the cost increase due to the metallurgy of the compression unit, if any, due to acid gas handling (scrubbers and air-coolers may require stainless steel instead of carbon steel if liquid water is present with high partial pressures of CO 2 ).

Amine units constitute an exception to the aforesaid, since gas treatment pressure does not have a striking impact on plant cost if it is above some 40 bar, and the content of CO 2 is higher than 10%, approximately. Moreover, the plant may become marginally more expensive when increasing the treatment pressure. Generally, the amine load is limited in order to avoid corrosion and solution degradation problems (to approximately 0.45 mol CO 2 /mol amine), therefore a higher treatment pressure does not influence the amine circulation rate and the regeneration section size (regeneration column, reboiler, lean amine cooler, etc.). However, it does impact on the shell thickness required for the absorption column, and in many cases the increase in thickness compensates or exceeds the reduction in column diameter due to treating smaller gas actual flow rates.

Other processes:

Even though acid gas removal is usually the first stage of gas processing, in some cases it may be advantageous to sweeten the gas downstream of liquid recovery units. For example:

- For low removal ratios of CO 2 , for example from 2.2% to 2%, installing a membrane unit downstream of a dew point conditioning unit may turn out to be convenient. The dew point unit removes the water and heavy hydrocarbons from the gas, and only a minimum pretreatment (filtering) is required to protect the membranes. Sweetening, in addition, will not moisten the gas again. - In turboexpansion plants for ethane recovery (C 2 ), an important percentage of the inlet CO 2 will liquefy and it will be recovered together with the C 2 (for example, 50% of CO 2 for a C 2 recovery of 90%, strongly depending on the gas pressure and the process employed). In these cases the residue gas specification can be met, and the liquids be treated to remove the CO 2 –a much smaller volume, at low pressure– as long as the carbon dioxide does not freeze in the turboexpansion process.

Units located downstream of the sweetening unit

Injection to pipelines:

If the heavy hydrocarbon content (C5+) of the gas to be treated is low and no dew point conditioning is required, the sweetened gas may be delivered to the gas transmission pipeline system (after dehydration, if necessary). In this case, the CO 2 and water content allowed by the country’s legislation or the transportation company’s specifications must be reached. Table 3 shows some specifications typical of South America, while Table 4 shows the water content of the sweet gas for different processes.

 

Table 3 – Gas specifications typical of South America

 

Contaminant

Units

Argentina (1)

Bolivia (2)

Venezuela (3)

       

Present: 8.5

CO2

% mol

2

2

2009: 6.5

2011: 4

2013: 2

N2

% mol

2

2

1

Total inerts

% mol

4

3.5

-

       

Present: 17.3 (12.0)

H2S

mg/Sm3 (ppmv)

3 (2.1)

5 (3.5)

2009: 13.3 (9.2)

2011: 9.8 (6.8)

     

2013: 6 (4.2)

       

Present: 112 (7.0)

Water

mg/Sm3 (lb/MMSCF)

65 (4.1)

95 (5.9)

2009: 105 (6.6)

2011: 97 (6.1)

     

2013: 90 (5.6)

Source:

(1) ENARGAS Resolution No. 622/1998, Basic specifications (non-relaxed). (2) Transredes – SSDH Administrative Resolution No. 0670/2001 – SSDH No. 0190/2002. (3) COVENIN 3568:2-2000; Resolution No. 162 issued by the Ministry of People's Power for Energy and Petroleum [Ministerio del Poder Popular para la Energía y Petróleo], 17/09/2007.

Table 4 – Water content in gas according to sweetening process

Process

Treated gas

Residual acid gas

Amines

Saturated with water

Saturated with water

Potassium carbonate

Saturated with water

Saturated with water

Physical solvents

Dehydrated (1)

(varies according to regeneration method)

Mixed solvents

Close to saturation (2)

Saturated with water

 

Heating

Dehydrated (1)

Sub-saturated (3)

Membranes; pre-treatment:

Refrigeration (mechanical, JT)

Dehydrated (1)

Sub-saturated (3)

Adsorption (TSA)

Dehydrated (4)

Dehydrated (4)

Physical adsorption

Dehydrated (4)

(varies throughout regeneration cycle)

Non-regenerable (batch)

Saturated with water

(in aqueous solution)

Notes:

(1) In general, water contents lower than 110 mg/Sm 3 (7 lb/MMSCF) are reached. It must be analyzed on a case-by-case basis whether it is sufficient to comply with transport specifications. (2) Treated gas is approximately 3 to 5ºC above its water dew point.

(3) Residual acid gas is approximately 20 to 40ºC above its water dew point. (4) Dehydrated down to ppm levels (e.g.: <50 ppm of water).

As may be observed, amine treatment requires dehydration of sweetened gas. On the other hand, membranes will usually remove enough water together with CO 2 to comply with the specification (it must be verified in each particular case). In an economic comparison of processes, costs must include a dehydration unit (generally with TEG) in cases that require it. As an approximate value, adding a TEG unit may increase the investments required by 10% to 15% above the cost of an amine unit.

It is worth pointing out that, in the cases of Bolivia or Argentina, where the total inert content is limited, if the nitrogen content of the gas is high, CO 2 removal may be required even up to lower levels than its maximum admissible content, in order to comply with the inerts specification.

Dew point conditioning:

If the heavy hydrocarbon content of the gas to be treated is relatively high, in addition to sweetening, its hydrocarbon dew point conditioning will be required in many cases, to comply with sales specifications and/or to obtain higher incomes for the production of gasoline.

Dew point conditioning processes resort to the generation of low temperatures to condense heavy hydrocarbons. Even though this seems detrimental to sweetening processes that heat the gas (e.g.:

potassium carbonate), in a global comparison this difference between processes is not a determining factor. For instance, in the case of membranes, gas is typically heated approximately 10 ºC above residue gas dew point; in an amine process, gas temperature increase ranges from 5 to 15 ºC, and can reach up to 30 ºC. This difference is compensated by installing an air cooler between the sweetening unit and the dew point conditioning unit: the total cost increase is not significant, specially in cases of high inlet gas temperature.

In accordance with Table 4, sweetening processes affect the water content of the gas being treated. Hydrocarbon dew point conditioning processes imply dehydration, and the amount of water to be removed will exert a slight impact on the cost of the dew point conditioning unit. In many cases, the water content of the gas after membrane sweetening is not enough to meet the dehydration requirements of a dew point conditioning process, and the continuous injection of a hydrate inhibitor (such as mono-ethylene-glycol) will be required to prevent the formation of hydrates in the cold separator.

In the case of membrane units with pretreatment based on adsorption with regenerable sieves, the removal of heavy hydrocarbons during pretreatment may be sufficient to comply with the hydrocarbon dew point specification, specially in the case of gases having heavy hydrocarbons (up to C20 or more) but a low C4+ content. In these cases, it is worth to consider integrating sweetening and dew point conditioning in the same unit, to keep facilities complexity level low (it may be necessary to add mechanical refrigeration in order to cool the inlet gas and perform adsorption at lower temperatures). In some cases, physical solvent absorption allows such integration among sweetening, dehydration and dew point conditioning.

Recovery of natural gas liquids (NGL):

To recover higher percentages of NGL (butane, propane and, depending on the case, ethane), it is also usual to resort to the generation of low temperatures. The technology most frequently applied is turboexpansion.

In these cases, the required CO 2 removal may be higher than that set forth by gas transportation specifications and will be prescribed by the process conditions in order to prevent the formation of solid CO 2 , mainly in those cases in which ethane is recovered (due to the very low temperatures involved).

Membrane sweetening and a pretreatment based on adsorption located upstream of a turboexpansion unit can result in an interesting integration. In this way, the dedicated molecular sieves located at the entry to the turboexpansion unit for dehydration may be reduced in size, or even eliminated if the expansion ratio is not very high.

Electric power generation:

If the treated gas is used for electric power generation, the allowable CO 2 content is higher than that

required by typical transportation specifications. In many cases sweetening is not even necessary, or a minor

conditioning is enough. With adaptations to combustion systems, fuel gases with heating values as low as 300 BTU/SCF can be used for turbo-generators (up to 65% CO 2 ). The lowest limit must be analyzed together with turbine vendors. In these cases, membranes benefit from the low removal ratios required.

Disposal of acid gas

A very important aspect to be considered is the destination of the acid gas separated. The following

table summarizes possible destinations:

Table 5 – Acid gas disposal options

 

Methane

 

LHV

content

 

Possible destinations according to gas lower heating value

 

(BTU/SCF)

(remainder:

Gas Engines

Gas Turbines

       

CO2)

Fired heaters

Flaring

Venting

Injection

> 600

> 66%

Ok

Ok

Ok

Ok

Not

Ok (higher

recommended

injection costs)

           

Not

 

600

to 300

66% to 33%

Ok

Ok

Ok

Ok

recommended

Ok

           

Not

 

300

to 200

33% to 22%

(lower limit)

(lower limit)

(lower limit)

Ok

recommended

Ok

           

Not

 

200

to 150

22% to 16%

Not feasible

Not feasible

Not feasible

(lower limit)

recommended

Ok

< 150

< 16%

Not feasible

Not feasible

Not feasible

Not feasible

Ok

Ok (lower

injection costs)

Venting:

For chemical solvents, the CO 2 released contains very low hydrocarbon levels (generally lower than 0.2%), and, pursuant to the legislation in force in many countries of South America, it may be vented to the atmosphere, provided it does not contain significant H 2 S levels. For acid gas containing H 2 S, calculations of hydrogen sulfide dispersion in the atmosphere must be developed to ensure that there is a suitable safety margin between toxicity limits and the concentration thereof in any area accessible to operators (for example, the closest platform to the acid gas stack). Were this is not possible, alternatives to venting must be contemplated. In the case of mixed and physical solvents, the hydrocarbon content of acid gas is higher, ranging approximately from 1 to 5%, and venting is usually not possible.

Flaring:

In the case of CO 2 with higher hydrocarbon contents (for example, membranes permeate gas) or in

such other cases in which venting is not an option (for example, amine regeneration gas because of its H 2 S

content), acid gas may be flared.

Depending on the heating value of the gas, the addition of fuel gas for flaring may be necessary. According to API STD 537 and flare manufacturers’ recommendations, below 300 BTU/SCF a higher number of pilots, or more intense heat release pilots in comparison to standard flares, are required. The minimum

lower heating value (LHV) for flaring is 150 BTU/SCF. In most cases, membranes permeate gas has a LHV above 150 BTU/SCF.

Use in fuel gas system:

Due to its high methane content, membranes permeate gas may be used as low heating value fuel gas. This greatly benefits this alternative, as will be shown in the following sections. In some instances, burners or combustion systems specially adapted to handle this gas will be required. In order to reach the supply pressure of some fuel gas systems, the permeate pressure must be increased (reducing the efficiency of the membranes), although compressing permeate gas may be more convenient, specially for its use in turbines.

Injection:

Even though many countries of South America have no legislation prohibiting venting CO 2 to the atmosphere, more and more projects are considering acid gas injection (AGI) to reduce greenhouse effect gas emissions, in accordance with the clean development mechanism laid down in the Kyoto Protocol. The cost of CO 2 injection units represents a considerable percentage of the total gas treatment cost, and may increase the required investments by up to 50% above the sweetening unit cost.

Almost all the technologies analyzed generate a CO 2 effluent containing water and different amounts of hydrocarbons. The corrosion of carbon steels by CO 2 results from the formation of carbonic acid when CO 2 dissolves in liquid water. In order to prevent it, water must be eliminated, its condensation must be avoided, or stainless steels must be used instead of carbon steels. If reinjecting the carbon dioxide is required, its corrosiveness at high pressures demands the use of stainless steel in great part of the injection system, and dehydrating the CO 2 to be injected is sometimes essential (typically with a TEG unit).

Membrane pretreatment based on adsorption is the only technology that generates a dry acid gas stream (Table 4). If CO2 injection is required, this has the advantage of avoiding the need for corrosion resistant alloys or acid gas dehydration for acid gas injection, which may lead to cost-reductions of up to 20% in the AGI unit.

Light hydrocarbons content in the acid gas also has a considerable impact on acid gas injection costs. Light hydrocarbons reduce the density of a CO 2 stream, and, therefore, imply higher pressures in the discharge of injection compressors, and, eventually, more compression stages. Moreover, for the same carbon dioxide removal, the injection flow rate resulting from a membrane unit will be higher than that from an amine unit, due to the permeation of hydrocarbons (HC) together with CO 2 . The following table shows a comparison derived from a recent study. Note the two-fold increase in power for case 3 in comparison to case 1.

Table 6 – Impact of sweetening on acid gas injection unit

 

Acid gas composition (% mol)

Density relative

Flow rate relative

Injection

Number of

Injection power

         

pressure

compression

 
 

Case

CO2

HC

to case 1

to case 1

(bar)

stages required

relative to case 1

1)

Amines

99,7

0,3

1,00

1,00

130

5

1,00

 

2

stage

     

1,25

145

5

1,33

2)

membranes

80

20

0,87

 

1

stage

     

1,82

165

6

1,94

3)

membranes

55

45

0,72

In the case of amine units, acid gas is obtained at a pressure slightly above atmospheric (10 psig). The limit is determined by the maximum temperature at the bottom of the regeneration column, in order to prevent amine decomposition. In the context of projects providing for acid gas injection, it is beneficial to regenerate the amine at the highest possible pressure.

An advantage of membrane units is that permeate gas may be provided at a higher pressure (at the expense of a somewhat larger area) and the number of acid gas compression stages may be reduced. But this does not usually compensate for the increase in flow rate and compression discharge pressure if compared to amines. The requirement of reinjecting acid gas is detrimental to the membranes in comparison to other treatment alternatives.

Location of facilities and supervision requirements

The simplicity of the treatment with non-regenerative scavengers (for very low CO 2 removals) and membranes (for higher CO 2 removals) makes these processes very attractive for remote facilities which require a minimum level of supervision. This is specially true in the case of one-stage membrane units with simple pretreatment (heating), where no recycle compression is required.

Economies of scale

The “size” of the facility may tip the balance of the decision in favor of certain technologies. For example, in the case of very low quantities of inlet CO 2 or low flow rates of gas to be treated, non- regenerative processes present clear advantages due to their low investment cost. Nevertheless, this technology abruptly loses appeal with the increase of the flow rate to be treated or the CO 2 content of the inlet gas owing to the high operating cost, that is to say, the cost of the scavenger used. The NPV (net present value) of this alternative is practically proportional to the treated flow rate. Because of their modular nature, membranes have a similar cost characteristic in relation to the flow rate, but, in this case, proportionality results from a linear increase in investment cost in relation to the flow rate. On the other hand, several technologies show an exponential relationship between cost and flow rate, typically “Capex = A x (Flow Rate)^B”, where B0.6-0.7 for the process industry. These technologies surpass the foregoing for high flow rates, as, in the event of a flow rate increase of 100%, their cost will increase only by 60% whereas membranes will record a cost increase of 100%. Accordingly, in the case of low flow rates, membranes benefit from the same behavior. This effect of economies of scale explains, in part, the reason why certain technologies are more appealing for low flow rates. For example, the following figure shows this effect for a particular case study, in which high CO 2 content gas had to be sweetened.

Figure 4 – Economies of scale

FLOWRATE SENSITIVITIES

60 50 40 30 20 10 0 0.25 0.75 1.25 1.75 2.25 FLOWRATE [MMSCMD] Amines
60
50
40
30
20
10
0
0.25
0.75
1.25
1.75
2.25
FLOWRATE [MMSCMD]
Amines
Membranes
CAPEX [MMUSD]

Contaminants in inlet gas

Some processes are highly sensitive to the composition of inlet gas. In the case of membranes, heavy hydrocarbons may irreversibly damage them and must be removed during pretreatment. A proper pretreatment design is of key importance in order to handle variations in the content of heavy hydrocarbons. In the case of pretreatment based on physical adsorption, in the event of an increase in the heavy hydrocarbon content of the inlet gas, the system may be adjusted by reducing the time of the adsorption – regeneration cycles.

The presence of H 2 S is an important point to consider, as the content thereof in sales gas is one of the most difficult specifications to comply with. While amine units easily remove large amounts of H 2 S, meeting very low specifications, membrane processes limitedly remove hydrogen sulfide, as its permeation capacity is similar to that of CO 2 . Therefore, both gases will permeate with similar ratios through membranes,

obtaining concentration removal ratios of the same magnitude. In this way, a membrane system designed to reduce CO 2 content by 50% will remove approximately 50% of the inlet H 2 S, regardless of its concentration.

b. Environmental conditions

Energy cost

The energy cost is an extremely relevant parameter in the decision-making process. In particular, the Latin American context is completely heterogeneous with regard to the price of gas agreed upon in the different regions of the continent. Broadly speaking, the heterogeneity is so that the price of gas ranges from 1 to 5 USD/MMBTU. Consequently, it is worth analyzing the impact of energy cost on the selection of the sweetening process.

The answer calls for a previous analysis, since not only must the energy consumption of the sweetening unit be analyzed, but also the hydrocarbon losses in the CO 2 rich stream to be disposed of, as both factors bring about a reduction in the flow rate of sales gas. Nonetheless, where the heating value of the CO 2 rich stream is above a minimum, it may be used as fuel gas. In this case, hydrocarbon losses do not entail "losses" in sales gas themselves, as the use of that low-heating-value gas reduces the consumption of fuel gas derived from sales gas. Therefore, we will not record the heat content of "reusable" residual streams as cost, but we will record that of "non-reusable" residual streams.

The following figure shows the results obtained in a recent case study developed by Tecna for a 5 MMSMCD plant treating high pressure inlet gas with 15% CO 2 . In accordance with different gas price scenarios, the figure provides a graphic representation of the net present value (NPV) for different alternatives, composed of three terms:

CAPEX:

1. cost of equipment multiplied by an installation factor.

2. operating costs, such as energy consumption, labor and other supplies throughout 15 years of production.

3. non-reusable hydrocarbons, such as fuel gas, disposed of together with the CO 2 removed during the period of 15 years.

OPEX:

Losses:

Figure 5 – Impact of energy cost

ENERGY PRICE vs TOTAL COST - SENSITIVITY

160 140 120 100 80 60 40 20 0 0.5 1.5 2.5 3.5 TOTAL COST
160
140
120
100
80
60
40
20
0
0.5
1.5
2.5
3.5
TOTAL COST NPV [ MM U$D ]
60 40 20 0 0.5 1.5 2.5 3.5 TOTAL COST NPV [ MM U$D ] GAS

GAS PRICE [ U$D / MMBTU ]

NPV AMINE UNIT

NPV MEMBRANE UNIT

NPV MEMBRANE UNIT - PERMEATE REUSE NPV HYBRID UNIT

NPV MEMBRANE UNIT - PERMEATE REUSE

NPV HYBRID UNIT

NPV 2ST MEMBRANE UNIT

NPV HYBRID UNIT - PERMEATE REUSE

On the basis of the figure, it may be observed that, within the framework of the study, the membranes turned out to be attractive for gas prices lower than 1 USD/MMBTU, but this technology ceased to be competitive for higher energy costs, due to the incidence of high hydrocarbon losses (in the order of 15% of the heat content of inlet gas) on the NPV. However, in the event of reuse of the permeate as fuel gas, membranes presented significant advantages over its competitors. Nevertheless, it is worth highlighting that this case contemplates a complete reuse of the permeate stream, and that, in many cases, specially where the gas flow rate to be treated is considerable, the heat content of the permeate may exceed fuel gas

requirements, as a consequence of which such excess must be disposed of and recorded as a hydrocarbon loss. Moreover, fuel gas facilities must be prepared to handle low-heating-value permeate. This alternative may not be aligned with the company’s environmental policy if it is a standard practice to reinject CO 2 , as, in fact, the CO 2 removed will be vented to the atmosphere together with combustion exhaust gases.

A similar analysis may be applied to the hybrid case, composed of a membrane unit placed upstream of an amine unit. The membranes carry out the “bulk" removal of carbon dioxide, while the amine unit "polishes" the gas, meeting the outlet specification. The rationale of this scheme is to exploit the advantages inherent in each process; membranes are not economically suitable for the purpose of obtaining low CO 2 outlet content with high inlet concentrations, as the CO 2 removal ratio and the hydrocarbon losses are high in this case, whereas the chemical nature of the absorption of CO 2 in amines makes it less dependent on partial pressure, allowing deep removals. In the case under analysis, the hybrid system was competitive only considering the reuse of membrane permeate as fuel gas, in order to meet the energy requirements of amine regeneration. The full exploitation of the symbiosis between both technologies occurs by fixing the outlet specification for the membrane unit so that the heat content of the permeate is lower than or similar to the one required for amine regeneration; in this way, no hydrocarbon losses per se were generated. Again, this alternative results in the venting of the CO 2 removed in the membrane unit.

In those cases in which the company's environmental policy requires the reinjection of CO 2 or there is no destination for all the permeate stream to be used as fuel gas, the amine alternative turned out to be the most convenient for the usual gas prices in our continent, followed by the 2-stage membrane process. The latter was prejudiced by its higher hydrocarbon losses (3% of the heating value of inlet gas), although the difference with the amine alternative is in the range of uncertainty of the estimate.

Preferences of the company

Another essential parameter is the previous experience of the company and its preferences regarding sweetening technology. There is certain inertia to change within each company; therefore, the technology having most successful experience has more possibilities than new technologies.

6 Flexibility over specification changes

Let us analyze the case of specification changes along plant operation lifecycle. For example, Venezuelan law provides for a gradual reduction in the specification of CO 2 in sales gas, as shown in Table 3, requiring the future expansion of the CO 2 removal capacity. In another hand, a similar challenge is faced when considering future increases in the inlet CO 2 content. In this context, let us analyze the flexibility of the alternatives to achieve these objectives in the most efficient manner. The analysis will focus on the study of solvent and, specially, amine processes, and membranes, together with a combination of both.

The size of an amine unit depends directly on the absolute amount of CO 2 removed (in kg/h). This means that, for an inlet CO 2 content of 6%, the removal of CO 2 to reach an outlet of 2% approximately doubles the removal necessary to reach 4%. Consequently, the amine circulation rate and the size of the regeneration section will increase in the same proportion (100%, possibly requiring the addition of a regeneration train identical to the original in parallel). If we analyze the same case, but for an inlet content of 10%, the specification change mentioned hereinabove requires a circulation rate increase of only 30%, which could be absorbed by a suitable overdesign of the unit, without having to add parallel trains.

Therefore, even though the technology is attractive from the viewpoint of operational reliability, it is also true that it has little flexibility for the purpose of expanding the CO 2 removal capacity, specially, for “low” inlet concentrations (< 8% approximately). The design of these units should consider extra capacity to face the greater removals required by future and more restrictive specifications.

On the other hand, the size of a membrane unit depends directly on the CO 2 removal ratio. Due to the modular nature of this technology, it is relatively easy to install additional membrane area to reduce the outlet CO 2 content, as a result of which the process has a good flexibility for expansions, in spite of presenting some economic disadvantages with respect to its competitors: it should be borne in mind that hydrocarbon losses also increase with the additional membrane area.

What is then the best proposal for specification changes? Undoubtedly, the answer will arise from a case-by-case analysis. Nevertheless, there is a process which presents remarkable advantages for the purpose of the changes in the CO 2 specification. It is the hybrid system of membranes and amines, which allow the exploitation of the specific advantages of each of these processes, specially in those cases in which it is possible to reuse the membrane permeate as fuel gas for the amine unit. The alternative may

consist, for instance, in installing an amine unit at a first stage, and installing the membrane unit at a second stage, when the change of specification is required. The most important decision variable is the outlet CO 2 content of the membrane unit, and, therefore, the relative size of both units. In this case, it is recommended that the amine unit be sized according to the most demanding of the following cases:

- Optimum concentration of CO 2 at membrane unit outlet: for the purpose of the analysis, the “final situation”, that is to say, the removal of CO 2 required in 2013, must be considered. The optimum concentration is that in which permeate gas from the membrane unit is completely used as fuel gas.

- Size required by the amine unit in order to meet the specifications prior to the installation of the membrane unit.

This sizing criterion is based on the fact that, as has been previously explained, the hybrid system loses competitiveness where the permeate exceeds the fuel gas requirements, and it is necessary to burn or dispose of the hydrocarbons of the permeate. Due to the easy installation of membranes, the expansion of the carbon dioxide removal capacity is relatively easily developed, both for lower outlet CO 2 specifications required and for increases in the inlet gas CO 2 concentration. This scheme allows phasing investments in two stages, instead of installing the entire capacity from the outset.

Another viable alternative could consider the installation of membranes, at a first stage, and the later installation of an amine unit, where so required. In this case, the lowest CAPEX during the first stage may exceed the hydrocarbon losses derived from the operation of the membrane unit.

7 Case study

There follows a case study of selection of sweetening technologies for a significant flow rate (>3 MMSCMD) of lean gas with 15% CO 2 , which must be treated to meet a CO 2 specification of 2%.

Given the flow rate of gas to be treated and the amount of CO 2 to be removed, the use of non-

regenerative scavengers or physical adsorption was discarded from the outset. Moreover, based on the experience of the operating company and the general experience in the region, among the solvent absorption processes, the amine process was selected. The alternatives studied are the following:

- Removal with amines (Amines)

- Removal with 1 stage membranes (Membranes 1 st.)

- Removal with 2 stage membranes (Membranes 2 st.)

- Hybrid system: Removal with 1 stage membranes, and, then, with amines (Hybrid)

Gas is available at approximately 40 barg and the delivery pressure required is higher (80 barg), therefore, we analyzed the location of each of the treatment alternatives mentioned: upstream and downstream of the compression unit. In whole, 8 cases were defined:

Table 7 – Analyzed alternatives

Conditions Process
Conditions
Process

High pressure

Low pressure

Amines

Amines HP

Amines LP

Membranes 1 stage

Membranes 1 st. HP

Membranes 1 st. LP

Membranes 2 stages

Membranes 2 st. HP

Membranes 2 st. LP

Hybrid (membr. 1 st. + amines)

Hybrid HP

Hybrid LP

Other conditions for the purpose of the study:

- The study included the comparison of capital expenditures (CAPEX, +/- 30% estimate) and operational expenditures (OPEX) during a period of 15 years, updated to their present value.

- In the case of operational expenditures, the replacement of membrane elements and solvent (amine) make up were taken into account.

- In all cases, the study considered a constant flow rate of gas to be treated, and penalized the reduction in flow rate of sales gas with the value of hydrocarbon losses (HC Losses) in such cases as may be applicable.

- A sales value for natural gas of 2 USD/MMBTU was adopted.

- Acid gas needed to be reinjected in all cases, due to the environmental policy of the operating company.

- For the alternatives of amine treatment and hybrid system, the additional cost of a gas dehydration unit with TEG was considered, in order to meet the sales gas specification.

- The reduction in flow rate to be compressed was taken into account in those cases where the sweetening unit was located upstream of the compression unit

The following figure shows the net present value (NPV) of the alternatives considered. The case of amine treatment at high pressure is taken as the basis (100% net present value) for the comparison.

Figure 6 – Net present value of cases analyzed

Net Present Value - Processing Alternatives

190% 180% 170% 160% 150% 140% 130% 120% 110% 100% 90% 80% 70% 60% 50%
190%
180%
170%
160%
150%
140%
130%
120%
110%
100%
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%
Amines
Hybrid
Amines
Hybrid
HP
M embranes 1st.
HP
M embranes 2 st.
HP
HP
LP
M embranes 1st.
LP
M embranes 2 st.
LP
LP
CAPEX
OPEX
HC Losses

Some conclusions derived from the foregoing figure:

- In all cases of membrane treatment, it is beneficial to locate the compression upstream of the sweetening unit.

- In this particular case, amine treatment before compression is more convenient than after compression.

- Under the conditions of this study, two-stage membrane processes have a present value comparable to amine sweetening processes, and are later followed by the hybrid scheme and the one-stage membrane treatment (prejudiced by the high CO 2 removal ratio and the high flow rates processed).

The following figures show hydrocarbon losses and utility consumptions for the cases under analysis:

Figure 7 – Hydrocarbon losses

Hydrocarbon Losses 25 20 15 10 5 0 Amines HP M embranes 1st. HP M
Hydrocarbon Losses
25
20
15
10
5
0
Amines
HP
M embranes 1st.
HP
M embranes 2 st.
HP
Hybrid
Amines
HP
LP
M embranes 1st.
LP
M embranes 2 st.
LP
Hybrid
LP
Figure 8 – Fuel gas consumption
Fuel gas consumption
10%
9%
8%
7%
6%
5%
4%
3%
2%
1%
0%
Amines
HP
M embranes 1st.
HP
M embranes 2 st.
HP
Hybrid
Amines
HP
LP
M embranes 1st.
LP
M embranes 2 st.
LP
Hybrid
LP
Membranes pre-treatment
Amines regeneration
LP to HP compression
Acid gas compression
Membrane recycle compression
Electric power generation
% treated gas
% inlet gas heating value

It is worth highlighting that the possibility of using permeate gas as fuel for one-stage membranes was discarded, as it implies a remarkable increase in CO 2 emissions, and there was no demand for fuel gas which allowed the total use thereof. Even considering the reduction in flow rate of sales gas, these alternatives were very convenient from an economic viewpoint. The following figure shows a net present value comparison of amine treatment over one-stage membranes considering the total reuse of the permeate as fuel gas. The amine treatment does not comprise the reinjection of acid gas, but considers its venting to the atmosphere, in order to compare the alternatives under identical circumstances.

Figure 9 – Reuse of permeate as fuel gas vs. Amines LP

Net Present Value - Processing Alternatives

120% 110% 100% 90% 80% 70% 60% 50% 40% 30% 20% 10% 0% M embranes
120%
110%
100%
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%
M embranes 1st.
HP
Permeate as FG
Amines
LP
M embranes 1st.
LP
Permeate as FG
CAPEX
OPEX

It can be observed how the application of different constraints for the disposal of acid gas reverts the results of the analysis, turning membranes into a more convenient alternative. The permeate available from these one-stage membranes alternatives is 15 to 20% of the heating value of the inlet gas. For high feed gas flow rates, the excess of low BTU fuel gas is significant and its application is attractive, for example, for electric power generation (which may not be an option in remote locations).

8 Conclusions and lessons learned

The selection of sweetening technologies is a complex process which calls for the analysis of the interaction of several agents, such as factors pertaining to the external environment, the internal environment and other gas processing units. Some of the conclusions reached are the following:

Preselect potential alternatives – several technologies are economically unviable for certain conditions.

Consider the integration with the rest of the processing facilities – a broad view of the project is required, which contemplates processing units located upstream and downstream of the sweetening unit.

First, choose the technology, and, then, optimize it – for those technologies which allow

alternative processing schemes, it is recommended to analyze only the basic scheme during the selection process.

Speed up and facilitate the selection process - a consultant having proven experience in CO 2

removal technologies may speed up the process and facilitate arriving at an optimum solution. The

consulting company may contribute a holistic approach, analyzing the project as a whole.

9 References

[1] Gas Conditioning and Processing Volume 4, Maddox & Morgan, 4 th edition. [2] Engineering Data Book, Gas Processors Suppliers Association, 12 th edition. [3] Oilfield Processing of Petroleum, Volume 1: Natural Gas, Thomas & Manning. [4] “Recent Developments in CO 2 Removal Membrane Technology”, David Dortmundt, Kishore Doshi, UOP webpage. [5] “Hybrid Systems: Combining Technologies Leads to More Efficient Gas Conditioning”, William Echt, Laurence Reid Gas Conditioning Conference, 2002.