Absorption

Absorption is a thermal separation process. During absorption one or more components of a gas stream are removed by being taken up in a non-volatile liquid.

Absorption can be physical or chemical. Physical and chemical scrubbing processes have dif-ferent scrubbing mechanisms. In physical absorption the gas is removed because it has greater solubility in the solvent than other gases. There are no chemical reactions between the com-pound to be removed and the washing liquid. In chemical absorption the gas comcom-pound to be removed reacts with the solvent and remains in solution. In a chemical scrubbing process an-other substance is formed besides the washing liquid and the compound to be removed.

Chemical scrubbers show better selectivity between various compounds while physical scrub-bers can remove wide spectra of substances. [16]

Another difference is that a chemical scrubber reacts to the amount of the component to be removed and a physical scrubber reacts to the total gas amount. In addition, physical bonds are reversible while in chemical processes there are at least some irreversible by-products.

[17]

The limit between physical absorption and absorption by chemical reaction often cannot be distinguished.

The basic equations to describe the process of absorption are (see chapter 7.1):

• Mass balance

• Energy balance

• Phase equilibrium equations

The general mass balance of a counter current absorber is stated in equation 3.1. Here, xH2S is the concentration of H₂S in the liquid phase and y_H2S is the concentration of H₂S in the gas phase. L is the liquid flow and G is the gas flow. The indices T and B refer to top and bottom of the column respectively.

The energy balances consider enthalpy and heat balances. The stationary enthalpy balance without heat losses is as indicated in equation 3.2. In the equation, hi refer to the enthalpies of the gas (G) and the liquid (L).

Phase equilibrium describes the solubility of gases (y) in liquids (x) and can be calculated us-ing Henry’s Law.

p Y

H

X_i⋅γ_i^*⋅ _i = _i⋅ϕ_i ⋅ (3.3)

The activity coefficient γ_i^* can be set to one for low mol fractions and the fugacity coefficient φ_i can be neglected for low pressures p (φ_i = 1). [18]

This means that the solubility of a gas in a liquid can be described mathematically according to Henry’s Law as follows.

X p H Y

i i

i = ⋅ (3.4)

The Henry coefficient H is a common parameter to characterise the absorption capacity of a substance. Theoretically, the Henry coefficient of H₂S in water at a temperature of 25 °C is 560 bar [19].

The absorption of a gas in a liquid is based on mass transfer with the difference in concentra-tion as the driving force. The concentraconcentra-tion gradient describes an imbalance of phase equilib-rium which results in mass transfer within and between the phases and through phase bounda-ries. The mass transfer depends mainly on the specific mass transfer coefficient. Figure 3 pre-sents the idealised concentration profile of a substance vertically towards the phase boundary according to the two film theory. An increase of the phase boundary between liquid and gas increases the mass transfer.

bulk gas phase

bulk liquid phase

liquid film gas film

Interface y_i

x_i yi*

x*_i

Figure 3: Concentration profile according to the two film theory

For describing the processes during absorption there are different methods, for example the method of theoretical stages (HETP method) and the method of transfer units (HTU-NTU concept) (see chapter 7.1).

3.2.1. Upgrade of solubility of H

2

S

Improving the efficiency of gas scrubbers can be achieved by using adapted washing liquids.

These washing liquids must satisfy certain requirements to ensure a safe, economic and envi-ronmentally-friendly absorption process. For application in biological desulphurisation, these solubilisers should offer, amongst others, the following characteristics:

• High selectivity for H2S

• Water-soluble

• Non-toxic

• Non- or hardly biologically degradable

• Non-volatile

• Available

• Cost-effective

In the following paragraphs, possible solubilisers as well as known washing solutions are pre-sented. Water is the most important solvent in physical absorption because of its availability at low cost. Therefore the effectiveness of other solvents is always compared to water. [20]

Absorptive desulphurisation with sodium hydroxide (NaOH) solution (pH of about 8.5) is an existing process for industrial desulphurisation [14]. The desulphurisation with amines is effi-ciently used in natural gas treatment, but for the desulphurisation of biogas, it is not economi-cally feasible [15]. Alkanolamines are often used as absorbents for acidic gases.

Triethanolamine (TEA) was used in early gas-treating plants and was the first commercially available alkanolamine. TEA has been replaced by monoethanolamine (MEA) and dietha-nolamine (DEA) which have proved to be of commercial interest. [20]

DMSO (dimethyl sulphoxide) is a polar aprotic solvent. It is often used in chemistry and in-dustry. DMSO is also applied in scrubbing H₂S from fuel gas. [21]

DMSO, TEA and MEA are used as comparative solvents in laboratory tests (see chapter 4).

Furthermore, normal tap water, as well as alkaline and acidic water, is used for comparative purposes.

Sulfa-Clear^TM 8640 is a water-soluble sulphide converter from the company Weatherford.

This product also fulfils the criteria as a solubiliser for application in biological desulphurisa-tion. It is a 60 - 65 % active aqueous amine resin solution containing surfactants, designed as a H2S scavenger for gas systems. Its application is mainly odour control in wastewater treat-ment. [22]

Sulfa-Clear^TM 8640 has been proven to be a cost-effective alternative to other chemicals due to significantly lower treatment rates and better performance. The normal dosage required is 4 to 6 ppm per ppm of H2S. Sulfa-Clear is a reddish-amber liquid which can be injected directly into the gas or liquid stream. The products do not foul or contaminate downstream operations.

[23] The characteristics of Sulfa-Clear^TM 8640 are listed in table 6.

Table 6: Characteristics of the Sulfa-Clear [22]

Trade name Sulfa-Clear^TM 8640 Chemical characterisation Aqueous amine solution

Chemical state Liquid

Colour Reddish-Amber

pH-value 10.3 - 11.0

Flash point 66 °C

Pour Point < -32 °C

Density 1 072 kg·m^-3

Solubility in water Soluble in water

Activity 60 - 65 %

Humic substances can also be used as solubiliser in this application. They are described in de-tail in chapter 3.3.

Table 7 presents some processes for the removal of H2S (and CO2) with industrially-adapted washing liquids.

Table 7: Absorption processes for the removal of H2S and CO2 [11]

Process Washing liquid Conditions

MDEA-process Methyldiethanolamine 10 – 25 % in water

p > 10 bar T: 50 - 70 °C

DEA-scrubbing 2n -3n diethanolamine p: 8 - 10 bar

T: 20 - 55 °C MEA-scrubbing 2.5n or 5n monoethanolamine p > p_atm

T = 40 °C Genosorb^®-scrubbing Tetraethylenglykoldimethylether p < 7 bar

T: 20 - 40 °C Selexol^®-scrubbing Polyethylenglykoldimethylether p < 20 - 30 bar

T: 0 - 40 °C

Rektisol-scrubbing Methanol p > 20 bar

T: -70 - -10 °C Purisol-scrubbing N-Methyl-2-pyrolidon p > 20 bar

T: -20 - 40 °C

Im Dokument Humic substances may not be beautiful, but they do beautiful things (Seite 28-31)