# Patent

## Title
System and method for pH control of lean MEG product from MEG regeneration and reclamation packages

## Abstract

A lean MEG stream having a first pH level is contacted with a CO2-rich gas stream to yield a lean MEG product having a second different and lower pH level preferably in a range of 6.5 to 7.0. The system and method can be readily incorporated into a slipstream MEG recovery package, with a source of the lean MEG stream being a MEG regeneration section of the package. The CO2-rich gas could be a vented CO2 stream from the MEG reclamation section of the package. Unlike hydrochloric and acetic acid overdosing, CO2 overdosing of the lean MEG stream does not lead to rapid acidification of the lean MEG product to be stored or injected.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a divisional application which claims priority to U.S. patent application Ser. No. 14/500,295 filed on Sep. 29, 2014, which is incorporated herein by reference.


BACKGROUND
Slipstream MEG recovery packages use a regeneration section to remove water from an incoming rich MEG feed stream and produce a lean MEG stream. A portion of this lean MEG stream is routed to a reclamation unit or section where the salt component is removed to yield a salt-free, pH neutral, lean MEG stream. This salt-free lean MEG stream is then blended with the remaining lean MEG stream to produce a lean MEG product having up to 3 wt % dissolved salts and available for re-injection into the gas production line as hydrate inhibitor.
For gas fields where significant quantities of calcium and other divalent cations are present in the formation water, a calcium removal unit or section is located upstream of the regeneration section. The calcium is removed from the rich MEG stream by elevating the pH through the addition of sodium or potassium carbonates, hydroxides, or some combination thereof. The lean MEG exits the calcium removal section with an elevated pH, typically above 9.5.
Because carbonate and hydroxide are often added in excess of the required stoichiometric quantity, un-reacted carbonate and hydroxide is carried through the regeneration system and into the lean MEG product. Removal of water from the rich MEG in the regeneration section further elevates the pH of the lean MEG product sent for reinjection. Mixing this high pH lean MEG with the calcium-rich formation water in the gas production pipeline can lead to increased scaling of the pipeline by precipitation of, for example, calcium carbonate.
Therefore, a need exists to reduce the pH of the lean MEG product prior to injection and, in turn, mitigate pipeline scaling. Acidification of the lean MEG with hydrochloric acid (HCl) is an option but overdosing with hydrochloric acid can lead to rapid reduction in pH to levels at which corrosion of carbon steel pipework and vessels may occur.
SUMMARY
A lean MEG stream having a first pH level (e.g., pH>9.5) is contacted with a CO2-rich gas stream to yield a lean MEG product having a second different pH level preferably in a range of 6.5 to 7.0. The CO2-rich gas could be a vented CO2 stream from a MEG reclamation unit.
Carbon dioxide has advantages to hydrochloric acid (HCl) and acetic acid (CH3CO2H) for pH control because overdosing with CO2—i.e., adding it in excess of the required stoichiometric quantity—does not lead to the significant reduction in pH observed with hydrochloric acid or the accumulation of acetates observed with acetic acid.
Objectives include providing a system and method that reduces the pH of lean MEG product prior to injection, mitigates the potential for pipeline scaling, does not make use of dosing with organic or inorganic acids to control the pH of the lean MEG product, is less sensitive to overdosing conditions than those organic and inorganic acids, and does not cause rapid reduction in pH levels when an overdose condition occurs.



BRIEF DESCRIPTION OF THE DRAWINGS
So that the manner in which the above recited features can be understood in detail, a more particular description may be had by reference to embodiments, some of which are illustrated in the appended drawings, wherein like reference numerals denote like elements. It is to be noted, however, that the appended drawings illustrate various embodiments and are therefore not to be considered limiting of its scope, and may admit to other equally effective embodiments.
FIG. 1 is a schematic of an embodiment of a system and method of this disclosure. A vessel located downstream of a MEG regeneration section receives a high pH lean MEG stream and allows the steam to come into contact with a CO2-rich gas.
FIG. 2 is a graph illustrating a lean MEG stream with alkalinity present as sodium carbonate as the stream is treated with CO2, acetic acid, and hydrochloric acid.
FIG. 3 is a graph illustrating a lean MEG stream with alkalinity present as sodium hydroxide as the stream is treated with CO2, acetic acid, and hydrochloric acid.



ELEMENTS AND NUMBERING USED IN THE DRAWINGS


    
    
        10 Vessel
        15 Rich MEG steam
        20 Lean MEG stream
        21 Portion of lean MEG stream 20
        30 MEG regeneration unit or section
        40 CO2-rich gas 40
        50 Lean MEG product exiting 10
        60 MEG reclamation unit or section
        61 Salt-free lean MEG stream
        70 Calcium removal unit or section
    
    


DETAILED DESCRIPTION
In the following description, numerous details are set forth to provide an understanding of some embodiments of the present disclosure. However, it will be understood by those of ordinary skill in the art that the system and/or methodology may be practiced without these details and that numerous variations or modifications from the described embodiments may be possible.
In the specification and appended claims: the terms “connect”, “connection”, “connected”, “in connection with”, and “connecting ” are used to mean “in direct connection with ” or “in connection with via one or more elements”; and the term “set” is used to mean “one element” or “more than one element”. Further, the terms “couple”, “coupling”, “coupled”, “coupled together”, and “coupled with” are used to mean “directly coupled together” or “coupled together via one or more elements”. As used herein, the terms “up” and “down”, “upper” and “lower”, “upwardly” and downwardly”, “upstream” and “downstream”; “above” and “below”; and other like terms indicating relative positions above or below a given point or element are used in this description to more clearly describe some embodiments of the disclosure.
Referring to FIG. 1, an embodiment of a system and method for adjusting a pH level of a lean MEG steam includes a vessel 10 which receives a lean MEG stream 20 from a lean MEG source such as a regeneration unit or section 30 of a slipstream MEG recovery package. Typically, stream 20 has a pH level above 9.5, as does rich MEG stream 15 upstream of the regeneration section 30. Within vessel 10, this high pH lean MEG stream 20 comes into contact with a CO2-rich gas 40 (i.e., greater than 50% CO2 content). Vessel 10 can be a contactor vessel of a kind known in the art.
The CO2 in gas 40 forms acidic solutions when dissolved in the MEG-water mixture of stream 20, thereby reducing the pH. A lean MEG product 50 having a second lower pH exits the vessel 10. Preferably, product 50 has a pH level in a range of 6.5 to 7. No inorganic acids such as HCl or organic acids such as acetic or citric acid is required for reducing the pH to this level.
The CO2-rich gas 40 can be from any source preferable but is more preferably a vent stream from a reclamation unit or section 60 of the slipstream MEG recovery package. Similar to MEG regeneration section 30, MEG reclamation section 60 is of a kind well-known in the art.
A salt-free lean MEG stream 61 which exits the reclamation section 60 can be mixed with the lean MEG stream 20 prior to stream 20 entering vessel 10. Additionally, a portion 21 of the lean MEG stream 20 which exits the regeneration section 30 can be routed to the reclamation unit 60.
In slipstream MEG recovery packages that make use of a calcium removal unit or section 70 upstream of the regeneration unit 30, excess carbonate that finds its way into the reclamation section 60 degrades to form CO2 (and hydroxide) under the elevated temperature, low pressure regime of a flash separator (not shown).
Referring to FIGS. 2 and 3, unlike hydrochloric and acetic acid overdosing, CO2 overdosing within vessel 10 does not lead to rapid acidification of the lean MEG product 50. In a CO2 overdosing condition, the pH level remains above 6 whereas in an acetic acid and hydrochloric acid overdosing condition the pH level falls below 4 and 2 respectively. Therefore, the system and method of this disclosure is less sensitive to overdosing conditions than prior art methods.
As mentioned above, acidification with CO2 removes the risk which occurs with inorganic acids (HCl) and the absence of carboxylates (acetate), namely, overdosing to the point of potentially damaging pH levels. In addition, carboxylates are highly soluble in MEG and are difficult to remove once added to the MEG system. The accumulation of carboxylates can lead to operational problems as the density and viscosity of the MEG increases with increasing carboxylate content. Hydrochloric acid converts readily to salt plus water; carbon dioxide converts to bicarbonate which is much more easily managed in the MEG system than carboxylates. Although the CO2 reduces the pH, the ‘alkalinity’ (OH— plus HCO3— plus CO2) is not reduced.
To examine the “scaling” potential for the system and method, the following software simulation was run employing OLI Analyzer v 9.1.5 (OLI Systems, Inc., Cedar Knolls, N.J.).
Starting Solution:
90 wt % MEG (on salt-free basis) at 40° C. containing 30,000 mg/kgsolvent sodium chloride, 250 mg/kgsolvent of sodium carbonate and 25 mg/kgsolvent of sodium hydroxide. The pH of this mixture was 10.053 or about 10 (see Table 1, col. A, below).
Acidification:
The MEG solution was neutralized to pH=7.0 and to pH=6.5 using HCl acetic acid and CO2. Quantities of HCl, CH3CO2H and CO2 added are shown in Table 1, rows 12-14, below.
Scaling Test:
Scaling potential of the acidified solutions was determined by adding in separate simulations MgCl2, CaCl2, FeCl2, SrCl2 and BaCl2 to the lean MEG solutions at the quantities shown in Table 1, rows 19-23.







TABLE 1







Software Simulation of Scaling Potential.















1

A
B
C
D
E
F
G



















2











3
TEMP

40
40
40
40
40
40
40


4


5
H2O
g
100,000
100,000
100,000
100,000
100,000
100,000
100,000


6
MEG
g
900,000
900,000
900,000
900,000
900,000
900,000
900,000


7
NaCl
g
30,000
30,000
30,000
30,000
30,000
30,000
30,000


8
Na2CO3
g
250
250
250
250
250
250
250


9
NaOH
g
25
25
25
25
25
25
25


10


11
ACIDIFICATION


12
HCl
g
0
136
—
—
160
—
—


13
CHCO2H
g
0
—
228
—
—
279
—


14
CO2
g
0
—
—
239
—
—
478


15


16
pH
—
10.05
7.01
7.01
7.01
6.50
6.50
6.50


17


18
SCALING TEST POST



ACIDIFICATION


19
MgCl2 for Mg
g



precipitation as Mg(OH)2


20
CaCl2 for Ca
g
1.4
840
880
250
4300
5300
800



precipitation as CaCO3


21
FeCl2 for Fe
g
0.1
1.5
1.7
0.8
6.7
7.7
2.4



precipitation as FeCO3


22
SrCl2 for Sr
g
0.5
650
660
200
3900
3950
620



precipitation as SrCO3


23
BaCl2 for Ba
g
0.2
7
13.7
2.1
35
80
6.3



precipitation as BaCO3









Results:
For the starting solution (col. A, pH=10.0) precipitation of divalent cations as carbonate occurs on addition of 1.4 g of CaCl2. After acidification to pH 7.0 with HCl, the quantity of calcium chloride added before precipitation of CaCO3 increases to 840 g from 1.4 g. The effect with acetic acid is similar with precipitation starting at 880 g of CaCl2. The equivalent scaling point with carbon dioxide occurs at 250 g, less than that for HCl or acetic acid but a considerable improvement on the 1.4 g for the untreated sample.
Similar trends are observed for the other divalent cations (Fe, Sr, Ba) although some are more insoluble than others. Iron, in particular, tends to precipitate out readily. At pH=6.5 (col. E-G) the trends agree with those shown at pH=7.0 (col. B-D), i.e. precipitation of divalent cations (Ca, Fe, Sr, and Ba) from the lean MEG is inhibited by addition of CO2 to the alkaline lean MEG mixture.
Although the preceding description has been described herein with reference to particular means, materials and embodiments, it is not intended to be limited to the particulars disclosed herein; rather, it extends to all functionally equivalent structures, methods, and uses, such as are within the scope of the appended claims.

## Claims

1. A MEG recovery system comprising a vessel for adjusting a pH level of a lean MEG stream exiting a MEG regeneration unit, the vessel including an inlet in fluid communication with the lean MEG stream and a port in fluid communication with a CO2-rich gas stream from a MEG reclamation unit, the lean MEG stream and the CO2-rich gas stream coming into contact with one another within the vessel, the vessel further including an outlet for a reduced pH lean MEG stream and a different outlet to vent a reduced CO2 gas stream.

2. A MEG recovery system according to claim 1 wherein an amount of the CO2-rich gas is at least equal to a stoichiometric quantity effective for achieving a desired reduced pH level.

3. A MEG recovery system according to claim 2 wherein the amount of CO2-rich gas exceeds the stoichiometric quantity.

4. A MEG recovery system according to claim 1 wherein the reduced pH lean MEG stream has a pH level-of at least 6.

5. A MEG recovery system according to claim 1 wherein the reduced pH lean MEG stream has a pH level of 7.

6. A MEG recovery system according to claim 1 wherein the lean MEG stream is mixed with a second lean MEG stream having a different pH level than a pH level of the lean MEG stream.

7. A MEG recovery system according to claim 6 further comprising the second lean MEG stream contains less salt than the lean MEG stream.

8. A MEG recovery system according to claim 6 wherein the second lean MEG stream has a pH level of 7.

9. A MEG recovery system according to claim 1 wherein a portion of the lean MEG stream exiting the regeneration unit is routed to the MEG reclamation unit.

10. A MEG recovery system according to claim 1 wherein the vessel is a gas-liquid contactor.

11. A MEG recovery system comprising a gas/liquid contactor vessel including an inlet in fluid communication with a lean MEG stream exiting a MEG regeneration unit and a port in fluid communication with a CO2-rich gas stream from a MEG reclamation unit, the lean MEG stream and the CO2-rich gas stream coming into contact with one another within the gas/liquid contactor vessel, the gas/liquid contactor vessel further including an outlet for a reduced pH lean MEG stream and a different outlet to vent a reduced CO2 gas stream.