Process scheme to improve divalent metal salts removal from mono ethylene glycol (MEG)

Abstract

A MEG reclamation process includes the step of increasing above 2,000 ppm the divalent metal salts concentration of a rich (wet) MEG feed stream flowing into a precipitator. The increasing step includes routing a salts-saturated MEG slipstream from the flash separator it to the precipitator. The slipstream may be mixed with a fresh water feed stream, a portion of the rich MEG feed stream, or some combination of the two. The rich MEG feed stream also may be split into two streams, with a portion of the stream being heated and routed to the flash separator and the other portion being combined as above with the removed slipstream. The process can be performed on the slipstream after dilution and prior to entering the precipitator or after being loaded into the precipitator. Removal of the insoluble salts may be done in either a batch or continuous mode.

Claims

1. A process for removing divalent metals from a mono ethylene glycol (“MEG”) stream, the process comprising: pre-heating a first MEG stream before a precipitation reaction of the first MEG stream; and increasing a divalent metal salts concentration of the first MEG stream by adding the first MEG stream and a second MEG stream to a precipitator, wherein the second MEG stream has a higher divalent metal salts concentration and a lower water content than the first MEG stream; wherein the increasing occurs between a hydrate inhibitor use of the first MEG stream and the precipitation reaction of the first MEG stream; and wherein the second MEG stream is removed from a flash separator located downstream of the precipitator when the divalent metal salts concentration within the flash separator reaches a preset high value and wherein the second MEG stream performs at least a portion of the pre-heating.

2. The process of claim 1, further comprising maintaining the divalent metal salts concentration in the flash separator below a plugging range of the flash separator.

3. The process of claim 1, wherein the divalent metal salts concentration in the flash separator is in a range of 25,000 to 50,000 ppm.

4. The process of claim 1, further comprising adjusting a temperature of the second MEG stream.

5. The process of claim 1, further comprising adjusting the higher divalent metal salts concentration of the second MEG stream.

6. The process of claim 5, wherein adjusting the higher divalent metal salts concentration of the second MEG stream comprises mixing the second MEG stream with a water stream.

7. The process of claim 5, wherein adjusting the higher divalent metal salts concentration of the second MEG stream comprises mixing the second MEG stream with a portion of the first MEG stream.

8. The process of claim 1, wherein, after the increasing step, the divalent metal salts concentration of the first MEG stream is at least 25,000 ppm.

9. The process of claim 1, wherein the flash separator receives a calcium salts-saturated MEG stream from the precipitator.

10. The process of claim 1, wherein the second MEG stream has a higher temperature than the first MEG stream.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) 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.

(2) FIG. 1 shows a schematic of a prior art process that considers the presence of calcium in the feed. The low calcium concentration (typically less than 2,000 ppm) of the wet MEG, fresh feed stream is heated and mixed with sodium carbonate. The mixture enters a precipitator where the calcium carbonate forms and precipitates. The precipitation process removes calcium from the stream and the salt-saturated MEG stream is further heated and routed to a flash drum or separator. In the flash separator, the water and most of the MEG are flashed off to be distilled downstream. Sodium chloride is removed as crystals from the bottom of the flash separator.

(3) FIG. 2 shows a schematic of a prior art process that does not properly consider the presence of calcium in the rich MEG feed stream. Therefore, calcium in the feed stream accumulates in the flash separator and impairs sodium chloride removal. Calcium accumulation in the flash separator may also lead to severe salt deposition and plugging. Operators may be forced to dump MEG from the flash separator and replace it with fresh MEG to purge calcium or lower its concentration in the flash separator. For an existing facility, it may not be feasible to turn the process shown in FIG. 2 into that of FIG. 1, with a full-fledged precipitator and preheating system. Additionally, the low calcium concentration in the rich MEG feed stream may lead to requiring a precipitator much larger in size than current space constraints can accommodate.

(4) FIG. 3 shows a preferred embodiment of a MEG reclamation process practiced according to this invention. The process removes calcium from a rich MEG feed stream by using smaller equipment than the process of FIG. 1 and effectively removes accumulated calcium from the flash separator.

(5) FIG. 4 presents another preferred embodiment of a MEG reclamation process practiced according to this invention in which the same concepts as those of FIG. 3 are used.

(6) FIG. 5 presents another embodiment of the MEG reclamation process suitable for operating in a batch mode using the same concepts as those of FIGS. 3 and 4.

ELEMENTS AND NUMBERING USED IN THE DRAWINGS AND THE DETAILED DESCRIPTION

(7) 10 MEG reclamation process with calcium removal

(8) 20 Fresh, wet (rich) MEG feed stream

(9) 22 Heating medium

(10) 24 Pre-Heated fresh feed stream

(11) 26 Precipitator feed stream

(12) 28 Precipitating agent

(13) 30 Fresh water feed stream

(14) 32 Fresh feed/fresh water stream

(15) 34 Diluted slipstream

(16) 40 Precipitator

(17) 42 Calcium carbonate stream

(18) 43 Recycle loop

(19) 44 Calcium salts-saturated MEG stream

(20) 46 Heating medium

(21) 48 Heated calcium salts-saturated MEG stream

(22) 50 Flash separator stream

(23) 60 Flash drum or separator

(24) 62 Slipstream

(25) 64 Salt crystal outlet stream

(26) 66 Vaporized water and MEG stream

(27) 68 Heat transfer medium

DETAILED DESCRIPTION

(28) 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.

(29) Referring first to FIG. 3, a preferred embodiment of a MEG reclamation process 10A practiced according to this invention begins with a fresh, wet (rich) MEG feed stream 20 which is then heated by way of a heating medium 22 to form a pre-heated fresh feed stream 24. Fresh feed stream 20 is typically low in calcium concentration (less than 2,000 ppm). The pre-heated fresh feed stream 24 is mixed with a slipstream 62 that has been removed from a liquid inventory of a flash drum or separator 60 to form a precipitator feed stream 26. A precipitating agent 28, preferably sodium carbonate, is added to the precipitator feed stream 26.

(30) Mixing slipstream 62 with the pre-heated fresh feed stream 24 increases the calcium concentration of the precipitator feed stream 26 above that of initial fresh feed stream 20 but below that of slipstream 62. In general terms, the calcium concentration of precipitator feed stream 26 is in a range of about 10,000 to 30,000 ppm. However, the exact calcium concentration of the stream 26 depends upon the flow rate and calcium concentration of the pre-heated fresh feed stream 24 and the slipstream 62 (which may be in a range of about 25,000 to 50,000 ppm). Slipstream 62 increases the temperature of the precipitator feed stream 26 because the flash separator 60 operates at higher temperature than does the precipitator 40. This allows the heating medium 22 to be reduced in size compared to prior art processes (see e.g. FIG. 1) and yet still meet the desired temperature for precipitator feed stream 26.

(31) A calcium carbonate stream 42 exits a bottom end of precipitator 40 and a calcium salts-saturated MEG stream 44 exits a top end. The calcium salts-saturated MEG stream 44 is heated by a flash separator heater 46 and the heated calcium salts-saturated MEG stream 48 is routed into flash separator 60. A salt crystals stream 64 exits a bottom end of flash separator 60 and a vaporized water and MEG stream 66 exits a top end. The water and MEG components of the vaporized water and MEG stream 66 are then separated from one another by partial condensation in what is commonly termed a “distillation” tower (not shown).

(32) To maintain a constant residence time in precipitator 40, a person of ordinary skill in the art would recognize the volume of the precipitator 40 must increase linearly with the total flow of precipitator feed stream 26. However, because the precipitation reaction is basically a second order one in calcium concentration, the effect of the increase in overall calcium concentration in the precipitator feed stream 26 (in most cases) more than offsets the need for increased residence time. Therefore, the same conversion of calcium removal can be reached now with less residence time compared to prior art processes.

(33) The size/volume of precipitator 40, the flow rate of the pre-heated fresh feed stream 24, the recirculation flow rate of the slipstream 62, and the heat exchange of the heated calcium salts-saturated MEG steam 48 are preferably designed so that the steady state calcium concentration in the flash separator 60 is maintained below the severe plugging range (typically in the range of 50,000 to 60,000 ppm). The removal of slipstream 62 from flash separator 60 may be operated in a batch mode, drawing the slipstream 62 from the flash separator 60 when the overall calcium concentration within the flash separator 60 reaches a preset but safe high value.

(34) Referring now to FIG. 4, another preferred embodiment of a MEG reclamation process 10B practiced according to this invention is illustrated. In this embodiment, fresh, wet (rich) MEG feed stream 20 is split into two fresh feed streams 20A, 20B, with fresh feed stream 20A being heated by heating medium 22 to produce a pre-heated fresh feed stream 24 which is combined the salt-saturated MEG stream 44 exiting precipitator 40 to form flash separator stream 50. Flash separator stream 50 is then routed to flash separator 60. A calcium carbonate stream 42 exits a bottom end of precipitator 40 and a salt-saturated MEG stream 44 exits a top end.

(35) Fresh feed stream 20B combines with slipstream 62 from the flash separator 60 to form precipitator feed stream 36. Unlike process 10A of FIG. 3, in process 10B slipstream 62 is partially diluted (to avoid crystallization upon cooling and improve heat transfer) with fresh feed stream 20B and fresh water stream 30 to form fresh feed/fresh water stream 32. The high concentration calcium slipstream 62 is then combined with fresh feed/fresh water stream 32 to form a diluted slipstream 34 whose temperature is further adjusted by the heat transfer medium 68 (cooling or heating depending on the specifics of the design situation) so that the resulting precipitator feed stream 36 is at the required precipitator temperature. The dilution and temperature adjustment of slipstream 62 could be provided by the fresh feed 20B itself but whether this is best or desired in any given application depends upon available utilities and other practical considerations. The removal of slipstream 62 can be operated in batch or continuous mode as previously described.

(36) Referring now to FIG. 5, another preferred embodiment of a MEG reclamation process 10C is illustrated which is very well suited for batch calcium removal applications, even though it can also operate in a continuous mode. The batch removal process is described herein.

(37) Fresh feed 20 is heated with a heating medium 22 and the resulting preheated fresh feed stream 24 is flashed in the flash separator 60. The soluble calcium salts accumulate in the flash separator 60 until reaching a high calcium concentrate trigger point (preferably within a range of 25,000 to 50,000 ppm).

(38) Upon reaching the calcium concentration trigger point, a slip stream 62 is taken from the flash separator 60 and preferably mixed with sodium carbonate 28 (the precipitating agent) to become the precipitator feed stream 26. The flows are kept until the batch to be treated is loaded into the precipitator 40 to start the precipitation reaction phase. After the precipitator 40 is loaded, the fluids in the precipitator 40 are allowed to react and form the calcium carbonate crystals. The fluids may be re-circulated in a recycle loop 43 (as depicted) or otherwise stirred to promote good contact of the calcium chloride and the sodium carbonate to form the calcium carbonate crystals. Reaction times will usually be such total batch treatment can be completed with an 8-hour work shift.

(39) At the completion of the precipitation reaction phase, the solids 42 are removed from the precipitator 40 and the (now) lower calcium-salts saturated MEG stream 44 is returned to the flash separator 60. The solid separation is not limited to decanting because separation can be enhanced by using centrifuges or other types of solid/liquid separators.

(40) While preferred embodiments of a MEG reclamation system and process have been described in detail, a person of ordinary skill in the art understands that certain changes can be made in the arrangement of process steps and type of components used in the process without departing from the scope of the following claims.

(41) 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.