Demulsifiers: Water-in oil emulsion separation results Chandran Udumbasseri, Technical Consultant cudumbasseri@yahoo.co.in; chandran.udumbasserif@gmail.com Introduction Crude oil emulsion breaking is one of the hardest operations in oil separation from entrapped saline water. The oil coming out of a crude oil drilling well is composed of dissolved natural gas, water trapped as free and emulsified, and solid materials like sand, mud, insoluble inorganics, sludge, and other rock sediments from the bottom of the well. The water is usually salty and varies from well to well. The composition of each well is different. It necessitates different types of processing chemistry for each well. There is only a general outline of processing for all types of crude emulsion separation but needs specific processing chemistry well. The crude oil coming out of a well is sent to separating plant where demulsifier is injected in the incoming pipeline. Due to turbulent flow the demulsifier gets mixed up evenly in the crude oil and initiates emulsion breaking. The crude then goes to high pressure separating tank (horizontal, slanted, spherical, hemispherical or vertical) where freed natural gas moves to collecting compressors, water separates at the bottom while oil float as top layer. The water is drained from the tank as the oil is allowed to move to low pressure separator where remaining gas is removed from the crude oil. The crude which is wet coming out of: this second separator is sometimes heated to facilitate emulsion breaking or allowed to go to dehydrator unit for removing residual water electro statically. After complete water removal by dehydrator the oil is dry in nature with some crystals of salt remaining in the suspended state in the oil. So the oil is again washed with water by mixing wash water. Outgoing oil is tested to ensure dryness and salt level. Some test results are given below for different oils Saudi oil Flow diagram 1, Plant 1 Process Data Process Information Total production rate 2330008D Total crude oil rate 14500080 Percentage water cut 38-42% ‘Temperature at production header | 130F Oil evel in separators & dryers | 50% Salt in crude, average PTB‘Water cut Free Water 20-40% Total water 52-58% Emulsion 12-38% After bottle testing the best performing demulsifier bases are given below Conc] Water Salt Demulsifier dropping | Ww content Bases mis/minutes | Q | 12 gremieny Ren pam [10 | 20 | 40 PTB DGI70 20/12 [20 _|32_|F [17.85 | Modified ester oz D138 20/6 [3 [12_[F | F—] 48.8 | Polymeric polyar 77. Croda-D350iX 20 | 9 | 16 [18 [F | F | 24.6 | Alkoxylated phenolicresin | 15 D311 20/9 [12 [18 |p |F [27.9 | Oxylate phenolic resin 18 0309 20 [ss [10 [@ Tr [46.6 | Oxylate phenolic resin 29 DBS95 20[7_}az [2a Te Te [27.9 | Tetrol aH 1945, 2010 [11 [18 F | F | 44.9 Amine alkonyiate 16 D3575X 20 [13 [19 |24 |G |G | 19.38 | Mixed resin ethoxylate 17. 1DB9393 20/0 fo [tr [- |- [3.4 | Amine ethoxylate 67 3422X 20 To [3 [a2 TF [r=] 3.56 | tmine alkoxylate 8 510 20 [4 fe [12 [p[P 7:28 | imine alkoxylate a 089947 20 [416 [18 _[F |G | 9.17 Resin E0/PO alkoxylate a 1089429 20 [5 [18 |22 |G | F+ | 35.4 | Resin alkoxylate 10-14 304 20s [a2 [14 1G 1G [13.17 | Resin alkoxylate 24 DRAZE 201914 [16 [Pp [P [8.25 1 Oxy phenolle resin 21 ‘DRI9030 20 [0 }5 [16 [F |G] 11.68 | Esterified phenolic polymer [7-8 1DR19037 20 fo [10 [16 [F [Fr | 7.68 | Polyol 78 RDM9S510 20 [0 |5 [8 |p |p [9.24 | Blend 79 13190 20 [9 fis [20 te tr 17.3 | Epoxy resin 76 PGLS 2010 to |s |p [Pp] 5.15 | Polyalyeot tad PG2.5 20/1 [5 [16 |F |r [95 | Poly giycol 173 DRCZIZ 20 [810 |14 |G [653.9 | Onylated resin 143 DEES 20[o}o —[o [= |- }1.48 | Polyethylene amine mixture | 6 aS19 20/10} 24 [306 | 617.82 | Alkoxylated resin 1 asi 20[s [14 |24[F [F | 29.2 | Alkoxylated resin cE C5361 20 [9 [16 [18 |G |F | 27.8 | NPF-E0/PO 089392 20 fo [9 [22 1G [P| 2.49 | Pel alkoxylated 83 Basorol-Pi7R2_20 [2 |2 6 1@ [Pp [55 Syn PELIOX | 20| 5] 9 [14 |G |G [35.4 Syn T1301 20/14 [20 [20 |G |F | 30.2 W033. 20/3 }10 [13 |G |G | 29.2 | Polyol 16 woso 2013 [s [10 [ete [24 3073 2014 te fis tr tp 37a The following formulations were found better performers Selected Formulations Formulation Ratio | Grading | Average activity 1DB9947/DB9392/DB9393 272A i 42% W033/089392/DB303 2A 2 W2% DB9947/DG270/DB9393, 22h 3 42% 1DB9958/0G270/DB9393, aya a W2% DRI9037/D89392/D89393 22 5 50% DGI70/DB5951/DB9393 Pit é 50%Conclusion-Final Formulation Cone | Water dropping Top oil water cut, | _ Salt Formulation mis/minutes | wQ| 1 % content ppm | 40 | 20 | 40 w, [w, [a {prs eanibene 20 | [4 1s |F|F [52 [5.2 (0 [249 30 {S18 /50 |r |e | 2.0 [2.15 | 0.15 | 5.67 (FibB9947/DB9352/089393 | 20 [4 6 42 ive|{G 0 |o [0 | 204 2pa/a 30 [14 [48 (54 [ve |G |o [o 0 [2.08 (F2)w033/0B9392/089393 [20 [5 [12/36 |G |F [0.05005 |0 [1.29 2p2/a 30 [20 [36 (52 [Fr [|G jo Jo [0 [0.84 Evaluation Evaluation of results: The final demulsifier is based on DB9947, D89392, DB9393, DB 5951, DB9958 (all BASF bases), DG270 (Marchem) and W033 (Deshi) The table of bases screening is giving the following data for using formulations Cane] Water dropping Sale Chemistry ‘mis/minutes conte Formulation wa] iq | cont ppm | i0 [20 140 PTE DG270 20 12/20 [32 | F | F | 17.85 | Ester DBS951 20 |? /12 [24 |e [r+ 27.9 | Tetrol 9392 20 0 [9 [22 fe |e 12.49 | Pel alkoxylate ‘DB9947 20 4116 [1s [F |G | 9.17 | ResinE0/PO alkoxylate ‘DRIS037 20 0/10 [16 [Ff |F | 7.68 | Polyol wo33 20 3/10 [13 |G |G | 29.2 | Polyol (89393 20 oto [tr [- }- 3.4 | Imine ethoxylate. Highest water dropper is DG270. The efficiency reduces down the line. Low salt content is present in DB9393 without any water dropping while DB9392 shows both low salt (2.49) and comparatively higher water dropping (22). W033 is poor water dropper and high salt, but with good water quality. DB9947 and DRI 9037 show similar behavior in water dropping and salt. The formulator used DB9947/DB9392/DB9393 (resin alkoxylate /PEI alkoxylate / amine alkoxylate), W033/DB9392/D89393 (polyols /PEI alkoxylate / amine alkoxylate), WO033/DB9392/DB9392 (polyols /PEI alkoxylate /amine ethoxylate) and DB9947/DG270/DB9393 (resin alkoxylate/ester/amine ethoxylate) as the first four formulations For the final approved selection the following two formulations were selected. Cone | Water dropping Top oll water | Salt Formulation rmisiminutes __| wa | 19 | cut, % content pom [10 | 20 [40 Wi |W; [A [PTs (F1)0B9947/089302/089303 20 4 6 | 42 |vG;G 0 |0 |0 | 204 22/1 (F2)w033/0B0392/085303 [20 [5 [12 |36 |G |F ]005)005|0 [129 2P/t In formulation F1, water dropping was 42ml, salt content 2.04PTB; top oil water cut 0%, very good water quality and good interface quality. How was the quantity of dropped water increased to 42? This is the synergistic effect that helped the formulation to drop more water. The salt content considerably reduced to 2.04PTB, which is due to the removal of most of the water from the organic layer. The top oil BS&W was 0% which supported the low salt 3content in the oil layer. In Fi the interface quality was reported as good which supported the very low BS&W (0%). Coming to F2 water dropping is a little less (36) but salt content was reported as low as 1.29PTB. This shows that F2 needed more time for flocculating the remaining water which was already separated and hangs in the oil layer. It was evident from the quality of interface which says Fair plus that means some more time is required for the clearing of interface. It appears a little bit complicated to come out with constructive formulations that can perform well in bulk trials. Mostly the formulators’ knowledge and experience matters a lot in the conclusion. Criteria for better performing demulsifier formulation: 1.1. Competent formulator with outstanding chemical knowledge and experience is a plus point for a formulation. Such formulator can bring out best performing formulation even if the demulsifier bases are not up to the requirements. 1.2. Well performing demulsifier bases can give very good performing formulations. Below are given more results from bottle testing which can be evaluated and understood. 2, Plant 2 Process Data Process Tnformation ‘Total preduction rate 2150008D Total crude oll rate 14700080 Total water cut 6800060 Percentage water cut 29-32% “Temperature at production header | 130F Oil level in separators & dryers 50% Salt in crude, average 6 PTB. BSaW. Free water 35% Total water 40-45% Emulsion 35-42% Demulsifier bases performed with this crude Cone | Water dropping Salt — mis/minutes | WQ| IQ | content Chemistry, RSN pem [io | 20 [40 PTB DISa7 50 [1.5 ]i3|/5 |F |F |a23 | Polymeric polyol 7 06270 50 |2 [25/9 Ff |G | 76 Modified ester 6.7 Di 50 [o2|7 [9 |p |F [93 Oxylate phenolic resin 18 D3575x 50/4 [65/8 F |F | 68.8 | Resin ethonylate 7 D510 s0_[o {o |o |- |-|76 Imine alkoxylate a ‘DRIS030 so [o [2/4 (F |F |7 Ester of phenolic polymer | 7-8 089429 50 [0 [25/5 |G |F+ | 77.8 | Resin alkoxylate 10-14 RSIS 50 |o [0513 (6 |G [77.8 | Alkoxylated resin 1214 R519 5s0_[t [i [4 [F [Fe [75 ‘Alkoxylated resin cH 350i% 50 [18[4 [6 (F |[F [75 71301 so jo |4 (sc |G |75 = - W-033 50 |o4|25 16 |G |G | 75 Polyol - 89955 so fo [2 i7 (r+ |e [7s 0/PO alkoxylate 13-15) Basorol 162 | 50 [0 [0d |12|F+ [Fe | 71 - : Kemelix-D3i0|50_[0 [2/4 [F |G | 7 camc238a | 50/03/04 10 F |F | 33 = - Croda-0300 | 50 [0 [0 0.6 /F |F# | 73 Blend 79 E4283 eo [9 a0 [42 [r+ [r+ [70.6 | Rsin alkoxylate 10.6ose 60 [3]? [9 [Fe [Fr [73 [Resnalonate 2 bssoie [60 [1.3 [910 ve [6/47 [Resin aleonate 10-12 SynPe25R [60 [0 [23 —/F [re [6 Pool akomate io Sta so [oes |r [es far : 1838 s0 [#9 errs fer LPatal ae Selected Formulations Formulation Ratio [Grading [Average acy W33/DP188/DB9393, afl 1 42% 85947/06270/089383 2pm [242% DB9947/DB9392/DB9393 2f2f 3 42% 19030/0510/089393 2pm [442% Conclusion-Final Formulation Cone | ~ Water dropoine Tap sil water et, | Sa Formulation wnisiminates’ | wa | 19 vs content ppm_[ 10] 20'] 30.40 we pw. [as ‘neumbene go 42 [1s | 20 or FF ps ps | saa Wig [2s fas ae | 8 pie | 8s WOSSOPIEBOESSS: | go | 15 | 20| 24 |26| ve [ve] s | s | 0 | 437 989947/06270/089593; | Go | 23 | 24| 28 36| G | G|oa|os| o | 02s Evaluation: In the Plant 2, efficient emulsion breakers are DB9947, DB9393, DB9392 (all from BASF), DP188 (Majorchem), DG270 (Marchem), D510 (Croda), DRI9030 (Akzo) and W033 (Deshi) Conc | Water droppin Salt Demulsifer mis/minutes. | wa |1q | conte | Chemistry aN Bases Hs DG270 502 [25]9 [fF [G6 (76 | Modified ester 62 D510 5010 [0 [o |- |- | 76 | Imine alkoxylate 11 DRIS030 so [0/2 [4 (Ff |F | 70 | Ester of phenolic polymer | 7-8 w-033 5004 /25/6 |G |G 75 | Polyol : The formulator has included the formulation from Plant 1 to see their performance. So he has taken corresponding bases from those formulations. This definitely reduces the time of scanning and formulations. As the salts were found high (in the range of 60-75 PTB) it appears that more time was required for individual bases to drop more water. The water cut was 45% but maximum water dropped was 12 and formulator did not consider particular base for formulation. Also the dosage concentration needed was more than 50ppm. The selected formulations Gone | Water dropping Top oil ‘Salt Formulation mis/minutes wa | 1 | water cut, % | content pom | 10 | 20 | 30 [40 wil W,[ A) PTB. wO033/DP188/DB9393; 4/i/1 60 | 16 | 20/24/26; VG VG] 5 | 5 [0] 4.37 'DB9947/DG270/DB9393; 2/2/1 oo | 23 [24 [28/36[ 6 |G [osloalol| 3.26 First formulation showed lower water dropping (26mI) while second formulation showed (36ml) higher dropping. But the formulator did not consider water dropping as the best criteria. First formulation showed very low salt content, 0% top oil BS&W, very good water and interface quality. Low salt content and 0% BS&W ensure that the emulsion has 5completely broken; good water quality and interface quality ensure that there is no over- treat and all the emulsion has broken. This justifies formulator’s selection considering first formula as best performer. It explains that more water dropping is_not the criteria for selection. Ensuring complete emulsion breaking is the criteria for selection of a formula. 3. Plant 3 Process Data Process Information ‘Total production rate '368000BD Total crude oll rate 26200060 Total water cut 10700080, Percentage water cut 29-34% “Temperature at production header | 110F(Winter); 150F(summer) Salt in crude, average 6 PTB BS&W Free water 416% Total water 20-34% Emulsion 430% Demulsifier bases performed better with this crude Cone | Water droppin Sit Pamir Imis/minutes” | Wq | 1Q | content Chemistry RSN Ss ppm | 10 | 20 | 40 PTB. DBI $5 a2 [ets [PF [F [40.7 | Poymer patyal Tz 06270 3312 [7 [slr [F166 | Wodiied ester 67 Dai 38 [28[¢ [sr [Fe [93 | oxylate phenoliéresin [18 03s75x_ [25 [4 [5 [5 [6 [F [62 | Resin ethoxylate 7 69303 25 [te [te [t= |= [40 Pel ethonyiated 65 89392 ost fa [Fe 173 | P etonylated $3 E10 380 [ope [=| [62 [imine alkanylate ti 89947 os [1 [1.8 [4 [Fe [Fox [69 | Resin €0/Po ethoxylate 13 prt9030_| 25 [3[7_|7 le [r+ [62 | Ester of phenolic polymer | 7-8 BCLS 2812 [45 [a [ve [Fs [90 | Polyaycol 14 sis alte ]é }7 [FFs 68] Alkonvlated resin = 14 pasoix 35 [23 fate ps W033 33 [e—[sts [ele [70 | Payal : BI936 33135] }e FE LF Les Reni palyar aa Basorol 2080 [28 [tr [3 [sre Fe [es z capisi0 25 fo fo fo |. |- [so |= ; peaes [25 fa [36 [ere [68 | Resin alkonylate 10.6 aDwg510——[ 25 Tae [slr [Fs [54 [Blend 79 Selected Formulations Formulation Ratio [ Grading | Average activity 189947/0B9392/089393 zat] 75% W033/ 089392/089303 zat [2 75% W033/06270/089393 za [3 75%Conclusion-Final Formulation Conc | Water dropping Top oll water cut, | Salt Formulation mis/minutes | wa | 19 Sb content pom | 10 | 20 | 30 | 40 WW, [| us/em 30 [65/95] 12|18| f+ | F | 0 | 04 | 04 | 19.84 Incumbent. 35 | 9 [14 | is) 24/ c | Fo | 04 | 04) 1945 40| 12} 17 | 20) 26| F | Fo | 03 | 03) 11.29 pp9947/089392/069393 | 35 |o5|18|24|30] c | c| o | o | o | 5.54 wos3/DB9392/089393 | a5 | 10 | 14] 18 | 31] ve | ve | 0.05] 0.05] 0 | 5.92 Evaluation: This plant (3) crude oil is similar to Plant 1 crude oil. So most of the demulsifiers performed in 1 also performed in Plant 3. So the final selected formulation is the same. 4. Plant 4 Process Data Process Information Total production rate 37400080 Total crude oil rate 28600080 Total water cu ‘3800080 Percentage water cut 22% Water separation in HPT. 10-15 mbd ‘Temperature at production header | 95-115F(W); 135F(S) Oil level in separators 35% Oil level dehydrator 50% Oil level desalter 50% Selt in crude, average 5-6 PTB Bsaw Free water = 2% Total water 24-26% Emulsion 24-26% Demulsifier bases performing with this crude Cone | Water dropping Sale Demulsifier rmis/minutes conte Peni wa] 1a |S" | chemistry RSN pom 10 [20 [40 PTB. i938 30 |? [25]3 |F|F [48.9 | Polymer polyol TZ 1937 30 [1 [3 [4 [ee |e [4a | Polymeric polyol 76 DG4283 30 [2 [3 [3 [Fe [Fe [46 | Resin alkoxylate 10.5 E9946 30 [0/1 |2 [6 [e+ [50 | Resin alkoxylate i 3627X 30 [tr [3 [4s [e+ [45 | Resin alkoxylate: 2 DaIL 30 [2 [3 _|4 [FF [44.6 | Oxylate phenolic resin 18 03575x 30 [3 [4 [4 [Fe [F [48.9 | Mixed resin ethoxylate 17 DB9393 30 [0 fo | tr [- [= [50 | Amine ethoxylate 6.7 E9947 30_[1 [1.1 |2 [Fs [Fe [50 | Resin £0/PO alkoxylate 2 DRIS037, 40 [2 [4 |4_[r+ [e+ [51 | Polyol re RDM9S10 40_|2 [4 _|4 [f+ [e+ [49 | Blend rT RSIS 40 [tr [18 [4 [Fe [Fe [46 | Alkoxylated resin 3 E9392 40 jo fo |o [= |= [55 | Pel alkoxylatea 8.3 wo33. 4o—[1_[3_|4_|@1¢ [52 Selected Formulations Formulation Ratio | Grading | Average activity W033/DB9392/DB9393 2/2/1 1 35% W033/RS15/ DB9393 mA | 2 35% W033/DRI9037/ DB9393 2/2/1 z 35%Conclusion-Final Formulation Cone | Water dropping Top oll water cut, | Salt Formulation mis/minutes we | 19. | %. content pom [10/20 | 30 [40 w,_[W; [apres Incumbent 60 8 10/42 [ie |F |F [4 [45 [05 | 249 w033/D89392/089393;2/2/1 | 40/9 |16 | 22 | 22 |vG | vG|o.05|005 10 | 4.74 WO33/RS15/ DB9393;2/2/1 40 [10/18 [22 [22 |vG [ve foi jo1 (0 | 4.79 W033/DRI9037/ DB9393;2/2/1 |40 |10/ 14 | 17 |22 |vG |vG [oi [0.15 |0.05| 671 Evaluation: The plant 4 crude oil appears similar to that of 1, 2 and 3. So the final formulation is similar to that of previous formulations. 5. Plant 5 Process Data Process Tnformation Total production rate 39200060 Totel crude oil rate 3270006) Total water cut ‘500008 Percentage water cut 14-17% Temperature at production header | 95-115F(W); 135H(5) evel in separators 50% Oil level dehydrator 50% Oil level desalter 50% Salt in crude, average 5-6 PTB BSEW Free water o= 3% Total water Emulsion Demulsifier bases performing with this crude Con | Water dropping Salt Demulsifier | mis/minutes conte Bases WQ | 1Q nt RSN pom [10 [20 [a0 PTB. DsDL 25 fo [os}i [re |F [42.7 | Polyel z D400) 2s [2 [3 [3 |G | F _| 36.7 | Ethoxylate phenolic resin | 18 PEL0100 30 [3 [4 [4 [re |F |48.9 | €0/PO Block polymer 204 wos 40 jo | [2a}e fe |- Polyol 10 RSIS 40_[tr [tr [os [rs [re | 42.7 | Alkoxylated resin 3 Ls2 40 [0 |t }o3|G |G |a2- cB-APO54 40 [0 [oi}iole |G [40 |- Daot 40 [0 [01 }o4|re [re [43 |- 03424 40 [o [02 [os [r+ [r+ [a2 | - DB99548 soo [a [a [r+ [r+ | 47 | Resin alkoxylate i DRIS037 30 [Tr_[Tr [od [P+ [Fs [a0 | Polymeric Polyol Te Conclusion-Final Formulation Cone | Water dropping Top oll water aut, % | Sale Formulation rmis/minutes wa, [29 conten pom_|10 [20 [30 | 40 [A 7 [3 [45/5 [6 [Fe [Fe li2 [12 [0 [435 Themen 7 |31/48/5 |e |re |r+ |12 [12 |o {as W033/D501/0R19037 Gz) with 10% (KH | 69 | 2) 48) 7] 8|ve)o] im | | o | 338 Ada)Evaluation The demulsifier bases that worked in this crude oil were very limited; a maximum of 57% water was dropped with the formulation. All the three bases in this formulation were polyols from different suppliers - D501 (polyol RSN 22), W033 (polyol RSN 10), DRI9037 (polyol RSN 7-8). As the RSN differs each of them works at different solvent conditions. Most of the time polyols appear as assisting demulsification rather than actual main emulsion breaker. So there is a lack of competent emulsion breaker in the list of demulsifiers that were used for screening this crude oil emulsion. The H-acid was used here to clarify both water quality and improve interface quality. Need of a highly branched flocculant demulsifier is lacking in this testing }. Plant 6 Process Data Process | Total pro 6700080. “Total crude oil rate 3270008 “Total water cut '400008D Percentage water cut 16-18% ‘Temperature at production header (Oil level in separators Oil level in dehydrator/desalter ‘Salt in crude, average ‘Water cut Free water ‘Total water 16-18% Emulsion Demulsifier bases performing with this crude Con | Water dropping Salt Demulsiir & | misyminates | yeq iq | 2 | Chemistry RSN ppm [10 [20 [40 us/em SOL 35 [tr [1e[2 [Fe |r [292 | Polyol 2 E9395 35_[tr [a [2 [F [F | 24.2 | amine ethoxviate 6.5 [03a ojo fo {-[-fs7 18 woa3 1 25/3 |» 16 RSIS 3_[tr [os [Fe [Fe | 42.7 | Alkoxylated resin 13 DRI037, 35 [te [te [a |r |r | 30. | Polymeric Polyol 78 CEDI950, 350 [a [2_[e [ep 133 | Polyot 3 1937 350 [01 [04 [Fr [Fr | 34.6 | Polymerized polyol 7S cB 461 35 [Te [1 [1.5 [r+ [Fe [32 | NPR rsin alkoxylate 125 CBROSIO 35 [0.6 [18/2 [Pp |F | 33.7 | Resin alkoxylate 20 Di9s4s 35_ [0 [1 [2 [Ff |F [30.7 | Amine oxyalkylate 16 0G4283 3505 [3 [3 |G [F | 32.7 | Resin alkoxylate 105 3575x 35 [1 [2 [3G [F | 29.4 | Modified resin ethoxylate | 17 03627x 35 [1 [15/15|F |F [30 | Resin alkoxylate 21 3535x 35 [a [2 [3 |e |r [32 | APF resin ethonylate 17 E9946 3515) 1.8/2.5 [fF | 28.2 | Resin alkoxylate 1 DB9947 351 [2 [2 [R[F | 29 | Resin (E0/PO) alkoxylate | 13 DB9955 35 [15/3 [3 |r [Ff [28 | Resin alkoxylate E0/PO | 14 E6400 35 [1 [15 /18[F |r [29 | £0/P0 block 20.1 DP-188 35 foal [2 |r |r 26 | Polyor 16. E9942 35 [tr 2 [3 [FF | 44 | Resin alkoxylate 3-9 9DRC232 3505 (1 [4 |[F |F | 40 | Resin alkoxylate 143 DPGa82 35 (05/1 [28/F |F | 44 | Polyglycol 18.8 0B9429 35 Tr [1 |2s[r fe - Resin alkoxylate 10-14 DE-ES. 35 [tr [1 [u2[F [Fr |26 | Amine alkoxylate 6 DRIS045 35 [12[18/2 [fF [F [40 |- cB361 35 1 (2 |2 |F [F | 42 | NPFEO/PO = DRC16S 350 (2 [2 [F (F [aa | - RSIL 35_ [tr [18[2 [Ff [F [40 | Alkoxylated resin 7 Liot 35 [0/1 [ie|F [F [39 | Conclusion-Final Formulation Cone | Water dropping Top oll water cut, | Salt Formulation mis/minutes wa |1Q | % content ppm_| 10 | 20 | 30 [40 w. [w. [a | PTB Incumbent. so) 7 [9] 9) 10) fe |e) 3 | 35/05) i471 W033/DP188/0B939, an 40 | 7 |10|43 155) 6 |G 06] 06 | 0 | 973 RS15/DEES/DB9303 | 40 | 4 |10|13| 14 | G | G|o2; 02 | 0] 897 2/afy Evaluation: The crude oil feed for this plant different in its behavior compared to 1, 2, 3, and 5. The water cut in this crude oil emulsion is 16-18% so the expected water dropping was around 11-12 ml from 100m! sample, taking in to account of an average dropping of 70% emulsion breaking. But the highest amount of water dropped is just free water. The screen test did not support the formulator with good information. The salt test also did not support with good information. So the formulator depended on synergism. The final formulations selected were W033/DP188/DB9393 and RS15/DEE5S/DB9393. The formulator reached at these formulations after a number of tests. W033 and DP188 are polyols, DB9393 and DEES are imine alkoxylates and RS15 is a resin alkoxylate. Polyol with imine alkoxylate synergism (F1) dropped almost 92% water in the emulsion. Salt content reduced to 9PTB and top oil BS&W 0% with a 0.6% suspended water. Resin with imine alkoxylates synergism dropped 85% water, salt content reduced to 9PTB and top oil BS&W 0% with suspended water of 0.2% The study of synergism was explained in the following article shown in Linkedin slideshare:” Review of demulsifier bottle testing procedure” by the same author. 7. Plant 7 Process Data Process Information. Total production rate 288000BD Total crude oll rate 115400080. Total water cut 13400080 Percentage water cut 46% Temperature at production header | 108F(W); 150F(S) Oil level in separators 50% Salt in crude, average 5-6 PTB BS&W Free water 30 56% Total water 50-56% Emulsion 0-2%Demulsifier bases performing with this crude Cone | Water dropping Salt Demulster mis/minutes | ya |1q | content | Chemistry a pom |10 [20 [40 PTB DG270 15 [24 [32 [34 [@ |G | 51.4 67 E9393 15_[ tr [02|7 |G [Ft [4.32 | Amine ethoxylate 67, DIs45 1541 [12 [20 [ve |G [61.2 | Amine oxyaikylate 16 D3575x 1512 [18 [io [F+ [F+ | 120 | Modified resin ethowylate | 17 DEES 15/0 [6 [33 |F | F+ | 6.32 Polyethylene amine alkoxy | 6 3422x 15/15 [5 [36 [Fe [F+ | 3.86 | Polyimine alkoxylate 8 DEPA1D. as [s [12 [22 [r+ [r+ [5.78 | Polyethylene imine alkox 9-10) 1DB9390 i5__[7_[14 27 [vo [G [5.88 | Pet alkoxylate DB9392 15/4 [16 [40 [vo |G | 5.12 | Petalkoxyiate DB9360 1513 [6 [10 [vs |G (17 | Petatkoxylate = DRI9037 15/4/10 [as [r+ [r+ | 22 | Polymeric Poiyol 78 1936 as_[3 [10 [20 [F [Fr | 32 | Acrylic polyol Ba DB9904 15_[10 [20 [26 [G_[F_ [73 Tetrol 11-12 DP1ss 15/1 [18 [42 [ve |F* | 3.78 | Polyol 16 DG4283 15/10 [1445 [F+ [F [98 | Resin alkoxylate 10.6 DB9947 15/13 [16 [24 [ve |G | 95 | Resin EO/PO alkoxylate 13 RDIS124 15/8 [12 [a6 [F |G | 123 | Resin oxyalkylate 13.9 ‘DRi9030 1s |2 [8 [19 [f+ [F | 5.85 | Ester phenolic polymer 78 DRM9510 15/3 [9 |14 [f+ Fe | 40 | Blend 79 DRC232 15 az [18 [21 [Ff (6 | 88 | Oxylated re 143 (CBs6i 1514 [10 [15 [Fe [F | 108 | NPF EO/PO = Conclusion-Final Formulation Cone Water dropping Top oll water] Salt Formulation | mis/minutes we | 19 cut, % content pom_|5 | 10 | 20 | 30 | 40 [60 w,_|w. [| usfem Incumbent 11/22/28 [36/43/48 [s2/ v6 | F [03 [04] 01 | 281 1D1945/D3422X/CB9393 15 | 20| 28] 39/48] 51] 54] VG|G| 01 [02] 01 | 795 (2/2/1), FA 1D3575x/DRM9510/D69393 | 15 |20/ 28] 35/43) 50]/S2| F |G |Oi5/0.2/0.05) 9.55 Qi), F2 3575x/D1936/0B9393 | 15 |20|36|48/ 50/50/52] F |G] 01/02) 01 | 9.79 (2a), F3 Evaluation: The water cut in this plant is 50-56%.better performers are: Cone | Water dropping Salt allel mis/minutes WQ | 1Q_ | content | Chemistry RSN pom | 10 [20 [40 PTB DG270 is [2a [32 [3a [@ |G [51.4 | Modified ester oz D3422X i5_[1.5[5 [36 [F+ [Fr [3.86 | Polyimine alkoxylate 8 DB9392 15/4 [16 [40 [vo |G | 5.12 | PET alkoxylate DP188 15/1/18 [42 [ve [Fe [3.78 | Polyol 16 DEES 150 [6 [33 [F | F+ | 6.32 | Polyethylene amine alkoxy | 6 Evaluation: In the final formulation the bases used were much different, may be the reproducibility of, performance lost or not found in the subsequent tests, which were not presented here by the formulator. The final formulations show good water dropping, low salt content, low top oil BS&W, good water quality (F1) and interface quality.DI945 (amine alkoxylate), D3422X (amine alkoxylate), CB9393 (resin alkoxylate), D3475X (resin alkoxylate), DRM9510 (blend formulation), DI936( polyol) and DB9393 (amine alkoxylate) are the selected bases for the final formulation Here amine alkoxyalte and resin alkoxylate are the blend of formulation, Fl ad F2, and polyol and amine alkoxylate are the blends of F3 formulation. Cone Water dropping Top oll water | Salt Formulation mis/minutes, wa | 19 cut, % content [pom 15 [a0 | 20 | 30 [40 | 60 W,| Ws [a [us/em DI945/D3422x/CB9393__| 15 | 20] 28] 39| 48] 51] 54] VG |G) oi for; oi} 795 (22/1), FA Plant crude oils and selected demulsifier blends [Plant crude oi Slected demulsifier blends z 2 3 Prantl Resin _alkexylate/amine | Polyol/amine alkoxylate alkoxylate Plant 2 Resin alkoxylate/amine | Polyol/ester/amine alkoxylate alkoxylate Plant 3 Resin. alkoxylate/amine | Polyol alkoxylate/amine alkoxylate alkoxylate Plant 4 Resin alkoxylate/ amine | Polyol/resin Polyal/amine alkoxylate alkoxylate alkoxylate/amine alkoxylate Plant 5 Palyol _(RSN22)/polyal (RSN_ 10)/polyol _(RSN 7.5) with sulfonate acid Plant 6 Polyol/amine alkoxylate | Resin alkoxylate/amine alkoxylate Plant 7 Resin alkexylate/amine | Polyol/amine alkoxylate alkoxylate From above data for all gas oil separating plants the demulsifier formulations that performed well in bottle tests (also in subsequent field trials) are blends of resin alkoxylates/amine alkoxylate and polyol/amine alkoxylates. In some cases resin alkoxylate/polyol/amine alkoxylate blend was also working. Esters give added advantage to the blends. Polyols are usually EO/PO co-polymers with multiple hydroxyl end groups. The hydroxyl end groups usually extend to water droplets of medium sized emulsions. Esters are also hydroxyl containing polymers which associate with water by hydrogen bonding. Amine/imine alkoxylates with their extended network functions as treaters that can break even small micro emulsions. The nitrogen in amines like oxygen in polyols can develop different types of association with water molecules using Vander Waals forces. The general concept is that nitrogen and oxygen containing polymers with net work character can break the water-in oil emulsion and flocculate. Some typical formulations for Saudi Crude oils are given below:Sosp/Plnt Formulation aw Material % ‘Aga? 7051 220 | 7036 2 a 1: ‘Abaaigs voi | 20 | p00 2 a L ‘Aloe emasia | 703s | 1706s 2 a 1 ‘nae poss | wasazx | cesa0e 2 2 1 Ain ‘pss | ait | 083303 | Dme 2 2 2[ or inert ess? | a9393 | pane | cnsa0o a a[ avs | 2 ‘name mse | aoa 2 1 ‘Alnaias caczoe | oui | opuse 2 2 1 Hema ‘wos | oso | onoos7_| wizsa a 2 1] os Horst persis | cees | oeoas8 2 a 1 Hora puss | piso | oasasaa a i 1 Heer pass | pio | pea9sin_| wo3s a 2) os] os Heron eve? | o100 | e9298 a a 1 Howaivat2 esos | orsss | as9sia a a 2 Howaivats evea7 | 100 a a 0309 | pra 1 2 2 pasrsx | papier | oeoa92 | wiaveH 1 2 1|_o5, shadgms esese | pes1oo | peasna | nassix 2 a af shadgme cos209 | oe9se2 | oess9s 2 a 1 Uthmainyanae | 89392 | pnoassa_| psaie a a 2 Uthmainiyaiae | 080392 | pagasaa | psarex | p02 | npase 4 4 2| or] o4 Linmainiyanae | 0312 | opes | oss30 | ooo | pao 2 a 1| 02] ars vthmainvana7 | woss | opis | ossisx | ao 4 a ata Uthmsinysras | 89047 | oases | onsa92 2 2 1 Ltnmainyanwo | os9047 | p60383_| x70 2 a 1 vthmainyana | ever | pesos | vaxvo | veaes as alas] oss Uthmainysrino | ops | p10 | oevano a 2 1 Uttmsinivaiaao | ortes | ps10__| oeraso | p03 __| cns209 4 2 1| 02] a3 inmaiivanina | 89393 | ope | ois a al 4 vthmainvanna | 80303 | ones | owas a al 4 Uttmsiniaiva? | 89947 | pno2s2 | pns393 2 2 1 Ltnmalniyaiin2 | 89007 | peo2s2 | veass5 2 2 1 Uthmainyanins | os0sa3 | woss | nsis a 2 2 Uthmainyanins | 89392 | won| onsa92 a 2 2 Sataiye ossisx | woo | vassxa_| os 4 2 1 | on unt evs | oso | cass o2s | 02s 2 Tanai riso26 | 893548 | 400 2 2 1 quite sbusatsn | 39047 | pn0303 | orsozs | wizsan 4 a 2| ooIranian o| The demulsifier formulations were developed for GOSPs having crude oils with API gravity in the range 16-25. The crude oil appeared to contain more asphaltene and very viscous and sticky in nature. The total retention time was 16-24 hours which shows bottle test result conclusion may be time consuming if replicated plant retention time. So the tests were restricted with 1 hour retention time for bottle testing. As the incumbent samples were also tested along with that of vendor's demulsifiers, the results can be comparable. The dry crude oil specification was - salt content < 10PTB, and water (BS&W) <0.5%. As the crude oil was sticky the demulsifiers were dosed at 60°C to have good mixing and distribution. 1. Plant 1 Process Data: Proce Information Quantity Unit Produion Rate ?s000e HD Mash ster 35088 5D Salt init 5120 ppm Free Water il os se Speatiation Sait Cult 3 i Screening valty | Top oF] Sar Sno Format ratio Cone, | Water Qua —Tvater| content ts | “brs 3 —[treumbere= too fo 21 ais a [vender = aoe 2a Las s—[oa0e = 100 Te Lo fae & | 586955/0510 tt |100 [18 02 fo 9 | basoss:osze0s:bs10 [asa /190 [13 17 [428 13 oses:baspia-biose 2115912 a2 Final selection s cone. | water at content S| rome novo | Game, | wate fone |1a | water" on Bt 3 Pncumbent 1 i501 [6 [ria TsEvaluation: The better performed demulsifier bases are given the table with final formulations. D309 was found good water dropper for this crude emulsion. The final formulations were with D309, DB5914 and DI938 Demulsifier base-supplier | Chemistry RSW '309-Croda Ethoxylated phenolic resin 21 DB5914-BASF Tetrol EO/PO. 39. ‘D1938-Marchem Polymeric polyol 72 In this formulation, the demulsifier with RSN7.7 can remain in the organic layer, while demulsifiers with RSN 21 and 39 can quickly move towards emulsion and thus to water. But dosing demulsifier with higher RSN is a negative mark for this formulation which may result in the poor performance of demulsifier while the needed dosage injection can go up during the emulsion breaking process. This shows that bottle test conclusion was not complete with the given timings and available demulsifier bases. In the laboratory the vendor's formulation did better performance than incumbent even at low dosage with high water dropping, salt content and water quality. The interface was not sharp as required. The top oil WS&W was above requirement even though much better than incumbent. 2. Plant 2 Process Data [Process information ‘Quantity Unit Production Rate 112000. BD Wash Water 4480 BD Salt inlet 12690 ppm Free Water inlet 3.6 8% ‘Specification ‘Salt Outlet 2 pam [Water Outlet 0.025 % Demulsifiers and formulation that performed well a Cone.| water [Quality | Top oil ] Salt Formula Ratio water | content No (ppm)| dropping | w | IF cut,% PTB. 1 | Incumbent 100 | 0.8 FF | 0.07 3A 2 | Vendor 1 100 | 0.5 GF for 3.5 3_[ Vendor 2 ‘100 [0.5 GF [0.15 3.6. “| Vendor 3 100 [0.5 GF | 0.05 22 5 | 0309 100 [2.8 GF jo 47 6 _| 01938:0309:089393 100 | 2.2 Fp jot 67, 7 50 [1.2 G ic fo 1.6 3 50 [12 ve_[6_[o 0.7, @_[109955:0309:DB9393 50 [16 ve_[F [0 07Top oil | Salt 4 Formula ratio | cone | water twig | 1g water” | content cuts _| “pre 1 [Tnewmbent 13038 e_te[o a7 2 [Wendor 1 230136. ¢—TeTo 70 3 ps0ess-Da0sBS363 [Tier [100 [38 er 10 25 Evaluation: The final formulation in Plant 2 is a blend of DB9955 D309 and DB9393 Demulsfier base-supplier | Chemisty BSN 309-Croda Ethoxylated phenol resin [21 80985 BASF Resin alkowjate 13555 DB9393-BASF Amine alkoxylate 6.7 | ‘Two resin alkoxylates were blended with amine alkoxylate. RSN range shows a complete distribution from oil to emulsion to water level. Water dropping by this formulation at a lower dosage was better with very good low salt content and top oil BS&W. Water quality for this formulation was good while interface quality was satisfactory. 3. Plant 3 Process data Proceis Infomation ‘Quantity Unit ash ster 4480 ® Salt 12680 om Sait Olt 3 a water Outi 0.025 *. Demulsifier formulations: jualit Top oilSalt $ No| Formula Ratio | Cone [water ONaltt ater eorent (ppm) | dropping | w | IF cut uS/em) 2 [Vendor = fa —f12 ps tos Hare 3 [ose too [os te fe fos es 6 p8s85s:0309:080305 too [os tp fe fos te Final selection wally] Top oak S| Formula Ratio | Conc, | Water | Quali water Fontent cut (uS/em) 1_| Incumbent -2_ 150 1.0 F G 0.1 2.5 2 | 0B9955:0B2903:D510,F2 75 1.0 E G 0.4 10.5 1 [incumvent-3 i0[30 [re [e102 [19 2 o309:08551 485305 75 _[21__[r [6 [oa [es 3-['b309:b85614:0e0353 75 _—[20—[f le 103185Evaluation: There were three flows to be evaluated for the different incumbent formulations. The selected demulsifier bases have the following chemistry. Demulsifier base-supplier | Chemistry RSN 1D309-Croda Ethoxylated phenolic resin 21 DB9955-BASF Resin alkoxylate 13.5-15.5 'D89393-BASF ‘Amine alkoxylate 67 'DB2903-BASF EO/PO block polymer 23 DB5914-BASF Tetrol 39-45 D510-Croda [APF resin alkoxyate 8 F18F2: DB9955(RSN: 14)/DB2903(RSN:23)/D510(RSN:8):resin alkoylate/ EO-PO polymer/Resin alkoxylate This formulation is more weighed towards water soluble area. But presence of D510 in the oil layer can support more emulsion breaking F3: D309 (RSN: 21) /DB5914 (RSN: 40) /DB9393 (RSN: 6.7) phenolic resin/tetrol/amine alkoxylate This formulation has amine alkoxylate which can break small emulsions Crude oils and demulsifier formulations PERE Selected formulations Plant Resin alkoxylate/tetrol/ polyol Plant 2 Resin alkoxylate/resin alkoxylate/amine alkoxylate Plant3-182 | Resin alkoxylate/block polymer Plant 3-3 Resin alkoxylate/tetrol/amine alkoxylate The general formulation for all these crude oil can be considered as resin alkoxylate and polyol (tetrol and EO/PO polymers are polyols by nature). Second formulation is resin alkoxylate with amine alkoxylate. Third one is resin alkoxylate, polyol and amine alkoxylate. Comparison of demulsifier formulations: Saudi oil & Iranian ‘Type. Saudi oil Tran oil 1 Resin alkoxylate/amine alkoxylate | Resin alkoxylate/amine alkoxylate 2 Resin alkoxylate/polyol Resin alkoxylate /polyol 3 Resin alkoxylate/polyol/amine Resin alkoxylate/polyol/amine alkoxylate alkoxylate a Polyol/amine alkoxylate WA 5 Polyol/ester/amine alkoxylate NA, 6 Polyols with RSN ranging from oll | NA solubility to water solubility As concluded above combination of resin alkoxylate with amine alkoxylate, resin alkoxylate with polyols and combination of all three types are the general formulation that works in both oils. The above conclusions are based on the available data. There are other types of demulsifiers with different chemistry (diepoxides, PU demulsifiers, ether polyols, vegetable oil based demulsifiers, sorbitan and starch based demulsifiers, silicone based demulsifiers, 18etc...). Further testing and screening with all types of demulsifiers may give more specific and high performing formulations.