MIXING MANUAL

Section
I-B-6
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Product
HCl-HF
Date
5/1/98
Revision
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GENERAL INFORMATION
HCl-HF (hydrochloric-hydrofluoric) Acid solutions are applicable for use in most sandstone
reservoirs where wellbore cleaning or near-wellbore matrix stimulation is desired. Various
concentrations of HCl-HF solutions can be used, depending upon the type of damage to be removed
and the nature of the formation.
Most sandstone formations are composed of sand quartz particles (silica, SiO
2
) bonded together by
various amounts of cementing material including carbonates (calcite) and clay minerals (silicates).
The amount of reaction a sandstone will have with HCl, acetic and formic acids is primarily limited
by the amount of carbonate material present in the formation. These three acids do not have any
appreciable reaction with quartz or silicates. HF acid behaves similarly to these acids; that is, it
reacts with carbonates in the same way as HCl does. However, it also has the ability to react with
silicates, which include clay, silt, shale, sand and other solids present in typical drilling muds. For
this reason, HF Acid is the most widely used acid system for stimulating sandstone reservoirs.
The reaction of HF acid with silicates produces fluosilicic acid, which, in the presence of certain
metal ions, can result in secondary precipitation problems. For example, the sodium and potassium
salts of fluosilicic acid are highly insoluble, gelatinous precipitates capable of plugging pores of the
reservoir. Such problems can be controlled by using proper preflush and overflush fluids in the
treatment.
Appropriate non-emulsifying agents can be added to acid solutions to provide low surface tension
properties and prevent emulsion. The proper kind and amount of non-emulsifier is best determined
by conducting emulsion prevention tests with the oil from the zone to be treated and the treating
fluid.
MATERIALS USED
The HF acid portion may be prepared using Ammonium bifluoride salt (ABF), a liquid solution of
Ammonium fluoride (AF) or in some rare cases, an aqueous solution of Hydrofluoric Acid (20 to
70%). This liquid HF is not used in most locations due to the extreme safety concerns. Tables are
included which provide information on how to prepare various mixtures of HCl:HF with both ABF
and AF.
Acid corrosion inhibitors are added to HCl-HF Acid solutions to protect well equipment. Inhibitors CI-
23 and CI-25 can be used, and for proper concentration, refer to the loading schedules for these
products in Section I-C.
Ammonium bifluoride can be used to prepare acid mixtures up to 15% HCl-6% HF. Ammonium
fluoride (36%) solution can be used to prepare HCl-HF acid mixtures up to 15% HCl-4% HF. If a HF
concentration higher than 4 % is required, laboratory tests should be conducted. At temperatures
of 64EF (17.8EC) or lower ammonium chloride salt may precipitate out of solution at HF
concentrations higher than 4% prepared with Ammonium fluoride.
The use of alcohol (Methanol) as an additive in HCl-HF acid systems is often required. Since the
addition of alcohol reduces the volume of mixing water presence, the overall solubility of the reaction
products formed by reacting ABF or AF with HCl are also reduced. Due to this condition there are
limits on how much alcohol can be added to the various HCl-HF acid solutions without causing
ammonium chloride precipitation.
NOTE: The precipitate that forms, ammonium chloride, is water soluble and would probably be
dissolved in the 3% ammonium chloride displacement fluid. The major problem would be
the potential plugging of the filters or valves during the acid job .
MAXIMUM ALCOHOL CONCENTRATION THAT CAN BE USED IN HCl-HF
MIXING MANUAL
Section
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Product
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HF Source
Maximum Alcohol (%)
@ 64E EF (17.8E EC)
Maximum Acid
%HCl %HF
Ammonium bifluoride 20 15 4
Ammonium bifluoride 30 14 3
Ammonium fluoride 20 12* 3
Ammonium fluoride 30 7.5 1.5
NOTE: * A small amount of solids began to form in the 12%-3% HCl-HF between 64 and
67E EF (17.8 and 19.4E EC).
CORROSION INHIBITORS
Consult the corrosion inhibitor section of the Mixing Manual or the Regional Technical Manger for
the proper concentration and type of inhibitor and intensifier needed.
PHYSICAL PROPERTIES
AMMONIUM BIFLUORIDE
Description - White crystals or flakes
Odor - Odorless
Sp. Gravity - 1.5
Solubility - 58.3 grams per 100 grams of water
pH - Between 4 and 5 in water
AMMONIUM FLUORIDE
Description - Clear to slightly cloudy liquid
Odor - Odorless
Sp. Gravity - 1.09 to 1.11 ( 36 % solution )
Solubility - 100% in water
pH - 7 to 7.7
Freezing Point- (-9 )EF or (-22.7)EC
MIXING PROCEDURE
1. Put all of the water needed to mix the required volume and concentration of HCl into the mixing
tank.
2. While stirring the water, add the required amount of inhibitor and other additives.
3. Continue agitation of the liquid in the tank and add the required amount of Ammonium biflouride
or Ammonium flouride. Agitate until it is completely dissolved.
4. Add raw acid to make 1000 gallons total.
5. Agitate final mixture until it is uniform.
MIXING MANUAL
Section
I-B-6
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Product
HCl-HF
Date
5/1/98
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Example
Acid needed for job: 12:3 HCl:HF, 500 gals.
Raw acid available: 22E Baume HCl (35.21%)
Well BHT: 180EF (82.2EC)
Pumping time (allowing for contingencies): 6 hours
HCl required: In Table I, find the suitable final HCl concentration = 12.0%.
Using the left column, find the final concentration of HF required.
On line "3" in column is the concentration of HCl required: 15.4% HCl required: 959 gallons.
In the last column the amount of ammonium bifluoride required is shown: 384 lbs.
Using the following equation, the volume of 22EBe' HCl required to prepare 959 gallons of 15.4% HCl
can be calculated:
Gals strong acid to make 1000 gals weak acid = (Vol. wk acid) (Sp.Gr. wk acid) (% wk acid
(Sp.Gr. strong acid) (% strong acid)
Gals of 22EBe HCl = (959) (1.0770) (15.4) = 383 gals.
(1.1789) (35.21)
The amount of water required is 959 - 383 = 576 gallons
The inhibitor requirement from Table II is 2 gpt of CI-25.
The above amounts will make 1000 gallons, so for the 500 gallons needed, each amount should be
multiplied by 500/1000.
MIXING PROCEDURE EXAMPLE
1. Place 288 gallons of water into the mixing tank.
2. While stirring the water, add one gallon CI-25.
3. Continue stirring the tank contents and add 192 lbs Ammonium BiFlouride.
4. After the Ammonium BiFlouride is completely dissolved, add 192 gallons of 22EBe HCl.
Continue stirring during this addition.
5. Agitate the final mixture until it is uniformly mixed.
MIXING MANUAL
Section
I-B-6
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Product
HCl-HF
Date
5/1/98
Revision
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TABLE I
MIX PROPORTIONS FOR HYDROCHLORIC - HYDROFLUORIC ACID
PREPARED WITH AMMONIUM BIFLUORIDE (ABF) AS HF SOURCE BASIS:
1000 GALLONS OF FINAL MIX
FINAL HF
CONC. %
HCl
%
REQUIRED
Gallons
ABF
LBS.
FINAL HF
CONC. %
HCl
%
REQUIRED
Gallons
ABF
LBS.
Final HCl Conc = 7.5% Final HCl Conc = 10%
1
2
3
4
5
6
7
8.5
9.6
10.7
11.8
13.0
14.2
15.4
985.
972.
960.
948.
935.
922.
908.
123.
249.
376.
506.
637.
770.
904.
1
2
3
4
5
6
7
11.1
12.2
13.3
14.5
15.7
16.9
18.2
984.
972.
959.
947.
934.
920.
907.
125.
252.
381.
511.
644.
779.
914.
Final HCl Conc = 11% Final HCl Conc = 12%
1
2
3
4
5
6
7
12.1
13.2
14.3
15.5
16.7
18.0
19.3
984.
972.
959.
946.
933.
920.
906.
125.
253.
383.
514.
647.
782.
918.
1
2
3
4
5
6
7
13.1
14.2
15.4
16.6
17.8
19.1
20.4
984.
971.
959.
946.
933.
919.
906.
126.
254.
384.
516.
650.
785.
922.
Final HCl Conc = 13% Final HCl Conc = 14%
1
2
3
4
5
6
7
14.1
15.3
16.4
17.6
18.9
20.2
21.5
983.
971.
958.
945.
932.
919.
905.
128.
255.
386.
518.
652.
788.
927.
1
2
3
4
5
6
7
15.1
16.3
17.5
18.7
20.0
21.3
22.6
983.
971.
958.
948.
932.
918.
905.
127.
256.
388.
521.
656.
792.
931.
Final HCl Conc = 15% Final HCl Conc = 16%
1
2
3
4
5
6
7
16.1
17.3
18.5
19.8
21.1
22.4
23.7
983.
971.
958.
945.
931.
918.
904.
128.
257.
390.
523.
658.
796.
935.
1
2
3
4
5
6
7
17.2
18.3
19.6
20.8
22.1
23.5
24.9
983.
970.
957.
944.
931.
917.
903.
128.
259.
392.
525.
662.
799.
939.
MIXING MANUAL
Section
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Product
HCl-HF
Date
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Revision
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TABLE II
MIX PROPORTIONS FOR HYDROCHLORIC - HYDROFLUORIC ACID
PREPARED WITH AMMONIUM BIFLUORIDE (ABF) AS HF SOURCE BASIS:
1000 GALLONS OF FINAL MIX
FINAL HCl
CONC. %
FINAL HF
CONC. %
WATER
Gallons
ABF
Pounds
22 E EBe HCl
Gallons
6.0
6.0
6.0
6.0
6.0
6.0
0.5
1.0
1.5
2.0
2.5
3.0
836
818
800
782
764
746
61
123
185
248
311
375
161
173
185
197
209
221
6.5
6.5
6.5
6.5
6.5
6.5
0.5
1.0
1.5
2.0
2.5
3.0
823
805
787
769
751
732
61
123
186
249
312
376
173
185
198
210
222
234
7.5
7.5
7.5
7.5
7.5
7.5
7.5
0.5
1.0
1.5
2.0
2.5
3.0
3.5
797
779
761
743
724
706
687
62
124
187
250
313
378
422
199
212
224
236
249
261
274
9.0
9.0
9.0
9.0
9.0
9.0
9.0
9.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
758
740
722
703
684
665
646
627
62
125
188
252
316
380
445
510
239
251
263
276
289
301
314
327
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
732
714
695
676
657
638
619
599
580
560
63
125
189
253
317
382
447
513
579
646
265
278
290
303
316
329
342
355
368
381
MIXING MANUAL
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Product
HCl-HF
Date
5/1/98
Revision
1
FINAL HCl
CONC. %
FINAL HF
CONC. %
WATER
Gallons
ABF
Pounds
22 E EBe HCl
Gallons
Confidential
12.0
12.0
12.0
12.0
12.0
12.0
12.0
12.0
12.0
12.0
12.0
12.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
678
660
641
621
602
582
563
543
523
503
482
462
63
127
191
255
320
385
451
517
584
651
719
787
319
331
344
357
371
384
397
410
424
437
451
465
13.0
13.0
13.0
13.0
13.0
13.0
13.0
13.0
13.0
13.0
13.0
13.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
651
632
613
594
574
554
534
514
494
474
453
433
63
127
192
256
321
387
453
520
587
654
722
791
346
359
372
385
398
412
425
439
452
466
480
493
14.0
14.0
14.0
14.0
14.0
14.0
14.0
14.0
14.0
14.0
14.0
14.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
624
605
585
566
546
526
506
485
465
444
424
403
64
128
192
257
323
389
455
522
589
657
725
794
373
386
400
413
426
440
467
481
494
508
522
535
15.0
15.0
15.0
15.0
15.0
15.0
15.0
15.0
15.0
15.0
15.0
15.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
596
577
557
537
517
497
476
456
435
415
394
372
64
128
193
259
324
391
457
524
592
660
729
798
400
414
427
441
454
468
482
496
509
524
537
552
MIXING MANUAL
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Product
HCl-HF
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5/1/98
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TABLE III
MIX PROPORTIONS FOR HYDROCHLORIC - HYDROFLUORIC ACID
PREPARED WITH LIQUID AMMONIUM FLUORIDE (AF) AS HF SOURCE BASIS:
1000 GALLONS OF FINAL MIX
FINAL HCl
CONC %
FINAL HF
CONC %
WATER
Gallons
AF (36%)
Gallons
22 E EBe HCl
Gallons
6.0
6.0
6.0
6.0
6.0
6.0
0.5
1.0
1.5
2.0
2.5
3.0
804
756
707
658
608
557
24
48
73
98
123
149
172
196
220
244
269
294
6.5
6.5
6.5
6.5
6.5
6.5
0.5
1.0
1.5
2.0
2.5
3.0
791
743
694
644
594
543
24
48
73
98
123
149
185
209
233
258
283
308
7.5
7.5
7.5
7.5
7.5
7.5
7.5
0.5
1.0
1.5
2.0
2.5
3.0
3.5
765
717
667
617
566
515
463
24
48
73
98
124
150
176
211
235
260
285
310
335
361
9.0
9.0
9.0
9.0
9.0
9.0
9.0
9.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
726
677
627
576
525
473
420
366
24
49
73
99
124
150
177
204
250
274
300
325
351
377
403
430
MIXING MANUAL
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Product
HCl-HF
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Revision
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FINAL HCl
CONC %
FINAL HF
CONC %
WATER
Gallons
AF (36%)
Gallons
22 E EBe HCl
Gallons
Confidential
10.0
10.0
10.0
10.0
10.0
10.0
10.0
10.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
699
650
599
548
496
444
391
337
24
49
74
99
125
151
178
204
277
301
327
353
379
405
431
459
12.0
12.0
12.0
12.0
12.0
12.0
12.0
12.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
645
595
544
492
439
385
332
276
25
49
75
100
126
153
179
207
330
356
381
408
435
462
489
517
13.0
13.0
13.0
13.0
13.0
13.0
13.0
13.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
618
567
515
463
410
356
302
246
25
50
75
101
127
153
180
208
357
383
410
436
463
491
518
546
14.0
14.0
14.0
14.0
14.0
14.0
14.0
14.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
590
539
487
434
381
326
271
215
25
50
75
101
127
154
181
209
385
411
438
465
492
520
548
576
15.0
15.0
15.0
15.0
15.0
15.0
15.0
15.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
563
511
458
405
351
296
241
184
25
50
76
102
128
155
182
210
412
439
466
493
521
549
577
606
MIXING MANUAL
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Product
HCl-HF
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5/1/98
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Confidential
(A ) ' % HF desired x 5.143 ' Lbs of NH
4
F per 100 lbs of final HCl&HF acid mixture
(B) '
Lbs of NH
4
F calculated in (A)
Density (lbs/gal of the solution of NH
4
F)
(A) in lbs
( 9.26 lbs/gal
' gals of NH
4
F per 100 lbs of HCl&HF mixture
( 9.26 density of 36% NH
4
F solution
(C ) '
% HF desired x 1.822 % HCl desired
% HCl acid used to prepare HCl&HF mixture
x 100 '
lbs of HCl required
per 100 lbs of HCl&HF mixture
(D ) '
Lbs of HCl calculated in (C)
Density in lbs/gal of % HCl used to prepare HCl&HF mixture
(C ) lbs
(Density of HCl
(lbs/gal)
' Gals of HCl required per 100 lbs of HCl&HF mixture
(Density of HCl used to prepare HCl&HF acid solution
(E ) ' 100 lbs & (A%C ) '
Lbs of water (H
2
O) required
per 100 lbs of HCl&HF mixture
Method for Calculating the Amount of Ammonium Fluoride and Hydrochloric Acid
Required to Prepare Various HCl-HF Acid Mixtures
The following equations listed below are used to determine the amounts of:
1) Ammonium Fluoride (NH
4
F) Required
2) Hydrochloric Acid (HCl) Required
3) Dilution Water (H
2
O) Required
Equations
or,
or,
MIXING MANUAL
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Product
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Confidential
(F ) '
(E ) lbs
Density of H
2
O in lbs/gal
' Gals of H
2
O required per 100 lbs of HCl&HF mixture
(G ) '
1000
(B) %(D)%(F )
' Volume Correction Factor
(H ) ' (G) x (B) ' Gals of NH
4
F required for 1000 gals of HCl&HF mixture
(I) '(G) x (D) ' Gals of HCl required for 1000 gals of HCl HF mixture
(J) ' (G) x (F) ' Gals of H
2
O required for 1000 gals of HCl&HF mixture
(A) % HF desired x 5.143 ' 3 x 5.143 '
15.429 lbs of NH
4
F
per 100 gals of acid solution
(B) '
Lbs NH
4
F from Eq. (A)
Density of the 36% NH
4
F solution)
15.429 lbs
9.26 lbs/gal
' 1.67 gal of 36% NH
4
F
(C)
% HF desired x 1.822 % HCl desired
% HCl used in preparing the HCl&HF mixture
x 100
(3 x 1.822 % 12)
35.2
x 100 ' 49.619 lbs of HCl
EXAMPLE:
Raw HCl in stock: 22Be
From mixing manual 22Be=35.2% HCl
Sp.Gr. = 1.179 or 1.179 x 8.33 = (9.821 lbs/gal)
Ammonium Fluoride in stock: 36% (NH
4
F)
Sp.Gr.= 1.110
Calculate amount of raw HCl (22Be) + Ammonium Fluoride required for 1000 gallons of
12% HCl-3% HF
or,
[Therefore, 1.67 gallons of 36% NH
4
F is required to prepare 100 lbs of the HCl-HF acid solution]
or,
MIXING MANUAL
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Product
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Confidential
(D)
Lbs of HCl calculated Eq. (C)
Density of the concentrated HCl
'
49.619 lbs
9.821 lbs/gal
' 5.052 gals of 22Be HCl Acid
(E) 100 lbs & (A%C) ' Lbs of H
2
O required for 100 lbs of acid solution
100 lbs & (15.429 lbs % 49.619 lbs) ' 100 lbs &65.048 lbs '34.952 lbs
(F)
Lbs of water Eq. (E)
Density of water
34.952 lbs
8.33 lbs/gal
' 4.196 gallons of water per 100 lbs of acid
(G) Volume Correction Factor '
1000
(B)%(D)%(F)
or,
[Therefore, 5.052 gallons of 22Be HCl is required to mix 100 lbs of the HCl-HF acid solution]
or,
or,
[Therefore, 4.196 gallons of water is required to prepare 100 lbs of the HCl-HF acid solution]
MIXING MANUAL
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Product
HCl-HF
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5/1/98
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Confidential
1000 gals
(1.67)%(5.052)%(4.196) gals
'
1000 gals
10.918 gals
' 91.592
(G) x (B) ' (91.592)(1.67gal) ' 152.959 gals
(G) x (D) ' (91.592)(5.052gals) ' 462.723 gals
(G) x(F) ' (91.592) (4.196 gals) ' 384.320 gals
or,
[Therefore, the volume correction factor to convert the amount of gallons required per 100 lbs to the
amount of gallons required per 1000 gallons was calculated to be 91.592)
(H) Amount of gallons of Ammonium Fluoride 36% required per 1000 gallons of the 12%
HCl-3% HF acid solution:
(I) Amount of gallons of conc. 22Be HCl acid required per 1000 gallons of the 12%
HCl-3% HF acid solution:
(J) Amount of gallons of water (H
2
O) required per 1000 gallons of the 12% HCl-3% HF
acid solution:
Results:
Materials Required for 1000 gallons of 12% HCl-3% HF
Water - 384.320 gallons
Ammonium Fluoride (36%) - 152.959 gallons
HCl (22Be) - 462.723 gallons