Documentos de Académico
Documentos de Profesional
Documentos de Cultura
(75)
US 7,135,439 B2
Nov. 14, 2006
References Cited
U.S. PATENT DOCUMENTS
Notice:
(87)
PCT Filed:
10/468,862
Jan. 30, 2002
PCT No.:
PCT/NO02/00039
371 (0X1)
(2), (4) Date:
Nov. 5, 2003
EP
EP
EP
WO
0572113
0 769 000
1 022 252
9742272
WO
WO98/08914
(30)
(NO)
................................ .. 20010930
Int. Cl.
C09K 8/03
(2006.01)
507/267; 562/609
See application ?le for complete search history.
12/1993
12/1999
7/2000
11/1997
*
3/1998
* cited by examiner
2/1936
L.L.P.
US 2004/0091408 A1
(52)
(58)
5,804,535 A
6,017,856 A
(65)
(51)
4/1974
(22)
2,030,082 A *
3,801,511 A *
ABSTRACT
agents.
3 Claims, No Drawings
US 7,135,439 B2
1
30, 2002.
The present invention relates to free-?oWing products
comprising potassium formate as the main component.
particles.
ing mud and completion ?uid in the oil and gas industry,
Within de-icing of airport runWays and as secondary coolant.
For the above applications it is often required that the
K-formate is delivered as a dry, free-?oWing product. Spe
cially Within the gas and oil industry this requirement has
25
30
35
product.
40
EXAMPLE 1
45
requirements:
Said agent shall preferably have loWer equilibrium
50
55
9*11).
60
temperatures.
Was used.
65
US 7,135,439 B2
4
EXAMPLE 2
TABLE 1
Product
test
temperature
Relative
humidity
recorded
Equilibrium
Water partial
pressure
Component
C.
% Rh
mbar
Potassium Formate
Lithium Carbonate
Lithium Bromide
Sodium Carbonate
Sodium BenZoate
23
23.4
23.9
25.6
23.5
16
43.5
10.3
23.7
26.6
4.6
12.4
3.0
7.7
7.7
Sodium Hydroxide
Disodium Phosphate*2 H2O
23.6
23.7
10.2
23.2
2.9
6.7
Potassium Carbonate
Potassium Bromide
24.0
23.1
10.3
57.0
3.0
16.0
Potassium Hydroxide
Potassium Thiocyanate
23.6
24.8
10.2
44.5
2.9
13.8
Potassium Acetate
Potassium/Sodium tatrate
Potassium Sorbate
23.8
23.8
23.8
16.1
37.0
23.5
4.7
10.8
6.9
23.3
23.9
22.8
23.9
23.8
22.5
23.1
11.3
10.4
10.3
63.7
24.5
13.2
17.4
3.2
3.1
2.8
18.7
7.2
3.5
4.9
23.3
23.3
42.8
37
12.6
11
23.9
24.1
46.7
38.9
13.7
11.6
Starch Caccava
Starch SP1
23.7
23.7
39.6
37.9
11.5
11.5
Mixture
K-Formate, fresh dried and
20 unconditioned
Calcium Formate, dry and
16.7 r 0.14 *
FloW time
Opening 22 mm
seconds
6.90 r 0.14 *
16.78 1 0.52
7.15 r 0.08
12.36 1 0.18
4.53 r 0.06
11.18 1 0.01
4.54 r 0.04
12.22 1 0.03
4.52 r 0.05
13.15 1 0.04
4.88 r 0.06
13.80 1 0.05
6.82 r 0.07
13.20 1 0.04
4.87 r 0.14
unconditioned
K-Formate + 1.5% Lithium
Bromide.
K-Formate + 3.0% Lithium
25 Bromide
K-Formate + 1.5% Potassium
Degussa)
Carbonate.
K-Formate + 3.0% Potassium
Carbonate
K-Formate + 1.5% Potassium
30
Hydroxide
K-Formate + 3.0% Potassium
Hydroxide
No How
No How
11.40 1 0.10
4.78 r 0.20
12.17 1 0.06
4.61 r 0.11 *
12.36 1 0.17
4.76 r 0.02
12.06 1 0.01
5.00 r 0.01
11.90 1 0.08
4.66 r 0.01
12.13 1 0.06
4.30 r 0.07 *
13.14 1 0.07
4.67 r 0.04 *
11.75 1 0.04
4.50 r 0.01
12.36 1 0.17
4.76 r 0.02
14.27 1 0.03
15.06 1 0.05
5.21 r 0.02
5.58 r 0.02
FloW impossible
FloW impossible
FloW impossible
FloW impossible
Acetate
35 K-Formate + 1.5% Pot./Sodium
tatrate
K-Formate + 3.0% Pot./Sodium
tatrate
K-Formate + 1.5% Sodium
Carbonate
40 K-Formate + 3.0% Sodium
Carbonate
K-Formate + 1.5% DiSodium
Phosphate
Phosphate
product.
Chloride
K-Formate + 3.0% Calcium
Chloride
50
K-Formate
K-Formate
K-Formate
K-Formate
K-Formate
K-Formate
+
+
+
+
+
+
1.5% Sipernate 22
3.0% Sipernate 22
1.5% Glucose
3% Glucose
1.5% Sucrose
3% Sucrose
14.63 1 1.52 *
14.25 1 1.20 *
6.75 r 0.354
6.75 r 0.495
55
65
US 7,135,439 B2
5
TABLE 3-continued
Average
hardening Hardening
detected in Table 2.
Some of the crystal product mixes in Table 2 that did not
ful?l the vapor pressure requirement in Table 1, Were
Sample
20
25
35
40
number
limit
<5
<5
2.6
1
86.4
67.0
<5
<5
<5
<5
+
+
+
+
1.5%
3.0%
1.5%
3.0%
<5
Caking
<5
No caking
0
0
0
2.3
0
<5
<5
<5
<5
<5
No
No
No
No
No
22.2
14.8
20.1
27.1
55.5
<5
<5
<5
<5
<5
Caking
Caking
Caking
Caking
Caking
+ 3.0% Sodium
92.1
<5
Caking
+ 1.5% Disodium
50.5
<5
Caking
56.9
<5
Caking
Caking
Pot. Acetate
Pot. Acetate
Lithium Bromide
Lithium Bromide
Sodium
caking
caking
caking
caking
caking
Phosphate
46.6
<5
50
laboratory.
Results
The results are presented in Table 4 and shoW dissolution
TABLE 4
Sp. gr. before
upgrade kg/l
upgrade kg/l
pH
Results
1.523
1.586
12.9
Clear brine
K-formate + 1.5%
1.523
1.587
11.6
Clear brine
LiBr
K-formate + 1.5%
1.523
1.584
11.5
Precipitate
1.523
1.585
15.4
Clear brine
Dry Product
60
K-formate + 1.5%
CaCl2
tatrate
tatrate
K2CO3
Phosphate
K-Formate + 1.5% Sodium/Pot.
No caking
No caking
Caking
Caking
1.5%
3.0%
1.5%
3.0%
1.5%
D-Sucrose
D-Sucrose
Sipernate 22
Sipernate 22
Comment
24
+
+
+
+
+
Caking
69.2
110.3
EXAMPLE 4
K-Formate
K-Formate
K-Formate
K-Formate
K-Formate
Carbonate
K-Formate
Carbonate
K-Formate
Caking
45
Average
hardening Hardening
K-Formate unconditioned
<5
TABLE 3
Sample
13.6
data in the hardening test. The tWo other agents tested With
Caking
dling.
30
<5
Way:
14.3
Comment
limit
shoWn in Table 3.
Test samples (approx. 100 g) as presented in Table 3 Were
number
31.6
<5
Caking
65 K-formate + 1.5%
KOH
US 7,135,439 B2
Dry Product
K-formate + 1.5%
Sucrose
TABLE 4-continued
upgrade kg/l
upgrade kg/l
pH
Results
1.523
1.58
10.5
Precipitate
15