GB2088839A - Borate Sequestered Vanadium Solutions - Google Patents
Borate Sequestered Vanadium Solutions Download PDFInfo
- Publication number
- GB2088839A GB2088839A GB8039130A GB8039130A GB2088839A GB 2088839 A GB2088839 A GB 2088839A GB 8039130 A GB8039130 A GB 8039130A GB 8039130 A GB8039130 A GB 8039130A GB 2088839 A GB2088839 A GB 2088839A
- Authority
- GB
- United Kingdom
- Prior art keywords
- borate
- vanadium
- sequestered
- ratio
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 30
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 7
- PTKWYSNDTXDBIZ-UHFFFAOYSA-N 9,10-dioxoanthracene-1,2-disulfonic acid Chemical compound C1=CC=C2C(=O)C3=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC=C3C(=O)C2=C1 PTKWYSNDTXDBIZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 7
- 229910021538 borax Inorganic materials 0.000 claims description 4
- 239000004328 sodium tetraborate Substances 0.000 claims description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 13
- 239000012670 alkaline solution Substances 0.000 abstract description 3
- 239000003352 sequestering agent Substances 0.000 description 6
- 150000001642 boronic acid derivatives Chemical class 0.000 description 5
- 230000003139 buffering effect Effects 0.000 description 5
- 238000010405 reoxidation reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- PSDQQCXQSWHCRN-UHFFFAOYSA-N vanadium(4+) Chemical compound [V+4] PSDQQCXQSWHCRN-UHFFFAOYSA-N 0.000 description 2
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical class O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229940063013 borate ion Drugs 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
Sequestered vanadium solutions comprise an aqueous solution of a metal or ammonium vanadate in a concentration of from 1 to 5 gm/litre together with a borate in which the ratio of vanadium to borate is from 2.0:1 to 3.0:1. Alkaline solutions of such borate sequestered vanadium together with at least one salt of an anthraquinone disulphonic acid may be used in the Stretford Process for the removal of hydrogen sulphide from gases or non-polar liquids.
Description
SPECIFICATION
Borate Sequestered Vanadium Solutions
This invention relates to sequestering or chelating agents, more particularly the invention relates sequestrants for use in redox systems employed for the removal of hydrogen sulphide from gases and non-polar liquids.
In U.K. Patent Specification No. 948270, there is described a process (known as the Stretford
Process) for removing hydrogen sulphide from gases or non-polar liquids wherein inter alia the gas is contacted with a redox system comprising an aqueous alkaline solution of a mixture of anthraquinone disulphonic acid salt and an alkali metal or ammonium vanadate. This aqueous alkaline solution is otherwise known as a "Stretform Liquor". In addition to the active redox constituents the Stretford Liquor may contain pH buffering agents to maintain the desired level of alkalinity and sequestrants to maintain the vanadium component in solution. Typical buffering agents include borax in a concentration of from about 5 to 10. gm/litre (calculated as
Na2B40,) and typical sequestrants which have been used include citrates and EDTA compositions.
We have surprisingly found that borates have a beneficial sequestering effect upon vanadium in concentrations outside of those required for pH buffering purposes.
Sequestering compounds which contain boron are known. For example U.S. Patent Nos.
3539463 and 3539464 describe the use of borate esters of sodium B-glucoheptonate as sequestrants for alumina and U.S. Patent No.
3852213 describes compositions comprising a copolymer of polyvinyl methyl ether and maleic anhydride and from 3~30% of a borate for use in chelating calcium, magnesium, iron or manganese ions.
However, the use of borates alone for chelating vanadium is not known.
In accordance with the present invention there is provided a chelated vanadium aqueous solution comprising a metal or ammonium vanadate and a water soluble borate wherein the concentration of vanadium in solution is from 1 to 5 gms/litre and the ratio of vanadium to borate is from 2.0:1 to 3.0:1.
The vanadate may be added as an ortho-, meta-, or pyrovanadate. The borate may be added in the form of a tetra-borate, borax being a conveniently available form. Alternative sources of borate ion may be used for example, sodium meta borate.
The invention is particularly useful for the chelation of vanadium in Stretford Liquors and the presence of borates has a beneficial effect upon the operation of the Stretford Process in that vanadium loss can be eliminated or substantially reduced.
Thus the present invention further provides a process for the removal of hydrogen sulphide from gases or non-polar liquids wherein said gas or liquid is contacted with an aqueous alkaline wash liquor comprising at least one salt of an anthraquinone disulphonic acid a vanadate, wherein the concentration of vanadium in the liquor is from 1 to 5 gms/litre and a borate wherein the ratio of vanadium to borate is from 2.0:1 to 3.0:1.
For typical Stretford application the vanadium to borate ratio is preferably about 2.5:1.
The present invention will be illustrated by the following Example in conjunction with the accompanying drawings, in which:
Figure 1 is a graph showing the effect of borates on the buffering capacity of Stretford
Solutions,
Figure 2 is a graph showing the effect of borate on the reoxidation of the Stretford Liquor during the oxidation phase of the redox cycle, and
Figure 3 is a graph showing the effect of borate as a sequestrant for vanadium.
A Stretford Solution precursor was prepared containing:
5 gm/l Na2C03-25 gm/l NaHCO3-pH 8.85
4 gm/I-sodium anthraquinone disulphonate M/32-sodium meta-vanadate (1.7 gm/l-- vanadium)
a) To each of six samples of the precursor solution was added borax (Na2B4O7) to give the following respective amounts of borate.
Borate
Concentration V:B 20 7 ratio (i) O gm/l.
(ii) 2.7gm/l. 2.5:1 (iii) 3.8gm/l. 1.76:1 (iv) 5.0gm/l. 1.32:1 (v) 10.gm/l. 0.66:1 (vi) 15.gm/l. 0.44:1
The acidity of each solution was increased by adding dilute sulphuric acid and the pH measured against increase in acidity. The results of plotting pH change against increase in acidity are shown in Figure 1.
The working pH range for Stretford Liquors is from pH 8.6 to pH 8.85. Thus from a consideration of Figure lit will be apparent that only solutions (v) and (vi) can provide adequate buffering whereas say solution (ii) has little buffering effect.
B) Each of solutions (i), (ii), (iv) and (v) was employed in a redox system wherein each solution was loaded with hydrogen sulphide to a level of 0.5 gm/l and left to stand for 10 minutes.
At the end of the standing period air was blown into the samples for 40 minutes at a rate of 80 mi/min.
During the air-blowing each sample was analysed at intervals to determine the amount of vanadium being reoxidised from vanadium (IV) (vanadium (V) was present prior to H2S loading but was reduced to vanadium (IV) on addition of
H2S). The amount of reoxidized vanadium is expressed as a percentage of the V present prior to commencement of H25 loading and is shown plotted against the reoxidation time in Figure 2. It will be seen from Figure 2 that 100% reoxidation can be achieved in 30 minutes with Stretford
Liquors containing 2.7 gm/l borate whereas with those solutions having effective pH buffering action the reoxidiation rates are only of the order of 80% at completion of the reoxidation period.
c) Three Stretford Liquors, each comprising the precursor, as described above, and respectively, 0.0 gum/1,1.35 gm/l and 2.7 gm/l of borate were subjected to H2S loading (reduction) for 25 minutes and allowed to stand under reduced conditions, samples being extracted periodically and analysed for total vanadium content. The vanadium loss (calculated as a percentage) was plotted against time and results shown in the graph of Figure 3. It will be noted that the V:B4O7 ratios for the samples containing 1.35 and 2.7 gm/i borate were 5:1 and 2.5:1 respectively.
From a review of the results given in Figure 3, it will be appreciated that significant vanadium loss can be prevented using V:B4O7 ratios in accordance with the invention and it will be seen that several advantages accrue to the Stretford
Process in that (a) Vanadium loss is significantly reduced and (b) Effectively complete reoxidation can be speedily achieved.
Claims (5)
1. A chelated vanadium composition comprising an aqueous solution of a metal or ammonium vanadate wherein the concentration of vanadium is from 1 to 5 gm/litre and a water soluble borate wherein the ratio of vanadium to borate is from 2.0:1 to 3.0:1.
2. A composition as claimed in Claim 1 wherein the borate is borax.
3. A composition as claimed in Claim 1 or
Claim 2 which also contains at least one salt of an anthraquinone disulphonic acid and has an alkaline pH.
4. A composition as claimed in any of Claims 1 to 3 wherein the vanadium to borate ratio is about 2.5:1.
5. A process for the removal of hydrogen sulphide from gases or non-polar liquids wherein said gas or liquid is contacted with an aqueous alkaline wash liquor comprising at least one salt of an anthraquinone disulphonic acid, a vanadate, wherein the concentration of vanadium in the liquor is from 1 to 5 gm/litre and a borate, wherein the ratio of vanadium to borate is from 2.0:1 to 3.0:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8039130A GB2088839B (en) | 1980-12-05 | 1980-12-05 | Borate sequestered vanadium solutions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8039130A GB2088839B (en) | 1980-12-05 | 1980-12-05 | Borate sequestered vanadium solutions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2088839A true GB2088839A (en) | 1982-06-16 |
| GB2088839B GB2088839B (en) | 1984-03-21 |
Family
ID=10517789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8039130A Expired GB2088839B (en) | 1980-12-05 | 1980-12-05 | Borate sequestered vanadium solutions |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2088839B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4460554A (en) * | 1983-03-31 | 1984-07-17 | Purtec Systems, Inc. | Method of removing H2 S from a gas stream utilizing boron-vanadium, quinone solution and iron scavaging composition |
| US5004588A (en) * | 1988-01-15 | 1991-04-02 | Chevron Research & Technology Company | Process for removal of hydrogen sulfide from gaseous stream |
-
1980
- 1980-12-05 GB GB8039130A patent/GB2088839B/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4460554A (en) * | 1983-03-31 | 1984-07-17 | Purtec Systems, Inc. | Method of removing H2 S from a gas stream utilizing boron-vanadium, quinone solution and iron scavaging composition |
| US5004588A (en) * | 1988-01-15 | 1991-04-02 | Chevron Research & Technology Company | Process for removal of hydrogen sulfide from gaseous stream |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2088839B (en) | 1984-03-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |