CN1087192C - Hydration-resisting and sulfur-resisting conversion catalyst and its preparation - Google Patents
Hydration-resisting and sulfur-resisting conversion catalyst and its preparation Download PDFInfo
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- CN1087192C CN1087192C CN98110348A CN98110348A CN1087192C CN 1087192 C CN1087192 C CN 1087192C CN 98110348 A CN98110348 A CN 98110348A CN 98110348 A CN98110348 A CN 98110348A CN 1087192 C CN1087192 C CN 1087192C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to a hydration-resisting sulphur-resisting conversion catalyst and a preparation method thereof. The hydration-resisting sulphur-resisting conversion catalyst adopts the compounds of cobalt and molybdenum as active components, and adopts alkali metal compounds as auxiliary agents; the carrier of the hydration-resisting sulphur-resisting conversion catalyst adopts the compounds of titanium as main components, the framework materials of the carrier comprise the oxides or hydroxides of aluminum, magnesium or the other alkaline earth metals, and rare earth compounds and/or alkaline earth metal compounds are used as anti-hydration auxiliary agents and added in the framework materials. The preparation method comprises: firstly, the framework materials of the carrier are modified by the anti-hydration auxiliary agents; secondly, the modified framework materials and the compounds of titanium are mixed; finally, the active components are immersed in the mixture to obtain the hydration-resisting sulphur-resisting conversion catalyst. The hydration-resisting sulphur-resisting conversion catalyst has good hydration resistance and good structural stability.
Description
The present invention relates to a kind of New CO sulphur-resistant transformation catalyst and preparation method, specifically, the present invention relates to a kind of sulfur-resistant transformation catalyst and preparation method of hydration-resisting.
At present, in the reconstruction of expanding production of China's large chemical fertilizer " coal for oil " and middle chemical fertilizer plant, major part selected for use with the coal be raw material, 4.0MPa gasification gas making, three sections sulphur-resistant conversions (middle change string is low to be become), after connect the technological process that methanation purifies.Because the low temperature shift process pressure of this flow process is higher, temperature is lower, catalyst will move under less than 20 ℃ harsh conditions in the distance dew-point temperature, therefore the sulfur-resistant transformation catalyst that requires to be adapted to this technology not only will have good low temperature active, also good anti-hydration and structural stability will be arranged.And the antisulphour Low Temperature Transform Catalyst of present industrial extensive use, how with γ-Al
2O
3Or with rare earth modified γ-Al
2O
3Be carrier, as Chinese patent CN1003979 and U.S. Pat 4,153, the catalyst described in 580.When the carrier of this class catalyst uses, all can hydration reaction take place to some extent, cause catalyst to produce phase transformation and inactivation under above-mentioned process conditions.In the Chinese patent application 96100935.7 before us, a kind of catalyst that carrier is carried out modification with the titanium component is provided, this catalyst has higher intensity and strength stability, also have better low temperature activity and curability, but when using under above-mentioned process conditions, hydration and inactivation also can take place in catalyst to some extent.
Purpose of the present invention just provides a kind of not hydration, not phase transformation when using, has good anti-hydration, low temperature active and structural stability under above-mentioned harsh conditions catalyst.
In sulfur-resistant transformation catalyst of the present invention, used active constituent is the compound of cobalt and molybdenum, and the adding alkali metal compound is made auxiliary agent, carrier is then selected the good titanium compound of hydration-resisting performance for use, and the quality percentage composition of titanium compound in carrier preferably is controlled in 30%～80% the scope (with TiO
2Meter).
The selected titanium compound of the present invention can be titanium oxide, metatitanic acid, four titanium oxide, the red stone of titanium or anatase, also can be the mixture of any two or more material in the above-mentioned substance.
The quality percentage composition of active constituent in catalyst is MoO
35%～20%, CoO0.5%～5%; Alkali metal promoter shared quality percentage composition in catalyst is 0.1%～20% (in oxide), and alkali metal can be potassium, also can be sodium.
Though titanium compound has good hydration-resisting performance, if carrier all uses titanium compound, then the mechanical strength of carrier and catalyst is not ideal enough, thereby in the present invention, makes the skeleton material with compounds such as aluminium, magnesium, improves the intensity of catalyst.These compounds can be that the oxide or the hydroxide of aluminium hydroxide, boehmite, gibbsite, alundum (Al, zinc oxide, magnesium hydroxide, magnesium carbonate, magnesia or other alkaline-earth metal is made the skeleton material.Also can adopt in the above-claimed cpd arbitrarily two or more mixture to make the skeleton material.
When preparation catalyst of the present invention, key is the preparation of carrier.During the preparation carrier, earlier the carrier framework material is carried out modification with the hydration-resisting auxiliary agent, soon the skeleton material mixes with the hydration-resisting auxiliary agent, roasting is decomposed and pulverizing, to improve the anti-hydration and the structural stability of carrier component; Then that the carrier framework material after the modification and hydration-resisting performance is good novel carriers component be the compound of titanium do mix, extrusion, roasting, make catalyst carrier; According to a conventional method the compound and the alkali metal compound of active constituent molybdenum, cobalt is mixed with co-impregnated solution again, impregnated carrier and roasting, decomposition make the sulfur-resistant transformation catalyst of hydration-resisting.
In the preparation process, the carrier framework material can be selected the oxide or the hydroxide of aluminium hydroxide, boehmite, gibbsite, alundum (Al, zinc oxide, magnesium hydroxide, magnesium carbonate, magnesia or other alkaline-earth metal, also can select any two or more mixture in the above-claimed cpd; The hydration-resisting auxiliary agent can be selected rare earth compound and/or alkaline earth metal compound, as the nitrate or the sulfate of the nitrate of the nitrate of lanthanum or oxide, cerium or oxide, alkali-metal nitrate or sulfate, alkaline-earth metal, also can be two or more mixture arbitrarily in the above-claimed cpd; The compound of titanium can the selective oxidation titanium, metatitanic acid, four titanium oxide, the red stone of titanium or anatase or its mixture.
In the catalyst carrier, make the hydration-resisting auxiliary agent if add rare earth compound, then its quality percentage composition is 0.01%～10% (in oxide); Make the hydration-resisting auxiliary agent if add alkaline earth compound, then its quality percentage composition is 10%～20% (in oxide); Titanium compound is the main component of carrier, and its quality percentage composition is preferably in titanium dioxide in 30%～80% the scope.
Carrier framework material and titanium compound are done when mixing, can add peptizing agent mixes, peptizing agent can be the liquid glue solvent, as the nitrate aqueous solution of nitric acid, alkaline-earth metal, alkali-metal nitrate aqueous solution, alkali-metal sulfate solution or its solution of two or more mixture arbitrarily; Peptizing agent also can be the peptizing agent of solid, as the oxide of alkaline-earth metal, the hydroxide of alkaline-earth metal or the sulfate of alkaline-earth metal.
Adopt sulfur-resistant transformation catalyst of the present invention when the distance dew point uses under less than 20 ℃ harsh conditions, not hydration of catalyst, not phase transformation has anti-hydration and structural stability preferably, and industrial low change catalyzer C
25-2-02, when QCS-02, EB-04 etc. use in same process conditions, all undergo phase transition (seeing accompanying drawing 1).In addition, the process that the present invention prepares catalyst is simple, can significantly reduce manufacturing cost.
Further specify the present invention below in conjunction with drawings and Examples, but scope of the present invention does not show in following examples of implementation.
Accompanying drawing 1 is the thing phase change figure before and after the catalyst CT-4 hydrothermal treatment consists of the present invention.
Accompanying drawing 2 is the thing phase change figure before and after several common used in industry catalyst hydrothermal treatment consists.
Accompanying drawing 3 is each catalyst of the present invention thing phase spectrograms after hydrothermal treatment consists.
Embodiment 1 Preparation of catalysts
Catalyst CT-1:
Get La
2O
310 gram wiring solution-formings are with MgCO
3100 grams mix, and 700 ℃ of following roastings 2 hours, pulverize; Add 400 gram titanium hydroxides, add again that 10% nitric acid is mediated, extrusion, and, make catalyst carrier in 500 ℃ of following roastings.Ammonium molybdate 55 grams, cobalt nitrate 5.0 grams and potash 50 grams are mixed with co-impregnated solution; Get the above-mentioned carrier of 50 grams,, and, make catalyst CT-1 in 400 ℃ of following roastings decomposition with this co-impregnated solution dipping.
Catalyst CT-2:
The preparation method is with catalyst CT-1, and different is to replace La with zinc nitrate aqueous solution
2O
3The aqueous solution and MgCO
3Mix, the catalyst of last gained is CT-2.
Catalyst CT-3:
The preparation method is with catalyst CT-2, and different is with Al (OH)
3MgCO among the replaced C T-2
3, the catalyst that makes at last is CT-3.
Catalyst CT-4:
The preparation method is with catalyst CT-3, and different is to replace zinc nitrate aqueous solution to mix with magnesium nitrate aqueous solution, and the catalyst that makes at last is CT-4.
Catalyst CT-5:
The preparation method is with catalyst CT-1, and different is with 400 gram titanium hydroxides among 200 gram titanium hydroxides and the 300 gram metatitanic acid replaced C T-1, makes the nitric acid of 10% among the peptizing agent replaced C T-1 with 20 gram potassium nitrate, and the catalyst of gained is CT-5 at last.The performance test of embodiment 2 catalyst
On former granularity pressurization evaluating apparatus, be medium with hydrogen and water vapour, at 18 ℃～20 ℃ of distance dew points (pressure 4.0Mpa, 220 ℃～222 ℃ of temperature, air speed 2000h
-1, water/gas 0.7) condition under, to catalyst of the present invention and industrial catalyst hydrothermal treatment consists 72 hours, detect its thing phase change, the results are shown in accompanying drawing 1, accompanying drawing 2 and accompanying drawing 3.As can be seen, catalyst of the present invention (CT-4) is after hydrothermal treatment consists from accompanying drawing 1 and accompanying drawing 2, and thing does not change mutually basically, and the hydration peak that occurs yet useless does not form algeldrate after showing hydrothermal treatment consists, and industrial catalyst C
25-2-02, QCS-02 and EB-4 be all having occurred hydration peak (peak between 10 °～20 ° is the hydration peak) after the hydrothermal treatment consists, shows that hydration has taken place these catalyst; As can be seen, hydration does not all take place in each catalyst CT-1, CT-2 of the present invention, CT-3, CT-4 after hydrothermal treatment consists from accompanying drawing 3, forms the hydration peak.
Then, measure each catalyst of the present invention and industrial catalyst C
25-2-02Fresh sample, boiling test sample and the intensity of hydrothermal treatment consists test sample, data see Table-1.From the table-1 data as can be seen, each catalyst of the present invention is not only than industrial catalyst C
25-2-02Have better initial strength, and strength retention ratio is also high after poach and hydrothermal treatment consists, shows that catalyst of the present invention has good strength stability.The field investigation of embodiment 3 catalyst
Under the following conditions, catalyst CT-4 of the present invention is carried out Simulation evaluation, the results are shown in Table-2.
Appreciation condition: the loadings of catalyst is 50ml, with α-Al
2O
3Bead by 1: 1 dilution proportion extremely
100ml
Conditions of vulcanization: pressure 1.5MPa; 260 ℃ of temperature; Air speed 1000h
-1Cure time 20 hours
The intensity of table-1 catalyst of the present invention and industrial catalyst and stability contrast thereof
The simulation operation test of table-2 catalyst CT-4 of the present invention
| Pressure (Mpa) | Air speed (h -1) | Water/gas | Inlet temperature (℃) | CO% (percent by volume) | CO interconversion rate (%) | |
| Inlet | Outlet | |||||
| 1.5 | 1000 | 1.0 | 260.6 | 5.89 | 0.47 | 91.58 |
| 3.8 | 3000 | 0.76 | 260.0 | 5.49 | 0.36 | 93.11 |
| 3.8 | 2000 | 0.76 | 260.1 | 5.41 | 0.27 | 94.75 |
| 3.8 | 2000 | 0.63 | 260.0 | 5.41 | 0.30 | 94.16 |
| 3.8 | 2000 | 0.63 | 220 | 5.20 | 0.34 | 93.14 |
| 3.8 | 2000 | 0.63 | 215 | 5.29 | 0.30 | 94.04 |
| 3.8 | 2000 | 0.63 | 210 | 5.16 | 0.28 | 94.31 |
| 3.8 | 2000 | 0.63 | 210 | 3.77 | 0.20 | 94.51 |
| 3.8 | 2000 | 0.63 | 210 | 1.67 | 0.10 | 94.52 |
| 3.8 | 2000 | 0.63 | 205 | 3.44 | 0.21 | 93.69 |
Claims (17)
1. the sulfur-resistant transformation catalyst of a hydration-resisting, its active component is the compound of cobalt and molybdenum, it is characterized in that adding in the catalyst alkali metal compound and make co-catalyst, catalyst carrier is to be made of the skeleton material and the titanium compound that contain aluminium, magnesium or other alkaline earth metal compounds, and the quality percentage composition of titanium compound counts 30%～80% with titanium dioxide.
2. by the described catalyst of claim 1, it is characterized in that the titanium compound in the catalyst carrier is titanium oxide, metatitanic acid, four titanium oxide, the red stone of titanium or anatase, or two or more mixture arbitrarily in the above-mentioned substance.
3. by the described catalyst of claim 1, it is characterized in that active component molybdenum, cobalt and the alkali metal promoter quality percentage composition in catalyst is respectively 5%～20%, 0.5%～5% and 0.1%～20% in oxide.
4. by the described catalyst of claim 1, it is characterized in that the skeleton material in the catalyst carrier is selected from the oxide of aluminium hydroxide, boehmite, gibbsite, alundum (Al, zinc oxide, magnesium hydroxide, magnesium carbonate, magnesia, other alkaline-earth metal or the hydroxide of other alkaline-earth metal, perhaps be selected from two or more combination arbitrarily in the above-claimed cpd.
5. by the described catalyst of claim 4, it is characterized in that adding rare earth compound and/or alkali metal compound and/or alkaline earth metal compound in the skeleton material of catalyst carrier makes the hydration-resisting auxiliary agent.
6. by the described catalyst of claim 5, the nitrate, cerium oxide, alkali-metal nitrate, alkali-metal sulfate, the nitrate of alkaline-earth metal or the sulfate of alkaline-earth metal that it is characterized in that added hydration-resisting auxiliary agent is a lanthanum in the carrier nitrate, lanthana, cerium perhaps are two or more combination arbitrarily in the above-claimed cpd.
7. by the described catalyst of claim 5, it is characterized in that added rare earth compound quality percentage composition counts 0.01%～10% with oxide in the carrier.
8. by the described catalyst of claim 5, it is characterized in that added alkaline earth compound quality percentage composition counts 10%～20% with oxide in the carrier.
9. the preparation method of a hydration-resisting sulfur-resistant transformation catalyst is characterized in that:
A. compound, extrusion, the roasting of the major constituent titanium of the skeleton material that will be made by aluminium, magnesium or other alkaline earth metal compounds and carrier make catalyst carrier;
B. compound and the alkali metal compound with activity of such catalysts component molybdenum, cobalt is mixed with co-impregnated solution, and impregnated carrier and roasting, decomposition make the sulfur-resistant transformation catalyst of hydration-resisting.
10. by the described method of claim 9, when it is characterized in that the carrier framework material mixes with the major constituent titanium compound of carrier, adding peptizing agent mixes, peptizing agent is the nitrate aqueous solution of nitric acid, alkaline-earth metal, alkali-metal nitrate aqueous solution, alkali-metal sulfate solution or the above-mentioned solution of two or more mixture arbitrarily, or the oxide of alkaline-earth metal, the hydroxide of alkaline-earth metal or the sulfate of alkaline-earth metal.
11. by claim 9 or 10 described methods, it is characterized in that the skeleton material in the catalyst carrier is selected from the oxide of aluminium hydroxide, boehmite, gibbsite, alundum (Al, zinc oxide, magnesium hydroxide, magnesium carbonate, magnesia, other alkaline-earth metal or the hydroxide of other alkaline-earth metal, perhaps be selected from two or more combination arbitrarily in the above-claimed cpd.
12. by claim 9 or 10 described methods, it is characterized in that at the skeleton material of carrier with before the major constituent titanium compound of carrier mixes, can in the carrier framework material, add as the rare earth compound of hydration-resisting auxiliary agent and/or alkali metal compound and/or alkaline earth metal compound carrier is carried out modification.
13. by claim 9 or 10 described methods, the nitrate, cerium oxide, alkali-metal nitrate, alkali-metal sulfate, the nitrate of alkaline-earth metal or the sulfate of alkaline-earth metal that it is characterized in that added hydration-resisting auxiliary agent is a lanthanum in the carrier nitrate, lanthana, cerium perhaps are two or more combination arbitrarily in the above-claimed cpd.
14. by claim 9 or 10 described methods, the major constituent titanium compound that it is characterized in that carrier is titanium oxide, metatitanic acid, four titanium oxide, the red stone of titanium or anatase, or two or more mixture arbitrarily in the above-mentioned substance.
15., it is characterized in that activity of such catalysts component aluminium, cobalt and the alkali metal promoter quality percentage composition in catalyst is respectively 5%～20%, 0.5%～5% and 0.1%～20% in oxide by claim 9 or 10 described methods.
16., it is characterized in that added rare earth compound quality percentage composition counts 0.01%～10% with oxide in the carrier framework material by the described method of claim 12.
17., it is characterized in that added alkaline earth compound quality percentage composition counts 10%～20% with oxide in the carrier framework material by the described method of claim 12.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110348A CN1087192C (en) | 1998-07-15 | 1998-07-15 | Hydration-resisting and sulfur-resisting conversion catalyst and its preparation |
| ZA9904562A ZA994562B (en) | 1998-07-15 | 1999-07-15 | Anti-hydrating and sulfur-resistant catalyst for Co-shift process and preparation method therof. |
| CZ0253199A CZ297807B6 (en) | 1998-07-15 | 1999-07-15 | Catalyst for conversion carbon monooxide with steam and process for preparing thereof |
| AU40129/99A AU747821B2 (en) | 1998-07-15 | 1999-07-15 | Anti-hydrating and sulfur-resistant catalyst for CO-shift process and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110348A CN1087192C (en) | 1998-07-15 | 1998-07-15 | Hydration-resisting and sulfur-resisting conversion catalyst and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1241452A CN1241452A (en) | 2000-01-19 |
| CN1087192C true CN1087192C (en) | 2002-07-10 |
Family
ID=5220404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98110348A Expired - Fee Related CN1087192C (en) | 1998-07-15 | 1998-07-15 | Hydration-resisting and sulfur-resisting conversion catalyst and its preparation |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN1087192C (en) |
| AU (1) | AU747821B2 (en) |
| CZ (1) | CZ297807B6 (en) |
| ZA (1) | ZA994562B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108940298A (en) * | 2017-05-29 | 2018-12-07 | 镇江瑞德新材料科技研发有限公司 | Cobalt molybdenum system CO sulfur-resistant transformation catalyst and preparation method thereof |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102151574B (en) * | 2011-02-16 | 2015-06-17 | 山东齐鲁科力化工研究院有限公司 | Novel CO sulfur-tolerant shift catalyst and preparation method thereof |
| GB201109376D0 (en) * | 2011-06-06 | 2011-07-20 | Johnson Matthey Plc | Water-gas shift catalyst |
| CN103480358A (en) * | 2013-10-11 | 2014-01-01 | 神华集团有限责任公司 | High temperature and sulfur resistant methanation catalyst and preparation method thereof |
| CN105478131B (en) * | 2014-10-09 | 2018-09-21 | 中国石油化工股份有限公司 | CO mesohigh low temperature resistant to sulfur pre-transform catalyst and preparation method thereof |
| CN106552637B (en) * | 2015-09-30 | 2019-03-29 | 中国石油化工股份有限公司 | Cobalt molybdenum system low temperature sulfur tolerant shift catalyst and preparation method |
| CN110237852B (en) * | 2018-03-09 | 2022-04-15 | 国家能源投资集团有限责任公司 | Sulfate ion-containing titanium compound modified sulfur-tolerant shift catalyst and preparation method thereof |
| CN114177912B (en) * | 2020-09-14 | 2024-02-13 | 中国石油化工股份有限公司 | Perovskite sulfur-resistant shift catalyst and preparation method and application thereof |
| CN114471589A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Catalyst, method for sulfur-tolerant shift catalytic reaction and method for preparing methane |
| CN115518661B (en) * | 2021-06-25 | 2023-12-05 | 中国石油化工股份有限公司 | Sulfur-tolerant shift catalyst, preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4153580A (en) * | 1977-12-09 | 1979-05-08 | United Catalysts Inc. | CO conversion catalyst |
| CN87107892A (en) * | 1987-11-14 | 1988-05-04 | 湖北省化学研究所 | Sulfur-resistant CO conversion catalyst and preparation thereof |
| CN1154271A (en) * | 1996-01-11 | 1997-07-16 | 中国石化齐鲁石油化工公司 | Method for prepn. of CO transformation catalyst of sulfur-resistant type |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08176034A (en) * | 1994-12-22 | 1996-07-09 | Cosmo Sogo Kenkyusho:Kk | Synthesis of methanol |
-
1998
- 1998-07-15 CN CN98110348A patent/CN1087192C/en not_active Expired - Fee Related
-
1999
- 1999-07-15 ZA ZA9904562A patent/ZA994562B/en unknown
- 1999-07-15 CZ CZ0253199A patent/CZ297807B6/en not_active IP Right Cessation
- 1999-07-15 AU AU40129/99A patent/AU747821B2/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4153580A (en) * | 1977-12-09 | 1979-05-08 | United Catalysts Inc. | CO conversion catalyst |
| CN87107892A (en) * | 1987-11-14 | 1988-05-04 | 湖北省化学研究所 | Sulfur-resistant CO conversion catalyst and preparation thereof |
| CN1154271A (en) * | 1996-01-11 | 1997-07-16 | 中国石化齐鲁石油化工公司 | Method for prepn. of CO transformation catalyst of sulfur-resistant type |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108940298A (en) * | 2017-05-29 | 2018-12-07 | 镇江瑞德新材料科技研发有限公司 | Cobalt molybdenum system CO sulfur-resistant transformation catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CZ297807B6 (en) | 2007-04-04 |
| CN1241452A (en) | 2000-01-19 |
| AU747821B2 (en) | 2002-05-23 |
| ZA994562B (en) | 2000-01-18 |
| AU4012999A (en) | 2000-02-10 |
| CZ253199A3 (en) | 2000-02-16 |
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