CN1310704C - Anti sulfur deoxidizing catalyst, its preparing process and application method - Google Patents
Anti sulfur deoxidizing catalyst, its preparing process and application method Download PDFInfo
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- CN1310704C CN1310704C CNB2003101218706A CN200310121870A CN1310704C CN 1310704 C CN1310704 C CN 1310704C CN B2003101218706 A CNB2003101218706 A CN B2003101218706A CN 200310121870 A CN200310121870 A CN 200310121870A CN 1310704 C CN1310704 C CN 1310704C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title abstract description 13
- 239000011593 sulfur Substances 0.000 title abstract description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000007789 gas Substances 0.000 claims abstract description 39
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 34
- 239000001301 oxygen Substances 0.000 claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 13
- JOKPITBUODAHEN-UHFFFAOYSA-N sulfanylideneplatinum Chemical compound [Pt]=S JOKPITBUODAHEN-UHFFFAOYSA-N 0.000 claims abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- -1 alkali metal salt Chemical class 0.000 claims description 3
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 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 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 239000002808 molecular sieve Substances 0.000 abstract description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 231100000572 poisoning Toxicity 0.000 abstract description 4
- 230000000607 poisoning effect Effects 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 abstract 2
- 239000000470 constituent Substances 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000000284 extract Substances 0.000 description 9
- 238000002803 maceration Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 238000006356 dehydrogenation reaction Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000000222 hyperoxic effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000013097 stability assessment Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Catalysts (AREA)
Abstract
The present invention discloses a sulfur resisting and deoxidizing catalyst, a preparation method thereof, and an application thereof. The catalyst of the present invention is composed of a carrier and platinum sulfide PtSx of an active constituent supported on the carrier, wherein counted by carrier weight, the platinum content is from 0.01 to 0.5%(wt), the molar ratio x of S to Pt is from 0.1 to 50, and the carrier is one of aluminum oxide, molecular sieve, silicon dioxide and active carbon. The catalyst of the present invention is applied to the deoxidation treatment of various hydrogen-bearing gases whose COS content of carbon oxysulfide is from 1 to 500 ppm and oxygen content is lower than 0.5% (volume), the reaction temperature is from 25 to 450 DEG C, and the reaction pressure is from 1 to 15MPa. The catalyst of the present invention has high sulfur poisoning resistance and is particularly suitable for eliminating trace oxygen in sulfurous gases.
Description
Technical field
The present invention relates to a kind of dehydrogenation catalyst, specifically, relate to a kind of Catalysts and its preparation method and application that is used for removing all gases (particularly sulfurous gas) micro amount of oxygen.
Background technology
As everyone knows, because contain a large amount of oxygen in the air, majority of gas is introduced micro amount of oxygen impurity in process of production inevitably, as water electrolysis hydrogen production, the absorption of air transformation or deep cooling system nitrogen, heavy oil portion oxidation synthesis gas (CO and H
2Mist) etc. production process.At synthesis gas, CO, CO
2, in a lot of gases such as alkane, natural gas, alkene, except that containing micro amount of oxygen impurity, also have the hydrogen sulfide (H of trace
2S), cos sulphur impurities such as (COS).In general, the existence of micro amount of oxygen and sulphur can make the major catalyst in the follow-up synthetic reaction lose activity in the gas.Therefore, the micro amount of oxygen impurity that removes in the gas is very important.
Micro amount of oxygen removes to be divided into and joins the hydrogen deoxidation and be unworthy of hydrogen deoxidation two classes in the gas.The principle of hydrogenation deoxidation agent is not appraise at the current rate oxide absorption process and carbon burning consumption method.The hydrogenation deoxidation agent does not mainly contain: MnO
x, Ag
2O, CuO
x, NiO
x, C etc. (referring to Wu Yanmin " purification for gas ", 23,1983, National Defense Industry Press).The deoxidation capacity of hydrogenation deoxidation agent is not little, and general every gram deoxidier deoxidation 5～15ml for hyperoxic gas, needs a large amount of deoxidiers, and cleaning equipment is huge, and is uneconomical economically.
The principle of joining the hydrogen dehydrogenation catalyst is under the effect that contains catalyst such as precious metals pd, Pt, makes the impurity oxygen and the hydrogen reaction that are blended in the unstripped gas generate steam, and micro amount of oxygen is removed.Noble metal is joined the hydrogen dehydrogenation catalyst, although can be used for the purification of elevated oxygen level (more than the 200ppm) gas micro amount of oxygen, this precious metals pd catalyst is very easily because of the existence poisoning and deactivation of Determination of Trace Sulfur.And, for removing micro amount of oxygen in the high concentration CO gas,, and produce the CO disproportionated reaction and tie carbon because CO toxicity causes noble metal to join hydrogen dehydrogenation catalyst deoxy activity and descend significantly, influence catalyst service life and deoxidation effect.CN85102710A discloses a kind of platinum, Pd/TiO 2 deoxygenationcatalyst, and this catalyst is used for general hydrogen, ultra-pure hydrogen, nitrogen are produced in the nitrogen deoxidation, and catalytic activity is good.CN1175478 discloses a kind of high strength, highly heat-resistant catalyst, and adopting titanium dioxide to add aluminium oxide is carrier, and active component is palladium and/or platinum, and this catalyst is used for the quantitative deoxidization by adding hydrogen reaction of thick hydrogen deoxygenation, nitrogen and inert gas, anti-H
2S, SO
2Poisoning capability strong.The embodiment of this patent is for being the bicomponent catalyst of active component with palladium and platinum, and bullion content is higher in the catalyst, is 0.5%.
In sum, join the hydrogen dehydrogenation catalyst in the prior art and exist impurity poisoning capability such as resisting sulfide and CO poor, active low, shortcomings such as life-span weak point.
Summary of the invention
One of purpose of the present invention is to overcome the above-mentioned shortcoming of existing deoxidier, provides a kind of production easy, and deoxidation effect is good, and anti-poisoning capability is strong, is applicable to the efficient sulfur-tolerance deoxidation catalyst of use of large-scale production.
Sulfur-tolerance deoxidation catalyst of the present invention is by carrier and the active component platinum sulfide PtS that loads on the carrier
xForm, wherein in vehicle weight, platinum content is 0.01～0.5% (wt), preferred 0.05～0.3% (wt); S/Pt mol ratio x is 0.1～50, preferred 1～20.
Sulfur-tolerance deoxidation catalyst of the present invention is with platinum sulfide PtS
xBe active component, described carrier can be selected from alundum (Al Al
2O
3, a kind of in active carbon, silica and the molecular sieve, preferred γ-Al
2O
3Wherein molecular sieve can be the 5A molecular sieve.
The used support shapes of catalyst of the present invention can be sphere, strip gear, sheet, cloverleaf pattern, column etc.
Two of purpose of the present invention provides a kind of preparation method of sulfur-tolerance deoxidation catalyst.
The preparation method of sulfur-tolerance deoxidation catalyst of the present invention comprises the following steps: successively
(1) be raw material with tetravalence platinum water soluble compound, the preparation platiniferous aqueous solution adds inorganic sulphide soluble in water then, and making the S/Pt mol ratio is 0.1～50, and the formation pH value is 6～14 load solution;
(2) by infusion process or spraying process, the load solution that step (1) is prepared loads on the carrier;
(3) with the carrier after the load of step (2) preparation, under air or nitrogen atmosphere, 100～500 ℃ of roastings 1～8 hour, preferred 150～350 ℃ of roastings 2～6 hours obtain described sulfur-tolerance deoxidation catalyst.
Tetravalence platinum water soluble compound is selected from chloroplatinic acid H in the preferred described step (1)
2PtCl
6, chloroplatinic acid alkali metal salt and PtCl
4The aqueous solution at least a, more preferably from H
2PtCl
6, K
2PtCl
6And PtCl
4One of the aqueous solution; Described inorganic sulphide is selected from least a in ammonium sulfide, vulcanized sodium and the potassium sulfide, more preferably ammonium sulfide (NH
4)
2S.
The load solution Pt (IV) that described step (1) is prepared forms a kind of stable complex compound homogeneous phase aqueous solution with sulfide, and the pH value of preferred load solution is 7～10, generates to prevent precipitation.
Three of purpose of the present invention provide a kind of can be in the gas that contains Determination of Trace Sulfur impurity the method for catalytic eliminating micro amount of oxygen.
Catalyst of the present invention can be applicable to cos COS content at 1～500ppm, the deoxidation treatment of all kinds of hydrogen-containing gas of oxygen content below 0.5% (volume), and reaction temperature is 25～450 ℃, preferred 50～350 ℃, reaction pressure is 1～15MPa.Concrete, catalyst of the present invention can be applicable to general hydrogen and general nitrogen, alkane etc. are joined hydrogen deoxidation, synthesis gas (CO and H
2Gaseous mixture) deoxidation treatment, CO concentration all can from 0.01～99%.
Beneficial effect of the present invention is as follows:
1,,, is specially adapted to removing of micro amount of oxygen in the sulfurous gas so have very strong anti-sulfur poisoning performance because catalyst activity sexual element of the present invention is the sulfide of Pt.
2, catalyst of the present invention does not need preliminary treatment promptly can be directly used in the deoxidation of hydrogen-containing gas.
The specific embodiment
Illustrate content of the present invention below, but protection scope of the present invention is not limited to following examples.
Estimate catalyst performance of the present invention, employed forming gas consists of: H
249.6%, CO 48.6%, N
21.0%, O
20.2%, CO
20.1%, COS 0.01%, H
2S 0.05%, and other is 0.4% years old.With micro-oxygen content in the gas after the Teledyne Ultra Trace 3000 trace oxygen analyzer detection reaction.As everyone knows, because the suction-operated of CO, it is more difficult than other gas to contain removing of micro amount of oxygen in the CO gas.In other words, be applicable to that the dehydrogenation catalyst that micro amount of oxygen purifies in the synthesis gas goes for other gas equally, and catalytic performance can be better.
Embodiment 1～8
Take by weighing 0.21 gram sponge Pt, aqua regia dissolution is diluted to the 150ml chloroplatinic acid aqueous solution.Adding 1.6 gram sulfur contents is the (NH of 8% (wt)
4)
2The S aqueous solution is used NH
3Water or rare HCl adjust pH between 7～8, are prepared into maceration extract.Take by weighing 260 gram Φ, 5 spherical γ-Al
2O
3Carrier is put into maceration extract, shakes beaker to whole maceration extracts and loads on the alumina support.Dried 3 hours for 120 ℃.Be divided into eight parts, under air atmosphere 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 450 ℃ respectively, 300 ℃, 350 ℃ roastings are 3 hours under blanket of nitrogen.The Pt content that makes catalyst is 0.08% (wt), and the S/Pt mol ratio is 1.74.The gained catalyst is carried out performance evaluation in 180 ℃, the synthesis gas of 2MPa, the results are shown in Table 1.
The deoxy performance of table 1 embodiment 1-8 catalyst
| Embodiment | Sintering temperature (℃) | Atmosphere | Air speed (hr -1) | Remaining oxygen (ppm) |
| 1 | 150 | Air | 3000 | ≤1 |
| 2 | 200 | Air | 3000 | ≤1 |
| 3 | 250 | Air | 3000 | ≤1 |
| 4 | 300 | Air | 3000 | ≤1 |
| 5 | 350 | Air | 2500 | ≤1 |
| 6 | 450 | Air | 1500 | ≤1 |
| 7 | 300 | Nitrogen | 3000 | ≤1 |
| 8 | 350 | Nitrogen | 3000 | ≤1 |
Embodiment 9～13
Take by weighing 0.133 gram sponge Pt, use aqua regia dissolution, be diluted to the 100ml chloroplatinic acid aqueous solution, be divided into every part of 20ml, totally five parts maceration extract adds 0.04,0.20,0.28,0.56, the 1.12 (NH that restrain sulfur contents 8% (wt) respectively
4)
2The S aqueous solution.Use NH
3Water or rare HCl adjust pH between 7～8.Add 33 gram Φ, 3 gear-like r-Al in every portion of maceration extract respectively
2O
3Carrier shakes the extremely whole maceration extracts of beaker by Al
2O
3Absorb.120 ℃ of oven dry 3 hours, 300 ℃ of roastings are 4 hours in the air atmosphere, obtain catalyst of the present invention.At 180 ℃, 2MPa, air speed 3000hr
-1Synthesis gas in carry out the evaluation of catalyst deoxy performance, the results are shown in Table 2.
The deoxy performance of table 2 embodiment 9-13 catalyst
| Embodiment | (NH 4) 2S aqueous solution addition (gram) | The S/Pt mol ratio | Remaining oxygen (ppm) |
| 9 | 0.04 | 0.34 | 30 |
| 10 | 0.20 | 1.74 | ≤1 |
| 11 | 0.28 | 2.44 | ≤1 |
| 12 | 0.56 | 4.87 | ≤1 |
| 13 | 1.12 | 9.74 | 80 |
Embodiment 14～16
According to three batches of catalyst of method preparation of embodiment 4, select Φ 3 spherical r-Al for use
2O
3Be carrier, add (the NH of 8% (wt) of the sulfur-bearing of same amount in the every batch of catalyst
4)
2The S aqueous solution 0.20 gram, the content of control catalyst metals Pt is 0.04% (wt), 0.08% (wt) and 0.12% (wt), the S/Pt mol ratio of catalyst of preparation is respectively 3.48,1.74 and 0.87, carries out the deoxy performance evaluation in 180 ℃, 2MPa synthesis gas, the results are shown in Table 3.
The deoxy performance of table 3 embodiment 14-16 catalyst
| Embodiment | Pt content (%wt) | Air speed (hr -1) | Remaining oxygen (ppm) |
| 14 | 0.04 | 2500 | ≤1 |
| 15 | 0.08 | 3000 | ≤1 |
| 16 | 0.12 | 3000 | ≤1 |
Embodiment 17～19
According to the preparation condition of embodiment 4, respectively with PtCl
4(embodiment 17), Na
2PtCl
66H
2O (embodiment 18) and K
2PtCl
66H
2O (embodiment 19) is for the raw material substitution chloroplatinic acid prepares catalyst, carries out catalytic performance test under the condition identical with embodiment 4, and the result shows that the deoxy performance of catalyst is constant.
Embodiment 20,21
According to the method for embodiment 12, be carrier with 5A molecular sieve, active carbon respectively, preparation Pt content is that 0.08% (wt), S/Pt mol ratio are 4.2 catalyst of the present invention.In 180 ℃, the synthesis gas of 2MPa, carry out the evaluation of catalyst deoxy performance, the results are shown in Table 4.
The deoxy performance of table 4 embodiment 20,21 catalyst
| Embodiment | Carrier | Air speed (hr -1) | Remaining oxygen (ppm) |
| 20 | The 5A molecular sieve | 3000 | ≤1 |
| 21 | Active carbon | 1500 | ≤1 |
The experiment of embodiment 22 catalyst stabilities
Take by weighing 11.25 gram sponge Pt, use aqua regia dissolution, be diluted to the 9000ml chloroplatinic acid aqueous solution, adding 99 gram sulfur contents is the (NH of 8% (wt)
4)
2The S aqueous solution, and adjust the pH of spray coating liquor between 8-9 with 12% ammoniacal liquor.Take by weighing γ-Al of 15Kg Φ 5
2O
3, pour in the coating pan of rotation.In 20 minutes, spray coating liquor is sprayed equably at γ-Al
2O
3On the carrier.Al after will spraying then
2O
3Change in the baking oven, 120 ℃ of oven dry 4hr, 250 ℃ of roasting 4hr get finished catalyst.Getting 50ml Pt content is 0.075% (wt), and the S/Pt mol ratio is this catalyst of 4.2, at 180 ℃, 2MPa, air speed 3000hr
-1Synthesis gas in carry out catalyst stability test.By the stability assessment of 250hr, the result shows that this catalyst can purify oxygen extremely≤1ppm from start to finish, does not see the catalytic activity decay.
Embodiment 23
With embodiment 3 preparation catalyst, be the H of 1000ppm with oxygen content
2Or oxygen content is 1000ppm, H
2/ O
2The nitrogen of=1.05 (mol ratios) is as estimating gas, under 180 ℃, 2MPa condition, estimates this activity of such catalysts.At H
2And N
2In oxygen is purified to more than the empty scooter 5000hr-1 of the highest use of≤1ppm.This shows that for the gas that does not contain CO, the deoxy performance of this catalyst can be better.
Comparative Examples 1
Take by weighing 0.0266 gram sponge Pt, use aqua regia dissolution, be diluted to the 20ml chloroplatinic acid aqueous solution.Use NH
3Water or rare HCl adjust pH between 7～8.In maceration extract, add 33 gram Φ, 3 gear-like r-Al
2O
3Carrier shakes the extremely whole maceration extracts of beaker by Al
2O
3Absorb.Dried 3 hours for 120 ℃, roasting is 4 hours in 300 ℃ of following air atmosphere, gets finished catalyst.With the catalyst that makes under the appreciation condition identical with embodiment 9-13, (promptly 180 ℃, 2MPa, air speed 3000hr
-1Synthesis gas in) carry out the evaluation of catalyst deoxy performance, reacted remaining oxygen is 500ppm.Compare as can be known with table 2 result, the existence of sulphur can significantly improve the deoxy activity of catalyst in the catalyst, and the platinum catalyst deoxy performance of sulfur-bearing is not very poor.
Comparative Examples 2
Take by weighing 0.0533 gram sponge Pt, aqua regia dissolution is diluted to 40ml chloroplatinic acid maceration extract, adds 66 gram Φ, 5 spherical r-Al
2O
3Be carrier, shake to the complete soln suppressed by vector and absorb, 120 ℃ of oven dry down, 400 ℃ of following roastings 4 hours.(promptly 180 ℃, 2MPa, air speed 3000hr under the condition identical with embodiment 9-13
-1Synthesis gas in) carry out the evaluation of catalyst deoxy performance, the residual quantity of oxygen is 600ppm in the reacted gas.
Claims (10)
1, a kind of sulfur-tolerance deoxidation catalyst is characterized in that this catalyst is by carrier and the active component platinum sulfide PtS that loads on the carrier
xForm, wherein in vehicle weight, platinum content is 0.01～0.5%, and S/Pt mol ratio x is 0.1～50; Described carrier is an alundum (Al.
2, sulfur-tolerance deoxidation catalyst as claimed in claim 1 is characterized in that described platinum content is 0.05～0.3%.
3, sulfur-tolerance deoxidation catalyst as claimed in claim 1, the mol ratio x that it is characterized in that S/Pt in the described catalyst is 1～20.
4, sulfur-tolerance deoxidation catalyst as claimed in claim 1 is characterized in that described catalyst carrier is γ-alundum (Al.
5, the preparation method of the described sulfur-tolerance deoxidation catalyst of one of claim 1-4 is characterized in that this method comprises the following steps: successively
(1) be raw material with tetravalence platinum water soluble compound, the preparation platiniferous aqueous solution adds inorganic sulphide then, and making the S/Pt mol ratio is 0.1～50, and the formation pH value is 6～14 load solution;
(2) by infusion process or spraying process, the load solution that step (1) is prepared loads on the carrier;
(3) with the carrier after the load of step (2) preparation, under air or nitrogen atmosphere, 100～500 ℃ of roastings 1～10 hour obtain described sulfur-tolerance deoxidation catalyst.
6, preparation method as claimed in claim 5 is characterized in that wherein said tetravalence platinum water soluble compound is selected from chloroplatinic acid H
2PtCl
6, chloroplatinic acid alkali metal salt and PtCl
4The aqueous solution at least a; Described inorganic sulphide is selected from least a in ammonium sulfide, vulcanized sodium and the potassium sulfide.
7, preparation method as claimed in claim 5 is characterized in that the pH value of wherein said load solution is controlled at 7～10.
8, preparation method as claimed in claim 5 is characterized in that catalyst that step (2) makes under air or nitrogen atmosphere, 150～350 ℃ of roastings 2～6 hours.
9, the described sulfur-tolerance deoxidation catalyst of one of claim 1-4 application in the micro amount of oxygen reaction in removing gas, it is characterized in that described catalyst is applied to cos COS content at 1～500ppm, oxygen content is with the deoxidation treatment of percent by volume at all kinds of hydrogen-containing gas below 0.5%, reaction temperature is 25～450 ℃, and reaction pressure is 1～15MPa.
10, method as claimed in claim 9 is characterized in that described reaction temperature is 50～350 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101218706A CN1310704C (en) | 2003-12-24 | 2003-12-24 | Anti sulfur deoxidizing catalyst, its preparing process and application method |
Applications Claiming Priority (1)
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| CNB2003101218706A CN1310704C (en) | 2003-12-24 | 2003-12-24 | Anti sulfur deoxidizing catalyst, its preparing process and application method |
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| CN102343271A (en) * | 2010-07-29 | 2012-02-08 | 中国石油化工股份有限公司 | Method for converting carbonyl sulfur in synthetic gas into hydrogen sulfide |
| CN106513037B (en) * | 2016-10-21 | 2019-01-18 | 南京大学 | A kind of preparation method of anti-silicon, sulfur resistive type dehydrogenation catalyst |
| CN108479827B (en) * | 2018-04-03 | 2021-06-15 | 太原理工大学 | Mid-temperature hydrolysis conversion carbonyl sulfide and deoxidation bifunctional coupling catalyst and preparation method thereof |
| CN108620063A (en) * | 2018-05-29 | 2018-10-09 | 湖北浚然新材料有限公司 | A kind of oil refinery dry gas dehydrogenation catalyst and its preparation method and application |
| CN112337487A (en) * | 2019-08-08 | 2021-02-09 | 中国石油化工股份有限公司 | Deoxygenation catalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5826004A (en) * | 1981-08-10 | 1983-02-16 | Kansai Coke & Chem Co Ltd | Removing method for oxygen from gas containing oxygen consisting essentially of hydrogen |
| JPS58174239A (en) * | 1982-04-02 | 1983-10-13 | Yoshinobu Takegami | Three-component catalyst for removing oxygen from gas containing oxygen consisting essentially of gaseous hydrogen and its production |
| US5498585A (en) * | 1993-06-14 | 1996-03-12 | Degussa Aktiengesellschaft | Sulphidized catalyst which contains platinum on activated carbon |
| CN1175478A (en) * | 1996-09-04 | 1998-03-11 | 中国科学院大连化学物理研究所 | High-strength, high heat-resistance and poisoning-resistance deoxidation catalyst |
| CN1198465A (en) * | 1997-05-07 | 1998-11-11 | 中国石化齐鲁石油化工公司 | Conversion process for dry gas purification and purifying agent thereof |
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| JPS5826004A (en) * | 1981-08-10 | 1983-02-16 | Kansai Coke & Chem Co Ltd | Removing method for oxygen from gas containing oxygen consisting essentially of hydrogen |
| JPS58174239A (en) * | 1982-04-02 | 1983-10-13 | Yoshinobu Takegami | Three-component catalyst for removing oxygen from gas containing oxygen consisting essentially of gaseous hydrogen and its production |
| US5498585A (en) * | 1993-06-14 | 1996-03-12 | Degussa Aktiengesellschaft | Sulphidized catalyst which contains platinum on activated carbon |
| CN1175478A (en) * | 1996-09-04 | 1998-03-11 | 中国科学院大连化学物理研究所 | High-strength, high heat-resistance and poisoning-resistance deoxidation catalyst |
| CN1198465A (en) * | 1997-05-07 | 1998-11-11 | 中国石化齐鲁石油化工公司 | Conversion process for dry gas purification and purifying agent thereof |
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| HSD型高效耐硫脱氧剂的研究 雷浩等，工业催化，第4期 1994 * |
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| 脱氧剂概述 张文慧等，山东化工，第29卷 2000 * |
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