CN1334140A - Dehydrogenating catalyst containing more rare-earth elements for CO2 gas used to synthesize urea - Google Patents
Dehydrogenating catalyst containing more rare-earth elements for CO2 gas used to synthesize urea Download PDFInfo
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- CN1334140A CN1334140A CN01114383A CN01114383A CN1334140A CN 1334140 A CN1334140 A CN 1334140A CN 01114383 A CN01114383 A CN 01114383A CN 01114383 A CN01114383 A CN 01114383A CN 1334140 A CN1334140 A CN 1334140A
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Abstract
A dehydrogenating catalyst for using CO2 as raw gas to synthesize urea contains Pt and Pd as active component, one or more assistances chosen from La, Ce, Pr, Sm, Nd, Eu, Er, Yb and Lu, and composound carrier (Al2O3-TiO2 or Al2O3-ZrO). Its advantages are high low-temp activity, high S resistance, easy regeneration after S poisoning, excellent low-oxygen adaptability, high conversion for synthesis of urea, high reaction rate and wide temp range from 100 to 400 deg.C.
Description
(1) technical field
The present invention relates to urea synthesis CO
2The purification catalyst for removing hydrogen of unstripped gas particularly contains the urea synthesis CO of multiple rare earth element
2The catalyst for removing hydrogen of unstripped gas.
(2) background technology
Since the early 1980s, in the domestic big-and-middle-sized urea production, for preventing in the tail gas because of H
2The blast that the content accumulation causes guarantees safety in production, adopts the method for catalytic combustion to remove urea synthesis CO
2H in the unstripped gas
2Used catalyst for removing hydrogen is the DH-2 type Pd-Pt/Al of Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences's development
2O
3The CN-101 type Pt/Al of catalyst and U.S. Engelhard company
2O
3Catalyst, these two kinds of catalyst all belong to loaded noble metal catalyst.The Chinese patent application of DH-2 type catalyst for removing hydrogen number is: 8810942.3, and this catalyst is with Al
2O
3Or contain Al
2O
3Silica-aluminium oxide be carrier, contain one or more auxiliary elements among Pd and Pt active component and Na, K, Mg, Ca, Ba, Fe, Co, Ni, Cu, Cr, the V, the content of Pd is than Pt height, this catalyst and CN-101 type catalyst are to sulfur content sensitivity in the unstripped gas, hypoxia adaptability and low temperature active are not good enough, under industrial condition, the major control index is: (1) total sulfur≤2mg/Nm
3(2) the highest (H
2+ CO)/O
2170～220 ℃ of-1.0 (3) inlet temperatures.Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences had proposed a kind of CO that is suitable for the urea synthesis sulfur-bearing in 1992
2The catalyst for removing hydrogen of unstripped gas, name is called the high antisulphuric ability catalyst for removing hydrogen, and code name is D-438, and number of patent application is 92125672.9, and this catalyst is made active component with Pd and Fe, adds a kind of alkali metal at least and makes auxiliary agent, with γ-Al
2O
3Be carrier, its catalyst sulfur resistance is stronger, but suitability for industrialized production not as yet.1999, I proposed a kind of catalyst for removing hydrogen from Co 2 raw gas used to synthesize urea and preparation, and number of patent application is 99120014.4, the catalyst code name is TH-2, this catalyst is made active component with Pd and Pt, is selected among La, Ce, Sm, the Pr at least a rare earth element and makes auxiliary agent, uses Al
2O
3-TiO
2Or Al
2O
3-ZrO composite oxides are made carrier, and this catalyst has been applied to the synthetic industrial production of urea, and raw material of industry gas consists of CO
296～98%, H
21.0% (v) O
21.1% (v) CO≤0.2% (v), CH
3OH100～360ppm, CH
40.1 total sulfur≤2mg/Nm～0.26%,
3, reaction pressure is 13.2～14.7MPa, gas space velocity is 3.0～3.2 * 10
4h
-1, the reaction inlet temperature is under 145～190 ℃ the condition, keeps the residual hydrogen amount of tail gas less than 50ppm, 18 months uptime.The major control index of TH-2 dehydrogenation under the industrial reaction condition is: 1. total sulfur≤2mg/Nm
32. the highest (H
2+ CO)/O
2-1.1.3. inlet temperature is 145～190 ℃.The hypoxia adaptability of this catalyst and low temperature active are better than DH-2 type and CN-101 type catalyst for removing hydrogen.
The TH-2 dehydrogenation can satisfy the dehydrogenation requirement of the urea production of natural gas or slag oil gas, though be used for the synthetic suitability for industrialized production of urea, but still have following deficiency:
(1) can not be at total sulfur＞2mg/Nm
3Unstripped gas in use.China's urea production is a raw material with coal or residual oil mostly, CO
2In the unstripped gas total sulfur actual be to be higher than 2mg/Nm
3Index.
(2) (H
2+ CO)/O
2The H that can not satisfy the urea plant technological transformation and adopt
2O
2The method requirement for anticorrosion.(H
2+ CO)/O
2Ratio is more little, means CO
2The air capacity that adds in the unstripped gas is many more, corresponding C O
2Purity reduces, and influences the synthetic conversion ratio (CO of urea
2The every reduction by 1% of purity, conversion rate of urea descend about 0.3～0.6%), increased the load of the circulatory system; Next CO
2Purity is low, and inert gas is many, the corresponding increase of the ammonia that tail gas emptying is taken away.H
2O
2Method is anticorrosion to CO
2(H in the unstripped gas
2+ CO)/O
2Requirement is controlled at greater than 1.25, therefore requires dehydrogenation to have good hypoxia adaptability energy.
(3) reaction inlet temperature higher (145～190 ℃).Therefore the dehydrogenation unit design, if dehydrogenation can be operated at low temperatures, will cut down the consumption of energy after carbon-dioxide gas compressor (about 110 ℃ of outlet temperatures) significantly in the urea production.
(3) summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of sulfur tolerance strong (total sulfur＞2mg/Nm
3), at high (H
2+ CO)/O
2Under (1.25～1.43) condition, show initiation temperature low (＜145 ℃), highly active advantage, and the novel dehydrogenation of restorability behind good heat endurance and the sulfur poisoning is arranged, be the dehydrogenation requirement of the urea production of raw material to satisfy with coal, residual oil or natural gas.
The present invention achieves the above object by improving catalyst composition and preparation method.
Catalyst for removing hydrogen from Co 2 raw gas used to synthesize urea of the present invention is a kind of urea synthesizing CO 2 catalyst for removing hydrogen that contains multiple rare earth element.Its composition contains Pd, Pt active component, is selected from least a rare earth element M among La, Ce, Pr, the Sm
1Auxiliary agent, and composite oxides Al
2O
3-TiO
2Or Al
2O
3-ZrO makes carrier, also contains Nd, Eu, Er, Yb, at least a rare earth element M of Lu
2Auxiliary agent, active component, auxiliary element M
1, M
2, the atomic ratio between the carrier closes is Pt, Pd: Al, Ti or Zr=1.7 * 10
-4～1.7 * 10
-1, Pt: Pd=1.0～30.0, Pt, Pd: auxiliary element M
1=0.03～0.6, Pt, Pd: auxiliary element M
2=0.05～3.0.
The Pt of described catalyst, Pd: Al, the better atomic ratio of Ti or Zr is 1.7 * 10
-3～1.7 * 10
-2
The better atomic ratio of the Pt of described catalyst: Pd is 1.0～10.0.
The Pt of described catalyst, Pd: auxiliary element M
1Better atomic ratio is 0.1～0.3.
The Pt of described catalyst, Pd: auxiliary element M
2Better atomic ratio is 0.15～1.0.
The carrier of this catalyst can be the Al of sphere or cloverleaf pattern
2O
3-TiO
2Or Al
2O
3-ZrO.Pt, Pd can be from different salts or metals, as H
2PtCl
66H
2O, PtCl
4, PdCl
2, H
2PdCl
4, Pt and Pd etc.Rare-earth elements La, Ce, Pr, Nd, Sm, Eu, Er, Yb, Lu can be from rare earth metal or salt.
The urea synthesis CO that contains multiple rare earth element of the present invention
2The catalyst for removing hydrogen of unstripped gas (code name TH-3) has been compared following characteristics with the known dehydrogenation of document:
1. this catalyst for removing hydrogen is identical with Pt, Pd content in the TH-2 dehydrogenation, and its Pt content is greater than Pd, and Pd content is greater than Pt in the domestic dehydrogenation of having used, and this catalyst has utilized catalytic oxidation activity and the anti-poisonous substance performance characteristics good than Pd of Pt.
2. this catalyst for removing hydrogen has added at least a element M among rare earth La, Ce, Pr, the Sm
1With at least a element M among Nd, Eu, Er, Yb, the Lu
2As auxiliary agent, improved the poison resistance of anti-sulphur of catalyst greatly, improved the low temperature active of catalyst, the restorability behind hypoxia adaptability and the sulfur poisoning has reduced the content of noble metal in catalyst.
3. because this catalyst for removing hydrogen has adopted Al
2O
3-TiO
2Or Al
2O
3-ZrO composite oxides are made carrier, and the anti-CO toxicity of catalyst is improved.Many TiO that experimental results show that
2With carried metal strong interaction is arranged, can improve the poison resistance of catalyst, TiO
2Weak point be that specific surface is less relatively, generally be not more than 100m
2/ g, active anatase crystalline form is at high temperature stable inadequately, easily becomes the rutile structure of inertia.Al
2O
3-TiO
2Binary composite oxide carrier utilizes Al
2O
3High surface and high thermal stability overcome TiO
2The defective of itself.Al
2O
3-TiO
2Complex carrier and carried metal interact strong, Heat stability is good, and surface area is suitable, and poison resistance is strong.
Application shows, this catalyst for removing hydrogen has sulfur tolerance strong (ability of promptly anti-high-sulfur impact capacity and long-term good operation under the high-sulfur condition), and hypoxia adaptability can be good, low temperature active height, easy advantage such as regeneration behind the sulfur poisoning.
(4) specific embodiment
The activity of catalyst and sulfur resistance test are atmospheric fixed bed anti-at φ 21.5 * 600mm Answer in the device and carry out, the granularity of catalyst is φ 2.5～3.2mm, and the loadings of catalyst is 6ml. The unstripped gas of activity test is pressed the used CO of commercial plant2Unstripped gas forms preparation.
The dehydrogenation activity of catalyst is to make the residual hydrogen amount of reaction end gas required less than 10ppm Low reaction temperatures represents the activity of catalyst. Minimum full conversion temperature is more low, then catalyst Activity more high.
The test of catalyst sulfur tolerance is with H2S concentration is 5.0mg/Nm3、50.0mg/Nm
3CO2Unstripped gas is kept the residual hydrogen amount of tail gas during respectively by dehydrogenation and is represented the sulfur tolerance of catalyst less than accumulative total reaction time of 10ppm, perhaps adopts under same reaction temperature H in accumulative total reaction time and unstripped gas2The product ppmh of S concentration represents anti-sulphur Energy. Keep the high activity reaction time (the residual hydrogen amount of tail gas＜10pmm) more long, then catalyst Sulfur tolerance more good.
The recovery test of catalyst is after keeping the complete sulfur poisoning inactivation of catalyst, to pass into the not CO of sulfur-bearing2Unstripped gas, until dehydrogenation reactor export residual hydrogen amount≤10ppm required the time Between represent the poisoning restorability of catalyst, required time is more short, expression catalyst extensive Renaturation can be more good.
Embodiment 1
Take by weighing diameter 2.0～3.0mm and contain TiO280% Al2O
3-TiO
2Bead 10 grams are for subsequent use. In the beaker of 250ml, add the 100ml deionized water, add concentration 0.01 gram Pt/ml's H2PtCl
6·6H
2O solution 2ml, adding concentration is the PdCl of 0.01 gram Pd/ml2Solution 1ml adds 0.31 gram cerous nitrate again, and 0.206 gram lanthanum nitrate and 0.2 gram ytterbium nitrate are poured the Al that weighs up into after stirring2O
3-TiO
2Bead floods it, stirs to add hydrazine hydrate (N after 30 minutes2H
4·4H
2O, 50%) 1ml continues to stir 1 hour, crosses the elimination raffinate, spend from The impregnated bead of sub-water washing obtains the grey catalyst 80～120 ℃ of oven dry then and produces Product, its Pt content are 0.2% (wt), and Pd content is 0.1% (wt), and Ce content is 1.0% (wt), La content is 1.0% (wt), and Yb content is 0.8% (wt).
Catalyst is placed reactor, use H2 1.0％(v)、O
2 0.84％(v)、CO 0.2％
(v)、H
2S 5.0mg/Nm
3CO2Unstripped gas, air speed 30000h-1, normal pressure is at hypoxemia [(H2＋CO)/O
2-1.43] carry out under the condition dehydrogenation activity of catalyst, anti-sulphur and in Restorability test behind the poison. Its minimum full conversion temperature is 120 ℃, the anti-sulphur time 12 of catalyst Hour, be 15 minutes recovery time after poisoning. Above-mentioned CO2H in the unstripped gas2S concentration 50.0mg/Nm3The time, its minimum full conversion temperature is 120 ℃, anti-sulphur time of catalyst 6 is little The time, be 20 minutes recovery time after poisoning.
Under the similarity condition, compare with TH-2 catalyst and domestic high-quality dehydrogenation E, at CO2H in the unstripped gas2S concentration 5.0mg/Nm3The time, the minimum full conversion of TH-2 catalyst Temperature is 120 ℃, and the 3 hours anti-sulphur time of catalyst, be 10 minutes recovery time after poisoning; The minimum full conversion temperature of E catalyst is 132 ℃, the 2.5 hours anti-sulphur time of catalyst, in Be 243 minutes recovery time behind the poison. At CO2The H of unstripped gas2S concentration is 50.0mg/Nm3The time, the minimum full conversion temperature of TH-2 catalyst is 135 ℃, the anti-sulphur time 1.2 of catalyst Hour, be 15 minutes recovery time after poisoning; The minimum full conversion temperature of E catalyst is 148 ℃, the 0.9 hour anti-sulphur time of catalyst, be 265 minutes recovery time after poisoning.
Embodiment 2
Employing is with the identical prescription of embodiment 1 and the catalyst of method preparation.
Catalyst is placed reactor, use H2 1.0％(v)、O
2 1.45％(v)、CO 0.2％
(v)、H
2S 5.0mg/Nm
3CO2Unstripped gas, air speed 30000h-1, normal pressure is at hyperoxia [(H2＋CO)/O
2-0.83] carry out under the condition dehydrogenation activity of catalyst, anti-sulphur and Restorability test after poisoning. Its minimum full conversion temperature is 120 ℃, during the anti-sulphur of catalyst Between 15.5 hours, be 15 minutes recovery time after poisoning. Above-mentioned CO2H in the unstripped gas2S concentration is 50.0mg/Nm3The time, its minimum full conversion temperature is 122 ℃, during the anti-sulphur of catalyst Between 7.9 hours, be 18 minutes recovery time after poisoning.
Under the similarity condition, compare with TH-2 catalyst and domestic high-quality dehydrogenation E, at CO2H in the unstripped gas2S concentration 5.0mg/Nm3The time, the minimum full conversion of TH-2 catalyst Temperature is 132 ℃, and the 7 hours anti-sulphur time of catalyst, be 16 minutes recovery time after poisoning; The minimum full conversion temperature of E catalyst is 137 ℃, the 1.4 hours anti-sulphur time of catalyst, in Be 156 minutes recovery time behind the poison.
Embodiment 3
According to the preparation method of embodiment 1, cut-off footpath 2.0～3.0mm contains TiO280% Al2O
3-TiO
2Bead 10 grams, samaric nitrate 0.444 gram, neodymium nitrate 0.3 gram, the H of concentration 0.01 gram Pt/ml2PtCl
6·6H
2O solution 2.0ml, concentration is the PdCl of 0.01 gram Pd/ml2Solution 1.0ml makes and contains Pt 0.2% (wt), Pd 0.1% (wt), Sm 1.5% (wt) The catalyst of Nd 1.0% (wt).
Catalyst is tested by experimental condition and the content measurement of embodiment 1. Work as CO2H in the unstripped gas2S concentration is 5.0mg/Nm3The time, its minimum full conversion temperature is 128 ℃, urges Changing the anti-sulphur time of agent is 9 hours, and be 30 minutes recovery time after poisoning. Work as CO2H in the unstripped gas2S concentration is 50.0mg/Nm3The time, its minimum full conversion temperature is 144 ℃, catalyst 3.8 hours anti-sulphur time, be 37 minutes recovery time after poisoning.
Embodiment 4
Preparation method according to embodiment 1. The Al of cut-off footpath 2.0～3.0mm2O
3-ZrO bead 10 grams, praseodymium nitrate 0.362 gram, lutecium nitrate 0.103 gram, erbium nitrate 0.133 gram, the H of concentration 0.01 gram Pt/ml2PtCl
6·6H
2O solution 2.5ml, concentration is the PdCl of 0.01 gram Pd/ml2Solution 0.5ml makes and contains Pt 0.25% (wt), Pd 0.05% (wt), and Pr 1.5% (wt), Lu 0.5% (wt), the catalyst of Er 0.5% (wt).
Catalyst is tested by experimental condition and the content measurement of embodiment 1. Work as CO2H in the unstripped gas2S concentration is 5.0mg/Nm3The time, its minimum full conversion temperature is 132 ℃, urges Changing the anti-sulphur time of agent is 8.6 hours, and be 32 minutes recovery time after poisoning. Work as CO2H in the unstripped gas2S concentration is 50.0mg/Nm3The time, its minimum full conversion temperature is 147 ℃, catalysis The 3.5 hours anti-sulphur time of agent, be 41 minutes recovery time after poisoning.
Embodiment 5
Preparation method according to embodiment 1. The Al of cut-off footpath 2.0～3.0mm2O
3-ZrO bead 10 grams, cerous nitrate 0.465 gram, europium nitrate 0.294 gram, the H of concentration 0.01 gram Pt/ml2PtCl
6·6H
2O solution 2.0ml, concentration is the PdCl of 0.01 gram Pd/ml2Solution 1.5ml makes and contains Pt 0.20% (wt) is arranged, Pd 0.15% (wt), Ce 1.5% (wt), Eu 1.0% (wt), Catalyst.
Catalyst is tested by experimental condition and the content measurement of embodiment 1. Work as CO2H in the unstripped gas2S concentration is 5.0mg/Nm3The time, its minimum full conversion temperature is 130 ℃, urges Changing the anti-sulphur time of agent is 9.8 hours, and be 28 minutes recovery time after poisoning. Work as CO2H in the unstripped gas2S concentration is 50.0mg/Nm3The time, its minimum full conversion temperature is 143 ℃, catalysis The 4.2 hours anti-sulphur time of agent, be 39 minutes recovery time after poisoning.
Embodiment 6
Preparation method according to embodiment 1. The Al of cut-off footpath 2.0～3.0mm2O
3Bead 10 grams, cerous nitrate 0.62 gram, lutecium nitrate 0.206 gram, the H of concentration 0.01 gram Pt/ml2PtCl
6·6H
2O solution 2.0ml, concentration is the PdCl of 0.01 gram Pd/ml2Solution 1.0ml makes and contains Pt 0.20% (wt) is arranged, Pd 0.1% (wt), Ce 2.0% (wt), Lu 1.0% (wt), Catalyst.
Catalyst is tested by experimental condition and the content measurement of embodiment 1. Work as CO2H in the unstripped gas2S concentration is 5.0mg/Nm3The time, its minimum full conversion temperature is 126 ℃, urges Changing the anti-sulphur time of agent is 10 hours, and be 25 minutes recovery time after poisoning. Work as CO2H in the unstripped gas2S concentration is 50.0mg/Nm3The time, its minimum full conversion temperature is 141 ℃, catalysis The 4.8 hours anti-sulphur time of agent, be 35 minutes recovery time after poisoning.
The most preferred embodiment that can find out catalyst for removing hydrogen of the present invention from the above embodiments is Example 1, example 2.
Embodiment 7
Certain urea synthesis factory uses the catalyst for removing hydrogen of pressing embodiment 1 prescription, and dehydrogenation reactor loads its catalyst 0.926m3, at urea synthesis CO2Contain H in the unstripped gas2 0.9～1.0％(v)、
O
2 0.9～1.0％(v)、CO 0.9～0.15％(v)，COS 0.33～0.78mg/Nm
3, total sulfur 1.04～23.0mg/Nm3，CH
3OH 398.6～432.1ml/m
3，CH
40.14～0.5%, air speed 31000h-1, pressure 14.3MPa, 120 ℃ of minimum full conversion temperatures, under 150 ℃ of conditions of operating temperature, H2All can take off to less than 2ppm, CO takes off to less than 10ppm, CH3OH takes off Extremely less than 10ppm.
The performance of dehydrogenation of the present invention and TH-2 and domestic high-quality dehydrogenation E Relatively list in table 1.
Application shows, novel TH-3 urea dehydrogenation catalyst, the dehydrogenation problem of the urea plant take residual oil, coal and natural gas as raw material since can solving better over a long period of time can fundamentally be eliminated the synthetic high pressure exhaust gas H of the large, medium and small urea plant of China2Content accumulation is too high to set off an explosion Dangerous.
The Performance Ratio of table 1 dehydrogenation of the present invention and TH-2 and E dehydrogenation
| The catalyst model | H 2/O 2 | Minimum full conversion temperature (℃) | H in the unstripped gas2S concentration (mg/Nm3) | The dehydrogenation reaction inlet temperature (℃) | The anti-sulphur time (h) | Restorability (min) |
| Example 1 | 1.43 | 120 120 | 5.0 50.0 | 150 150 | 12 6 | 15 20 |
| TH-2 | 1.43 | 120 135 | 5.0 50.0 | 150 150 | 3.0 1.2 | 10 15 |
| E | 1.43 | 132 148 | 5.0 50.0 | 150 150 | 2.5 0.9 | 243 265 |
| Example 2 | 0.83 | 120 122 | 5.0 50.0 | 120 120 | 15.5 7.9 | 15 18 |
| TH-2 | 0.83 | 120 132 | 5.0 50.0 | 120 120 | 13.5 7.0 | 10 16 |
| E | 0.83 | 125 137 | 5.0 50.0 | 120 120 | 3.0 1.4 | 127 156 |
| Example 3 | 1.43 | 128 144 | 5.0 50.0 | 150 150 | 9 3.8 | 30 37 |
| Example 4 | 1.43 | 132 147 | 5.0 50.0 | 150 150 | 8.6 3.5 | 32 41 |
| Example 5 | 1.43 | 130 143 | 5.0 50.0 | 150 150 | 9.8 4.2 | 28 39 |
| Example 6 | 1.43 | 126 141 | 5.0 50.0 | 150 150 | 10 4.8 | 25 35 |
Claims (5)
1. catalyst for removing hydrogen from Co 2 raw gas used to synthesize urea, its composition contains Pt, Pd active component, is selected from least a rare earth element M among La, Ce, Pr, the Sm
1Auxiliary agent, and composite oxide Al
2O
3-TiO
2Or Al
2O
3-ZrO carrier is characterized in that also containing and is selected from least a rare earth element M among Nd, Eu, Er, Yb, the Lu
2Auxiliary agent, active component, auxiliary element M
1, M
2, the atomic ratio between the carrier closes and is: Pt, Pd: Al, Ti or Zr=1.7 * 10
-4～1.7 * 10
-1Pt: Pd=1.0～30.0; Pt, Pd: auxiliary element M
1=0.03～0.6; Pt, Pd: auxiliary element M
2=0.05～3.0.
2. catalyst as claimed in claim 1 is characterized in that Pt, Pd: Al, Ti or Zr=1.7 * 10
-3～1.7 * 10
-2
3. catalyst as claimed in claim 1 is characterized in that Pt: the atomic ratio of Pd is 1.0～10.0.
4. catalyst as claimed in claim 1 is characterized in that Pt, Pd: auxiliary element M
1Atomic ratio be 0.1～0.3.
5. catalyst as claimed in claim 1 is characterized in that Pt, Pd: auxiliary element M
2Atomic ratio be 0.15～1.0.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01114383A CN1113693C (en) | 2001-07-27 | 2001-07-27 | Dehydrogenating catalyst containing more rare-earth elements for CO2 gas used to synthesize urea |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01114383A CN1113693C (en) | 2001-07-27 | 2001-07-27 | Dehydrogenating catalyst containing more rare-earth elements for CO2 gas used to synthesize urea |
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| Publication Number | Publication Date |
|---|---|
| CN1334140A true CN1334140A (en) | 2002-02-06 |
| CN1113693C CN1113693C (en) | 2003-07-09 |
Family
ID=4661031
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1330419C (en) * | 2005-05-19 | 2007-08-08 | 湖北省化学研究院 | Method for regenerating urea dehydrogenation noble metal catalyst |
| CN100371073C (en) * | 2005-07-27 | 2008-02-27 | 中国船舶重工集团公司第七一八研究所 | Metal carrier type hydrogen-eliminating catalyst and preparation process thereof |
| CN101711987B (en) * | 2009-11-11 | 2012-05-30 | 浙江工业大学 | Dehydrogenation catalyst and method for preparing same |
| CN102974344A (en) * | 2012-10-30 | 2013-03-20 | 大连凯特利催化工程技术有限公司 | Dehydrogenation catalyst applicable to raw gas rich in carbon monoxide, and preparation and application thereof |
-
2001
- 2001-07-27 CN CN01114383A patent/CN1113693C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1330419C (en) * | 2005-05-19 | 2007-08-08 | 湖北省化学研究院 | Method for regenerating urea dehydrogenation noble metal catalyst |
| CN100371073C (en) * | 2005-07-27 | 2008-02-27 | 中国船舶重工集团公司第七一八研究所 | Metal carrier type hydrogen-eliminating catalyst and preparation process thereof |
| CN101711987B (en) * | 2009-11-11 | 2012-05-30 | 浙江工业大学 | Dehydrogenation catalyst and method for preparing same |
| CN102974344A (en) * | 2012-10-30 | 2013-03-20 | 大连凯特利催化工程技术有限公司 | Dehydrogenation catalyst applicable to raw gas rich in carbon monoxide, and preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1113693C (en) | 2003-07-09 |
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