CN1096494A - Sulfur-resistant CO conversion catalyst and method for making - Google Patents
Sulfur-resistant CO conversion catalyst and method for making Download PDFInfo
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- CN1096494A CN1096494A CN93106918A CN93106918A CN1096494A CN 1096494 A CN1096494 A CN 1096494A CN 93106918 A CN93106918 A CN 93106918A CN 93106918 A CN93106918 A CN 93106918A CN 1096494 A CN1096494 A CN 1096494A
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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
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Abstract
A kind ofly widely usedly in petrochemical industry can adapt to the doctor negative wide temperature range and sulfurrange type sulfur-resistant CO conversion catalyst of high temperature, be with cobalt (or nickel), molybdenum (or tungsten) is an active ingredient, magnesium oxide, aluminum oxide and titanium dioxide are carrier component, rare earth oxide is a coagent, the suspension intermediate processing prepares carrier, kneading method prepares catalyzer, catalyzer shift activity height of the present invention, good stability, the intensity height, especially strong to the low-sulfur adaptive faculty, good to low water-gas ratio and high-speed adaptability, be suitable for the conversion sulfur-bearing and contain CO (carbon monoxide converter) gas, the sulfur-bearing CO (carbon monoxide converter) gas that contains higher or that sulfur-bearing is lower that is particularly suitable for conversion residual oil or coal high pressure (as 8.5MPa) gasification generation is produced ammonia synthesis gas, oxo-synthesis gas and plant hydrogen.
Description
The present invention relates in the petrochemical industry sulfur-bearing contain CO (carbon monoxide converter) gas and water vapor carries out employed sulfur-resistant CO conversion catalyst of transformationreation and preparation method.
Technical background
People are known, are that raw material is that raw material gas making contains sulfide usually at containing of being produced in the CO (carbon monoxide converter) gas through partial oxidation gas making with the coal with heavy oil or vacuum residuum, and its content is relevant with the sulphur content of raw material, generally at hundreds of between several thousand PPM.Generally copper-the zinc of Shi Yonging be low temperature shift catalyst and iron-chromium be high temperature conversion catalyst since to sulfide responsive and not anti-high-load sulfide and can not using, shift activity reduces greatly when perhaps using.
Make ammonia synthesis gas in order to adapt to the petrochemical industry field, the needs of oxo-synthesis gas and the raw materials used heaviness of hydrogen, people's development is appeared with transformation catalyst.This class catalyzer is an active ingredient with cobalt or nickel, molybdenum or tungsten usually, with Al
2O
3, MgO-Al
2O
3And ZnO-Al
2O
3Deng oxide compound or composite oxides is carrier substance, and the also interpolation basic metal that has etc. have only active constituent to be in sulfided state and just have sufficient activity as coagent, they be suitable for the conversion sulphur content higher contain CO (carbon monoxide converter) gas.For example in patents such as U.P.3.529.935, U.P.4.153.580, mention this class catalyzer.At present, worldwide use than the wide industrial sulfur-resistant transformation catalyst and have: the German K8-11Co-Mo/MgO-Al of BASF AG
2O
3, Denmark ToPS φ e company, SSKCo-Mo-K/Al
2O
3With the C25-2-02 of U.S. UCI company, Co-Mo-K/ReO-Al
2O
3Catalyzer.Practice shows that this class catalyzer has advantages such as shift activity height, active wide temperature region, anti-sulphur ability are strong, renewable, but also there are some weak points, if any catalyzer under high pressure and high steam partial pressure because structural instability, intensity is low and can not under high pressure use; Basic metal in the catalyzer is easy to run off and causes that activity descends, pollutes etching apparatus; The low temperature active that has is poor, and what have uses active decline more in the lower process gas of sulphur content, and use range is restricted.
Goal of the invention
For solving foregoing problems, the present invention makes a kind of novel sulfur-resistant CO conversion catalyst, this catalyzer does not add basic metal, under high pressure and high steam partial pressure Stability Analysis of Structures, intensity is good, shift activity is high, the low temperature property controlled height, good to high-speed and low water-gas ratio adaptability particularly, strong to containing CO (carbon monoxide converter) gas sulphur content variation adaptive faculty, thereby use range is wide, both can high-sulfur (several thousand PPM or more than) also can low-sulfur (hundreds of PPM so that 〉=use under 100PPM) the condition.
Summary of the invention
The active constituent of sulfur-resistant CO conversion catalyst of the present invention is cobalt or nickel and molybdenum or tungsten, utilizes conventional method to prepare active constituent, wherein Co or Ni to the atomic ratio of Mo or W between 0.1-2.5.Carrier substance can be from Al in the catalyzer
2O
3, MgO and TiO
2In select, one or both or collocation by a certain percentage between three kinds separately for example can be MgO-Al
2O
3, MgO-TiO
2, Al
2O
3-TiO
2Or MgO-Al
2O
3-TiO
2Wherein MgO and Al
2O
3Ratio 0.3-10, MgO and the TiO of mol
2Mol than for 1.0-20 more suitable, TiO
2With Al
2O
3The mol ratio is more suitable for 0.05-2.0.Can add an amount of non-basic metal coagent in the catalyzer, as alkaline-earth metal Ca, Mg, Ba, Sr etc., other elements such as rare-earth elements La, Ce or mishmetal and Mn, Zn, Cu, its content is 0-10%(m/m).
Preparation of catalysts of the present invention, at first with magnesium oxide, preferably light magnesium oxide or magnesium hydroxide add the proper amount of deionized water pulp, add to then in the aqueous solution of aluminum nitrate (or using nitric acid dissolve aluminium hydroxide) or other aluminum soluble salt, under agitation under 10-90 ℃ of condition, adopt the alkaline precipitating agent commonly used precipitation that suspends, pH value is controlled at 7-12, dope filtration with obtaining is washed till neutrality with deionized water then.Filter cake is pulled an oar and the interpolation active ingredient: solubility cobalt salts such as ammonium molybdate solution and Xiao Suangu or Cobaltous diacetate, making the CoO add-on is 1.0-10.0%(m/m), add coagent dissolvable agents salts solution again, make Re
2O
3Add-on is 0-10%(m/m), both ratios are 1: 9-9: 1, add metatitanic acid or titanium dioxide then and mix, also both with activity component impregnation to carrier substance.At last, drying and crushing is sieved under normal temperature, will add common shaping additive by general method before being shaped, and extrusion is shaped again, makes finished catalyst then in roasting 1-5 hour.
The characteristics of catalyzer of the present invention are: 1. add the TiO carrier component, constitute MgO-TiO
2-Al
2O
3The ternary carrier gives catalyzer some excellent properties; 2. contain in the catalyzer small amount of alkali earth metals or mishmetal and Mn, Zn, Cu, etc., help the dispersion of active constituent and stable; 3. adopt the precipitation that suspends, magnesium oxide and aluminum oxide are mixed.Because this catalyzer has These characteristics aspect component and the preparation, therefore have excellent catalyst performance and over-all properties, as: be easy to sulfuration, the active height of shift activity high and low temperature, active wide temperature region, good stability, advantage such as strong and intensity is good to the adaptive faculty of low water-gas ratio, high-speed, especially low sulfur content.
The invention effect
Aforesaid purpose of the present invention reaches, and sulfur-resistant CO conversion catalyst of the present invention can be at high pressure (as normal pressure-10.0MPa) and high steam partial pressure (as 5.0-6.0MPa) down conversion sulfur-bearing wide ranges (as 100-50000P.P.MH
2S) contain CO (carbon monoxide converter) gas.Its shift activity, particularly low temperature shift are active high, and strong to low water-gas ratio, high-speed, the particularly adaptive faculty of low in hydrogen sulphide concentration, intensity and strength stability are good.More than all performances all be better than using similar widely industrial sulfur-resistant transformation catalyst.
Experimental technique and condition
Catalyst performance evaluation reactor φ 45 * 5mm stainless steel tubular type reactor, built-in shaft is managed outer nichrome wire heating and insulation to φ 8 * 2mm Thermal couple casing pipe.Wet process gas enters by catalyst bed from the reactor top, and reacted gas is discharged from the bottom, removes the water that does not have reaction through condensation separation, and the analysis of hplc tail gas that degass is after metering formed or emptying.
Test is formed with unstripped gas, %(v/v)
CO CO
2CH
4H
2S H
2S H
2
A 40-50 0-5.0 0.25-0.4 0.2-0.4 surplus
B 40-50 0-5.0 0.25-0.4 0.01-0.03 surplus
Test conditions: catalyzer loading amount, the dilution in 1: 1 of ml 50-100(φ 4mma-AlO ball)
Catalyst size: mm φ 4 * 4
Sulfide stress: Mpa 2.0
Curing temperature: ℃ 250
Sulfuration water to steam ratio: 1.0-1.4
Sulfuration air speed (doing): h
-12000
Curing time: h 20
Conversion pressure: MPa 8.0-8.5
Transformation temperature: ℃ 250-500
Conversion water-gas ratio: 0.8-1.4
Conversion air speed (doing): h
-11000-1000
The main physical index of catalyzer of the present invention and composed as follows:
Form:
CoO 1.0-10.0 (% m/m)
MoO
32.0-20.0 (% m/m)
Re
2O
30-10.0 (% m/m)
TiO
21.0-50 (% m/m)
MgO 10-40 (% m/m)
Al
2O
320-80 (% m/m)
Profile and size: mm bar shaped φ 4
Bulk density: Kg/l 0.75-0.82
Crushing strength: N/cm〉120
Pore volume (press pump): cm
3/ g 0.2-0.5
Specific surface (press pump): m
2/ g 40-130
Test-results
1, sulfuration
Table 1 provides catalyzer of the present invention and the cure efficiency of industrial widely used sulfur-resistant transformation catalyst under two kinds of water-gas ratio conditions.Data show in the table 1, and catalyzer shift activity of the present invention is better than commercial catalysts under identical cure conditions, and water/gas variation is little to catalysts influence of the present invention, but big to the commercial catalysts influence, and water-gas ratio increases active decline obviously.
2, conversion
Table 2 provides the present invention to have the different characteristics catalyzer and contrasts commercial catalysts at 270-500 ℃, and then is back to 350 ℃ of shift activities under the condition.Data show, before catalyst B and the C500 ℃ burin-in process, and all preferred commercial catalysts of back shift activity.
Table 3 provides catalyzer of the present invention and the contrast commercial catalysts is 0.01-0.03%(v/v at the unstripped gas concentration of hydrogen sulfide) shift activity under the condition of low levels.
* heating makes temperature out be increased to 450 ℃
The * catalyzer contains and rare earth element
Test conditions: catalyzer φ 4 * 4mm100ml, dilution in 1: 1,
8.2MPa, water/gas 1.2, air speed (doing) 3000h, unstripped gas B.
Data show that the shift activity of catalyzer of the present invention is better than commercial catalysts in the test warm area, and is particularly more obvious in the cold zone advantage.And the real transform rate is more near the balanced transformation rate, and the balance temperature is apart from less than commercial catalysts.
3, water-gas ratio and shift activity
Table 4 provides catalyzer of the present invention and the shift activity of contrast commercial catalysts under different water/gas.Data show that catalyst outlet CO content of the present invention all is lower than commercial catalysts in test water/gas scope, and reduce very unobviously with water/gas, illustrate that the shift activity of catalyzer of the present invention is better than commercial catalysts, and are stronger to the adaptive faculty of low water/gas.
4, dry gas air speed and shift activity
Table 5 provides catalyzer of the present invention and the shift activity of contrast commercial catalysts under different air speeds.Data show that the outlet CO content of catalyzer of the present invention is lower than commercial catalysts in test air speed scope, and it is not obvious to increase rising with air speed.The shift activity that catalyzer of the present invention is described is better than commercial catalysts, and is strong than commercial catalysts to the adaptive faculty of high-speed.
5, stability test
Table 6 provides 1020 hours stability test results of catalyzer of the present invention and contrast commercial catalysts continuous operation.Data show that under 250 ℃ of identical cure conditions, the interconversion rate of catalyzer of the present invention illustrates that apparently higher than the interconversion rate of commercial catalysts the former is easy to sulfuration, low temperature active height; Under variant temperature, the shift activity of catalyzer of the present invention all is higher than the commercial catalysts under the corresponding conditions, and the former real transform rate is more near the balanced transformation rate, and the balance temperature illustrates that apart from little catalyzer shift activity of the present invention obviously is better than commercial catalysts.Under the identical situation of interconversion rate, the comparable commercial catalysts of the temperature in of catalyzer of the present invention is low more than 25 ℃; When getting back to low temperature after high temperature, the shift activity of catalyzer of the present invention more significantly is better than commercial catalysts, illustrates that catalyzer of the present invention is than the commercial catalysts good stability.
Table 7 provides catalyzer of the present invention and the variation that contrasts commercial catalysts intensity after the 1020h running.Data show that no matter be before the running or intensity or strength retention ratio after the running, catalyzer of the present invention all is higher than commercial catalysts, illustrates that the former intensity and strength stability all are better than the latter.
Is raw material at certain with low sulfur resid, 8.5MPa used catalyzer of the present invention (on industrial installation, preparing) on the general shift converter side line of the large-scale ammonia plant device of pressure lower section oxidation gas making, loading amount 751, running is 86 days under one section conversion operating mode, operating condition:
Curing medium process gas: contain H
2S0.01-0.03% (v/v)
Curing temperature: ℃ 200-250
Curing time: h 40
Sulfuration water-gas ratio: 1.4
Sulfide stress: MPa about 1.0
Conversion pressure: 0.8
Conversion water-gas ratio: 1.4
Conversion tolerance: M/h 536 (being equivalent to dry gas air speed 3000h)
Unstripped gas is formed: % (v/v)
CO CO
2N
2+Ar CH
4H
2S H
2
43.5 surplus in the of ± 1.0 6.0 ± 0.5 0.55 ± 0.05 1.2 ± 0.2 0.02 ± 0.01
Data are listed in table 8, data show, in the inlet temperature is 294-330 ℃, hot(test)-spot temperature is that catalyzer of the present invention has quite high activity under the 425-480 ℃ of situation, and the low interconversion rate of temperature in does not descend, illustrate that this catalyzer is active high at low-sulfur condition down conversion, can use under high temperature low-sulfur condition, this is the premium properties that existing industrial co-mo antisulphuric transforming catalyst does not have, and has widened the use range of this class catalyzer.
Comprehensive above-mentioned test-results, can clear and definite conclusion:
1, in 250-500 ℃ of test temperature scope, sulfur-resistant transformation catalyst shift activity, particularly low temperature active of the present invention obviously are better than commercial catalysts.
2, at 0.01-0.03%(v/v) to test in the concentration of hydrogen sulfide scope, the present invention anti-sulphur activity, particularly low temperature active also obviously are better than commercial catalysts, are being commonly referred to be the MoS of keep-out area
2Hydrolysis area is also referred to as under the condition of reversal of cure and still has higher activity, can use under high temperature low-sulfur condition.Illustrate and both can be used for height by catalyzer of the present invention to contain sulfur resid or high-sulfur coal be that the conversion process of raw material gas making flow process also can be used for the low conversion process that to contain sulfur resid or low sulfur-bearing coal be raw material gas making.
3, under the identical condition of CO interconversion rate, catalyzer of the present invention can be operated under water/gas low than commercial catalysts and high air speed.
4, the shift activity stability of catalyzer of the present invention and strength stability are good, are better than commercial catalysts.
Embodiment 1
Take by weighing 883g Al(NO)
3.9HO(or use HNO
3The dissolved hydrogen aluminum oxide) is dissolved in the 2000ml deionized water, 70g light magnesium oxide (MgO content 74.3%m/m) added in the 500ml deionized water pull an oar evenly, under agitation be added in the above-mentioned aluminum nitrate solution.Slowly add ammoniacal liquor again, the precipitation that under 50 ℃, suspends, PH=8 then filters, and is washed till no NO with deionized water
- 3, under room temperature,, add (NH) the filter cake making beating
6Mo
7O
24.4H
2O concentration is 24.5%(m/m) aqueous solution 100g and 31.1%(m/m) Co(NO
2)
2.6H
2O aqueous solution 100g, it is even to mix pulp.110 ℃ of dryings, pulverized 100 mesh sieves, make work in-process.Press powder weight and calculate, add 1.5%(m/m) the sesbania powder, stir and be kneaded into plastic material group, on banded extruder, extrude into φ 4mm bar shaped catalyst.Through seasoning,, make finished catalyst 500 ℃ of roasting temperatures 4 hours.
Embodiment 2
The preparation method is with embodiment 1, different cobalt nitrate solutions dark.Concentration is 27.2%(m/m) add 4.0%(m/m) La(NO)
3.6H
2O and 4.0%(m/m) Ce(NO)
3.6H
2O solution 100g makes catalyzer.
Embodiment 3
The preparation method is with embodiment 1, and that different is Al(NO)
3.9H
2The O consumption is 771g, adds 15g powdery TiO before making beating adds cobalt nitrate solution earlier
2, make catalyzer.
Embodiment 4
The preparation method is with embodiment 3, and different is that the light magnesium oxide consumption is 68.7g, and cobalt nitrate solution contains 4.0%(m/m), La(NO)
3.6H
2O and 4.0%(m/m) Ce(NO)
3.6HO, make catalyzer.
Embodiment 5
The interpolation TiO that the preparation method with embodiment 3,4 differences is
27.5g, Al(NO) .9H
2O799g.Make catalyzer.
Embodiment 6
The preparation method is with embodiment 5, and that different is TiO
2Addition is 62g, Al(NO)
3.9HO consumption is 598g, makes catalyzer.
Claims (5)
1, a kind of sulfur-bearing that is suitable for contains the sulfur-resistant transformation catalyst that CO gas and water vapor carry out transformationreation, it is characterized in that having following composition:
CoO 1.0-10.0 (% m/m)
MoO
32.0-20.0 (% m/m)
Re
2O
30-10.0 (% m/m)
TiO
21.0-50 (% m/m)
MgO 10-40 (% m/m)
Al
2O
320-80 (% m/m)
2, a kind of sulfur-bearing that is suitable for contains the preparation method that CO gas and water vapor carry out the sulfur-resistant transformation catalyst of transformationreation, it is characterized in that:
The a preparing carriers at first with magnesium oxide or magnesium hydroxide deionized water pulp, is added in the solution of aluminum nitrate or other aluminum soluble salt then;
B adopts the alkaline precipitating agent precipitation that suspends, and PH7-12 filters then, washs;
C adds active constituent ammonium molybdate and solubility cobalt salt solution with filter cake making beating, and add-on makes that CoO content is 1.0-10.0%m/m in the catalyzer, MoO
3Be 2.0-20.0%m/m;
D preferably adds the active rare-earth auxiliary agent again, the soluble salt solution of La and Ce, and it is Re that add-on makes the content of rare earth in the catalyzer
2O
30-10.0%m/m, wherein La: Ce=1: 9-9: 1(m/m);
E adds metatitanic acid or titanium dioxide again and mixes.
3, by the described method of claim 2, the magnesium oxide that uses when it is characterized in that described preparing carriers is best with light magnesium oxide.
4, by the described method of claim 2, it is characterized in that described active ingredient cobalt (or nickel) and molybdenum (or tungsten), their atomic ratio is best between 0.1-2.5, the weight content of cobalt oxide (or nickel oxide) is 1%-10% the best, and the weight content of molybdenum oxide (or Tungsten oxide 99.999) is 2%-20% the best.
5, by the prepared catalyzer of claim 1-4, it is characterized in that can be in process gas H
2S content＞0.01%(v/v), water/gas 0.8-1.6, dry gas air speed-4500h
-1Temperature 250-500 ℃, 0-9.0MPa(gauge pressure) using under the condition, can be to use under MoS hydrolysis or the so-called reversal of cure condition at the high temperature low-sulfur particularly, has widened the use range of cobalt molybdenum class sulfur-resistant transformation catalyst.Catalyzer of the present invention both had been applicable to high-sulfur residual oil or gasification flow process conversion process, also was applicable to low sulfur resid or gasification flow process conversion process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93106918A CN1045399C (en) | 1993-06-17 | 1993-06-17 | Sulfur and carbon monoxide resistant conversion catalyst and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93106918A CN1045399C (en) | 1993-06-17 | 1993-06-17 | Sulfur and carbon monoxide resistant conversion catalyst and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1096494A true CN1096494A (en) | 1994-12-21 |
| CN1045399C CN1045399C (en) | 1999-10-06 |
Family
ID=4986475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93106918A Expired - Lifetime CN1045399C (en) | 1993-06-17 | 1993-06-17 | Sulfur and carbon monoxide resistant conversion catalyst and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1045399C (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049262B (en) * | 2009-10-28 | 2013-01-02 | 中国石油化工股份有限公司 | Method for preparing clean CO sulfur tolerant shift catalyst |
| CN102950004A (en) * | 2011-08-31 | 2013-03-06 | 中国石油化工股份有限公司 | Carbon monoxide sulphur-tolerant pre-shift catalyst applicable under condition of low water-air ratio and preparation method |
| CN103464164A (en) * | 2013-08-27 | 2013-12-25 | 中国华能集团清洁能源技术研究院有限公司 | Method for preparing methanation catalyst by tartaric acid complex method |
| CN103596682A (en) * | 2011-06-15 | 2014-02-19 | H.C.施塔克股份有限公司 | Cobalt- and molybdenum-containing mixed oxide catalyst, and production and use thereof as water gas shift catalyst |
| CN103586028A (en) * | 2013-10-25 | 2014-02-19 | 中国华能集团清洁能源技术研究院有限公司 | Method for preparing methanation catalyst through glucose complexation process |
| CN103769116A (en) * | 2012-10-20 | 2014-05-07 | 中国石油化工股份有限公司 | Sulfur tolerant shift catalyst and preparation method |
| WO2014103074A1 (en) * | 2012-12-28 | 2014-07-03 | 三菱重工業株式会社 | Co shift catalyst, co shift reactor, and method for purifying gasification gas |
| CN106552648A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | Sulfur-bearing sulfur-resistant transformation catalyst and preparation method |
| CN106964363A (en) * | 2017-04-14 | 2017-07-21 | 山东科技大学 | A kind of anti-arsenic CO sulfur-resistant transformation catalysts and preparation method |
| CN117303312A (en) * | 2023-11-28 | 2023-12-29 | 上海电气集团国控环球工程有限公司 | Method for producing ammonia synthesis gas by water gas shift gas |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4389335A (en) * | 1981-04-14 | 1983-06-21 | United Catalysts Inc. | Catalyst for carbon monoxide conversion in sour gas |
-
1993
- 1993-06-17 CN CN93106918A patent/CN1045399C/en not_active Expired - Lifetime
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049262B (en) * | 2009-10-28 | 2013-01-02 | 中国石油化工股份有限公司 | Method for preparing clean CO sulfur tolerant shift catalyst |
| CN103596682A (en) * | 2011-06-15 | 2014-02-19 | H.C.施塔克股份有限公司 | Cobalt- and molybdenum-containing mixed oxide catalyst, and production and use thereof as water gas shift catalyst |
| CN102950004A (en) * | 2011-08-31 | 2013-03-06 | 中国石油化工股份有限公司 | Carbon monoxide sulphur-tolerant pre-shift catalyst applicable under condition of low water-air ratio and preparation method |
| CN103769116A (en) * | 2012-10-20 | 2014-05-07 | 中国石油化工股份有限公司 | Sulfur tolerant shift catalyst and preparation method |
| CN103769116B (en) * | 2012-10-20 | 2016-03-02 | 中国石油化工股份有限公司 | Sulfur-resistant transformation catalyst and preparation method |
| WO2014103074A1 (en) * | 2012-12-28 | 2014-07-03 | 三菱重工業株式会社 | Co shift catalyst, co shift reactor, and method for purifying gasification gas |
| CN103464164B (en) * | 2013-08-27 | 2015-11-18 | 中国华能集团清洁能源技术研究院有限公司 | Tartaric acid complexometry prepares the method for methanation catalyst |
| CN103464164A (en) * | 2013-08-27 | 2013-12-25 | 中国华能集团清洁能源技术研究院有限公司 | Method for preparing methanation catalyst by tartaric acid complex method |
| CN103586028A (en) * | 2013-10-25 | 2014-02-19 | 中国华能集团清洁能源技术研究院有限公司 | Method for preparing methanation catalyst through glucose complexation process |
| CN106552648A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | Sulfur-bearing sulfur-resistant transformation catalyst and preparation method |
| CN106552648B (en) * | 2015-09-30 | 2019-03-29 | 中国石油化工股份有限公司 | Sulfur-bearing sulfur-resistant transformation catalyst and preparation method |
| CN106964363A (en) * | 2017-04-14 | 2017-07-21 | 山东科技大学 | A kind of anti-arsenic CO sulfur-resistant transformation catalysts and preparation method |
| CN117303312A (en) * | 2023-11-28 | 2023-12-29 | 上海电气集团国控环球工程有限公司 | Method for producing ammonia synthesis gas by water gas shift gas |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1045399C (en) | 1999-10-06 |
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