CN1219500A - New CO sulphur-resistant transformation catalyst and its preparation method - Google Patents
New CO sulphur-resistant transformation catalyst and its preparation method Download PDFInfo
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Abstract
A sulfur-resistant non-alkali-metal Co-Mo series catalyst for transformation reaction between CO and water steam features that its active components contain the compound of at least one of Co and Ni, also the compound of at least one of Mo and W, its composite carrier is composed of TiO2, MgO and/or Al2O3 and/or cement, and it exists in the form of Mg-Al spinel structure when its carrier contain both MgO and A2O3. Said catalyst is suitable for the transformation process in the condition of wide temp. range (200-500 deg.C), wide sulfur content (greater than 0.01% v/v), and wide water steam ratio (0.4-1.8 mol/mol).
Description
The present invention relates to a kind of Catalysts and its preparation method that carbon monoxide and steam reaction are produced hydrogen and carbonic acid gas that is used for, specifically, the present invention relates to a kind of non-alkali-metal Co-Mo is sulfur-resistant transformation catalyst and its preparation method:
The transformationreation of carbon monoxide and water vapor is widely used in producing ammonia synthesis gas, hydrogen and oxo-synthesis gas, and this reaction needs just can carry out in the presence of catalyzer usually.Initial catalyzer commonly used is Fe-Cr series catalysts and Cu-Zn series catalysts, and this two classes catalyzer only just has activity under no sulphur or low-sulfur condition.The sixties are the needs that raw material is produced the higher synthetic gas of sulphur content in order to adapt to heavy oil, coal and vacuum residuum, and having succeeded in developing Co-Mo is sulfur-resistant transformation catalyst.
Early stage Co-Mo is that sulfur-resistant transformation catalyst mainly contains two big classes: a class is that non-alkali-metal Co-Mo is a sulfur-resistant transformation catalyst, and its low temperature active is poor, and the sulphur content in the process gas is had certain limitation, and it is serious to be lower than the limits value activity decay; Another kind of is that the promoted Co-Mo of basic metal is a sulfur-resistant transformation catalyst, as European patent EP 62, catalyzer described in 912, such catalyst low-temperature activity is good, the broad that requires to sulphur content in the process gas, but depress the catalyst activity decline seriously at high temperature or high steam branch, and carrier structure is stable inadequately.
A kind of alkali-metal sulfur-resistant transformation catalyst that do not add is disclosed among the Chinese patent CN1096494A, this catalyst low-temperature activity is good, and is good to high-speed and low water-gas ratio adaptability, and it is strong that sulphur content in the process gas is changed adaptive faculty, but in this catalyzer, its carrier is MgO-TiO
2-Al
2O
3The ternary carrier, in use, MgO and Al
2O
3Form magnesium-aluminium spinel MgAl
2O
4, cause the loss of strength and the lost of life of catalyzer.
It is sulfur-resistant transformation catalyst that purpose of the present invention just provides a kind of novel non-basic metal Co-Mo, and this catalyzer in use has strength stability and activity stability preferably.
In order to realize the foregoing invention purpose, in catalyzer of the present invention, its active constituent contains the compound of a kind of element among Co and the Ni at least, also contains the compound of a kind of element among Mo and the W at least; The carrier of catalyzer is a complex carrier, by TiO
2, MgO and/or Al
2O
3And/or the cement composition, and in carrier, contain MgO and Al simultaneously
2O
3The time, adopt water or steam treatment process, making its main existence form is magnesia-alumina spinel structure, i.e. MgO and Al
2O
3Be converted into spinel by stoichiometric ratio.Can add auxiliary agent in the catalyzer,, but not adopt basic metal to do its promotor as rare earth metal, alkaline-earth metal, Cu, Zn, Mn etc.
The each component of complex carrier shared quality percentage composition in catalyzer is: TiO
2Be 5～80%, be preferably 8～30%; MgO is 0～45%, is preferably 15～30%; Al
2O
3Be 0～60%, be preferably 5～15%.Wherein, TiO
2The interpolation form can be industrial titanium oxide or its hydrate, also can adopt any through handling other raw material can form titanium oxide; The interpolation form of MgO can be industrial magnesium oxide or magnesium hydroxide, also can adopt any process to handle and can form magnesian other raw material, but preferably adopt light magnesium oxide; Al
2O
3The interpolation form be generally commercial alumina or its hydrate, also can adopt any through handling other raw material can form aluminum oxide; Cement is common industrial cement, is preferably aluminous cement.
Among the present invention, the activity of such catalysts component can add with the form of Co, Ni, Mo, W soluble salt, as its nitrate, acetate, ammonium salt etc.The compound that must contain a kind of element among Co and the Ni in the active constituent at least, its quality percentage composition in catalyzer counts 1～10% with oxide form, is preferably 2.5～5%; Also must contain the compound of a kind of element among Mo and the W in the active constituent at least, its quality percentage composition counts 1～30% with oxide form, is preferably 6～12%.In addition, can add the compound of one or more elements among rare earth metal, alkaline-earth metal, Cu, Zn, the Mn in the catalyzer, as the auxiliary agent of catalyzer, its quality percentage composition in catalyzer counts 0.1～20% with oxide compound, is preferably 0.3～2%.
When preparing catalyzer of the present invention, at first the each component with the catalyzer complex carrier mixes; The solution that adds the active constituent soluble salt is then mediated evenly and moulding; Dry, roasting; At 0～200 ℃ of following water or steam treatment catalyzer; And under 300～650 ℃ calcined catalyst once more; After 160～350 ℃ of sulfurations, can use.
The order by merging of the each component of complex carrier does not have much affect to the performance of catalyzer, can adopt any order to mix; And the adding mode of active constituent soluble salt has two kinds: first kind of mode is the soluble salt solution that elder generation adds Mo and/or W, mediates evenly dry then, pulverizing, the solution that adds moulding extrusion aid, peptizing agent and Co and/or Ni soluble salt again, mediate evenly moulding, drying; The second way is the soluble salt solution that adds Mo and/or W, and not drying, pulverizing adds the solution of moulding extrusion aid, peptizing agent and Co and/or Ni soluble salt again, mediates evenly moulding, drying.
Above-mentioned drying can adopt any drying means.Carry out roasting then, the temperature of roasting is 300～600 ℃, is preferably 450～580 ℃, and the time of roasting can be 0.1～20 hour, is preferably 1～5 hour.After the roasting, water or steam are handled catalyzer down at 0～200 ℃, are preferably in 10～150 ℃ of following waters or steam treatment catalyzer, can make simultaneous MgO and Al in the carrier like this
2O
3Change magnesia-alumina spinel structure into by stoichiometric ratio, improved the intensity of catalyzer.Otherwise, in the use of catalyzer, MgO in the carrier and Al
2O
3Transform to magnesium-aluminium spinel, cause the variation of catalyst structure.After the processing, roasting once more, maturing temperature is 300～650 ℃, is preferably 450～580 ℃.
The catalyzer that aforesaid method makes needs could use through sulfuration.The sulfurized temperature is generally 160～350 ℃, and better curing temperature is 200～270 ℃, and curing time is generally about 20 hours by the sulphur concentration decision of sulfuration gas.
Because sulfur-resistant transformation catalyst of the present invention adopts water or steam to handle in preparation process, has improved its strength stability and activity stability in use; Cement component in the catalyzer complex carrier of the present invention also helps to improve the intensity and the stability of catalyzer.In addition, owing to do not add basic metal in the catalyzer of the present invention, thereby can under high temperature, high water-gas ratio, work, and the TiO in the carrier
2The auxiliary agent composition of composition and catalyzer has improved the low temperature shift activity of this catalyzer again.The net effect of these factors make this catalyzer can be applied to wide temperature (200～500 ℃), wide sulphur (＞0.01%v/v) and wide water-gas ratio (under 0.4～1.8mol/mol) the condition.
Further specify the present invention below in conjunction with embodiment.Embodiment 1 Preparation of catalysts
Listed the composition of industrial Co-Mo sulfur-resistant transformation catalyst QCS-01 and prepared catalyst of the present invention in the table 1:
Table 1 catalyzer is formed
| Catalyzer | Chemical constitution % (m/m) | |||||||
| Al 2O 3 | ?TiO 2 | ?MgO | Cement | CoO | MoO 3 | ?La 2O 3 | Ce 2O 3 | |
| ?QCS-01 | ?46.5 | ?12.0 | ?22.4 | ?3.5 | ?8.9 | ?0.25 | ?0.25 | |
| ????A | ?46.7 | ?12.1 | ?22.1 | ?3.6 | ?8.7 | |||
| ????B | ?42.0 | ?12.1 | ?21.9 | ?4.9 | ?3.7 | ?8.9 | ||
| ????C | ?37.5 | ?12.3 | ?22.5 | ?9.1 | ?3.5 | ?8.6 | ||
| ????D | ?32.9 | ?12.5 | ?22.4 | ?14.0 | ?3.4 | ?8.7 | ||
| ????E | ?46.1 | ?12.0 | ?22.5 | ?3.7 | ?8.6 | |||
| ????F | ?60.1 | ?18.7 | ?3.9 | ?8.7 | ||||
| ????G | ?57.5 | ?24.7 | ?3.4 | ?8.5 | ||||
| ????H | ?56.0 | ?25.4 | ?3.5 | ?8.4 | ||||
| ????I | ?45.6 | ?12.8 | ?21.3 | ?3.6 | ?8.5 | ?0.25 | ?0.25 | |
Each Preparation of catalysts method of the present invention is as follows:
Catalyst A: at first 130g TiO
2, 240g lightweight MgO and contain Al
2O
360% Al
2O
3-nH
2O 833g mixes; Add then and contain MoO
3The ammonium molybdate solution of 100g, and mediate evenly; 120 ℃ of dry 2hr pulverize; Add moulding extrusion aid 30g, mixing adds the solution that contains peptizing agent citric acid 30g, CoO 40g (Xiao Suangu) again, mediates evenly and moulding; 120 ℃ of drying 2～3hr, 500 ℃ of roasting 2～3hr; Use water treatment catalyzer 10～20hr under the room temperature; At last at 550 ℃ of following roasting 2～3hr.
Catalyst B: add cement 50g except that in the catalyzer, contain Al
2O
360% Al
2O
3-nH
2O changes into outside the 750g, and other composition is identical with catalyst A with preparation technology.
Catalyzer C: add cement 100g except that in the catalyzer, contain Al
2O
360% Al
2O
3-nH
2O changes into outside the 667g, and other composition is identical with catalyst A with preparation technology.
Catalyzer D: add cement 150g except that in the catalyzer, contain Al
2O
360% Al
2O
3-nH
2O changes into outside the 583g, and other composition is identical with catalyst A with preparation technology.
Catalyzer E: at first 130g TiO
2, 240g lightweight MgO, contain Al
2O
360% Al
2O
3-nH
2O833g and moulding extrusion aid 30g mix; Add then and contain MoO
3The ammonium molybdate solution of 100g, and mediate evenly; Add the solution that contains peptizing agent citric acid 30g, CoO 40g (Xiao Suangu) again, mediate evenly and moulding; 120 ℃ of drying 2～3hr, 500 ℃ of roasting 2～3hr; With 100 ℃ of steam treatment catalyzer 10～20hr; At last at 550 ℃ of following roasting 2～3hr.
Catalyzer F: 200gTiO
2, contain Al
2O
360% Al
2O
3-nH
2O 1100g and moulding extrusion aid 30g mix; After, E is identical with catalyzer.
Catalyzer G: 600gTiO
2, 260g lightweight MgO and moulding extrusion aid 30g mix; After, E is identical with catalyzer.
Catalyzer H: 600g TiO
2, cement 260g and moulding extrusion aid 30g mix; After, E is identical with catalyzer.
Catalyst I: at first 130g TiO
2, 240g lightweight MgO and contain Al
2O
360% Al
2O
3-nH
2O828g mixes; Add then and contain MoO
3The ammonium molybdate solution of 100g, and mediate evenly; 120 ℃ of dry 2hr pulverize; Add moulding extrusion aid 30g, mixing adds and contains peptizing agent citric acid 30g, CoO 40g (Xiao Suangu), La
2O
30.25g and Ce
2O
30.25g solution, mediate evenly and moulding; 120 ℃ of drying 2～3hr, 500 ℃ of roasting 2～3hr; With 120 ℃ of steam treatment catalyzer 10～20hr; At last at 550 ℃ of following roasting 2～3hr.Embodiment 2 catalyst performance evaluation
Activity of such catalysts test respectively normal pressure minisize reaction evaluating apparatus and pressurization former surmise on the evaluating apparatus carry out, wherein the appreciation condition of normal pressure minisize reaction evaluating apparatus is:
Catalyzer loading amount: 0.30g catalyst grain size: 40～60 orders
H
2O/ dry gas: 1.0 (mol/mol) dry gas air speed: 10000h
-1
H
2S concentration: 0.30～0.40% (v/v) curing temperature: 250 ℃
The pressurize appreciation condition of former granularity assessment device of curing time: 4hr is:
Catalyzer loading amount: 100ml (φ 4mm α-Al
2O
3Ball dilution in 1: 1)
Catalyst grain size: φ 4 * 4mm H
2O/ dry gas: 1.2 (mol/mol)
H
2Concentration: 0.20～0.40% (v/v)
Curing temperature: 250 ℃ of curing time: 20hr
Sulfuration air speed: 2000h
-1Sulfide stress: 2.0MPa
Conversion air speed: 3000h
-1Conversion pressure: the 8.0MPa activity of such catalysts is represented with the CO interconversion rate:
And the mensuration of catalyst stability is carried out its appreciation condition on the former granularity assessment device of pressurization:
Pressure: 8.0MPa temperature: 500 ℃
H
2O/N
2: 1.6 (mol/mol) time: 20hr
Table 2, table 3, table 4 have provided the result of each evaluation test, and the percentage composition in the table is volumn concentration.Wherein, table 2 has provided the result who measures catalyst stability on the former granularity assessment device of laboratory.Contrast each catalyzer and use forward and backward intensity and normal pressure shift activity, show that the stability of the intensity of catalyzer of the present invention and shift activity is all good than commercial catalysts QCS-01.
Table 2 catalyst stability test-results
| QCS-01 | ????A | ????B | ????C | ????D | ????E | ||
| Strength stability | Preceding N/cm | ????156 | ????240 | ????227 | ????231 | ????254 | ????219 |
| Back N/cm | ????85 | ????158 | ????152 | ????160 | ????176 | ????151 | |
| Retention rate % | ????54.5 | ????65.8 | ????67.0 | ????69.3 | ????69.3 | ????68.9 | |
| Activity stability * | Before | ????32.1 | ????35.7 | ????34.0 | ????36.2 | ????31.9 | ????27.8 |
| After | ????15.3 | ????23.5 | ????27.8 | ????29.1 | ????26.3 | ????25.7 | |
| Retention rate % | ????47.7 | ????65.8 | ????81.8 | ????80.4 | ????82.4 | ????92.4 |
* active normal pressure CO interconversion rate % with 450 ℃ represents
Table 3 has provided the active result of catalyzer normal pressure eigentransformation who measures on breadboard normal pressure minisize reaction evaluating apparatus.The result shows that catalyst activity of the present invention is most of suitable with commercial catalysts QCS-01, and catalyst A, B, C are better than commercial catalysts QCS-01.
Table 3 catalyzer normal pressure shift activity
*
| Temperature ℃ | ??QCS ??-01 | ????A | ????B | ????C | ????D | ????E | ????F | ????G | ????H | ????I |
| ?250 | ??2.8 | ??4.2 | ??5.1 | ??4.7 | ??3.0 | ??2.6 | ??2.9 | ??2.7 | ??2.6 | ??2.8 |
| ?350 | ??6.5 | ??8.3 | ??9.4 | ??9.1 | ??6.9 | ??5.9 | ??6.3 | ??6.5 | ??5.8 | ??6.7 |
| ?450 | ?32.1 | ??35.7 | ?34.0 | ?36.2 | ?31.9 | ?27.8 | ?31.7 | ?31.0 | ?29.2 | ?30.0 |
*Shift activity is CO interconversion rate %
Table 4 has provided on the former granularity assessment device of breadboard pressurization, sample A, B, C, E and commercial catalysts QCS-01 is carried out apparent shift activity comparative evaluation's result.Table 4 result shows that the apparent shift activity of catalyzer of the present invention is suitable with commercial catalysts QCS-01, and low temperature active is better than commercial catalysts QCS-01.
Table 4 catalyzer pressurization shift activity
| Catalyzer | ????250℃ | ????350℃ | ????450℃ | ||||||
| Inlet CO% | Outlet CO% | Interconversion rate % | Inlet CO% | Outlet CO% | Interconversion rate % | Inlet CO% | Outlet CO% | Interconversion rate % | |
| QCS-01 | ????42.2 | ????1.08 | ????96.4 | ????42.2 | ????1.40 | ????95.3 | ????42.2 | ????3.68 | ????88.0 |
| ????A | ????46.4 | ????0.93 | ????97.1 | ????46.4 | ????1.70 | ????94.7 | ????46.4 | ????3.3 | ????89.9 |
| ????B | ????46.4 | ????0.72 | ????97.7 | ????46.4 | ????1.67 | ????94.8 | ????46.4 | ????3.15 | ????90.4 |
| ????C | ????46.5 | ????0.80 | ????97.5 | ????46.5 | ????1.50 | ????95.3 | ????46.5 | ????3.60 | ????89.1 |
| ????E | ????46.5 | ????0.80 | ????97.5 | ????46.5 | ????1.25 | ????96.1 | ????46.5 | ????3.10 | ????90.5 |
Claims (13)
1. one kind is used for the non-basic metal sulfur-resistant transformation catalyst that carbon monoxide and steam reaction are produced hydrogen and carbonic acid gas, at least the compound that contains a kind of element among Co and the Ni in the activity of such catalysts component, also contain simultaneously the compound of a kind of element among Mo and the W at least, it is characterized in that each component shared quality percentage composition in catalyzer of catalyzer complex carrier is:
TiO
2???5～80％
MgO?????0～45％
Al
2O
3?0～60％
Cement 0～30% wherein, MgO, Al
2O
3With the content of cement be not zero simultaneously, and in carrier, contain MgO and Al simultaneously
2O
3The time, MgO and Al
2O
3Be mainly magnesia-alumina spinel structure by stoichiometric ratio.
2. catalyzer according to claim 1 is characterized in that each component shared quality percentage composition in catalyzer of complex carrier is:
TiO
2???8～30％
MgO????15～30％
Al
2O
340～60％
Cement 5～15%
3. catalyzer according to claim 1 is characterized in that in the catalyzer, and the quality percentage composition of active constituent CoO and/or NiO is 1～10%.
4. catalyzer according to claim 1 is characterized in that in the catalyzer, and the quality percentage composition of active constituent CoO and/or NiO is 2.5～5%.
5. catalyzer according to claim 1 is characterized in that in the catalyzer, active constituent MoO
3And/or WO
3The quality percentage composition be 1～30%.
6. catalyzer according to claim 1 is characterized in that in the catalyzer, active constituent MoO
3And/or WO
3The quality percentage composition be 6～12%.
7. catalyzer according to claim 1, it is characterized in that being added with in the catalyzer compound of one or more elements among rare earth metal, alkaline-earth metal, Cu, Zn, the Mn, as the auxiliary agent of catalyzer, its quality percentage composition counts 0.1～20% with oxide compound.
8. catalyzer according to claim 7 is characterized in that in the catalyzer, and the quality percentage composition of catalyst adjuvant counts 0.3～2% with oxide compound.
9. the preparation method of a sulfur-resistant transformation catalyst comprises: TiO
2With MgO, Al
2O
3, at least a the mixing in the cement; Add Mo and/or the soluble salt solution of W and the soluble salt solution of Co and/or Ni, mediate evenly and moulding; Dry, roasting; Adopt water or steam treatment catalyzer, and roasting once more; At 160～350 ℃ of following sulphurized catalysts.
10. the described method of claim 9 is characterized in that maturing temperature is 300～650 ℃.
11. the described method of claim 9 is characterized in that maturing temperature is 450～580 ℃.
12. the described method of claim 9, the temperature when it is characterized in that adopting water or steam treatment catalyzer is 0～200 ℃.
13. the described method of claim 9, the temperature when it is characterized in that adopting water or steam treatment catalyzer is 10～150 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97121053A CN1066415C (en) | 1997-12-07 | 1997-12-07 | New CO sulphur-resistant transformation catalyst and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97121053A CN1066415C (en) | 1997-12-07 | 1997-12-07 | New CO sulphur-resistant transformation catalyst and its preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN1219500A true CN1219500A (en) | 1999-06-16 |
| CN1066415C CN1066415C (en) | 2001-05-30 |
Family
ID=5176172
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|---|---|---|---|
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| CN102151574A (en) * | 2011-02-16 | 2011-08-17 | 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 |
| 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 |
| 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 |
| CN103127901A (en) * | 2013-03-13 | 2013-06-05 | 福州大学 | Protection agent for catalyst in coal pressurization and gasification and sulfur-resisting conversion technologies and preparation method for protection agent |
| CN103127901B (en) * | 2013-03-13 | 2015-02-25 | 福州大学 | Protection agent for catalyst in coal pressurization and gasification and sulfur-resisting conversion technologies and preparation method for protection agent |
| CN104248961A (en) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | Sulfur-tolerant shift catalyst and preparation method thereof |
| CN103495421A (en) * | 2013-09-05 | 2014-01-08 | 刘博男 | Sulfur-tolerant methanation catalyst and preparation method thereof |
| CN103495421B (en) * | 2013-09-05 | 2015-10-14 | 刘博男 | A kind of catalyst for methanation in presence of sulfur and preparation method thereof |
| CN105562022A (en) * | 2014-10-09 | 2016-05-11 | 中国石油化工股份有限公司 | High-air speed sulfur-resistant pre-shift catalyst and preparation method thereof |
| CN105562022B (en) * | 2014-10-09 | 2018-09-21 | 中国石油化工股份有限公司 | High-speed resistant to sulfur pre-transform catalyst and preparation method thereof |
| 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 |
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