CN1569330A - Monolithic catalyst and its preparation and application - Google Patents
Monolithic catalyst and its preparation and application Download PDFInfo
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- CN1569330A CN1569330A CNA031337546A CN03133754A CN1569330A CN 1569330 A CN1569330 A CN 1569330A CN A031337546 A CNA031337546 A CN A031337546A CN 03133754 A CN03133754 A CN 03133754A CN 1569330 A CN1569330 A CN 1569330A
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- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention relates to catalyst technology field, especially provides a monolith catalyst and the manufacturing method. It uses Ni as active component, the Al2O3 is used as carrier, and the invention uses sol-gel particle in situ decoration technology, and introduces the Ni2+ and Li+, and La3+ ion to produce the product. The active component particle size is small, and it is dispersed evenly.
Description
Technical field
The present invention relates to the technology of catalyst and method for preparing catalyst and application, a kind of only stone (monolith) catalyst and preparation method and application are provided especially.
Background technology
In recent years, methane portion oxidation (POM) preparing synthetic gas technology has caused that people pay close attention to widely.The catalyst type of POM is varied at present.Monolith (solely stone) has good heat endurance and mechanical strength, can be used for high-speed, pyroreaction as catalyst support.Because the specific surface of monolith is very little, at first is coated with the carrier of one deck Large ratio surface (as γ-Al on monolith usually
2O
3) adopt infusion process or organic metal sedimentation to introduce active constituent subsequently, also can directly adopt the slurry of active constituent dipping back carrier directly to be coated in the monolith surface.Be used for the POM reaction with monolith as the catalyst of carrier or supporter report is also arranged, but great majority concentrate on the noble metal catalyst aspect, be supported on catalyst based unsatisfactory (the document 1:P.M.Tomiainen of stability of Ni on the monolith, X.Chu, L.D.Schmidt, " Comparison of monolith-supported metalsfor the direct oxidation of methane to syngas ", J.Catal.Vol, 146, page 1-10,1994).Adopt the activity of such catalysts component skewness of method for preparing, and combine defective tightness with the monolith supporter, therefore easy-sintering and loss in roasting or course of reaction, thus cause the reduction of its catalytic performance.The Ni catalyst that the only stone barbell of reports such as Schmidt carries slow inactivation in the POM course of reaction, after 22 hours, it is original 0.1% that the active constituent Ni on catalyst top is reduced to, and the big crystal grain that has diameter to be about 100 μ m exists.The selectivity of methane conversion and carbon monoxide reduces by 2%, and the main cause of its catalyst activity reduction is owing to Ni crystal grain unstable volatile causing in course of reaction runs off.Other researchers also have similar report (document 2:K.Heitnes, S.Lindberg, O.A.Rokstad and A.Holmen, " Catalytic partial oxidation of methane tosynthesis gas ", Catal.Today, 1995, (24), 211-216).
Summary of the invention
The object of the present invention is to provide a kind of active constituent to be uniformly dispersed, not easy-sintering and loss, monolith surface and the compact monolith catalyst of catalyst layer and preparation method and application.
To achieve these goals, the technical solution used in the present invention is as follows:
Monolith catalyst: with Ni is active component, Al
2O
3Be carrier, adopt collosol and gel micelle in-situ modification technology, introduce Ni
2+And Li
+And La
3+The promoter metal ion makes; Be specially: 1) preparation Al
2O
3Sol solution; 2) active constituent Ni is added into described Al with the nitrate solution form
2O
3In the sol solution, introduce Ni
2+And Li
+And La
3+The promoter metal ion carries out in-situ modification to the colloid micelle, gets the aluminium colloidal sol after micelle is modified; 3) add additive in the aluminium colloidal sol after modifying toward described micelle, addition is Al
2O
30.5～4% of sol solution weight, the sol solution after must modifying; 4) only stone of excision forming is immersed in the sol solution after the described modification, keep taking out 1～10 ℃ of drying, in 500～1000 ℃ of following roastings behind 1～10min; Repeating step 1 again)～4) get final product in 500～1000 ℃ of following roastings after 1～10 time.
Its preparation method: with Ni is active component, Al
2O
3Be carrier, adopt collosol and gel micelle in-situ modification technology, introduce Ni
2+And Li
+And La
3+The promoter metal ion makes; Be specially: 1) preparation Al
2O
3Sol solution; 2) active constituent Ni is added into described Al with the nitrate solution form
2O
3In the sol solution, introduce Ni
2+And Li
+And La
3+The promoter metal ion carries out in-situ modification to the colloid micelle, gets the aluminium colloidal sol after micelle is modified; 3) add additive in the aluminium colloidal sol after modifying toward described micelle, addition is Al
2O
30.5～4% of sol solution weight, the sol solution after must modifying; 4) only stone of excision forming is immersed in the sol solution after the described modification, keep taking out 1～10 ℃ of drying, in 500～1000 ℃ of following roastings behind 1～10min; Repeating step 1 again)～4) get final product in 500～1000 ℃ of following roastings after 1～10 time;
Described only stone is selected the foaming only stone of shape (foam monolith) for use, and its main component is Al
2O
3Described Al
2O
3The concentration of sol solution is controlled between 0.5～1.0M; Described additive can be plasticizer and binder, and plasticizer and binder weight ratio are 2; Wherein: plasticizer and binder are respectively PVA (polyvinyl alcohol) and PEG (polyethylene glycol);
Described monolith catalyst is applied to methane portion oxidation synthesis gas reaction, and wherein: reaction temperature is 700 ℃～900 ℃, air speed less than, equal 6.0 * 10
5L/kg.h and greater than, equal 1.0 * 10
3L/kg.h, the CH in the unstripped gas
4/ O
2Molar ratio is 1.5～2.0, and reaction pressure is a normal pressure.
The present invention has the following advantages:
Prepare gained catalyst activity component by the present invention and be difficult for running off and sintering, the monolith surface combines closely with catalyst layer, is difficult for peeling off, and has high selectivity and conversion ratio (CH in reaction
4Conversion ratio also can reach more than 93%, the CO selectivity can reach more than 95%), methane conversion in the course of reaction, the ratio of hydrogen and carbon monoxide all keeps stable in the selectivity of carbon monoxide and hydrogen and the product, can prove the generation of catalyst no deactivation phenomenom in 120 hours course of reaction by experiment, have good operational stability and anti-carbon performance.
Description of drawings
Accompanying drawing 1-1 is Al not modified in the prior art
2O
3The particle size analysis distribution map of colloidal sol.
Accompanying drawing 1-2 is Al after the modification of one embodiment of the invention
2O
3The particle size analysis distribution map of colloidal sol.
Accompanying drawing 2-1 is the profile scanning Electronic Speculum figure of the monolith catalyst of one embodiment of the invention; Wherein: a represents the monolith surface; B represents monolith surface catalyst layer.
Accompanying drawing 2-2 is the front scan Electronic Speculum figure of monolith catalyst of the present invention.
Accompanying drawing 3 is the crystalline phase figure of the catalyst on the monolith supporter of the present invention.Wherein: represent 850 ℃ of calcined catalysts; * represent NiAl
2O
4Δ is represented the peak position of NiO.
Accompanying drawing 4 be in the one embodiment of the invention air speed to the influence of the catalytic activity of monolith catalyst.
Accompanying drawing 5 is the test of monolith catalyst stability in the one embodiment of the invention, wherein: CH
4/ O
2=2.0, GHSV=13.4 * 10
4L.kg
-1H
-1, 850 ℃.
The specific embodiment
The present invention is further elaborated below in conjunction with drawings and Examples.
Embodiment 1 (preparation Ni load capacity is about the monolith catalyst of 10wt%)
Aluminium colloidal sol and micelle are modified the preparation of aluminium colloidal sol:
A.20.4g (German Condea company provides PURAL SB powder, a kind of industrial powder of making by the hydrolysis of n-hexyl alcohol aluminium) adds the 283ml secondary deionized water in a diaspore crystal formation, stir, 85 ℃ of constant temperature 0.5 hour, add 1.6M nitric acid 16.9ml and carry out dispergation, reflux condensation mode 6 hours, making concentration is the aluminium colloidal sol of 1M.
B. get Ni (NO
3)
234.7g, LiNO
35.5g, La (NO
3)
310.4g add the 1000ml secondary deionized water, stir and be made into Ni
2+, Li
+, La
3+Concentration is respectively 0.19M, 0.08M, the mixing salt solution of 0.03M.
C. get aluminium colloidal sol 50ml, and prepare mixing salt solution 50ml among the b and mix, stir, make the aluminium sol solution after micelle is modified.
The size distribution such as the accompanying drawing 1-1 of not modified colloidal sol and modification back colloidal sol are shown in the 1-2.
Add additive
Adopt described micelle to modify aluminium colloidal sol, add polyvinyl alcohol (PVA) and polyethylene glycol (PEG), both weight ratios are 2, and addition is respectively prepared aluminium colloidal sol weight 2% and 1%, the sol solution after must modifying.
Monolith after the cutting washing is immersed sol solution 10min wherein after modifying, carried out drying 36 hours at 5 ℃, 550 ℃ are carried out roasting 180min, repeat 4 times.850 ℃ of roastings 4 hours, get the monolith catalyst subsequently.Wherein active component Ni content is 10wt%, auxiliary agent Li
2O content is 1.25wt%, La
2O
3Content is 5wt%.
Obtained monolith catalyst is carried out ESEM (SEM) to be characterized, the microscopic pattern of catalyst surface such as Fig. 2-1, shown in the 2-2, can see that from the surface configuration of catalyst catalyst evenly covers the surface of monolith, its thickness is about 10 μ m, smooth surface does not have grained sintered phenomenon and takes place.
Accompanying drawing 3 is the crystalline phase figure of catalyst, calculates by the Scherrer formula, finds that catalyst crystal grain is very little, and does not observe the diffraction maximum of the NiO crystal grain of free state, illustrates that the crystal grain of the active constituent Ni in the catalyst is very little, and is uniformly dispersed.
Catalyst of the present invention is applied in partial oxidation reaction of methane, adopts the prepared catalyst of present embodiment, and reaction condition is that temperature is 850 ℃, and air speed is respectively 3.5 * 10
4L/kg.h, 9.0 * 10
4L/kg.h, 1.3 * 10
5L/kg.h, 1.8 * 10
5L/kg.h, CH in the unstripped gas
4/ O
2=2.0, reaction pressure is a normal pressure.Reaction result as shown in Figure 4, with the increase of reaction velocity, the selectivity of methane conversion and carbon monoxide is on a declining curve, even but reaction velocity reaches 1.8 * 10
5L.kg
-1h
-1The time CH
4Conversion ratio also can reach more than 93%, the CO selectivity can reach more than 95%.
In addition, the monolith catalyst is at 850 ℃, CH
4/ O
2=2.0, the air speed of reaction is 1.34 * 10
5The variation of 120 hours reactivity worth of continued operation as shown in Figure 5 during l/kg.h, methane conversion in the course of reaction, the ratio of hydrogen and carbon monoxide all keeps stable in the selectivity of carbon monoxide and hydrogen and the product, and the generation of catalyst no deactivation phenomenom in 120 hours course of reaction is described.Post catalyst reaction detects through SEM-EDS, and Ni-based does not run off, and does not have carbon distribution on the catalyst substantially, and the sintering phenomenon of catalyst-free takes place.
Difference from Example 1 is:
The sintering temperature of monolith catalyst is 950 ℃, roasting 4 hours, and gained monolith catalyst is at 850 ℃, CH
4/ O
2=2.0, the air speed of reaction is 1.34 * 10
5Carry out partial oxidation reaction of methane under the condition of l/kg.h, initial activity is lower, and is active suitable with embodiment 1 described catalyst activity after reaction in 10 hours, and keeps stable.
Embodiment 3
Difference from Example 1 is:
PVA that is added and the amount of PEG are respectively preparation aluminium colloidal sol weight 4% and 2%, and the monolith after the cutting washing is immersed wherein 5min, carry out drying 24 hours at 10 ℃, and 850 ℃ were carried out roasting 4 hours, repeating step 1)～4) 2 times.Gained monolith catalyst result is with embodiment 1.
Embodiment 4
Difference from Example 1 is:
PVA that is added and the amount of PEG are respectively preparation aluminium colloidal sol weight 1% and 0.5%, monolith after the cutting washing is immersed wherein 1min, carried out drying 24 hours at 10 ℃, 550 ℃ were carried out roasting 2 hours, repeating step 1)～4) 10 times, subsequently 850 ℃ of roastings 4 hours.Gained monolith catalyst result is with embodiment 1.
Embodiment 5
Difference from Example 1 is:
A. get 10.2g PURAL SB powder, middle adding 283ml secondary deionized water stirs, and 85 ℃ of constant temperature 0.5 hour adds 1.6M nitric acid 8.4ml and carries out dispergation, reflux condensation mode 6 hours, and making concentration is the aluminium colloidal sol of 0.5M.
B. get Ni (NO
3)
217.4g, LiNO
32.8g, La (NO
3)
35.2g add the 1000ml secondary deionized water, stir and be made into Ni
2+, Li
+, La
3+Concentration is respectively 0.1M, 0.04M, the mixing salt solution of 0.02M.
Gained monolith catalyst result is with embodiment 1.
Comparative example 1
Professor Schmidt of U.S. Minnestota university adopts the Ni-based monolith catalyst of immersion process for preparing, and after 22 hours reaction, the content of the Ni of catalyst front end only is original 1%, and the selectivity of methane conversion and hydrogen has descended 2%.And the reaction back finds to have the big sintering crystal grain of 100 μ m to occur.(referring to document 1:P.M.Tomiainen, X.Chu, L.D.Schmidt, " Comparisonof monolith-supported metals for the direct oxidation of methane to syngas ", J.Catal.Vol, 146, page 1-10,1994)
Comparative example 2
The Heitnes report adopts the monolith Ni that floods the preparation of dip-coating more earlier catalyst based under the reaction condition of POM, 800 ℃, react after 8 hours, though the selectivity of methane conversion and carbon monoxide does not significantly reduce, the decentralization of active constituent reduced by 57% in 8 hours.(referring to document 2:K.Heitnes, S.Lindberg, O.A.Rokstad and A.Holmen, " Catalytic partialoxidation of methane to synthesis gas ", and Catal.Today, 1995, (24), 211-216)
Claims (9)
1. a monolith catalyst is an active component with Ni, Al
2O
3Be carrier, it is characterized in that: adopt collosol and gel micelle in-situ modification technology, introduce Ni
2+And Li
+And La
3+The promoter metal ion makes; Be specially: 1) preparation Al
2O
3Sol solution; 2) active constituent Ni is added into described Al with the nitrate solution form
2O
3In the sol solution, introduce Ni
2+And Li
+And La
3+The promoter metal ion carries out in-situ modification to the colloid micelle, gets the aluminium colloidal sol after micelle is modified; 3) add additive in the aluminium colloidal sol after modifying toward described micelle, addition is Al
2O
30.5～4% of sol solution weight, the sol solution after must modifying; 4) only stone of excision forming is immersed in the sol solution after the described modification, keep taking out 1～10 ℃ of drying, in 500～1000 ℃ of following roastings behind 1～10min; Repeating step 1 again)～4) get final product in 500～1000 ℃ of following roastings after 1～10 time.
2. by the described monolith catalyst of claim 1, it is characterized in that: described only stone is selected the only stone of foaming shape for use, and its main component is Al
2O
3
3. by the described monolith catalyst of claim 1, it is characterized in that: described Al
2O
3The concentration of sol solution is controlled between 0.5～1.0M.
4. by the described monolith catalyst of claim 1, it is characterized in that: described additive can be plasticizer and binder, and plasticizer and binder weight ratio are 2; Wherein: plasticizer and binder are respectively polyvinyl alcohol and polyethylene glycol.
5. the preparation method of a monolith catalyst is an active component with Ni, Al
2O
3Be carrier, it is characterized in that: adopt collosol and gel micelle in-situ modification technology, introduce Ni
2+And Li
+And La
3+The promoter metal ion makes; Be specially: 1) preparation Al
2O
3Sol solution; 2) active constituent Ni is added into described Al with the nitrate solution form
2O
3In the sol solution, introduce Ni
2+And Li
+And La
3+The promoter metal ion carries out in-situ modification to the colloid micelle, gets the aluminium colloidal sol after micelle is modified; 3) add additive in the aluminium colloidal sol after modifying toward described micelle, addition is Al
2O
30.5～4% of sol solution weight, the sol solution after must modifying; 4) only stone of excision forming is immersed in the sol solution after the described modification, keep taking out 1～10 ℃ of drying, in 500～1000 ℃ of following roastings behind 1～10min; Repeating step 1 again)～4) get final product in 500～1000 ℃ of following roastings after 1～10 time.
6. by the preparation method of the described monolith catalyst of claim 1, it is characterized in that: described only stone is selected the only stone of foaming shape for use, and its main component is Al
2O
3
7. by the preparation method of the described monolith catalyst of claim 1, it is characterized in that: described Al
2O
3The concentration of sol solution is controlled between 0.5～1.0M.
8. by the preparation method of the described monolith catalyst of claim 1, it is characterized in that: described additive can be plasticizer and binder, and plasticizer and binder weight ratio are 2; Wherein: plasticizer and binder are respectively polyvinyl alcohol and polyethylene glycol.
9. the application of a monolith catalyst is characterized in that: be used for methane portion oxidation synthesis gas reaction, wherein: reaction temperature is 700 ℃～900 ℃, air speed less than, equal 6.0 * 10
5L/kg.h and greater than, equal 1.0 * 10
3L/kg.h, the CH in the unstripped gas
4/ O
2Molar ratio is 1.5～2.0, and reaction pressure is a normal pressure.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031337546A CN1261210C (en) | 2003-07-18 | 2003-07-18 | Monolithic catalyst and its preparation and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031337546A CN1261210C (en) | 2003-07-18 | 2003-07-18 | Monolithic catalyst and its preparation and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1569330A true CN1569330A (en) | 2005-01-26 |
| CN1261210C CN1261210C (en) | 2006-06-28 |
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ID=34470096
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101347734B (en) * | 2007-07-18 | 2011-07-20 | 中国石油化工股份有限公司 | Large hole nickel-based catalyst |
| CN101884919B (en) * | 2009-05-13 | 2012-08-01 | 中国石油化工股份有限公司 | Preparation method of composite silica gel WOx/ZrO2 monolith catalyst |
| CN110152674A (en) * | 2019-05-14 | 2019-08-23 | 华南农业大学 | A kind of Ni nanoparticle/Al2O3Catalyst and its preparation method and application |
-
2003
- 2003-07-18 CN CNB031337546A patent/CN1261210C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101347734B (en) * | 2007-07-18 | 2011-07-20 | 中国石油化工股份有限公司 | Large hole nickel-based catalyst |
| CN101884919B (en) * | 2009-05-13 | 2012-08-01 | 中国石油化工股份有限公司 | Preparation method of composite silica gel WOx/ZrO2 monolith catalyst |
| CN110152674A (en) * | 2019-05-14 | 2019-08-23 | 华南农业大学 | A kind of Ni nanoparticle/Al2O3Catalyst and its preparation method and application |
| CN110152674B (en) * | 2019-05-14 | 2022-04-29 | 华南农业大学 | Nano Ni/Al2O3Catalyst, preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1261210C (en) | 2006-06-28 |
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