CN101020139A - Catalyst for preparing methanol with synthetic gas and its prepn process - Google Patents
Catalyst for preparing methanol with synthetic gas and its prepn process Download PDFInfo
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- CN101020139A CN101020139A CNA2006100822317A CN200610082231A CN101020139A CN 101020139 A CN101020139 A CN 101020139A CN A2006100822317 A CNA2006100822317 A CN A2006100822317A CN 200610082231 A CN200610082231 A CN 200610082231A CN 101020139 A CN101020139 A CN 101020139A
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- catalyst
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- molecular sieve
- synthesising gas
- systeming carbinol
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to catalyst, and is especially one kind of catalyst for preparing methanol through synthesis reaction between CO and H2 and its preparation process. The catalyst is heat resisting Cu-base catalyst with low operation temperature, high activity and high heat stability. The catalyst consists of heat insulating agent, which is selected from gamma-Al2O3, white carbon black, silica-alumina molecular sieve, etc and accounts for1-20 wt%; and mixed Cu-Zn-Al oxide, which has Cu to Zn to Al atom ratio of 30-70 to 20-60 to 7-15, and is prepared through calcining soluble salt.
Description
Technical field
The present invention relates to a kind of catalyst of making methyl alcohol, especially relate to a kind of by CO and H
2The Catalysts and its preparation method of reaction synthesizing methanol.
Background technology
Methyl alcohol is a kind of important basic Organic Chemicals.In recent years, along with the develop rapidly of science and technology and the change of energy resource structure, methyl alcohol has been opened up how new purposes again.By the zinc chrome catalyst that German BASF AG succeeds in developing, because its activity is lower,, need under the condition of high temperature (317-319 ℃) high pressure (25-35MPa), operate in order to obtain advantages of high catalytic activity and higher conversion ratio, little by little be eliminated at present.The copper-based catalysts of succeeding in developing by Britain ICI company and German Lurgi company, because its activity is good, the selectivity height, and be a kind of low pressure (5-10MPa) catalyst, so adopted widely.At present the industrial methanol synthetic catalyst mainly is the Cu-Zn-Al catalyst system and catalyzing, because by the fuel factor of synthesising gas systeming carbinol big (greater than 94Kcal), therefore simple ternary copper-based catalysts heat endurance is relatively poor, the catalyst life cycle is short.
In order to overcome the deadly defect of industrial methanol synthetic catalyst, in recent years, some patent had been reported a series of heat-resisting copper-based catalysts about synthesizing methanol again both at home and abroad.European patent EP 0864360 discloses a kind of highly active heat-resisting copper-based catalysts, is Cu/Zn/Al/SiO
2The metal oxide of/N coexistence, N be zirconium, sow, one or more oxides of palladium, and its mass fraction is: 20%-60%, and 10%-50%, 2%-10%, 0.3%-0.9%, 0%-10%, 0%-10%, calcining heat is 480-690 ℃.
Chinese patent CN1173393 has introduced the Cu/Zn/Al/M '/M that mixes the coprecipitation preparation " catalyst of the metal oxide of five components coexistence.M ' is selected from metal scandium (Se), yttrium (Y) or the lanthanide rare of IIIB family; M " be selected from titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), molybdenum (Mo), the tungsten (W) of IVB family or VB family or group vib, its component (atomic ratio) Cu is 20-60, Zn is 25-45, Al is 8-10, M ' is 0.1-5, M " be 0.1-6.
Chinese patent CN1660493 has introduced a kind of new catalyst for synthesizing copper based methanol, and main component is the big surface-active carrier of copper zinc reactive precursor and submember heat endurance.
Summary of the invention
The object of the present invention is to provide a kind of low temperature, high activity, Heat stability is good, by CO and H
2Heat-resisting copper-based catalysts of reaction synthesizing methanol and preparation method thereof.
Catalyst by synthesising gas systeming carbinol of the present invention consist of insulation agent M and Cu-Zn-Al mixed oxide, described insulation agent M is selected from γ-Al
2O
3, white carbon black, Si-Al molecular sieve, hydrotalcite, magnesium aluminate spinel, titanium dioxide, at least a in 5A molecular sieve, ZSM-5, the 3A molecular sieve, described Cu, Zn, Al oxide are no Cl
-, SO
4 2-Soluble-salt calcine resulting oxide, soluble-salt preferably nitrate or acetate.Each set of dispense of catalyst is preferably 35～65 than being 30～70 by the atomic ratio metering for Cu; Zn is 20～60, is preferably 30～50; Al is 7～15, is preferably 8～12; Insulation agent M adds with mass ratio, and addition is 1%～20% of a catalyst quality, is preferably 8%～12%.
Preparation of catalysts method by synthesising gas systeming carbinol of the present invention, its step is as follows:
1) by the catalytic component proportioning Cu, the Zn of metering, the soluble-salt of Al are made into mixed aqueous solution;
2) stir in the precipitant solution that is added to 65～70 ℃ down, control pH=7.0～8.5 are terminal point; Described precipitating reagent is
Content 〉=98.5%, Cl
-≤ 0.1% Na
2CO
3
3) arrive no Cl with deionized water washing sediment
-
4) the insulation agent M that measures by the proportioning handle is added to and stirs 15～25min in the sediment, and filtration is drained;
5) 110～120 ℃ of oven dry, levigate behind 450～500 ℃ of calcination 2-3h, compression molding, pulverizing then is 16～40 orders.
Catalyst needs can activate (reduction) through overactivation in fixed bed reactors before use, adopts low H
2(H
2/ N
2=3/97) reduction 16～20h, the highest reduction temperature is 245 ℃.
The activity of such catalysts evaluation adopts one road gas shunting to enter 2 fixed bed reactors, parallel heating reduction and the activity rating of carrying out.Loaded catalyst is 0.5ml, and unstripped gas consists of CO: H
2: CO
2: N
2=14: 76: 5: 5, reaction pressure was 2.0MPa, air speed 3000h
-1, evaluation temperature is 245 ℃, measurement result becomes initial activity.Catalyst through 450 ℃ of heat treatment 5h, drops to 245 ℃ again in synthesis gas atmosphere then, and the result of mensuration claims after the heat treatment active.Product gas chromatograph analysis, activity of such catalysts is with space-time yield (g.ml
-1 Cat.h
-1) expression.Catalyst of the present invention has characteristics such as Heat stability is good and methyl alcohol selectivity height, and after 450 ℃ of heat treatments, accessory substance is few, and the selectivity of methyl alcohol is steady.
The specific embodiment
The invention will be further described below by embodiment.
Embodiment 1
1) gets 1M Cu (NO
3)
2Solution 90ml, 1M Zn (NO
3)
2Solution 45ml and 1M Al (NO
3)
3Solution 16.5ml places the 400ml beaker to mix.
2) get 150ml1M Na
2CO
3Solution places the 1000ml beaker, is heated to 70 ℃, stirs down the mixed liquor of step 1 gained is added to Na with the speed of 20ml/min
2CO
3In the solution, stop to add thermal agitation behind the aging 2h, at this moment the pH=7.5 of mixed liquor.
3) with the prepared sediment of 60 ℃ of deionized water washing steps 2 to there not being Cl
-, be added to the 1.0g hydrotalcite in the sediment and stir 20min.
4) filter, filter cake pulverizes at 110 ℃ of oven dry 4h, 450 ℃ of calcining 3h.
5) at last step 4 gained mixed oxide compressing tablet, pulverize that to be screened into the 16-40 order standby.The gained catalyst proportion is Cu: Zn: Al=60: 30: 11 (atomic ratio).
Catalyst activates (reduction) before use in fixed bed reactors, adopt low H
2(H
2/ N
2=3/97) reduction 16～20h, the highest reduction temperature is 245 ℃.
The activity of such catalysts evaluation adopts one road gas shunting to enter two fixed bed reactors, parallel heating reduction and the activity rating of carrying out.Product gas chromatograph analysis, activity of such catalysts is with space-time yield (g.ml
-1 Cat.h
-1) expression.Loaded catalyst is 0.5ml, and unstripped gas consists of CO: H
2: CO
2: N
2=14: 76: 5: 5, reaction pressure was 2.0MPa, air speed 3000h
-1, evaluation temperature is 245 ℃, the measurement result initial activity is 0.15g.ml
- Cat.h
-, catalyst through 450 ℃ of heat treatment 5h, drops to 245 ℃ again in synthesis gas atmosphere then, and activity is 0.12g.ml after the measurement result heat treatment
-1 Cat.h
-1
Comparative Examples 1
Step and condition such as embodiment 1 do not add insulation agent M in the step 3), then the initial activity of this catalyst is 0.13g.ml
-1 Cat.h
-1, the activity after the heat treatment is 0.08g.ml
-1 Cat.h
-1
Embodiment 2～3
Change the insulation agent kind and add quality, all the other conditions and method for making are with embodiment 1, and the determination of activity result is as shown in table 1.
Embodiment 4
1) gets 1M Cu (NO
3)
2Solution 90ml, 1M Zn (NO
3)
2Solution 45ml and 1M Al (NO
3)
3Solution 12ml places the 400ml beaker to mix.
2) get 150ml1M Na
2CO
3Solution places the 1000ml beaker, is heated to 70 ℃, stirs down the mixed liquor of step 1 gained is added to Na with the speed of 20ml/min
2CO
3In the solution, stop to add thermal agitation behind the aging 2h, at this moment the pH=7.5 of mixed liquor.
3) with the prepared sediment of 60 ℃ of deionized water washing steps 2 to there not being Cl
-, be added to the 1.1g3A molecular sieve in the sediment and stir 20min.
Step 4～5 are with the step 4 among the embodiment 1～5, and the activity of such catalysts evaluation the results are shown in Table 1 with embodiment 1.
Embodiment 5
1) gets 1M Cu (NO
3)
2Solution 90ml, 1M Zn (NO
3)
2Solution 90ml and 1M Al (NO
3)
3Solution 24ml places the 400ml beaker to mix.
2) get 200ml 1M Na
2CO
3Solution places the 1000ml beaker, is heated to 70 ℃, stirs down the mixed liquor of step 1 gained is added to Na with the speed of 20ml/min
2CO
3In the solution, stop to add thermal agitation behind the aging 2h, at this moment the pH=7.5 of mixed liquor.
3) with the prepared sediment of 60 ℃ of deionized water washing steps 2 to there not being Cl
-, be added to the 1.0g titanium dioxide in the sediment and stir 15min.
Remaining step is with embodiment 1, and the activity of such catalysts measurement result is as shown in table 1.
Embodiment 6
1) gets 1M Cu (NO
3)
2Solution 110ml, 1M Zn (NO
3)
2Solution 60ml and 1M Al (NO
3)
3Solution 20ml places the 400ml beaker to mix.
2) get 190ml1M Na
2CO
3Solution places the 1000ml beaker, is heated to 70 ℃, stirs down the mixed liquor of step 1 gained is added to Na with the speed of 20ml/min
2CO
3In the solution, stop to add thermal agitation, the pH=7.5 of mixed liquor behind the aging 2h.
3) with 60 ℃ of deionized water washing sediments to there not being Cl
-, 1.2g MgAl
2O
4Be added in the sediment and stir 25min.Remaining step is with embodiment 1, and the activity of such catalysts measurement result is as shown in table 1.
Embodiment 7
1) gets 1M Cu (NO
3)
2Solution 80ml, 1M Zn (NO
3)
2Solution 70ml and 1M Al (NO
3)
3Solution 20ml places the 400ml beaker to mix.
2) get 170mll1M Na
2CO
3Solution places the 1000ml beaker, is heated to 70 ℃, stirs down the mixed liquor of step 1 gained is added to Na with the speed of 20ml/min
2CO
3In the solution, stop to add thermal agitation, the pH=7.5 of mixed liquor behind the aging 2h.
3) with 60 ℃ of deionized water washing sediments to there not being Cl
-, be added to the white carbon black of 1.0g in the sediment and stir 20min.Remaining step is with embodiment 1, and the activity of such catalysts measurement result is as shown in table 1.
Table 1 adds the evaluation result of different insulation agents
| Embodiment | Composition of raw materials | Methyl alcohol yield (g.ml -1 cat.h -1) | ||
| Cu∶Zn∶Al | The addition of M | Initial activity | Active after the heat treatment | |
| 2 | 60∶30∶11 | 1.0g ZSM-5 | 0.13 | 0.10 |
| 3 | 60∶30∶11 | 0.8g 5A molecular sieve | 0.12 | 0.09 |
| 4 | 60∶45∶8 | 1.1g 3A molecular sieve | 0.13 | 0.11 |
| 5 | 45∶45∶12 | 1.0g titanium dioxide | 0.14 | 0.11 |
| 6 | 55∶30∶10 | 1.2g MgAl 2O 4 | 0.13 | 0.09 |
| 7 | 40∶35∶10 | 1.0g white carbon black | 0.13 | 0.12 |
Embodiment 8
1) gets 1M Cu (C
2H
4O
2)
2Solution 72ml, 1M Zn (C
2H
4O
2)
2Solution 100ml and 1MAl (NO
3)
3Solution 18ml places the 400ml beaker, mixes.
2) get 180ml1M Na
2CO
3Solution places the 1000ml beaker, is heated to 70 ℃, stirs down the mixed liquor of step 1 gained is added to Na with the speed of 20ml/min
2CO
3In the solution, stop to add thermal agitation behind the aging 2h, at this moment the pH=7.8 of mixed liquor.
3) with 70 ℃ of deionized water washing sediments to there not being Cl
-, be added to the white carbon black of 1.0g in the sediment and stir 20min.
4) filter, filter cake pulverizes at 110 ℃ of oven dry 4h, 500 ℃ of calcining 3h.
5) at last the gained mixed oxide is pulverized that to be screened into the 16-40 order standby.
The gained catalyst formulation is Cu: Zn: Al=36: 50: 9 (atomic ratio), activity of such catalysts is measured with embodiment 1.The result is initial activity 0.13g.ml
-1 Cat.h
-1, the activity after the heat treatment is 0.11g.ml
-1 Cat.h
-1
Embodiment 9～10
Change the insulation agent kind and add quality, all the other conditions and method for making are with embodiment 8.The determination of activity result is as shown in table 2.
Embodiment 11
1) gets 1M Cu (C
2H
1O
2)
2Solution 90ml, 1M Zn (C
2H
4O
2)
2Solution 45ml and 1M Al (NO
3)
3Solution 16.5ml places the 400ml beaker, mixes.
2) get 142ml1M Na
2CO
3Solution places the 1000ml beaker, is heated to 70 ℃, stirs down the mixed liquor of step 1 gained is added to Na with the speed of 20ml/min
2CO
3In the solution, stop to add thermal agitation behind the aging 2h, at this moment the pH=7.8 of mixed liquor.
3) with 70 ℃ of deionized water washing sediments to there not being Cl
-, 0.9g γ-Al
2O
3Be added in the sediment and stir 20min.
Remaining step is with embodiment 8, and the activity of such catalysts measurement result is as shown in table 2.
Embodiment 12
1) gets 1M Cu (C
2H
4O
2)
2Solution 90ml, 1M Zn (C
2H
4O
2)
2Solution 66ml and 1M Al (NO
3)
318ml solution places the 400ml beaker, mixes.
2) get 165ml1M Na
2CO
3Solution places the 1000ml beaker, is heated to 70 ℃, stirs down the mixed liquor of step 1 gained is added to Na with the speed of 20ml/min
2CO
3In the solution, stop to add thermal agitation behind the aging 2h, at this moment the pH=7.8 of mixed liquor.
3) with 70 ℃ of deionized water washing sediments to there not being Cl
-, be added to the 0.7g3A molecular sieve in the sediment and stir 20min.
Remaining step is with embodiment 8, and the activity of such catalysts measurement result is as shown in table 2.The determination of activity result is as shown in table 2
Embodiment 13
1) gets 1M Cu (C
2H
4O
2)
2Solution 90ml, 1M Zn (C
2H
4O
2)
2Solution 45ml and 1M Al (NO
3)
318ml solution places the 400ml beaker, mixes.
3) get 141ml 1M Na
2CO
3Solution places the 1000ml beaker, is heated to 70 ℃, stirs down the mixed liquor of step (1) gained is added to Na with the speed of 20ml/min
2CO
3In the solution, stop to add thermal agitation behind the aging 2h, at this moment the pH=7.8 of mixed liquor.
3) with 70 ℃ of deionized water washing sediments to there not being Cl
-, be added to the 1.1g3A molecular sieve in the sediment and stir 20min.
Remaining step is with embodiment 8, and the activity of such catalysts measurement result is as shown in table 2.
Embodiment 14
1) gets 1M Cu (C
2H
4O
2)
2Solution 90ml, 1M Zn (C
2H
4O
2)
2Solution 90ml and 1M Al (NO
3)
320ml solution places the 400ml beaker, mixes.
2) get 190ml1M Na
2CO
3Solution places the 1000ml beaker, is heated to 70 ℃, stirs down the mixed liquor of step 1 gained is added to Na with the speed of 20ml/min
2CO
3In the solution, stop to add thermal agitation behind the aging 2h, at this moment the pH=7.8 of mixed liquor.
3) with 70 ℃ of deionized water washing sediments to there not being Cl
-, be added to the 1.4g3A molecular sieve in the sediment and stir 20min.
Remaining step is with embodiment 8, and the activity of such catalysts measurement result is as shown in table 2.
Table 2 adds the evaluation result of different insulation agent M
| Embodiment | Composition of raw materials | Methyl alcohol yield (g.ml - cat.h -) | ||
| Cu∶Zn∶Al | The addition of M | Initial activity | Active after the heat treatment | |
| 9 | 36∶50∶9 | 0.3g titanium dioxide and 0.7g5A molecular sieve | 0.12 | 0.09 |
| 10 | 36∶50∶9 | 1.0g hydrotalcite | 0.12 | 0.10 |
| 11 | 60∶30∶11 | 0.9gγ-Al 2O 3 | 0.11 | 0.10 |
| 12 | 30∶22∶8 | 0.7g 3A molecular sieve | 0.10 | 0.08 |
| 13 | 60∶30∶12 | 1.1g 3A molecular sieve | 0.12 | 0.10 |
| 14 | 45∶45∶10 | 1.4g 3A molecular sieve | 0.13 | 0.11 |
Claims (7)
1. by the catalyst of synthesising gas systeming carbinol, it is characterized in that described catalyst consists of insulation agent M and Cu-Zn-Al mixed oxide, described insulation agent M is selected from γ-Al
2O
3, white carbon black, Si-Al molecular sieve, hydrotalcite, magnesium aluminate spinel, titanium dioxide, at least a in 5A molecular sieve, ZSM-5, the 3A molecular sieve, described Cu, Zn, Al oxide are no Cl
-, SO
4 2-The oxide of soluble-salt calcining gained, each set of dispense of catalyst is than being 30～70 by atomic ratio metering Cu, Zn is 20～60, Al is 7～15; Is 1%～20% of catalyst quality by quality than the addition of insulation agent M.
2. the catalyst by synthesising gas systeming carbinol as claimed in claim 1 is characterized in that each set of dispense of described catalyst is 35～65 than measuring Cu by atomic ratio; Zn is 30～50; Al is 8～12.
3. the catalyst by synthesising gas systeming carbinol as claimed in claim 1 is characterized in that described is 8%～12% of catalyst quality by quality than the addition of insulation agent M.
4. the catalyst by synthesising gas systeming carbinol as claimed in claim 1 is characterized in that described soluble-salt is selected from nitrate or acetate.
5. the Preparation of catalysts method by synthesising gas systeming carbinol as claimed in claim 1 is characterized in that its step is as follows:
1) by the catalytic component proportioning Cu, the Zn of metering, the soluble-salt of Al are made into mixed aqueous solution;
2) stir in the precipitant solution that is added to 65～70 ℃ down, control pH=7.0～8.5 are terminal point; Described precipitating reagent is Na
2CO
3
3) arrive no Cl with deionized water washing sediment
-
4) the insulation agent M that measures by the proportioning handle is added to and stirs 15～25min in the sediment, and filtration is drained;
5) 110～120 ℃ of oven dry, levigate behind 450～500 ℃ of calcination 2-3h, compression molding, pulverizing then is 16～40 orders.
6. the Preparation of catalysts method by synthesising gas systeming carbinol as claimed in claim 5 is characterized in that described precipitating reagent is content 〉=98.5%, Cl
-≤ 0.1% Na
2CO
3
7. the Preparation of catalysts method by synthesising gas systeming carbinol as claimed in claim 5 is characterized in that its time of described oven dry is 4h.
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|---|---|---|---|
| CNA2006100822317A CN101020139A (en) | 2006-05-13 | 2006-05-13 | Catalyst for preparing methanol with synthetic gas and its prepn process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100822317A CN101020139A (en) | 2006-05-13 | 2006-05-13 | Catalyst for preparing methanol with synthetic gas and its prepn process |
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| Publication Number | Publication Date |
|---|---|
| CN101020139A true CN101020139A (en) | 2007-08-22 |
Family
ID=38708063
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|---|---|---|---|
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| CN105618088B (en) * | 2016-01-28 | 2018-09-25 | 中国科学院上海高等研究院 | A kind of copper fluoride base class hydrotalcite catalyst and its preparation method and application |
| CN105944723A (en) * | 2016-05-21 | 2016-09-21 | 中山市绿浪助剂有限公司 | Preparation method of catalyst for preparation of low carbon alcohol by synthesis gas |
| CN105944723B (en) * | 2016-05-21 | 2019-06-25 | 陕西长青能源化工有限公司 | A kind of preparation method of low carbon alcohol by synthetic gas catalyst |
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| WO2021056572A1 (en) * | 2019-09-24 | 2021-04-01 | 东北大学 | Aluminum shared metal-zeolite bifunctional catalyst, and preparation method and application |
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