CN101269334A - Catalyst for meanwhile producing low carbon mix alcohol and olefin hydrocarbon, preparing method and application thereof - Google Patents
Catalyst for meanwhile producing low carbon mix alcohol and olefin hydrocarbon, preparing method and application thereof Download PDFInfo
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- CN101269334A CN101269334A CNA2008100551066A CN200810055106A CN101269334A CN 101269334 A CN101269334 A CN 101269334A CN A2008100551066 A CNA2008100551066 A CN A2008100551066A CN 200810055106 A CN200810055106 A CN 200810055106A CN 101269334 A CN101269334 A CN 101269334A
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- catalyst
- nitrate
- mas
- alcohol
- mixed solution
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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
Abstract
The invention relates to a catalyst which can simultaneously produce low-carbon mixed alcohol and olefin, the molar ratio of metals is as follows: Cu: Zn: Fe: Mn is equal to 35 to 55:0.5 to 50:35 to 54:0.5 to 50. According to the mixture ratio of the catalyst, a uniform mixed solution is composed of copper nitrate, iron nitrate, zinc nitrate and manganese nitrate; ammonia, used as a precipitant, is fully stirred with the mixed solution at the temperature ranging from 60 DEG C to 90 DEG C and a pH value between 7 and 9 so as to evenly mix with the precipitant; the mixed solution is aginged for 1 to 3 hours after precipitating; the sediment is filtered and washed, and the sediment is dried for 8 to 12 hours at the temperature ranging from 100 DEG C and 140 DEG C, then the sediment is baked for 3 to 6 hours at the temperature ranging from 350 DEG C and 550 DEG C; in this way, the obtained catalyst is crushed by a presser bit between 40 and 60 mu; the catalyst is made by the steps. The catalyst has high reactivity, good selectivity of higher alcohol or low-carbon olefin and mild reaction condition.
Description
Technical field
The invention belongs to a kind of catalyst and method for making and application, relate to a kind of catalyst and method for making and application that synthesis gas prepares MAS and alkene simultaneously that be used for specifically.
Background technology
Low-carbon alkene such as ethene, propylene is very important basic Organic Chemicals, and along with the development of chemical industry, its demand is more and more big.And at present, low-carbon alkene along with the shortage day by day of petroleum resources, is badly in need of seeking alternate resources mainly from light oil cracking.MAS can be used as fuel additive, compares with methyl alcohol, has improved the intersolubility with gasoline, has reduced the content of formaldehyde during the burning back is discarded; Compare MAS cost lower (only be gasoline 2/3) with ethanol.Moreover MAS itself is a kind of good clean fuel, and from more profound, the economic worth of MAS is that it is as chemical products itself or as the immense value of large Chemical Manufacture raw material.Based on the industrial applications of the coal-based C-1 chemistry of CO hydrogenation synthetic fuel and chemicals, reduce dependence to limited petroleum resources, all have crucial meaning for the guarantee of economic development, environmental protection especially national energy security.
Catalyst system and catalyzing by synthesis gas preparation MAS and alkene mainly contains following a few class at present:
The Cu-Co catalyst series of France Petroleum Institute (IFP) development, the space-time yield of alcohol is 0.2g/mLh, C
2+The selectivity of alcohol is 50-70%, wherein mainly is straight-chain fatty alcohol, and the selectivity of hydro carbons is 20-30%, mainly is methane.
The Cu-Co-Zr-K catalyst of Mobil oil company development, the selectivity of alcohol is 81.9% in the product, the selectivity of hydro carbons is 8.9%, ester class 4.9%, C in the alcohol product
2+Alcohol accounts for 65%.
Rotti etc. have reported the performance that has MAS synthetic on the Fe-Cu catalyst, but owing to accessory substance on the iron catalyst is more, product mainly is the mixture of pure and mild hydrocarbon.
Uchiyama etc. utilize coprecipitation and use TiO
2Dipping Ni salting liquid makes contains the Ni catalyst, has the selectivity of certain synthesis of low-carbon alcohol, and main accessory substance is a methane; And loaded Ni/TiO
2Catalyst and Ni/MnO catalyst activity and stability are all poor.
Venter etc. have obtained activated carbon supported high dispersive K-Fe-Mn and K-Fe catalyst by the carbonyl complex decomposition method, and catalyst has very high activity, C in the product of K-Fe-Mn catalyst
2-C
4Alkene accounts for 85-90wt%, and methane is detected other unique products.The average molar mass of K-Fe catalyst reaction product kind is big slightly, but olefine selective is also very high.
T.SANO etc. have prepared and have had C preferably
2, C
3The Fe-Ti-V-of olefine selective and Fe-Ti-Mn-zeolite-catalyst.Hydrocarbon product mainly is C on the Fe-Ti-Mn-zeolite catalyst
1-C
3, C
2, C
3The selectivity of alkene is 44.7%, and as Fe: Ti=1: at high temperature the selectivity of methane is still lower in the time of 1.
The Zhang Jingchang of Beijing University of Chemical Technology etc. utilizes laser pyrolysis processes to prepare high degree of dispersion amorphous superfine iron powder and carbon dust, successfully makes F-T synthesizing activity new species Fe through solid phase reaction
3C.Prepare with Fe
3C is the Fe-C of main body, Fe-C-Mn, and nanocatalysts such as Fe-C-Mn-K, the CO conversion ratio reaches 96%, and olefine selective reaches more than 80%.
Above-mentioned catalyst system and catalyzing is all being obtained progress preferably aspect synthesis gas preparation MAS or the low-carbon alkene, but exist reactivity low, the poor selectivity of higher alcohol or low-carbon alkene, problems such as severe reaction conditions are with the industrialized actual very big gap that requires to still have.
Summary of the invention
The purpose of this invention is to provide a kind of reactivity height, the selectivity of higher alcohol or low-carbon alkene is good, and the synthesis gas of reaction condition gentleness prepares catalyst and the preparation method and the application of MAS and alkene simultaneously.
Applications catalyst metal molar content ratio of the present invention is:
Cu∶Zn∶Fe∶Mn＝(35～55)∶(0.5～50)∶(35～54)∶(0.5～50)
Preparation of catalysts method of the present invention has following steps:
(1) presses catalyst and form proportioning, copper nitrate, ferric nitrate, zinc nitrate and manganese nitrate are mixed with homogeneous mixture solotion;
(2) with ammoniacal liquor being precipitating reagent, is 7～9 conditions under fully to stir make precipitate evenly mix at 60～90 ℃ with the pH value with ammoniacal liquor and (1) middle mixed solution for preparing, and precipitates the aging 1～3h in end back;
(3) gained sediment in the filtration washing (2), dry 8～12h under 100～140 ℃ of temperature, at 350～550 ℃ of roasting 3～6h, the catalyst that makes is crushed to the 40-60 order through compressing tablet then, promptly gets catalyst.
Application of Catalyst of the present invention is:
Catalyst reaction condition of the present invention is: H
2/ CO=1.0～2.5, pressure: 2.0～4.0MPa, temperature: 220～280 ℃, air speed: 3000～6000h
-1
The present invention possesses following characteristics:
The catalyst that utilizes the present invention to prepare is used for synthesis gas preparation MAS and olefin catalytic performance study, possesses the synthesizing low-carbon mixed alcohol and the alkene performance of high selectivity, and has lower CH
4(10-21% in the hydro carbons) selectivity all has than higher selectivity, C MAS and alkene
2+The selectivity of alcohol accounts for more than 40% in total alcohol, mainly comprises low-carbon alkene and C in the hydrocarbon product simultaneously
5-C
11Alkane, and CH
4Selectivity catalyst based much lower than other Cu-Co or Cu-Fe.
Key of the present invention is the catalyst based middle different auxiliary agent that adds of Cu-Fe, the i.e. selection of Zn and Mn auxiliary agent.For for synthesis gas preparation MAS and alkene, the selection of catalyst system and catalyzing and preparation are key factors.
The present invention is in catalyst preparation process, the Zn, Mn metal that select more effectively to improve the electronic structure of catalyst and bulk structure are as auxiliary agent, it is catalyst based to have prepared the Fe-Cu that has high-ratio surface after the reduction preliminary treatment, has obtained MAS, selectivity of light olefin and lower methane selectively preferably.
Be the feature of this catalyst of detailed presentations, now specify as follows in conjunction with the embodiments:
The specific embodiment
Embodiment 1:
Take by weighing Cu (NO
3)
23H
2O22.0g, Fe (NO
3)
39H
2The O37.6 gram, Zn (NO
3)
26H
2O0.28g, Mn (NO
3)
2Solution (50wt%) 0.33g is mixed with even mixing salt solution 200mL; The pH value is under 8 conditions, and ammonia spirit and mixing salt solution under stirring and flow co-precipitation, are left standstill, and aging 3h filters, washing, 120 ℃ of dry 10h, and at 450 ℃ of roasting 3h, the catalyst compressing tablet that makes is crushed to the 40-60 order with the dry thing of gained.Catalyst metals molar content ratio is: Cu: Zn: Fe: Mn=44: 0.5: 50: 0.5.Evaluating catalyst, reaction temperature are 240 ℃; Pressure is 4.0MPa; H
2/ CO=2.0; Air speed is 6000h
-1, reaction result sees Table 1.
Embodiment 2:
Take by weighing Cu (NO
3)
23H
2O22.0g, Zn (NO
3)
26H
2O25.2g, Fe (NO
3) 39H
2O37.6g, Mn (NO
3)
2Solution (50wt%) 0.40g is mixed with even mixing salt solution 200mL; The pH value is under 7 conditions, and under stirring, and stream co-precipitation is left standstill with ammonia spirit and mixing salt solution, and aging 2h filters, washing, 100 ℃ of dry 12h, and at 350 ℃ of roasting 6h, the catalyst compressing tablet that makes is crushed to the 40-60 order with the dry thing of gained.Catalyst metals molar content ratio is: Cu: Zn: Fe: Mn=44: 45.5: 50: 0.6.Evaluating catalyst, reaction temperature are 220 ℃; Pressure is 4.0MPa; H
2/ CO=1.0; Air speed is 3000h
-1, reaction result sees Table 1.
Embodiment 3:
Take by weighing Cu (NO
3)
23H
2O18.0g, Fe (NO
3)
39H
2The O26.3 gram, Zn (NO
3)
26H
2O14.1g, Mn (NO
3)
2Solution (50wt%) 6.7g is mixed with even mixing salt solution 200mL; The pH value is under 8 conditions, and ammonia spirit and mixing salt solution under stirring and flow co-precipitation, are left standstill, and aging 1h filters, washing, 100 ℃ of dry 8h, and at 400 ℃ of roasting 3h, the catalyst compressing tablet that makes is crushed to the 40-60 order with the dry thing of gained.Catalyst metals molar content ratio is: Cu: Zn: Fe: Mn=40: 25.5: 35: 10.Evaluating catalyst, reaction temperature are 280 ℃; Pressure is 2.0MPa; H
2/ CO=2.0; Air speed is 5000h
-1, reaction result sees Table 1.
Embodiment 4:
Take by weighing Cu (NO
3)
23H
2O24.8g, Fe (NO
3)
39H
2O33.8g, Zn (NO
3)
26H
2O3.0g, Mn (NO
3)
2Solution (50wt%) 20.0g is mixed with even mixing salt solution 200mL; The pH value is under 9 conditions, and ammonia spirit and mixing salt solution under stirring and flow co-precipitation, are left standstill, and aging 3h filters, washing, 140 ℃ of dry 10h, and at 550 ℃ of roasting 5h, the catalyst compressing tablet that makes is crushed to the 40-60 order with the dry thing of gained.Catalyst metals molar content ratio is: Cu: Zn: Fe: Mn=55: 5.5: 45: 30.Evaluating catalyst, reaction temperature are 260 ℃; Pressure is 3.0MPa; H
2/ CO=2.5; Air speed is 6000h
-1, reaction result sees Table 1.
Embodiment 5:
Take by weighing Cu (NO
3)
23H
2O15.8g, Fe (NO
3)
39H
2O37.6g, Zn (NO
3)
26H
2O24.9g, Mn (NO
3)
2Solution (50wt%) 33.3g is mixed with even mixing salt solution 200mL; The pH value is under 7 conditions, and ammonia spirit and mixing salt solution under stirring and flow its precipitation, are left standstill, and aging 2h filters, washing, 120 ℃ of dry 8h, and at 450 ℃ of roasting 4h, the catalyst compressing tablet that makes is crushed to the 40-60 order with the dry thing of gained.Catalyst metals molar content ratio is: Cu: Zn: Fe: Mn=35: 45: 50.1: 500.Evaluating catalyst, reaction temperature are 240 ℃; Pressure is 4.0MPa; H
2/ CO=1.5; Air speed is 4000h
-1, reaction result sees Table 1.
Embodiment 6:
Take by weighing Cu (NO
3)
23H
2O21.6g, Fe (NO
3)
39H
2O30.7g, Zn (NO
3)
26H
2O6.9g, Mn (NO
3)
2Solution (50wt%) 30.7g is mixed with even mixing salt solution 200mL; The pH value is under 8 conditions, and ammonia spirit and mixing salt solution under stirring and flow co-precipitation, are left standstill, and aging 3h filters, washing, 120 ℃ of dry 12h, and at 500 ℃ of roasting 5h, the catalyst compressing tablet that makes is crushed to the 40-60 order with the dry thing of gained.Catalyst metals molar content ratio is: Cu: Zn: Fe: Mn=48: 12.5: 40.8: 46.0.Evaluating catalyst, reaction temperature are 240 ℃; Pressure is 3.0MPa; H
2/ CO=2; Air speed is 6000h
-1, reaction result sees Table 1.
Table 1
Claims (3)
1, a kind of catalyst of producing MAS and alkene simultaneously is characterized in that catalyst metals molar content ratio is:
Cu∶Zn∶Fe∶Mn＝35～55∶0.5～50∶35～54∶0.5～50
2, a kind of Preparation of catalysts method of producing MAS and alkene simultaneously as claimed in claim 1 is characterized in that comprising the steps:
(1) presses catalyst and form proportioning, copper nitrate, ferric nitrate, zinc nitrate and manganese nitrate are mixed with homogeneous mixture solotion;
(2) with ammoniacal liquor being precipitating reagent, is 7～9 conditions under fully to stir make precipitate evenly mix at 60～90 ℃ with the pH value with ammoniacal liquor and (1) middle mixed solution for preparing, and precipitates the aging 1～3h in end back;
(3) gained sediment in the filtration washing (2), dry 8～12h under 100～140 ℃ of temperature, at 350～550 ℃ of roasting 3～6h, the catalyst that makes is crushed to the 40-60 order through compressing tablet then, promptly gets catalyst.
3, a kind of Application of Catalyst of producing MAS and alkene simultaneously as claimed in claim 1 is characterized in that the reaction condition of catalyst is: H
2/ CO=1.0～2.5, pressure: 2.0～4.0MPa, temperature: 220～280 ℃, air speed: 3000～6000h
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100551066A CN101269334A (en) | 2008-05-19 | 2008-05-19 | Catalyst for meanwhile producing low carbon mix alcohol and olefin hydrocarbon, preparing method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100551066A CN101269334A (en) | 2008-05-19 | 2008-05-19 | Catalyst for meanwhile producing low carbon mix alcohol and olefin hydrocarbon, preparing method and application thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101269334A true CN101269334A (en) | 2008-09-24 |
Family
ID=40003716
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|---|---|---|---|
| CNA2008100551066A Pending CN101269334A (en) | 2008-05-19 | 2008-05-19 | Catalyst for meanwhile producing low carbon mix alcohol and olefin hydrocarbon, preparing method and application thereof |
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|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104857972A (en) * | 2015-04-22 | 2015-08-26 | 大连瑞克科技有限公司 | Catalyst for co-producing lower alcohol and liquid fuel from synthetic gas, and preparation method thereof |
| CN110975934A (en) * | 2019-11-28 | 2020-04-10 | 中国科学院山西煤炭化学研究所 | Cation exchange resin-based catalyst for preparing low-carbon mixed alcohol from synthesis gas, preparation method and application thereof |
-
2008
- 2008-05-19 CN CNA2008100551066A patent/CN101269334A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104857972A (en) * | 2015-04-22 | 2015-08-26 | 大连瑞克科技有限公司 | Catalyst for co-producing lower alcohol and liquid fuel from synthetic gas, and preparation method thereof |
| CN110975934A (en) * | 2019-11-28 | 2020-04-10 | 中国科学院山西煤炭化学研究所 | Cation exchange resin-based catalyst for preparing low-carbon mixed alcohol from synthesis gas, preparation method and application thereof |
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Open date: 20080924 |