CN1785519A - Preparation method of catalyst used for synthesizing dimethylether by biomass base synthetic gas one step method - Google Patents
Preparation method of catalyst used for synthesizing dimethylether by biomass base synthetic gas one step method Download PDFInfo
- Publication number
- CN1785519A CN1785519A CN 200410052571 CN200410052571A CN1785519A CN 1785519 A CN1785519 A CN 1785519A CN 200410052571 CN200410052571 CN 200410052571 CN 200410052571 A CN200410052571 A CN 200410052571A CN 1785519 A CN1785519 A CN 1785519A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- oxalic acid
- preparation
- molecular sieve
- ratio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A catalyst for one-step synthesis of dimether from the biomass-based synthetic gas is composed of a methanol synthesizing catalyst and the HZSM-5 molecular sieve as dewatering catalyst. Said methanol synthesizing catalyst is prepared by oxalate deposition in alcohol. Said HZSM-5 molecular sieve is prepared from NaZSM-5 molecular sieve through ion exchange. Its advantages are high mechanical strength, high selectivity and high conversion rate of dimether.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method, particularly relate to a kind of Preparation of catalysts method that is used for biomass-based synthesis of dimethyl ether with synthesis gas one-step.
Background technologyDimethyl ether (CH
3-O-CH
3) be a kind of important green industrial products, can be used as clean fuel, aerosol, cold-producing medium, blowing agent, organic synthesis raw material etc.Particularly after it was as diesel oil co-combustion agent and alternative domestic fuel liquefied gas, its cry grew with each passing day.Current along with oil price goes up day by day, the research of dimethyl ether and production more and more come into one's own.The synthetic many of dimethyl ether are raw material with natural gas and coal at present, and methanol synthesis catalyst and dehydration catalyst are mixed sticking method, coprecipitation and direct dipping process mixing as synthesizing dimethyl ether catalyst with mixed sticking method, precipitation.Day by day exhausted along with traditional energy is that the technology of raw material one-step method dimethyl ether synthesis obtains paying attention to day by day with reproducible living beings.But at biomass-based synthesis gas nitrogen content height, carbon dioxide content height and the characteristics that contain a certain amount of methane, one-step method dimethyl ether synthesis appropriate catalyst yet there are no report.
Summary of the invention
The objective of the invention is provides the preparation method of one-step method dimethyl ether synthesis appropriate catalyst at biomass-based synthesis gas nitrogen content height, carbon dioxide content height and the characteristics that contain a certain amount of methane.
Biomass-based synthesis gas is mainly got by three kinds of modes: the gas after the gasification of (1) living beings obtains the living beings reformation gas (patent No.: 03126935.4) through purifying, reforming; (2) gas after the living beings gasification is referred to as rich CO through purifying the back without reformation
2Gas; (3) gas after the living beings gasification adds suitable hydrogen through purifying the back, and make H2: CO=1.5～2.0: 1 (volume ratio) is referred to as to join the hydrogen biogas.Because biomass material is more extensive: timber, stalk, cotton bar, husk etc., so biomass-based synthesis gas contains five kinds of key components, the content range of all gases is: H
2Can be 30%-60%, CO can be 10%-35%, CO
2Can be 4%-25%, CH
4Can be 2%-8%, N
2Can be 10%-30%.
The present invention adopts following method to realize: catalyst system therefor is made up of self-control methanol synthesis catalyst and dehydration catalyst HZSM-5 type molecular sieve two parts.
The oxalate precipitation method that methanol synthesis catalyst adopts alcohols (being preferably ethanol) to make solvent makes.With Cu (NO
3)
2, Zn (NO
3)
2, Al (NO
3)
36: 3: 1 in molar ratio, be made into mixed solution with alcohols as solvent, according to 1.0 times of the required oxalic acid amount of precipitate metal ion, prepare oxalic acid solution.Nitrate mixed solution is added oxalic acid solution apace, stir fast, aging (under 353K, left standstill 2 hours, and wore out), evaporating solvent (under the 353K).Carry out drying, roasting under the precipitation 383K with evaporation back gained, sintering temperature is 573K～623K, and roasting time is 4 hours.
The HZSM-5 molecular sieve is to be got through ion-exchange by the NaZSM-5 molecular sieve, is a kind of industrial solid acid catalyst.Preferred NaZSM-5 molecular sieve is Catalyst Factory, Nankai Univ production (patent No. 85100463), this product is to adopt " direct method " synthetic this molecular sieve, promptly directly use waterglass, inorganic salts, aluminium salt (or aluminate) is synthetic, owing to do not contain organic amine, " direct method " synthetic NaZSM-5 molecular sieve can be without roasting, directly carries out ion-exchange and makes various catalyst.
Methanol synthesis catalyst and HZSM-5 type molecular sieve mechanical mixture also can be mixed in water or in the alcohols (being preferably ethanol), and mixed proportion is by 1.5～5: 1.
In addition, can in the catalyst for methanol preparation process, add molecular sieve, following two kinds of preparation methods can be arranged according to the order difference that adds:
One, uses the oxalic acid precipitation salting liquid earlier, add molecular sieve then, fully stir evaporating solvent, roasting.
Concrete steps are as follows:
A) with Cu (NO
3)
2, Zn (NO
3)
2, Al (NO
3)
36: 3: 1 in molar ratio with water or alcohols (being preferably ethanol) as solvent, be made into mixed solution, according to 1.0 times of the required oxalic acid amount of precipitate metal ion, the preparation oxalic acid solution;
B) nitrate mixed solution is added oxalic acid solution apace;
C) according to calculating deserved CuO/ZnO/Al
2O
3The catalyst quality ratio is 1.5～5: 1 ratio, adds dehydration catalyst HZSM-5 type molecular sieve, fully stirs;
D) under 353K, left standstill 2 hours, wear out;
E) evaporating solvent under 353K;
F) will evaporate the back gained precipitation 383K under dried overnight, carry out roasting, sintering temperature is 573K～623K, roasting time is 4 hours.
Two, earlier molecular sieve is added salting liquid, add oxalic acid precipitation then, stir evaporating solvent, roasting.Specifically may further comprise the steps:
A) with Cu (NO
3)
2, Zn (NO
3)
2, Al (NO
3)
36: 3: 1 in molar ratio with water or alcohols as solvent, be made into mixed solution, according to 1.0 times of the required oxalic acid amount of precipitate metal ion, the preparation oxalic acid solution;
B) according to calculating deserved CuO/ZnO/Al
2O
3The catalyst quality ratio is 1.5～5: 1 ratio, and dehydration catalyst HZSM-5 type molecular sieve is added in the nitrate solution;
C) add oxalic acid solution apace, fully stir;
D) under 353K, left standstill 2 hours, wear out;
E) evaporating solvent under 353K;
F) will evaporate the back gained precipitation 383K under dried overnight, carry out roasting, sintering temperature is 573K～623K, roasting time is 4 hours.
The catalyst that makes as stated above, its active testing carries out in miniature fixed bed high pressure reaction assembly, and tube inner diameter is the 6mm stainless steel tube.Product remains on 393K and enters two online gc analyses.Catalyst quality 2.0 grams (about 1.8 milliliters).Raw material is 3 kinds.A kind of is the living beings gasification rich CO in back
2Gas; A kind of is living beings gasification back gas, reforms, and adjusts gas composition; A kind of is that living beings gasification back gas is allocated suitable H into
2, it is synthetic to make it to be suitable for dimethyl ether.Activity is represented with the conversion ratio that CO is converted into dimethyl ether.
With the dimethyl ether catalyst that preparation method of the present invention makes, be suitable for biomass-based one-step method from syngas and generate dimethyl ether, have the following advantages: (1) preparation section is simple, high efficiency, less energy consumption; (2) mechanical strength height, the life-span is long.(3) selection of catalysts that records is good, and CO changes into the conversion ratio height of dimethyl ether.(4) it is low to change into conversion of methanol.
The specific embodiment
Further specify this preparation method below by embodiment.
Embodiment 1:
22.44 gram copper nitrates and 11.37 gram zinc nitrates and 4.26 gram aluminum nitrates are made solvent with ethanol and are made into 1 mol mixed solution, get 18.91 gram oxalic acid and be made into 1 mol solution, make solvent with ethanol, nitrate mixed solution is added oxalic acid solution apace, stir fast.Aging.Evaporating solvent.The precipitation of evaporation back gained is carried out drying, roasting, and sintering temperature is 573K, and roasting time is 4 hours.Methanol synthesis catalyst mixes by mass ratio with HZSM-5 type molecular sieve at 4: 1.At 3Mpa, air speed 3000h
-1Down, with living beings reformation gas H
2: CO: N
2: CO
2: CH
4=45: 30: 16: 4: 5 (volume ratio) estimated catalyst.
Embodiment 2:
Two kinds of catalyst among the embodiment 1 are pressed mass ratio 4: 1, in water, stir drying, compressing tablet.At 3Mpa, air speed 3000h
-1With living beings reformation gas catalyst is estimated down.
Embodiment 3:
Two kinds of catalyst among the embodiment 1 are pressed mass ratio 4: 1, in ethanol, stir drying, compressing tablet.At 3Mpa, air speed 3000h
-1With living beings reformation gas catalyst is estimated down.At 3Mpa, air speed 3000h
-1With living beings reformation gas catalyst is estimated down.
Embodiment 4:
18.91 gram oxalic acid are made solvent with water and are made into 1 mol solution, 22.44 gram copper nitrates and 11.37 gram zinc nitrates and 4.26 gram aluminum nitrates are made solvent with water be made into 1 mol nitrate solution.Earlier precipitate nitrate solution, then according to calculating deserved CuO/ZnO/Al with oxalic acid solution
2O
3The catalyst quality ratio is 4: 1 a ratio, adds dehydration catalyst HZSM-5 type molecular sieve 16.47 grams, fully stir, and evaporating solvent, roasting is 4 hours under the 580K.At 3Mpa, air speed 3000h
-1With living beings reformation gas catalyst is estimated down.
Embodiment 5:
18.91 gram oxalic acid are made solvent with ethanol and are made into 1 mol solution, 22.44 gram copper nitrates and 11.37 gram zinc nitrates and 4.26 gram aluminum nitrates are made solvent with ethanol be made into 1 mol nitrate solution.Earlier precipitate nitrate solution, then according to calculating deserved CuO/ZnO/Al with oxalic acid solution
2O
3The catalyst quality ratio is 4: 1 a ratio, adds dehydration catalyst HZSM-5 type molecular sieve 16.47 grams, fully stirs evaporating solvent, 600K roasting.At 3Mpa, air speed 3000h
-1With living beings reformation gas catalyst is estimated down.
Embodiment 6:
22.44 gram copper nitrates and 11.37 gram zinc nitrates and 4.26 gram aluminum nitrates are made solvent with water and are made into 1 mol nitrate solution.18.91 gram oxalic acid are made solvent with water be made into 1 mol solution.Earlier according to calculating deserved CuO/ZnO/Al
2O
3The catalyst quality ratio is 4: 1 a ratio, and dehydration catalyst HZSM-5 type molecular sieve 16.47 grams are added in the nitrate solution, adds the oxalic acid solution precipitation then, stirs evaporating solvent, roasting under the 610K.At 3Mpa, air speed 3000h
-1With living beings reformation gas catalyst is estimated down.
Embodiment 7:
18.91 gram oxalic acid are made solvent with ethanol and are made into 1 mol solution, 22.44 gram copper nitrates and 11.37 gram zinc nitrates and 4.26 gram aluminum nitrates are made solvent with ethanol be made into 1 mol nitrate solution.Earlier according to calculating deserved CuO/ZnO/Al
2O
3The catalyst quality ratio is 4: 1 a ratio, and dehydration catalyst HZSM-5 type molecular sieve 16.47 grams are added in the nitrate solution, adds the oxalic acid solution precipitation then, stirs evaporating solvent, roasting under the 623K.At 3Mpa, air speed 3000h
-1With living beings reformation gas catalyst is estimated down.
Embodiment 8:
18.91 gram oxalic acid are made solvent with ethanol and are made into 1 mol solution, 22.44 gram copper nitrates and 11.37 gram zinc nitrates and 4.26 gram aluminum nitrates are made solvent with ethanol be made into 1 mol nitrate solution.Nitrate mixed solution is added oxalic acid solution apace, stir fast.Aging.Evaporating solvent.The precipitation of evaporation back gained is carried out drying, roasting, and sintering temperature is 573K, and roasting time is 4 hours.Methanol synthesis catalyst and HZSM-5 type molecular sieve in ethanol stir drying, compressing tablet at 4: 1 by mass ratio.At 5.0Mpa, air speed 8000h
-1Use rich CO down,
2Gas H
2: CO: N
2: CO
2: CH
4=33: 11: 27: 22: 7 (volume ratio) estimated catalyst.
Embodiment 9:
18.91 gram oxalic acid are made solvent with ethanol and are made into 1 mol solution, 22.44 gram copper nitrates and 11.37 gram zinc nitrates and 4.26 gram aluminum nitrates are made solvent with ethanol be made into 1 mol nitrate solution.Nitrate mixed solution is added oxalic acid solution apace, stir fast.Aging.Evaporating solvent.The precipitation of evaporation back gained is carried out drying, roasting, and sintering temperature is 573K, and roasting time is 4 hours.Catalyst for methanol and HZSM-5 type molecular sieve in ethanol stir drying, compressing tablet at 4: 1 by mass ratio.At 3.5Mpa, air speed 2000h
-1, with joining hydrogen biogas H
2: CO: N
2: CO
2: CH
4=42: 26: 15: 14: 3 (volume ratio) estimated catalyst.
The evaluation result of the prepared dimethyl ether catalyst of the foregoing description is listed as table 1:
Table 1
| Routine number | Probe temperature | The CO conversion ratio | Selectivity | |
| K | ％ | Dimethyl ether | Methyl alcohol | |
| 1 | 538 | 74.89 | 98.50 | 1.08 |
| 2 | 541 | 65.21 | 91.46 | 5.18 |
| 3 | 540 | 70.40 | 97.48 | 2.34 |
| 4 | 551 | 53.80 | 96.46 | 2.68 |
| 5 | 529 | 73.24 | 96.97 | 2.55 |
| 6 | 554 | 59.60 | 93.64 | 5.23 |
| 7 | 529 | 74.06 | 96.66 | 3.22 |
| 8 | 543 | 31.48 | 97.97 | 1.42 |
| 9 | 531 | 76.45 | 99.38 | 0.30 |
By embodiment 1-7 result in the table 1 as can be seen, the catalyst for preparing for several hybrid modes of living beings reformation gas all has than higher CO conversion rate (53.80%～74.89%), and the selectivity ratios of dimethyl ether is higher, and the selectivity ratios of methyl alcohol is lower.To embodiment 8 results as can be seen, to rich CO without reformation and hydrogenation step
2System also has higher CO conversion rate 31.48%, has reduced equipment investment, and gas can be directly used in generating without circulation, and dimethyl ether production and energy supply are combined, and favorable economic benefit is also arranged.To embodiment 9 results as can be seen, to joining the hydrogen biogas, the CO conversion ratio is up to 76.45%, and the selectivity of dimethyl ether reaches the highest by 99.38%, the selectivity of methyl alcohol minimum 0.30%.
More than nine embodiment at catalyst for methanol component and HZSM-5 type molecular sieve by mass ratio 1.5～5: when arbitrary proportion mixes in 1 scope, can both obtain reasonable effect.
With embodiment 3 is the example explanation, embodiment 3 is done the experiment of two kinds of catalyst mix mass ratioes: 22.44 gram copper nitrates and 11.37 gram zinc nitrates and 4.26 gram aluminum nitrates are made solvent with ethanol be made into 1 mol mixed solution, get 18.91 gram oxalic acid and be made into 1 mol solution, make solvent with ethanol, nitrate mixed solution is added oxalic acid solution apace, stir fast.Aging.Evaporating solvent.The precipitation of evaporation back gained is carried out drying, roasting, and sintering temperature is 573k, and roasting time is 4 hours.Methanol synthesis catalyst and HZSM-5 type molecular sieve were pressed mass ratio 1.5: 1, and 3: 1, mass ratio evenly mixed in ethanol in 5: 1.At 3Mpa, air speed 3000h
-1Down, with living beings reformation gas H
2: CO: N
2: CO
2: CH
4=45: 30: 16: 4: 5 (volume ratio) estimated catalyst.The result lists in table 2 together with embodiment 3:
Table 2
| Mixed proportion | Probe temperature | The CO conversion ratio | Selectivity | |
| K | ％ | Dimethyl ether | Methyl alcohol | |
| 1.5∶1 | 557 | 64.25 | 94.96 | 4.32 |
| 3∶1 | 546 | 71.24 | 94.48 | 4.11 |
| 4∶1 | 540 | 70.40 | 97.48 | 2.34 |
| 5∶1 | 512 | 75.13 | 94.76 | 4.21 |
Found out that by table 2 data catalyst for methanol and HZSM-5 type molecular sieve are pressed mass ratio 1.5～5: 1 mixes, and all has higher CO conversion rate 64.25%～75.13%, dimethyl ether selectivity height, the methyl alcohol selectivity is low, and when two kinds of catalyst quality ratios were 4: 1～5: 1, effect was best.
With embodiment 5 is the example explanation, the ratio of the amount that adds dehydration catalyst HZSM-5 type molecular sieve among the embodiment 5 is done the experiment of different mixing proportion: 18.91 gram oxalic acid are made solvent with ethanol be made into 1 mol solution, 22.44 gram copper nitrates and 11.37 gram zinc nitrates and 4.26 gram aluminum nitrates are made solvent with ethanol be made into 1 mol nitrate solution.Earlier precipitate nitrate solution, then according to calculating deserved CuO/ZnO/Al with oxalic acid solution
2O
3The catalyst quality ratio is 1.5: 1, and 3: 1,5: 1 ratio added dehydration catalyst HZSM-5 type molecular sieve, fully stir, and evaporating solvent, roasting is 4 hours under the 580K.At 3Mpa, air speed 3000h
-1Down, with living beings reformation gas H
2: CO: N
2: CO
2: CH
4=45: 30: 16: 4: 5 (volume ratio) estimated catalyst.
The result lists in table 3 together with embodiment 5:
Table 3
| Mixed proportion | Probe temperature | The CO conversion ratio | Selectivity | |
| K | ％ | Dimethyl ether | Methyl alcohol | |
| 1.5∶1 | 557 | 68.45 | 95.32 | 3.51 |
| 3∶1 | 546 | 71.86 | 95.26 | 3.89 |
| 4∶1 | 529 | 73.24 | 96.97 | 2.55 |
| 5∶1 | 512 | 76.90 | 95.33 | 3.12 |
Find out by table 3 data, in preparation process according to calculating deserved CuO/ZnO/Al2O
3The catalyst quality ratio is 1.5～5: 1 ratio, adds dehydration catalyst HZSM-5 type molecular sieve, and the catalyst of gained all has higher CO conversion rate 68.45%～76.90%, dimethyl ether selectivity height, the methyl alcohol selectivity is low, and when two kinds of catalyst quality ratios were 4: 1～5: 1, effect was best.
With embodiment 7 is example explanation, the ratio of the amount that adds dehydration catalyst HZSM-5 type molecular sieve among the embodiment 7 is done the experiment of different mixing proportion: 22.44 gram copper nitrates and 11.37 gram zinc nitrates and 4.26 gram aluminum nitrates are made solvent with ethanol be made into 1 mol nitrate solution.18.91 gram oxalic acid are made solvent with ethanol be made into 1 mol solution.Earlier according to calculating deserved CuO/ZnO/Al
2O
3The catalyst quality ratio is 1.5: 1, and 3: 1,5: 1 ratio added dehydration catalyst HZSM-5 type molecular sieve in the nitrate solution, added the oxalic acid solution precipitation then, stirred evaporating solvent, roasting under the 610K.At 3Mpa, air speed 3000h
-1Down, with living beings reformation gas H
2: CO: N
2: CO
2: CH
4=45: 30: 16: 4: 5 (volume ratio) estimated catalyst.The result lists in table 4 together with embodiment 7:
Table 4
| Mixed proportion | Probe temperature | The CO conversion ratio | Selectivity | |
| K | ％ | Dimethyl ether | Methyl alcohol | |
| 1.5∶1 | 557 | 68.34 | 95.72 | 3.50 |
| 3∶1 | 546 | 71.49 | 95.42 | 3.76 |
| 4∶1 | 529 | 74.06 | 96.66 | 3.22 |
| 5∶1 | 512 | 76.32 | 95.60 | 3.14 |
Find out by table 4 data, in preparation process according to calculating deserved CuO/ZnO/Al
2O
3The catalyst quality ratio is 1.5～5: 1 ratio, adds dehydration catalyst HZSM-5 type molecular sieve, and the catalyst of gained all has higher CO conversion rate 68.34%～76.32%, dimethyl ether selectivity height, the methyl alcohol selectivity is low, and when two kinds of catalyst quality ratios were 4: 1～5: 1, effect was best.
Catalyst to the foregoing description gained has carried out the active lifetime test, CO conversion ratio in the highest CO conversion ratio of the initial stage that records and the 500h, and its result is listed as table 5:
Table 5
| Routine number | Temperature (K) | Initial activity | 120h | 240h | 360h | 500h |
| 1 | 538 | 75.00 | 72.82 | 72.53 | 72.12 | 72.06 |
| 5 | 529 | 74.23 | 73.54 | 73.50 | 73.41 | 73.32 |
| 7 | 529 | 74.06 | 73.87 | 73.62 | 73.56 | 73.41 |
| 9 | 531 | 77.45 | 75.91 | 75.84 | 75.75 | 75.43 |
Notes condition: form identical with used biomass synthesis gas among the embodiment.
Find out that by table 5 data the catalyst of the method for the invention preparation has the long life-span, be suitable for biomass-based one-step method from syngas and produce dimethyl ether.
Claims (7)
1, a kind of Preparation of catalysts method that is used for biomass-based synthesis of dimethyl ether with synthesis gas one-step is characterized in that:
Catalyst system therefor is made up of methanol synthesis catalyst and dehydration catalyst HZSM-5 type molecular sieve two parts, is that 1.5～5: 1 mixing obtains dimethyl ether catalyst with two kinds of catalytic components by mass ratio;
Described methanol synthesis catalyst preparation method may further comprise the steps:
A) with Cu (NO
3)
2, Zn (NO
3)
2, Al (NO
3)
3Make solvent with alcohols in 6: 3: 1 in molar ratio, and be made into mixed solution, according to 1.0 times of the required oxalic acid amount of precipitate metal ion, the preparation oxalic acid solution;
B) nitrate mixed solution is added oxalic acid solution apace, stir fast;
C) under 353K, left standstill 2 hours, wear out;
D) evaporating solvent under 353K;
E) will evaporate the back gained precipitation 383K under dried overnight, carry out roasting, sintering temperature is 573k～623K, roasting time is 4 hours.
2, method according to claim 1 is characterized in that: the mixed proportion of described two kinds of catalytic components is 4～5: 1 by mass ratio.
3, method according to claim 1 is characterized in that: the hybrid mode of described methanol synthesis catalyst and dehydration catalyst HZSM-5 type molecular sieve is a mechanical mixture.
4, method according to claim 1 is characterized in that: the hybrid mode of described methanol synthesis catalyst and dehydration catalyst HZSM-5 type molecular sieve is to stir in water or alcohols, drying, compressing tablet.
5, a kind of Preparation of catalysts method that is used for biomass-based synthesis of dimethyl ether with synthesis gas one-step is characterized in that, may further comprise the steps:
A) with Cu (NO
3)
2, Zn (NO
3)
2, Al (NO
3)
36: 3: 1 in molar ratio with water or alcohols as solvent, be made into mixed solution, according to 1.0 times of the required oxalic acid amount of precipitate metal ion, the preparation oxalic acid solution;
B) nitrate mixed solution is added oxalic acid solution apace;
C) according to calculating deserved CuO/ZnO/Al
2O
3The catalyst quality ratio is 1.5～5: 1 ratio, adds dehydration catalyst HZSM-5 type molecular sieve, fully stirs;
D) under 353K, left standstill 2 hours, wear out;
E) evaporating solvent under 353K;
F) will evaporate the back gained precipitation 383K under dried overnight, carry out roasting, sintering temperature is 573K～623K, roasting time is 4 hours.
6, a kind of Preparation of catalysts method that is used for biomass-based synthesis of dimethyl ether with synthesis gas one-step is characterized in that, may further comprise the steps:
A) with Cu (NO
3)
2, Zn (NO
3)
2, Al (NO
3)
36: 3: 1 in molar ratio with water or alcohols as solvent, be made into mixed solution, according to 1.0 times of the required oxalic acid amount of precipitate metal ion, the preparation oxalic acid solution;
B) according to calculating deserved CuO/ZnO/Al
2O
3The catalyst quality ratio is 1.5～5: 1 ratio, and dehydration catalyst HZSM-5 type molecular sieve is added in the nitrate solution;
C) add oxalic acid solution apace, fully stir;
D) under 353K, left standstill 2 hours, wear out;
E) evaporating solvent under 353K;
F) will evaporate the back gained precipitation 383K under dried overnight, carry out roasting, sintering temperature is 573K～623K, roasting time is 4 hours.
7, according to claim 1 or 3 or 5 or 6 described methods, it is characterized in that: described alcohols solvent is an ethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100525716A CN100341622C (en) | 2004-12-08 | 2004-12-08 | Preparation method of catalyst used for synthesizing dimethylether by biomass base synthetic gas one step method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100525716A CN100341622C (en) | 2004-12-08 | 2004-12-08 | Preparation method of catalyst used for synthesizing dimethylether by biomass base synthetic gas one step method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1785519A true CN1785519A (en) | 2006-06-14 |
| CN100341622C CN100341622C (en) | 2007-10-10 |
Family
ID=36783182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100525716A Expired - Fee Related CN100341622C (en) | 2004-12-08 | 2004-12-08 | Preparation method of catalyst used for synthesizing dimethylether by biomass base synthetic gas one step method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100341622C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101658805B (en) * | 2009-09-16 | 2011-12-07 | 中国科学院广州能源研究所 | Method for preparing catalyst for synthesizing LPG by synthetic gas in one-step method |
| CN101837299B (en) * | 2009-03-18 | 2012-08-08 | 中国石油天然气股份有限公司 | Catalyst for catalytic gasoline hydrogenation modification and preparation method thereof |
| CN103012062A (en) * | 2012-12-20 | 2013-04-03 | 上海戊正工程技术有限公司 | Process for indirectly producing alcohol with synthetic gas and application of process |
| CN103212418A (en) * | 2013-04-25 | 2013-07-24 | 太原理工大学 | Dual-function catalyst for directly preparing dimethyl ether from synthesis gas and preparation method of dual-function catalyst |
| CN114920627A (en) * | 2022-04-11 | 2022-08-19 | 南方海洋科学与工程广东省实验室(广州) | Method for preparing dimethyl ether by one-step catalytic method of natural gas hydrate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1524618A (en) * | 2003-09-17 | 2004-09-01 | 中国石化集团南京化学工业有限公司催 | Catalyst for synthesis of dimethyl ether in fluid bed |
-
2004
- 2004-12-08 CN CNB2004100525716A patent/CN100341622C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101837299B (en) * | 2009-03-18 | 2012-08-08 | 中国石油天然气股份有限公司 | Catalyst for catalytic gasoline hydrogenation modification and preparation method thereof |
| CN101658805B (en) * | 2009-09-16 | 2011-12-07 | 中国科学院广州能源研究所 | Method for preparing catalyst for synthesizing LPG by synthetic gas in one-step method |
| CN103012062A (en) * | 2012-12-20 | 2013-04-03 | 上海戊正工程技术有限公司 | Process for indirectly producing alcohol with synthetic gas and application of process |
| CN103012062B (en) * | 2012-12-20 | 2015-04-22 | 上海戊正工程技术有限公司 | Process for indirectly producing alcohol with synthetic gas and application of process |
| CN103212418A (en) * | 2013-04-25 | 2013-07-24 | 太原理工大学 | Dual-function catalyst for directly preparing dimethyl ether from synthesis gas and preparation method of dual-function catalyst |
| CN103212418B (en) * | 2013-04-25 | 2015-05-20 | 太原理工大学 | Dual-function catalyst for directly preparing dimethyl ether from synthesis gas and preparation method of dual-function catalyst |
| CN114920627A (en) * | 2022-04-11 | 2022-08-19 | 南方海洋科学与工程广东省实验室(广州) | Method for preparing dimethyl ether by one-step catalytic method of natural gas hydrate |
| CN114920627B (en) * | 2022-04-11 | 2024-02-20 | 南方海洋科学与工程广东省实验室(广州) | Method for preparing dimethyl ether by catalyzing natural gas hydrate through one-step method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100341622C (en) | 2007-10-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Goeppert et al. | Recycling of carbon dioxide to methanol and derived products–closing the loop | |
| CN104148106B (en) | Synthesis gas produces catalyst of low-carbon alkene and preparation method thereof | |
| TWI462777B (en) | Method of fabricating cu-zn-al catalyst through synthesizing methanol and dimethyl ether | |
| Wei et al. | A facile ethanol fuel synthesis from dimethyl ether and syngas over tandem combination of Cu-doped HZSM35 with Cu-Zn-Al catalyst | |
| CN106076344A (en) | Activated carbon supported copper-metal oxide catalyst and preparation method and application thereof | |
| WO2012119958A1 (en) | Catalytic process for converting carbon dioxide to a liquid fuel or platform chemical | |
| CN106890668A (en) | A kind of catalyst for producing methyl acetate, its preparation method and application | |
| CN111760582A (en) | MOF-based MoP-Cu3P transition metal phosphide heterojunction photocatalyst | |
| CN100341622C (en) | Preparation method of catalyst used for synthesizing dimethylether by biomass base synthetic gas one step method | |
| CN101574658A (en) | Method for synthesizing nanometer nickeliferous ternary houghite compound catalyst | |
| CN1883804A (en) | Catalyst for preparation of dimethyl ether from synthesis gas | |
| CN1883798A (en) | Catalyst for direct preparation of dimethyl ether by using synthesis gas | |
| Cao et al. | Hydrogen generation by heterogeneous catalytic steam reforming of short-chain alcohols: a review | |
| CN117282432B (en) | Catalyst for synthesizing green methanol by biomass gasification coupling renewable energy source hydrogen production and preparation method and application thereof | |
| CN111359644B (en) | Non-noble metal-based molybdenum carbide catalyst for dimethyl ether steam reforming hydrogen production and preparation method and application thereof | |
| CN1856441A (en) | Process for the preparation of a hydrogen-rich stream | |
| CN103551182A (en) | Catalyst for splitting decomposition of biomass tar and preparation method thereof | |
| CN102653393A (en) | Method for preparing hydrogen by utilizing waste biomass | |
| CN1753727A (en) | Catalyst for producing liquefied petroleum gas, process for producing the same, and process for producing liquefied petroleum gas with the catalyst | |
| CN103537282B (en) | For the synthesis of gas synthesizing alcohol methanogenic rhodium base catalyst in parallel and preparation method thereof | |
| CN111389436A (en) | Preparation method of efficient and stable molybdenum carbide catalyst for dimethyl ether steam reforming hydrogen production | |
| EP3427821A1 (en) | Catalytic composition for co2 conversion | |
| CN117696056B (en) | Multi-element doped copper-iron-based catalyst, and preparation method and application thereof | |
| US20220395811A1 (en) | Catalyst composition and method of making thereof for carbon monoxide production | |
| WO2019061342A1 (en) | Method for directly producing ethanol from syngas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20071010 Termination date: 20111208 |