CN1413767A - Preparation method of catalyst for directed preparing dimethyl ether by synthetic gas - Google Patents
Preparation method of catalyst for directed preparing dimethyl ether by synthetic gas Download PDFInfo
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- CN1413767A CN1413767A CN 01136842 CN01136842A CN1413767A CN 1413767 A CN1413767 A CN 1413767A CN 01136842 CN01136842 CN 01136842 CN 01136842 A CN01136842 A CN 01136842A CN 1413767 A CN1413767 A CN 1413767A
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- dimethyl ether
- catalyst
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- synthetic gas
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Abstract
A process for preparing the catalyst used to prepare dimethylether directly from synthetic gas feattures that the nitrate containing Cu, Zn, and Al and/or Zr, where the atom ratio of Cu/Zn/Al+Zr is 1/0.4-0.7/0.03-0.3, it used as raw material and the solid acid is used as dewatering component, the ratio of synthetic component and dewatering component is 1:1-5:1 (weight ratio). Its advantages are simple process, small granularity, high specific surface area and high activity.
Description
Technical field
The present invention relates to a kind of by synthesis gas (CO and H
2) the direct method for preparing catalyst of preparing dimethy ether, specifically, relate to a kind of employing colloidal deposition method preparation and contain Cu, Zn and other components and with the well-mixed dimethyl ether catalyst preparation method of solid acid.
Background technology
Dimethyl ether is a kind of broad-spectrum chemical products, can replace fluorochlorohydrocarbon to do aerosol spray and environment friendly refrigerating fluid, also can be used as the important source material of producing low-carbon alkene.Studies show that in recent years, dimethyl ether can be used as the use that directly acts as a fuel of liquefied petroleum gas and diesel oil substitute.Therefore the potential market of dimethyl ether is very huge beyond doubt.
At present existing many patents and document have been announced the process of one-step method from syngas preparing dimethy ether.United States Patent (USP) for example, 4098809,4417000,3894102,4177167; Japan Patent 63-254188, Chinese invention patent, application publication number 1153080.Catalyst in these patents is many to form with synthetic component of methyl alcohol and acid methanol dehydration component mechanical mixture.Because these two kinds of components contact defective tightness, make that the synergy between component is relatively poor in the catalyst, thereby catalyst performance is lower.The method for preparing catalyst of using in the Chinese patent 1153080 is a precipitation of joint sedimentation, because contacting of synthetic component and dehydration component is comparatively tight, so activity of such catalysts increases to some extent.But, using Na owing in the catalyst preparation process, the rate of addition of temperature, Acidity of Aikalinity and solution is all had strict demand
2CO
3The Na that introduces when doing precipitating reagent
+Ion will influence activity of such catalysts, need fully washing, therefore, the preparation process complexity, preparation repeatability is relatively poor relatively.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing catalyst of directed preparing dimethyl ether by synthetic gas, this method is simple, and repeatability is reliable, and prepared catalyst has a higher activity for dimethyl ether is synthetic.
The present invention realizes that the technical scheme of above-mentioned purpose is:
Employing contains Cu, Zn and Al or Cu, Zn and Zr or Cu, Zn, the nitrate of Al and Zr is as the raw material of Preparation of Catalyst, the atomic ratio of each component is Cu/Zn/ (Al+Zr)=1/0.4-0.7/0.03-0.3, and dehydration component is a solid acid, and synthetic component and dehydration component ratio are 1: 1-5: 1 (weight ratio).
Concrete steps of the present invention are:
(1) earlier with commerce solid acid such as HZSM-5, USY, Al
2O
3Be crushed to below 200 orders, 500 ℃ of roastings 2 hours are standby.
(2) take by weighing a certain amount of copper nitrate, zinc nitrate, aluminum nitrate or/and the zirconium nitrate sample is dissolved in the absolute ethyl alcohol; Take by weighing a certain amount of oxalic acid again, be dissolved in the absolute ethyl alcohol.Under intensively stirred effect, the ethanolic solution that will contain oxalic acid is added to rapidly and contains Cu, Zn, Al or/and in the ethanolic solution of Zr ion, form colloidal solution.Colloidal solution was placed 1 hour under the effect of gentle agitation, added the solid acid sample of the following particle of 200 orders again, continued to stir and placed 1 hour.
(3) taking precipitate air dry or in baking oven, dry, roasting in muffle furnace again, sintering temperature is 300-400 ℃, roasting time is 3-5 hour, promptly makes dimethyl ether synthetic catalyst.
Catalyst of the present invention is used for the reaction of direct synthesis of dimethyl ether from synthesis gas, H in the synthesis gas
2The volume ratio of/CO is 1-6, can contain a certain amount of N in the synthesis gas
2, CH
4And CO
2, reaction pressure is 3.0-8.0Mpa, reaction temperature is 200-350 ℃.
The advantage of catalyst of the present invention is that catalyst grain size is little, and the specific surface height contacts tight between each component thereby synergy is strong, makes catalyst have higher activity.
The specific embodiment
The present invention will be further described below by embodiment.
Embodiment 1
Earlier the HZSM-5 with commerce usefulness is crushed to below 200 orders, and 500 ℃ of roastings 2 hours are stand-by.Take by weighing 7.25 gram Cu (NO
3)
2.3H
2O, 4.46 gram Zn (NO
3)
2.6H
2O and 1.29 gram Zr (NO
3)
4.5H
2O is dissolved in the 150ml absolute ethyl alcohol; Take by weighing the oxalic acid of 12.1 grams again, be dissolved in the 100ml absolute ethyl alcohol.Under the strong agitation effect, the ethanolic solution that will contain oxalic acid joins rapidly in the ethanolic solution that contains Cu, Zn and Zr ion, has formed colloidal solution at once.Colloidal solution was placed 1 hour under the effect of gentle agitation, added 3.4 grams again through the HZSM-5 of calcination process molecular sieve, continued to stir and placed 1 hour.After the sediment centrifugation, in baking oven in 110 ℃ of oven dry, roasting in muffle furnace again, sintering temperature are 360 ℃, and roasting time is 4 hours, obtain the dimethyl ether synthetic catalyst powder, behind the 20Mpa lower sheeting, 20-40 purpose beaded catalyst is got in fragmentation again, and wherein copper/zinc/zirconium mol ratio is 10: 5: 1, the weight ratio of oxide and molecular sieve is 1: 1, and the activity of such catalysts evaluation result sees Table 1.
Embodiment 2: method, step and condition have just added 0.5625 gram Al with embodiment 1 in the ethanolic solution of copper, zinc and zirconium
2(NO
3)
3.9H
2O, and replace the HZSM-5 molecular sieve with the USY zeolite, prepared colloid be with absolute ethanol washing 2 times, 90 ℃ of oven dry, and 400 ℃ of roasts are ruined hour.The mol ratio of copper/zinc in the gained catalyst/zirconium/aluminium is 10: 5: 1: 0.5, and the weight ratio of oxide and molecular sieve is 1: 1, the catalyst activity evaluation result sees Table 2.
Embodiment 3: method, step and condition just restrain Al with 1.13 with embodiment 1 in embodiment 2
2(NO
3)
3.9H
2O has replaced 1.29 gram Zr (NO
3)
4.5H
2O, and with the HZSM-5 of the 1.7g among the 3.4g Al with 1.7g
2O
3Replace.The mol ratio of copper/zinc in the gained catalyst/aluminium is 10: 5: 1, oxide and (HZSM-5+Al
2O
3) weight ratio be 1: 1, the activity of such catalysts evaluation result sees Table 3.
Embodiment 4: with embodiment 1, wherein copper/zinc/zirconium mol ratio is 10: 5: 1, and prepared colloid is with 2 oven dry of absolute ether washing, air dry, 300 ℃ of roasts hour.The weight ratio of oxide and molecular sieve becomes 3: 1, and the activity of such catalysts evaluation result sees Table 4.
Comparative example 1: with industrial Denmark Topsoe methanol synthesis catalyst and HZSM-5 ratio mechanical mixture, grind with 1: 1, compression molding, the activity of such catalysts evaluation result sees Table 5.
The catalyst activity evaluation method:
In continuous fixed bed reactor, pack into 1 the gram catalyst, with containing 5%H
2Ar-H
2Gaseous mixture reduces by certain procedure under normal pressure, is raised to 220 ℃ with the speed of 1 ℃/min by room temperature, and constant temperature is 4 hours under 220 ℃ of conditions.Logical then synthesis gas reacts.Unstripped gas consists of H
2/ CO=2: 1 o'clock, the reaction pressure of employing was 3.0Mpa, and air speed is 1500h
-1
Unstripped gas used in embodiment 4 consists of: 0.95%CH
4, 7.55%CO
2, 19.0%CO, 37.5%H
2And 35.0%N
2, the reaction pressure of employing is 5.0Mpa, temperature is 230 ℃.
The reaction result temperature CO selective d ME of table 1 embodiment 1 catalyst (℃) conversion ratio (%) yield
(％) CH
3OH DME C
2 CO
2 (％)210 61.1 2.63 78.2 0.17 19.0 47.8234 88.4 1.83 75.6 0.17 22.4 66.8243 92.3 1.72 75.3 0.28 22.7 69.5251 92.8 2.08 76.9 0.42 20.6 71.4262 90.7 1.97 74.9 0.73 22.4 67.9270 88.3 2.39 74.2 1.51 21.9 65.5
The reaction result of table 2 embodiment 2 catalyst
Selectivity temperature CO transforms DME and receives
(%) (℃) rate (%) rate (%)
CH
3OH DME C
2 CO
2224 65.5 1.74 78.8 0.26 19.2 51.6240 89.9 1.80 70.5 0.20 27.5 63.4250 90.1 1.58 70.6 0.32 27.5 63.6260 87.7 1.80 69.4 0.60 28.2 60.9270 84.1 1.55 68.0 1.15 29.3 57.2
The reaction result temperature CO of table 3 embodiment 3 catalyst transform selective d ME receive (℃) (%) rate (%) of rate (%)
CH
3OH DME C
2 CO
2232 76.5 1.17 71.4 0.23 27.2 54.6242 88.1 1.18 69.7 0.32 28.8 61.4251 88.3 1.54 68.8 0.46 29.2 60.8260 87.4 1.36 69.4 0.84 28.4 60.7270 83.8 1.47 67.0 1.43 30.1 56.1
The reaction result air speed CO of table 4 embodiment 4 catalyst transforms selective d ME and receives (%) rate (%) of (h-1) rate (%)
CH
3OH DME C
2 CO
21000 92.1 0.54 77.6 0.06 21.8 71.51500 91.9 0.44 77.3 0.06 22.2 71.02000 91.3 0.56 76.9 0.04 22.5 70.22500 87.2 0.55 77.3 0.05 22.1 67.43000 80.1 0.56 75.2 0.04 24.2 60.2
The reaction result of table 5 comparative example 1 catalyst
Selectivity temperature CO transforms DME and receives
(%) (℃) rate (%) rate (%)
CH
3OH DME C
2 CO
2210 43.3 0 71.7 0.10 28.2 31.0220 64.5 0.49 70.6 0.21 28.7 45.5230 80.5 0.96 69.9 0.24 28.9 56.3240 86.1 0.80 70.0 0.30 28.9 60.3250 88.4 0.96 69.4 0.54 29.1 61.3260 87.6 0.94 67.3 0.96 30.8 59.0270 85.1 1.64 65.2 1.66 31.5 55.5
Claims (8)
1, a kind of method for preparing catalyst of directed preparing dimethyl ether by synthetic gas, it is characterized in that, to contain Cu, Zn and other components comprise Al, one or both nitrate and oxalic acid among the Zr are dissolved in absolute ethyl alcohol respectively, after above-mentioned two kinds of solution mix, add fine grain solid acid, fully mix back elimination solution, the colloid dry roasting is decomposed.
2, the method for preparing catalyst of directed preparing dimethyl ether by synthetic gas as claimed in claim 1 is characterized in that, other component=1/0.4-0.7/0.03-0.3 of described Cu/Zn/ (mol ratio).
3, the method for preparing catalyst of directed preparing dimethyl ether by synthetic gas as claimed in claim 1 is characterized in that, described solid acid is a kind of or its mixture in HZSM-5 molecular sieve, overstable gamma zeolite, the acidic alumina.
4, the method for preparing catalyst of directed preparing dimethyl ether by synthetic gas as claimed in claim 1 is characterized in that, the granularity of described solid acid is less than 200 orders.
5, the method for preparing catalyst of directed preparing dimethyl ether by synthetic gas as claimed in claim 1 is characterized in that, wherein synthetic component and solid acid ratio are 1: 1-5: 1 (weight ratio).
6, the method for preparing catalyst of directed preparing dimethyl ether by synthetic gas as claimed in claim 1 is characterized in that, colloid is air dry or in oven for drying.
7, the method for preparing catalyst of directed preparing dimethyl ether by synthetic gas as claimed in claim 1 is characterized in that, washs with absolute ethyl alcohol or ether before the colloid oven dry.
8, the method for preparing catalyst of directed preparing dimethyl ether by synthetic gas as claimed in claim 1 is characterized in that, the roasting decomposition temperature is 300 ℃-400 ℃, time 3-5 hour.
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|---|---|---|---|
| CN 01136842 CN1131108C (en) | 2001-10-26 | 2001-10-26 | Preparation method of catalyst for directed preparing dimethyl ether by synthetic gas |
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|---|---|---|---|
| CN 01136842 CN1131108C (en) | 2001-10-26 | 2001-10-26 | Preparation method of catalyst for directed preparing dimethyl ether by synthetic gas |
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| CN1413767A true CN1413767A (en) | 2003-04-30 |
| CN1131108C CN1131108C (en) | 2003-12-17 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100352547C (en) * | 2005-06-22 | 2007-12-05 | 中国石油化工股份有限公司 | Catalyst for direct preparation of dimethyl ether from synthesis gas |
| 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 |
| CN103725331A (en) * | 2013-12-13 | 2014-04-16 | 济南开发区星火科学技术研究院 | Method for producing ether gasoline |
| CN104801337A (en) * | 2015-03-19 | 2015-07-29 | 沈阳化工大学 | Ethanol catalyst prepared from synthesis gas and dimethyl ether with one-step method as well as preparation method of ethanol catalyst |
| CN105170179A (en) * | 2015-09-15 | 2015-12-23 | 沈阳化工大学 | Method for preparing dimethyl ether mesoporous catalyst by hydrogenating carbon dioxide |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100556538C (en) | 2006-12-14 | 2009-11-04 | 太原理工大学 | A kind of slurried catalyst and preparation method thereof |
-
2001
- 2001-10-26 CN CN 01136842 patent/CN1131108C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100352547C (en) * | 2005-06-22 | 2007-12-05 | 中国石油化工股份有限公司 | Catalyst for direct preparation of dimethyl ether from synthesis gas |
| 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 |
| CN103725331A (en) * | 2013-12-13 | 2014-04-16 | 济南开发区星火科学技术研究院 | Method for producing ether gasoline |
| CN104801337A (en) * | 2015-03-19 | 2015-07-29 | 沈阳化工大学 | Ethanol catalyst prepared from synthesis gas and dimethyl ether with one-step method as well as preparation method of ethanol catalyst |
| CN105170179A (en) * | 2015-09-15 | 2015-12-23 | 沈阳化工大学 | Method for preparing dimethyl ether mesoporous catalyst by hydrogenating carbon dioxide |
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| Publication number | Publication date |
|---|---|
| CN1131108C (en) | 2003-12-17 |
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Granted publication date: 20031217 Termination date: 20091126 |