CN103483118A - Liquefied petroleum gas preparation method - Google Patents
Liquefied petroleum gas preparation method Download PDFInfo
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- CN103483118A CN103483118A CN201210197581.3A CN201210197581A CN103483118A CN 103483118 A CN103483118 A CN 103483118A CN 201210197581 A CN201210197581 A CN 201210197581A CN 103483118 A CN103483118 A CN 103483118A
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Abstract
The invention relates to a methanol-to-liquefied petroleum gas method, and concretely relates to a liquefied petroleum gas preparation method. Main components of liquefied petroleum gas comprise propane and butane, so the liquefied petroleum gas is an environmentally-friendly liquid fuel. In the invention, an inert or non-inert gas is used as a carrying gas, molecular sieve or metal modified molecular sieve is used as a catalyst, the carrying gas carries methanol steam to a reactor, and the liquefied petroleum gas can be obtained under the action of the catalyst in a high selectivity (>60%) and a high yield mode. The method has the advantages of less required apparatus investment and low synthesis cost, so the method has a very good application prospect.
Description
Technical field
The present invention relates to a kind of preparation method of liquefied petroleum gas (LPG).Specifically take molecular sieve or metal-modified molecular sieve is catalyzer, and the methanol/dimethyl ether of take directly prepares liquefied petroleum gas (LPG) as raw material.
Technical background
Liquefied petroleum gas (LPG) (LPG) main component is propane and butane, be gaseous state under normal temperature and pressure, press a little or lower the temperature to be converted into liquid state, it is not only a kind of environmentally friendly clean fuel, or important industrial chemicals, the rate of rise of its demand is far above oil.But LPG is mainly derived from and take alkane as main associated gas and the by product in the petroleum refining process at present, and its output can not meet the growing market requirement, in the urgent need to developing new explained hereafter LPG.
The methanol/dimethyl ether synthesis technique is quite ripe, and raw material sources are abundant, can be by coal, Sweet natural gas and biomass by synthetic gas (CO+H
2) directly synthesize and obtain.Directly prepare liquefied petroleum gas (LPG) by methanol/dimethyl ether, for this novel process, suitable catalyzer is key point.Methanol/dimethyl ether can dehydration be converted into hydro carbons under the effect of acid site.According to different process, the course of industrialization of now having realized can be divided into MTO, MTP and MTG.The MTO process is to take SAPO-34 as catalyzer, and principal product is ethene and propylene.The MTP process is to take ZSM-5 as catalyzer, and principal product is propylene.The MTG process is to take ZSM-5 as catalyzer, and principal product is gasoline.Yet, relatively less about the report of methanol/dimethyl ether LPG process processed.The research group of Japan Kitakyushu municipal university has investigated take methyl alcohol and prepares the process of liquefied petroleum gas (LPG), C as raw material
3and C
4the selectivity of component in hydro carbons be about 50% (Fuel Processing Technology, 2004,85,1151 ~ 1164) only.In addition, this group has also investigated dme on the beta-molecular sieve and has prepared the process (Catalysis Letter, 2008,120,95 ~ 99) of liquefied petroleum gas (LPG), and has applied for Patents (CN101511477A).
Now, industrially can if can develop the technique of methanol/dimethyl ether production liquefied petroleum gas (LPG), must provide clean liquid fuel for us by coal, Sweet natural gas, biomass through a large amount of methanol/dme of synthetic gas, thereby reduce the dependence to petroleum resources.
Summary of the invention
Technical problem to be solved by this invention is to propane in the standby liquefied petroleum gas (LPG) of Methanol in previous literature and the butane selectivity is low, yield is low problem, and a kind of method of the new standby liquefied petroleum gas (LPG) of Methanol is provided.The method is during for the standby liquefied petroleum solid/liquid/gas reactions of Methanol, has propane and the butane selectivity is high, yield is high characteristics.
For solving the problems of the technologies described above, the present invention adopts following technical scheme: the method for a kind of methanol conversion liquefied petroleum gas (LPG) processed, take methyl alcohol as raw material, inertia or non-rare gas element are carrier gas, 250 ~ 500 ℃ of temperature of reaction, under reaction pressure 0.1 ~ 5.0MPa, methyl alcohol transforms and generates liquefied petroleum gas (LPG) by beds.
The present invention uses molecular sieve in catalyzer to comprise MCM-22 and Y molecular sieve.Modified molecular screen metal used comprises Pd, Pt, Ru, Rh, Cu.
The process that metal of the present invention supports on molecular sieve comprises following two kinds of methods:
A. will be containing the aqueous solution and Y molecular sieve ion-exchange in the water-bath situation of described metal component, suction filtration, drying, 500 ~ 800 ℃ of roastings, obtain target product;
Or B. will be containing the aqueous solution and the Y molecular sieve incipient impregnation of described metal component, drying, 500 ~ 800 ℃ of roastings, obtain target product;
Target product can be applied after by hydrogen reducing, 30 ~ 250 ℃ of hydrogen atmosphere reductase 12s, 2-5 hour;
In molecular sieve modified method of the present invention, drying temperature is 100 ~ 120 ℃, and be 5 ~ 12 hours time of drying; Maturing temperature is 500 ~ 800 ℃, preferably 500 ~ 600 ℃; Roasting time at least 2 hours, take 4-6 hour as good; Temperature rise rate is at least 0.5 ℃/min, take 3-5 ℃/min as good.In methanol/dimethyl ether conversion of the present invention liquefied petroleum gas (LPG) process processed, temperature of reaction is 250 ~ 500 ℃, and better temperature of reaction is 280 ~ 450 ℃, reaction pressure 0.1 ~ 3.0MPa.
The MCM-22 that the present invention adopts and Y molecular sieve and metal-modified after MCM-22 and Y molecular sieve as catalyzer, its catalytic performance has had obvious improvement than bibliographical information catalyzer.Y molecular sieve is as catalyzer, and methyl alcohol is that feed stock conversion can reach 100%, and the yield of liquefied petroleum gas (LPG) can reach more than 80%, has obtained technique effect preferably.
Embodiment
Liquefied petroleum gas (LPG) main component prepared by the present invention is propane and butane, is a kind of environmentally friendly liquid fuel.It is carrier gas that inertia or non-rare gas element are take in the present invention, molecular sieve or metal-modified molecular sieve are catalyzer, by carrier gas, methanol steam is brought in reactor, under the effect of catalyzer, product can obtain higher liquefied petroleum gas (LPG) selectivity (> 60%) and yield.The method required equipment less investment, synthetic with low cost, thereby good application prospect is arranged.
The technology of the present invention details is by following embodiment detailed description in addition.It should be noted that lifted embodiment, its effect just further illustrates technical characterictic of the present invention, rather than limits the present invention.
Embodiment 1
By specific surface area, be 445m
2/ g (BET), the H type Y molecular sieve fine powder that bulk density is 0.54g/ml is placed in air, and under 150 ℃, drying is 2 hours, makes subsequently 20 ~ 40 order particles, for methanol dewatered liquefied petroleum solid/liquid/gas reactions.
The Y molecular sieve amount of fill is 0.5g, and temperature of reaction is 400 ℃, and reaction pressure is 1.5MPa, H
2flow is 25ml/min, and methanol feeding is 0.007ml/min.Adopt gas chromatographic detection, the results are shown in Table 1.The methyl alcohol fully dehydrating is converted into hydro carbons, only contains a small amount of hydrocarbon in product, and the selectivity of LPG in hydro carbons can reach more than 80%.
Table 1 methanol conversion liquefied petroleum gas (LPG) processed
Annotate: contain a small amount of carbon monoxide or carbonic acid gas in product.
Embodiment 2
Take the Y molecular sieve carrier of processing in 10g embodiment 1 and be scattered in the 190ml aqueous solution, 60 ℃ of heating in water bath, magnetic agitation speed 1000r/min.Measure 2.5ml PdCl
2solution (0.020gPd/ml) is diluted to 10ml, in 5min, 10ml solution is slowly splashed in the aqueous solution that has disperseed carrier, ion-exchange 8 hours, washing suction filtration to washings electricity is led below 50 μ s/cm, 120 ℃ of dryings 12 hours, in 540 ℃ of air, roasting is 4 hours, hydrogen atmosphere reductase 12 50 ℃, 2 hours, make subsequently 20 ~ 40 order particles, for methanol dewatered liquefied petroleum solid/liquid/gas reactions.
The catalyst filling amount is 0.5g, and temperature of reaction is 400 ℃, and reaction pressure is 1.5MPa, N
2flow is 25ml/min, and methanol feeding is 0.007ml/min.The results are shown in Table 2.
Table 2 methanol conversion liquefied petroleum gas (LPG) processed
Embodiment 3
Take the Y molecular sieve carrier of processing in 10g embodiment 1 and be scattered in the 190ml aqueous solution, 60 ℃ of heating in water bath, magnetic agitation speed 1000r/min.Measure 10ml PdCl
2solution (0.020gPd/ml), in 5min, 10ml solution is slowly splashed in the aqueous solution that has disperseed carrier, ion-exchange 8 hours, washing suction filtration to washings electricity is led below 50 μ s/cm, 120 ℃ of dryings 12 hours, in 540 ℃ of air, roasting is 4 hours, hydrogen atmosphere reductase 12 40 ℃, 5 hours, make subsequently 20 ~ 40 order particles, for methanol dewatered liquefied petroleum solid/liquid/gas reactions.
The catalyst filling amount is 0.4g, and temperature of reaction is 400 ℃, and reaction pressure is 1.0MPa, H
2flow is 80ml/min, and methanol feeding is 0.058ml/min.The results are shown in Table 3.Compare with embodiment 1, in embodiment 2 and embodiment 3, on Y molecular sieve, introduced metal Pd.Methyl alcohol still can all transform, and in product, the proportion of hydrocarbon significantly increases, and the selectivity of LPG decreases, but catalyst stability obviously improves.
Table 3 methanol conversion liquefied petroleum gas (LPG) processed
Embodiment 4
The H type MCM-22 molecular sieve fine powder that is 0.2g/ml by bulk density is placed in air, and under 150 ℃, drying is 2 hours.Take the MCM-22 molecular sieve carrier that 10g processed and be scattered in the 190ml aqueous solution, 60 ℃ of heating in water bath, magnetic agitation speed 1000r/min.Measure 2.5ml PdCl
2solution (0.020g Pd/ml), in 5min, 10ml solution is slowly splashed in the aqueous solution that has disperseed carrier, ion-exchange 8 hours, washing suction filtration to washings electricity is led below 50 μ s/cm, 120 ℃ of dryings 12 hours, in 540 ℃ of air, roasting is 4 hours, hydrogen atmosphere reductase 12 50 ℃, 3 hours, make subsequently 20 ~ 40 order particles, for methanol dewatered liquefied petroleum solid/liquid/gas reactions.
The catalyst filling amount is 0.4g, and temperature of reaction is 325 ~ 400 ℃, and reaction pressure is 1.0MPa, H
2flow is 80ml/min, and methanol feeding is 0.058ml/min.The results are shown in Table 4.The MCM-22 of load P d is upper, and during low temperature, in hydro carbons, primary product is methane.After temperature reaches 400 ℃, in hydro carbons, LPG becomes principal product.And along with temperature raises, in product, hydrocarbon selective is increasing, and the dme selectivity is reducing.
Table 4 methanol conversion liquefied petroleum gas (LPG) processed
Embodiment 5
The catalyzer of preparation in embodiment 2 is used for to methanol dewatered liquefied petroleum solid/liquid/gas reactions.
The catalyst filling amount is 0.5g, and temperature of reaction is 325 ℃, and reaction pressure is 1.0MPa, and carrier gas consists of CO:CO
2: HCs:DME:H
2: N
2=30.9:0.8:0.6:0.2:61.9:5.6, methanol feeding is 0.003ml/min.The results are shown in Table 5.The multi-component gas mixture of take is introduced reactor as carrier gas by methyl alcohol, and the selectivity of LPG is still higher.Now, due to multi-component, coexist, the selectivity of hydrocarbon decreases.
Table 5 methanol conversion liquefied petroleum gas (LPG) processed
Embodiment 6
The catalyzer of preparation in embodiment 2 is used for to dme Dehydration liquefied petroleum solid/liquid/gas reactions.
The catalyst filling amount is 0.5g, and reaction pressure is 1.5MPa, and raw material consists of DME:H
2: Ar=2:5:18, feed gas flow rates is 20ml/min.The results are shown in Table 6.
Table 6 dimethyl ether conversion liquefied petroleum gas (LPG) processed
* in the reaction, a small amount of dimethyl ether conversion is carbon monoxide or carbonic acid gas
Comparative Examples:
Reported in document Fuel Processing Technology 85 (2004) 1151-1164 and take the method that methyl alcohol is raw material production LPG, in the method under minute-pressure, temperature of reaction be 603K to 673K, the methanol liquid air speed is 10-20h
-1, take H2 and N2 as carrier gas, catalyzer is selected respectively SAPO-34, ZSM-5, USY, SAPO-5, five kinds of molecular sieves of Beta, and evaluation result is as following table.
In this piece of document, also reported in addition, by methyl alcohol through low-carbon alkene again to the production method of low-carbon alkanes, what in this method, adopt is ZSM-5 and Pt-C catalyzer, two kinds of catalyzer can be divided into two sections fillings filling that also can mix.Experimental result is as following table.
Results?of?hydrocarbon?synthesis?from?methanol?on?various?zeolite?catalysts
a
aMethanol/H
2/N
2?mole?ratio-1∶1∶1，LHSV-20h
-1，and?all?the?reaction?data?given?in?this?table?and?Tables3?and?4?and?Figs.1?4?are?chosen?at?the?point?of?3-h?time?on-stream.
Results?for?hydrogenation?of?whole?hydrocarbons?synthesized?from?methanol
a
aMethanol/H
2/N
2?mole?ratio-1∶1∶1，the?LHSV(based?on?methanol)is?10h
-1?relative?to?the?mixed?hed?and?the?two-segment?bed?with?the?same?volume?of?ZSM-5?and?Pt/C?catalysts.
Claims (6)
1. a method for preparing liquefied petroleum gas (LPG), it is characterized in that: take methyl alcohol as raw material, inertia or non-rare gas element are carrier gas, 250 ~ 500 ℃ of temperature of reaction, under reaction pressure 0.1 ~ 5.0MPa, methyl alcohol transforms and generates liquefied petroleum gas (LPG) by beds;
Catalyzer is molecular sieve or metal modified molecular screen, and molecular sieve can be Y or MCM-22.
2. method according to claim 1, it is characterized in that: material benzenemethanol can be used as the mixture replacing of dme or methyl alcohol and dme.
3. method according to claim 1, is characterized in that: the hydro carbons that carrier gas is nitrogen, argon gas, helium, hydrogen, carbonic acid gas, C1-6 and one or two or more kinds in CO.
4. method according to claim 1, it is characterized in that: metal-modified molecular sieve metal used comprises one or two or more kinds in Pd, Pt, Ru, Rh, Cu, and in metal-modified molecular sieve, the ratio of metal active constituent and molecular sieve is 0.01 ~ 5wt%.
5. catalyzer according to claim 4, is characterized in that metal-modified molecular sieve metal used is one or two or more kinds in Pd, Cu.
6. according to the described catalyzer of claim 4 or 5, it is characterized in that: in metal-modified molecular sieve, metal component supports on molecular sieve by pickling process or ion exchange method.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104529727A (en) * | 2014-12-03 | 2015-04-22 | 中国石油大学(北京) | Process for co-producing low-carbon mixed aldehyde in methanol-to-olefin process |
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|---|---|---|---|---|
| CN1733871A (en) * | 2004-08-10 | 2006-02-15 | 日本气体合成株式会社 | Liquefied petroleum gas production catalyst and process for producing liquefied petroleum gas using this catalyst |
| JP2006052304A (en) * | 2004-08-11 | 2006-02-23 | Nippon Gas Gosei Kk | Method for producing liquefied petroleum gas |
| CN101511477A (en) * | 2006-07-31 | 2009-08-19 | 日本煤气合成株式会社 | Catalyst for liquefied petroleum gas production and method for producing liquefied petroleum gas using the catalyst |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1733871A (en) * | 2004-08-10 | 2006-02-15 | 日本气体合成株式会社 | Liquefied petroleum gas production catalyst and process for producing liquefied petroleum gas using this catalyst |
| JP2006052304A (en) * | 2004-08-11 | 2006-02-23 | Nippon Gas Gosei Kk | Method for producing liquefied petroleum gas |
| CN101511477A (en) * | 2006-07-31 | 2009-08-19 | 日本煤气合成株式会社 | Catalyst for liquefied petroleum gas production and method for producing liquefied petroleum gas using the catalyst |
Non-Patent Citations (3)
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|---|
| W. ZHU ET AL.: "Selective Transformation of Dimethyl Ether into Small Molecular Hydrocarbons", 《CATAL LETT》 * |
| YINGJIE JIN ET AL: "Synthesis of liquefied petroleum gas via methanol/dimethyl ether from natural gas", 《FUEL PROCESSING TECHNOLOGY》 * |
| 马现刚 等: "合成气制液化石油气复合催化剂的性能", 《催化学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104529727A (en) * | 2014-12-03 | 2015-04-22 | 中国石油大学(北京) | Process for co-producing low-carbon mixed aldehyde in methanol-to-olefin process |
| CN104529727B (en) * | 2014-12-03 | 2016-10-12 | 中国石油大学(北京) | A kind of technique of methanol-to-olefins coproduction low-carbon (LC) mixed aldehyde |
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Application publication date: 20140101 |