CN103508828A - Method used for preparing ethane and propane from synthetic gas - Google Patents
Method used for preparing ethane and propane from synthetic gas Download PDFInfo
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Abstract
本发明涉及一种合成气制乙烷和丙烷的方法，在温度260-450°C、空速500-5000h-1、压力1.0-5.0MPa、H2/CO摩尔比为0.5-5.0的反应条件下，将合成气通过一种多功能复合催化剂转化为乙烷和丙烷。该方法可在高CO转化率下，高选择性生产乙烷和丙烷。所说的复合催化剂指CO加氢催化剂与金属改性的分子筛中的一种或两种以上混合。本发明技术开发了一条从煤炭和天然气制取乙烷和丙烷的新途径。The invention relates to a method for producing ethane and propane from syngas, under the reaction conditions of temperature 260-450°C, space velocity 500-5000h -1 , pressure 1.0-5.0MPa, H 2 /CO molar ratio 0.5-5.0 Syngas is converted to ethane and propane through a multifunctional composite catalyst. The process can produce ethane and propane with high selectivity at high CO conversion. The composite catalyst refers to the mixture of CO hydrogenation catalyst and metal-modified molecular sieve. The technology of the invention develops a new way to produce ethane and propane from coal and natural gas.
Description
Technical field
The present invention relates to synthetic gas and prepare the method for low-carbon alkanes, specifically by the method for synthesis gas through methanol/dme one-step synthesis ethane and propane.
Background technology
Ethene in low-carbon alkene, propylene, as the starting material of synthetic detergent, plastics, fiber and all kinds of chemical materialss, play a part very important in modern petrochemical industry.Along with market is to the rapid growth of ethene, propylene demand and cheapness, the minimizing day by day of easily adopting petroleum resources, the raw material sources of producing alkene, all in active development low-carbon alkene production new technology, are expanded in countries in the world.Ethene and propylene are mainly derived from the cracking of petroleum naphtha, solar oil at present, the shortcoming of this route is too to rely on oil, simultaneously expense of raw materials accounts for 70%～75% of ethene, production of propylene cost, and ethene, propylene cost directly affect the cost of its derived product.Therefore how Optimization of Ethylene, propylene feedstocks, reduce ethene, production of propylene cost just becomes a very important techno-economic question.Along with the worsening shortages of petroleum resources, from ethane and the propane of Sweet natural gas and coal resources, the potential cheap raw material of preparing ethylene and propylene will be become.
On the other hand, 21 century petrochemical materials may to turn to more cheap Sweet natural gas class alkane be main, thereby raw material route will be one of emphasis of new millennium petrochemical technology research and development by alkene to the transfer of alkane.For utilizing natural gas source from far-off regions, by cracking or dehydrogenation, do not produce alkene and make the technique of alkane activation direct production chemical intermediate just at Speeding up development.More promising alkane activating technology has at present: ethane preparing chloroethylene (VCM) technique, ethane acetic acid technique processed, propane acrylonitrile production technique, propane vinylformic acid technique processed etc.
Now, the minimizing day by day of petroleum resources, produces hydro carbons by coal or natural gas via synthetic gas, is the study hotspot of current academia.Bibliographical information is more be by synthetic gas through Fischer-Tropsch route synthin, the method products obtained therefrom be take heavy hydrocarbon as main, C
2/ C
3component is less.Up to the present, by synthetic gas highly selective, produce lower carbon number hydrocarbons (C
2/ C
3) relatively less.CN102219628 discloses a kind of method of synthesis of gas produced low-carbon hydrocarbon, and the method adopts Th/SiO
2for catalyzer, can realize one-step method from syngas and generate low-carbon alkanes and low-carbon alkene.In product, ethane, ethene, propane and propylene overall selectivity in hydro carbons can reach 48.6%, and the selectivity of methane is only 4.5% (to be converted into CO up to the transformation efficiency of 32.3%, CO
2part is deducted).
At present mostly ethane and propane are to separate from Sweet natural gas or refinery's byproduct, can not meet the growing market requirement.Therefore the technique of finding a kind of high conversion, highly selective is produced low-carbon alkanes, has become current ethane and propane and has been widely used in problem in the urgent need to address in ethene processed, production of propylene.
Summary of the invention
Technical problem to be solved by this invention be to ethane and propane yields poorly and previous literature in synthetic gas ethane processed and propane selectivity is low, methane selectively is high problem, the method for a kind of new synthetic gas ethane processed and propane is provided.The method is during for the synthesis of the reaction of gas ethane processed and propane, has that CO transformation efficiency is high, ethane and propane content is high, methane content is a low feature in hydro carbons.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A method for synthetic gas ethane processed and propane, synthetic gas is transformed and is generated ethane and propane by a kind of multi-functional composite catalyst one step; Said composite catalyst refer to by CO hydrogenation catalyst as catalyzer the first component, with metal-modified molecular sieve one or two or more kinds as second component, mix; The first component and second component mass ratio are 10:1～1:10, are preferably 5:1～1:5, more elect 3:1～1:3 as.
Temperature of reaction is that 260-450 ° of C, volume space velocity are 500-5000h
-1, reaction pressure is H in 1.0-5.0M Pa, synthetic gas
2/ CO mol ratio is 0.5-5.0.
Temperature of reaction is that 300-400 ° of C, volume space velocity are 500-1500h
-1, reaction pressure is H in 1.5-3.0MPa, synthetic gas
2/ CO mol ratio is 1.0-4.0.
CO hydrogenation catalyst is CuO/ZnO/Al
2o
3, Cu/ZrO
2, ZnO/Cr
2o
3, Pd/ZnO/Cr
2o
3, Pd/CeO
2in one or two or more kinds.
Modified molecular screen metal used comprises one or more in Pd, Pt, Ru, Rh, Cu, Fe, Co, Mn; Molecular sieve used is SAPO-n class, ZSM-5 type;
When metal is Pd, Pt, Ru, Rh, its ratio in modified molecular screen is 0.01～5wt%;
When metal is Cu, Fe, Co, Mn, its ratio in modified molecular screen is 2～20wt%.
Modified molecular screen metal used is Pd or Cu, and molecular sieve used is SAPO-34, SAPO-18 and ZSM-5.
When molecular sieve modified, metal component supports on molecular sieve by pickling process or ion exchange method.
The first component is CuO/ZnO/Al
2o
3, Cu:Zn mol ratio is 1:3～3:1, is preferably 1:2～3:1, Al:(Cu+Zn) and mol ratio is 0.01～0.1;
The first component is ZnO/Cr
2o
3or Pd/ZnO/Cr
2o
3, Cr:Zn mol ratio is 1:10～1:1;
The first component is Cu/ZrO
2, the mass percent of Cu is 10-70%.
Synthetic gas comprises H
2volumetric concentration 5-83%, H
2/ CO mol ratio is 0.5-5.0, and not containing or contain surplus is N
2, CO
2, one or two or more kinds in methane, rare gas element, water vapor etc.
A method for synthetic gas ethane processed and propane, take synthetic gas as raw material, at temperature 260-450 ° C, air speed 500-5000h
-1, pressure 1.0-5.0MPa, H
2/ CO mol ratio is under the reaction conditions of 0.5-5.0, and raw material is transformed and generated ethane and propane by a kind of multi-functional composite catalyst bed.
Said composite catalyst is to be mixed by CO hydrogenation catalyst and metal-modified molecular sieve.
Concrete synthetic gas ethane processed and the propane method of the present invention comprises the following steps:
(1) the preparation of catalyzer
The preparation of a.CO hydrogenation catalyst
Adopting commercially available Cu system and Cr is that methyl alcohol synthesizes or water-gas shift catalyzer, as Cu/ZnO/Al
2o
3, Cu/ZrO
2, ZnO/Cr
2o
3, Pd/ZnO/Cr
2o
3, Pd/CeO
2or any modified catalyst wherein.
B. the preparation of modified molecular screen
1. adopt ion exchange method by metal load to molecular sieve.The solution that contains a certain amount of metal component is mixed with molecular sieve, in the water-bath of 30-80 ° of C, carry out ion-exchange, ion-exchange 6-10h, suction filtration, washing, oven dry, 400-800 ° of C roasting 4-6h, obtains metal modified molecular screen.
2. adopt pickling process by metal load to molecular sieve.By the solution that contains a certain amount of metal component and molecular sieve incipient impregnation, dry, 400-800 ° of C roasting 4-6h, obtains metal modified molecular screen.
C. composite catalyst preparation
Adopt in two ways CO hydrogenation catalyst and modified molecular screen are mixed and made into multi-functional composite catalyst.
Particle mixes: by CO hydrogenation catalyst and modified molecular screen difference compressing tablet, be broken into 20-40 order, with certain mass, than particle, mix.
Powder mixes: by the powder of two or more modified molecular screen with certain mass than mixing, grinding, compressing tablet, be broken into after 20-40 order, then carry out particle mixing with CO hydrogenation catalyst.
(2) catalyst performance evaluation
While preparing ethane and propane by synthetic gas, made composite catalyst is loaded in fixed-bed reactor, after catalyst loading, at H
2230～300 ° of C reductase 12-5h under atmosphere, H
2flow 10-30ml/min.After reduction finishes, be adjusted to temperature of reaction, and reducing gas is switched to reaction gas.Reaction product is all introduced chromatogram with gaseous form and is carried out on-line analysis.Wherein CO, N
2, CH
4and CO
2by TCD, detect, methyl alcohol, DME and hydro carbons detect by FID.
The inventor finds through a large amount of Experimental Research, and CO hydrogenation catalyst and a certain or certain two or more metal-modified molecular sieve are mixed and make composite catalyst, and this catalyzer reacts for the synthesis of gas one step ethane processed and propane.Result demonstration, CO transformation efficiency can reach more than 75%, and ethane and the propane overall selectivity in hydro carbons can reach more than 70%, and the selectivity of methane in hydro carbons is lower than 5%.This gas product, for cracking ethylene preparation and production of propylene, can reduce facility investment, reduce energy consumption, reduce process cost, and byproduct is few, can bring good economic benefit.
Embodiment
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
Taking 15g SAPO-34(or ZSM-5) molecular sieve is scattered in 200ml deionized water, by the PdCl of 3.75ml
2solution (metal Pd content 20mg/ml) is slowly added drop-wise on molecular sieve, 60 ° of C exchange 8h of water-bath, then carry out filtering and washing, after 120 ° of C are dried, 520 ° of C roasting 6h, make 0.5%Pd/SAPO-34 (or 0.5%Pd/ZSM-5).By Catalysts Cu-ZnO-Al
2o
3(Cu-Zn-Al) and 0.5%Pd/SAPO-34 (or 0.5%Pd/ZSM-5), compressing tablet, is broken into 20-40 order respectively, with Cu-Zn-Al:0.5%Pd/SAPO-34:0.5%Pd/ZSM-5=1:2:1 ratio, carries out particle mixing.
Get above-mentioned 0.8g(1ml) mixed catalyst is placed in stainless steel fixed-bed reactor, at H
2the lower 250 ° of C reduction of atmosphere 5h, H
2flow 10ml/min.Be warming up to 300 ° of C, pass into synthetic gas (H
2the N of+CO+ volumetric concentration 4%
2), boost to 2.0MPa, gas overall flow rate 1500ml/h, H
2/ CO=2.Change temperature, the variation of catalyst activity and selectivity of product under the same pressure of investigation differing temps, shown in table with test results 1.
Result shows, with temperature of reaction, raises, and CO transforms and takes the lead in increasing gradually rear reduction.This is owing to raising with temperature, the water separation capability of molecular sieve strengthens gradually, promote methyl alcohol and DME dehydration to generate hydrocarbon, broken the thermodynamic(al)equilibrium of methyl alcohol building-up reactions, the reaction that ethane and propane building-up process comprise mostly is thermopositive reaction, with temperature, raises, and chemical equilibrium is moved to the left, so CO transformation efficiency starts to reduce when temperature further raises.Temperature rises to 375 ° of C by 300 ° of C, and ethane and propane overall selectivity raise gradually, and the selectivity of DME reduces gradually, CO
2selectivity impact little.
The impact of table 1 temperature on reactivity worth
Embodiment 2
The catalyzer of preparing according to embodiment 1 method, carries out catalyzer after particle mixing, to get above-mentioned 0.8g(1ml with this ratio of Cu-Zn-Al:0.5%Pd/SAPO-34:0.5%Pd/ZSM-5=1:2:1) mixed catalyst is placed in stainless steel fixed-bed reactor, H
2the lower 250 ° of C reduction of atmosphere 5h, H
2flow 10ml/min.Be warming up to 325 ° of C, pass into synthetic gas (H
2the N of+CO+ volumetric concentration 4%
2), boost to 1.0MPa, gas overall flow rate 1000ml/h, H
2/ CO=2.Change pressure, investigate catalyst activity and ethane and the variation of propane overall selectivity under different pressures same temperature.Test result is as shown in table 2.
The building-up reactions of ethane and propane is a process that volume reduces, and increase pressure and be conducive to reaction forward and carry out, so CO transformation efficiency is along with the rising of reaction pressure increases gradually.With the raising of CO transformation efficiency, the molecular sieve in composite catalyst can not meet the demand of their dehydrations gradually, so ethane and propane overall selectivity in hydro carbons first raises and declines afterwards.
The impact of table 2 pressure on reactivity worth
Embodiment 3
The catalyzer of preparing according to embodiment 1 method, Cu-ZnO-Al
2o
3catalyzer is got 0.2g, and 0.5%Pd/SAPO-34 and 0.5%Pd/ZSM-5 carry out after particle mixing with 1:2,1:1,2:1, then with Cu-ZnO-Al
2o
3catalyzer carries out particle mixing.Get above-mentioned 0.8g(1ml) mixed catalyst is placed in stainless steel fixed-bed reactor, H
2the lower 250 ° of C reduction of atmosphere 5h, H
2flow 10ml/min.Be warming up to 325 ° of C, pass into synthetic gas (H
2the N of+CO+ volumetric concentration 4%
2), boost to 2.0MPa, gas overall flow rate 1000ml/h, H
2/ CO=2.Investigate the variation that under same pressure same temperature, catalyst activity and product distribute.Test result is as shown in table 3.
Different constructional feature and the acidity of these two kinds of molecular sieves of SAPO-34 and ZSM-5 owing to adopting, has had influence on the distribution of transformation efficiency and the product of CO.
The impact of table 3 catalyst ratio on reactivity worth
Embodiment 4
The catalyzer of preparing according to embodiment 1 method, carries out catalyzer after particle mixing, to get above-mentioned 0.8g(1ml with this ratio of Cu-Zn-Al:0.5%Pd/SAPO-34=1:3) mixed catalyst is placed in stainless steel fixed-bed reactor, H
2the lower 250 ° of C reduction of atmosphere 5h, H
2flow 10ml/min.Be warming up to 325 ° of C, pass into synthetic gas (H
2the N of+CO+ volumetric concentration 4%
2), boost to 2.0MPa, gas overall flow rate 1000ml/h.Under same reaction conditions, hydrogen-carbon ratio in feed change gas, test result is as shown in table 4.
High hydrogen-carbon ratio is beneficial to CO and transforms, CO
2selectivity is also lower, and hydrocarbon selective is higher.And be not too large on the overall selectivity impact of ethane and propane.
Table 4H
2the impact of/CO on reactivity worth
Embodiment 5
According to the method for embodiment 1 Kaolinite Preparation of Catalyst, prepare respectively 0.03%Pd/SAPO-34 catalyzer 5g and 3%Pd/SAPO-34 catalyzer 5g.With this ratio of Cu-Zn-Al:0.03%Pd/SAPO-34 (or 3%Pd/SAPO-34)=1:3, catalyzer being carried out, after particle mixing, getting above-mentioned 0.8g(1ml) mixed catalyst is placed in stainless steel fixed-bed reactor, H
2the lower 250 ° of C reduction of atmosphere 5h, H
2flow 10ml/min.Be warming up to 325 ° of C, pass into synthetic gas (H
2the N of+CO+ volumetric concentration 4%
2), boost to 2.0MPa, gas overall flow rate 1000ml/h, H
2/ CO=2.Test result is as shown in table 5.
The demonstration of table 5 result, carrying metal Pd content is from 0.03%～3% variation, and CO transformation efficiency all can reach more than 75%, and the overall selectivity of ethane and propane can reach more than 72%.
The impact of table 5Pd content on reactivity worth
Embodiment 6
First take 5g SAPO-34 molecular sieve.Take again 0.95g Cu (NO
3)
2h
2o is dissolved in 4ml deionized water, is made into Cu (NO
3)
2solution, by the Cu (NO preparing
3)
2solution splash into the SAPO-34 molecular sieve that weighed up in, and constantly stir with glass stick, after mixing, place 20h.After 120 ° of C are dried, 420 ° of C roasting 4h, make 5%Cu/SAPO-34 catalyzer.Change Cu content, in kind make 15%Cu/SAPO-34 catalyzer.With Cu-Zn-Al:5%Cu/SAPO-34(or 15%Cu/SAPO-34) this ratio of=1:3 carries out catalyzer after particle mixing, to get above-mentioned 0.8g(1ml) mixed catalyst is placed in stainless steel fixed-bed reactor, H
2the lower 250 ° of C reduction of atmosphere 5h, H
2flow 10ml/min.Be warming up to 325 ° of C, pass into synthetic gas (H
2the N of+CO+ volumetric concentration 4%
2), boost to 2.0MPa, gas overall flow rate 1000ml/h, H
2/ CO=2.Test result is as table 6.
Cu content changes in 5%～15% scope, and CO transformation efficiency impact is little, from hydrocarbon distribution, can find out, ethane and propane overall selectivity change 69%～73%, and the content of methane is in 2% left and right, be when selecting carrying metal Pd the content of methane.
The impact of table 6Cu content on reactivity worth
Embodiment 7
The catalyzer of preparing according to embodiment 1 method, carries out catalyzer after particle mixing, to get above-mentioned 0.8g(1ml with Cu-Zn-Al:0.5%Pd/SAPO-34=1:1 or this ratio of 1:3) mixed catalyst is placed in stainless steel fixed-bed reactor, H
2the lower 250 ° of C reduction of atmosphere 5h, H
2flow 10ml/min.Be warming up to 325 ° of C, pass into synthetic gas (H
2the N of+CO+ volumetric concentration 4%
2), boost to 2.0MPa, gas overall flow rate 1000ml/h, H
2/ CO=2.Test result is as table 7.
Composite catalyst performance when having investigated Cu-Zn-Al and 0.5%Pd/SAPO-34 ratio and being 1:1 and 1:3, the ratio between two components is larger on CO transformation efficiency and hydrocarbon distribution impact, has a kind of synergistic effect between the two.
The impact of table 7CO hydrogenation catalyst and modified molecular screen ratio
Embodiment 8
The catalyzer of preparing according to embodiment 1 method, with ZnO/Cr
2o
3(or Pd/ZnO/Cr
2o
3) and 0.5%Pd/SAPO-34 than for this ratio of 1:1, catalyzer is carried out after particle mixing, get above-mentioned 0.8g mixed catalyst and be placed in stainless steel fixed-bed reactor, H
2the lower 300 ° of C reduction of atmosphere 5h, H
2flow 10ml/min.Be warming up to 400 ° of C, pass into synthetic gas (H
2the N of+CO+ volumetric concentration 4%
2), boost to 3.0MPa, gas overall flow rate 1500ml/h, H
2/ CO=2.Test result is as table 8.
Table 8ZnO/Cr
2o
3(or Pd/ZnO/Cr
2o
3) catalytic performance while being CO hydrogenation catalyst
Embodiment 9
The catalyzer of preparing according to embodiment 1 method, carries out catalyzer after particle mixing, to get above-mentioned 0.8g(1ml with this ratio of Cu-Zn-Al:0.5%Pd-SAPO-34=1:3) mixed catalyst is placed in stainless steel fixed-bed reactor, H
2the lower 250 ° of C reduction of atmosphere 5h, H
2flow 10ml/min.Be warming up to 325 ° of C, pass into synthetic gas (H
2the N of+CO+ volumetric concentration 4%
2), H
2/ CO=4, boosts to 2.0MPa, gas overall flow rate 1000ml/h.Under above-mentioned reaction conditions, carry out 25h stability experiment.Test result is as shown in table 9.
The stability of table 9 composite catalyst Cu-Zn-Al/0.5%Pd-SAPO-34
Claims (9)
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| WO2016007607A1 (en) | 2014-07-11 | 2016-01-14 | Dow Global Technologies Llc | Conversion of carbon monoxide, carbon dioxide, or a combination thereof over hybrid catalyst |
| WO2017074558A1 (en) | 2015-10-30 | 2017-05-04 | Dow Global Technologies Llc | Process to convert synthesis gas to olefins over a bifunctional chromium oxide/zinc oxide-sapo-34 catalyst |
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