CN1067878A - A kind ofly directly produce low-carbon alkene reaction by synthetic gas - Google Patents
A kind ofly directly produce low-carbon alkene reaction by synthetic gas Download PDFInfo
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- CN1067878A CN1067878A CN 91106157 CN91106157A CN1067878A CN 1067878 A CN1067878 A CN 1067878A CN 91106157 CN91106157 CN 91106157 CN 91106157 A CN91106157 A CN 91106157A CN 1067878 A CN1067878 A CN 1067878A
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Abstract
A kind of by synthetic gas (H
2, CO) directly produce the reaction process of low-carbon alkenes such as ethene, propylene.Comprise two consecutive steps, at first, carry out catalytic cracking reaction again and make low-carbon alkenes such as ethene, propylene by the synthetic oxygenatedchemicals of unstripped gas based on dme.Adopt industrial synthesizing methanol with containing the mixed composite catalyst that gets of copper-based catalysts and solid acid oxide compound and having the shape of selecting effect high-silicon ZSM-5-5 or mordenite catalyst or pinhole phosphorus-silicon-aluminum zeolite catalyst in this reaction.This processing method is simple, and easily-controlled reaction conditions, synthetic gas per pass conversion and yield height are suitable for adopting in the suitability for industrialized production.
Description
The present invention relates to the synthetic method of low-carbon alkenes such as a kind of ethene, propylene, specifically provide a kind of with synthetic gas (CO+H
2) be unstripped gas, directly produce the reaction process of low-carbon alkene and provide required catalyzer for this two-step reaction process through two successive reaction steps.
Low-carbon alkene such as ethene, propylene is important basic Organic Chemicals, along with development light, chemical industry will be more and more big to their demand.Up to now, the approach of producing these low-carbon alkenes mainly is by the light oil cracking reaction process.Because the restriction that petroleum resources are not enough and oil such as lays particular stress at the aspect, light oil cracking method are difficult to obtain further developing and satisfy the growing demand in market.Therefore, the development non-oil resource technology of producing out carbon olefin causes that day by day people pay attention to.In these researchs, be considered to provide the more satisfactory method of basic organic chemical industry's product such as ethene, propylene by the two-step approach of preparing low carbon olefinic hydrocarbon with methanol from the synthetic gas footpath from non-oil resource.This reaction process at first is that methanol dehydration is converted into dme, then further is cracked into low-carbon alkene again.Yet methyl alcohol has been the wider Chemicals of purposes, if obtain low-carbon alkene by methyl alcohol in a large number economically may not be reasonable, its technological process is also more loaded down with trivial details simultaneously.The prior art scheme more approaching with technology of the present invention is directly to produce the oxygenate reaction process that dme is the master by synthetic gas, for example U.S. Pat 4,536,485 and US4,481,305 grades reported by synthesis gas through methanol, oxygenatedchemicalss such as dme are produced the process of stop bracket gasoline.Though its reaction process fs of these technology all is to produce methyl alcohol by synthetic gas earlier, oxygenatedchemicalss such as dme, with these oxygenatedchemicals cracking, the purpose product of being produced is a gasoline fraction in the subordinate phase reaction for they.
The purpose of this invention is to provide a kind of by synthetic gas (CO+H
2) directly produce the reaction process of low-carbon alkenes such as ethene, two alkene, and for realizing that this reaction process prepares required catalyzer.
Provided by the invention by synthetic gas (CO, H
2) directly produce the reaction process of low-carbon alkenes such as ethene, two alkene, it comprises two consecutive steps: (1) is by synthetic gas (CO, H
2) directly synthetic oxygenatedchemicals based on dme.Adopting industry to produce the used copper-based catalysts of methyl alcohol (active ingredient is copper and zinc or chromium etc.) by synthetic gas in this reaction is catalyzer with the composite catalyst that can make methanol dehydration become solid acid oxide catalyst two components of dme to be mixed and made into by a certain percentage.(2) reactant that is obtained by (1) process carries out low-carbon alkenes such as catalytic cracking reaction generation purpose product ethene, propylene.Adopt the central hole zeolite catalyst with five yuan of oxidation rings, for example ZSM-5 or mordenite or pinhole phosphorus-silicon-aluminum zeolite catalyst in this reaction.
In above-mentioned reaction process (1), reactant synthetic gas (CO, H
2) following three kinds of reactions will take place on the composite catalyst that copper-based catalysts and solid acid oxide compound are mixed and made into:
It always comprises that reaction can be expressed as:
Because the methyl alcohol that synthesis gas reaction generates in this process (reaction 1) will be converted into dimethanol as reaction 2 reactant serials, thereby the restriction of the thermodynamic(al)equilibrium when being beneficial to CO and being converted into methyl alcohol, be reflected under the lower pressure and can carry out thereby can make, and can reach higher CO conversion rate.In addition by total reaction 4 as can be known, unique by product is CO in the said process
2And anhydrous generation, this shows this process less energy consumption, also will play active effect to reducing moisture content in following the 2nd step reaction process to the disadvantageous effect of catalyzer simultaneously, can prolong the life-span of relevant zeolite catalyst effectively.The reaction conditions that this reaction process (1) is selected is: 1) reactant H
2/ CO mol ratio should be between 1～5, and optimal proportions is 1～2, and can contain a certain amount of CO in the synthetic gas
2, its CO/CO
2Mol ratio is advisable to be no less than 5, is preferably 10～20.2) control reaction temperature is at 150～350 ℃, and working pressure carries out under 1.0～8.0MPa, and its preferable temperature of reaction can be controlled in 200～300 ℃, and working pressure is 2.0～5.0MPa.3) reaction process (1) catalyst system therefor can adopt industrial synthesizing methanol copper-based catalysts and solid acid oxide compound, and for example faujusite (X or Y type) or r type aluminium oxide catalyst two components account for 30～70% ratio thorough mixing in copper-based catalysts weight and make; Also can utilize salt such as Cu and Zn or Cr directly and faujusite or the co-precipitation of r type aluminum oxide make.The preparation method of its copper-based catalysts can or adopt the corresponding commodity catalyzer with reference to the method for the industrial catalst for synthesis of methanol of known preparation, and the solid acid oxide compound also can adopt common preparation faujusite (X or Y type) or r type method of alumina or adopt corresponding commodity.Oxygenatedchemicals catalytic pyrolysiss such as dme are that low-carbon alkene is second step reaction that the invention provides reaction process.Except that purpose product dme and small amount of methanol are arranged, unconverted reactant CO and H are arranged still in the outflow species of reaction process (1)
2And by product CO
2With a small amount of methane etc., these species can all directly enter in the reaction of second step, also can be with the CO in the effluent, and H
2And CO etc. participates in the next step after telling in advance again, promptly can increase separation circuit between reaction process (1) and (2), be provided with in will reacted resultant of the 1st step and participate in unstripped gas CO and the H that reacts
2, by product CO
2Isolate from resultant, and reclaim and to join in the unstripped gas, the reactant after the separation entered for (2) step and carries out catalytic cracking reaction.In reaction process (2), adopt and have shape selective action mesopore Pentasll high silica zeolite catalyst, for example silica alumina ratio is 40～100 ZSM-5 or mordenite, and elements such as available phosphorus, magnesium, boron or rare earth carry out upgrading to be handled, and can adopt ion-exchange or impregnating means to add the upgrading element.Simultaneously also can adopt pore zeolite, for example the phosphorus Si-Al zeolite is made catalyzer, and this zeolite also can add transition metals such as Nl, Pt.The reaction conditions of the 2nd step is: at normal pressure (0.1MPa), temperature of reaction is carried out under 400～600 ℃, and preferably control reaction temperature is to carry out under 480～550 ℃, and air speed can reach 1000h
-1About.In reaction process (2) gained split product, except that containing low-carbon alkenes such as a large amount of purpose product ethene and propylene, a small amount of by product C is arranged still
1～C
5Stable hydrocarbon.Below by example to the content of the present invention into explanation of knowing clearly.
The preparation A of embodiment 1 composite catalyst
Y zeolite 10g and methyl alcohol is synthetic with the broken also mechanically mixing of copper-based catalysts 10g, at 600 normal atmosphere lower sheetings, be broken into the particle of 40-60 mesh sieve degree again.Used catalyst for methanol contains CuO40-55%, ZnO30～15%, Al
2O
320-15%, K
2O10-15%.The resulting catalyst A that is called.
The preparation B of embodiment 2 composite catalysts
With the pulverous r-Al of 10g
2O
3Carry out mechanically mixing with the pulverous methanol synthesis catalyst of 10g (form with example 1 with), at 600 normal atmosphere lower sheetings, be broken into the particle of 40-60 mesh sieve degree again, the resulting catalyst B that is called.
Embodiment 3 reaction experiments 1
The made catalyst A 5ml of the above-mentioned example of filling 1 at first uses the hydrogen reducing catalyst A by nitrogen dilution on continuous flow fixed bed reactor.About gas flow 50ml/mln, the ratio of hydrogen and nitrogen is 1: 4, before heat-up rate is controlled to be room temperature to 220 ℃, and 1 ℃/mln, 180 ℃ of constant temperature 1 hour, 220 ℃ of constant temperature 2 hours, and then change CO+H
2Gas mixture (H
2: CO=2: 1), continue slowly to heat up) in reaction pressure 3.5MPa(gauge pressure, 255 ℃ of temperature of reaction, and synthetic gas volume air speed is 1000h
-1Reaction conditions under, the reaction result of catalyst A is mainly: CO transformation efficiency 70%(mol), H
2Transformation efficiency 60%, dme selectivity 90-95%, and methyl alcohol selectivity 5～10%(is all for organic product).
Embodiment 4 reaction experiments 2
The 5ml catalyst B that above-mentioned example 2 is made is seated on the continuous flow fixed bed reactor, adopts reductive condition and the reaction conditions identical with above-mentioned example 3.The reaction result of catalyst B is mainly: CO transformation efficiency 70%(mol), and H
2Transformation efficiency 60%, dme selectivity 80～85%, methyl alcohol selectivity 10～15%, and also have a small amount of methane to generate.
The preparation of embodiment 5 zeolite catalysts
Get 2889 milliliters and contain Na
2O62.8mg/ml and SlO
2193.21mg/ml water glass solution, the quadrol of 1980 ml pure waters and 244g98% mixes, other gets content is 99% Al
2(SO
4)
318H
2The O69.3 gram, 2000 milliliters of 482 milliliters in 4M sulfuric acid and pure water, and mix; Under violent stirring two solution are mixed into glue, present and continue behind the glue to stir 30 minutes again, it is in rotary (or stirring-type) stainless steel autoclave of 10 liters that gelatigenous object is shifted the system volume.At first under 110 ℃ of conditions aging 12 hours, crystallization 50 hours under 105 ℃ of conditions again.After crystallization process was finished, product was cooled off rapidly, and inclining mother liquor, again with a pure water washing and a precipitation number an ancient unit of weight equal to 20 or 24 *taels of silver, was 8-9 until the pH value of solution, gained filtrate 120 ℃ dry 10 hours down, promptly get Pentasall type silicon brill zeolite.The SlO of back finished product
2/ Al
2O
3(molecular ratio) is 50.Use 1NMH
4NO
3And 0.5NMH
4The OH mixing solutions carries out the ammonium ion exchange operation; Sodium content＜the 0.05%Wt of products therefrom.Dry good ammonium type zeolite sample is packed in the tube furnace, at N
2Slowly heat up with (about oxygen level 1%) in the Air mixing air-flow, 540 ℃ of roastings 4 hours, cut off source of the gas subsequently, improve pure water and intensification simultaneously, flooding quantity 5-10 milliliter/gram sample hour was kept 4 hours under 500 ℃ of-600 ℃ of temperature, after the hydrothermal treatment consists operation is finished, change again with dry air and purge cooling, take out to room temperature.Obtain H type silicon and bore zeolite, use H again
3PO
4Modification adopts pickling process to make that P content reaches 3% in the molecular sieve, promptly obtains catalyzer C.
Embodiment 6 reaction experiments 3
The microreactor that the 2ml catalyst A is housed is connected in series mutually with the microreactor front and back that 20ml catalyzer C is housed.The anti-celebrating condition of catalyst A: 260 ℃ of temperature, pressure 3.5MPa, synthetic gas (H
2/ CO=2: 1) volume space velocity is 1000h
-1; The service temperature that second section reactor of catalyzer C is housed is 550 ℃, and pressure is normal pressure (0.1MPa), and the material of second section reactor outlet with 103 type chromatogram on-line analyses, main result is:
Oxycompound transformation efficiency～90%
CH
4～10%
A small amount of C is still arranged in the product
4Above hydro carbons and unconverted CO and H
2
As seen from the above-described embodiment, adopt method provided by the invention directly to produce low-carbon alkenes such as ethene, propylene through oxygenatedchemicalss such as dme by synthetic gas, its synthetic gas per pass conversion and purpose product yield are significantly improved.Simple, the easily-controlled reaction conditions of this method technology provides a kind of new way that is suitable for adopting for directly produced low-carbon alkenes such as ethene, propylene by synthetic gas in suitability for industrialized production simultaneously.
Claims (7)
1, a kind of by synthetic gas (H
2, CO) produce the reaction process of low-carbon alkenes such as ethene, propylene, it is characterized in that this reaction comprises two consecutive steps:
(1) by synthetic gas (CO, H
2) directly synthetic oxygenatedchemicals based on dme, adopt industry to produce the used copper-based catalysts of methyl alcohol (active ingredient is copper and zinc or chromium etc.) by synthetic gas in this reaction and become solid acid oxide catalyst two components of dme with making methanol dehydration, the composite catalyst that is mixed and made into by a certain percentage is a catalyzer;
(2) reactant that is obtained by (1) process carries out low-carbon alkenes such as catalytic cracking reaction generation ethene, propylene, adopts the central hole zeolite catalyst with five yuan of oxidation rings in this reaction, for example ZSM-5 or mordenite or pinhole phosphorus-silicon-aluminum zeolite catalyst.
2, according to the described reaction process of claim 1, it is characterized in that reaction (1) is 150～350 ℃ of temperature of reaction, working pressure (carries out material synthesis gas H under .0～8.0MPa condition
2/ CO molar reactive is 1～5.Reaction (2) is 300～600 ℃ of temperature of reaction, carries out under working pressure normal pressure～0.1MPa condition.
3, according to claim 1,2 described reaction process, it is characterized in that reacting (1) preferably 20.0～300 ℃ of temperature of reaction, carry out reactant H under working pressure 2.0～5.0MPa
2/ CO mol ratio is 1.0～2.0 to be advisable.
4,, it is characterized in that reaction (1) is as containing a certain amount of CO in the unstripped gas according to claim 1,2,3 described reaction process
2, its CO/CO
2Than being advisable, be preferably 10～20 to be not less than 5.
5, according to claim 1,2 described reaction process, it is characterized in that reaction (2) preferably is controlled under 450～550 ℃ of the temperature carries out.
6,, it is characterized in that contained its active ingredient of copper-based catalysts also comprises zinc and/or chromium in the used composite catalyst of reaction (1) according to the described reaction process of claim 1; The preferable weight of copper-based catalysts accounts for 45～55% of composite catalyst; The preparation process of composite catalyst is with two groups of catalyzer thorough mixing by a certain percentage, makes after the compression moulding.
7, according to the described reaction process of claim 1, it is characterized in that and can between process (1) and (2), increase separation circuit, do not participate in the unstripped gas (CO+H of reaction in the resultant that (1) the step process that is about to produces
2) and by product CO
2Isolate from resultant, and reclaim and to join among the raw material, the reactant after the separation entered for (2) step and carries out catalytic cracking reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91106157 CN1036131C (en) | 1991-06-22 | 1991-06-22 | Reaction for direct making low-carbon olefin from synthetic gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91106157 CN1036131C (en) | 1991-06-22 | 1991-06-22 | Reaction for direct making low-carbon olefin from synthetic gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1067878A true CN1067878A (en) | 1993-01-13 |
| CN1036131C CN1036131C (en) | 1997-10-15 |
Family
ID=4907593
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91106157 Expired - Lifetime CN1036131C (en) | 1991-06-22 | 1991-06-22 | Reaction for direct making low-carbon olefin from synthetic gas |
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|---|---|
| CN (1) | CN1036131C (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065853C (en) * | 1996-05-24 | 2001-05-16 | 中国科学院大连化学物理研究所 | Preparation of ethylene, propylene and other low-carton olefine from methyl alcohol or dimethyl ether |
| CN101190415B (en) * | 2006-11-28 | 2011-05-11 | 韩国燃气公社 | Method of producing a catalyst used for synthesizing dimethylether from a synthesis gas containing carbon dioxide |
| CN101610835B (en) * | 2006-11-22 | 2013-03-27 | 英国石油化学品有限公司 | Process for producing alkenes from oxygenates by using supported heteropolyacid catalysts |
| CN104203885A (en) * | 2012-01-31 | 2014-12-10 | 巴斯夫欧洲公司 | Method for the conversion of synthesis gas into olefins |
| CN106311317A (en) * | 2015-07-02 | 2017-01-11 | 中国科学院大连化学物理研究所 | Catalyst and method for directly preparing light olefins from synthesis gas by one-step process |
| CN107661774A (en) * | 2016-07-27 | 2018-02-06 | 中国科学院大连化学物理研究所 | The method that a kind of catalyst and synthesis gas directly convert producing light olefins |
| CN107661773A (en) * | 2016-07-29 | 2018-02-06 | 中国科学院大连化学物理研究所 | The method that a kind of catalyst and synthesis gas directly convert preparing liquid fuel co-producing light olefins |
| WO2018161670A1 (en) * | 2017-03-07 | 2018-09-13 | 中国科学院大连化学物理研究所 | Catalyst and process for producing ethylene by direct conversion of synthesis gas |
| CN109939669A (en) * | 2018-01-26 | 2019-06-28 | 中国科学院大连化学物理研究所 | A kind of method of base-modified composite catalyst and carbon monoxide hydrogenation ethylene |
| CN109939668A (en) * | 2018-01-26 | 2019-06-28 | 中国科学院大连化学物理研究所 | A method of the B acid catalyst of type containing LF and synthesis gas directly convert ethylene processed |
| WO2020073598A1 (en) * | 2018-10-11 | 2020-04-16 | 中国科学院大连化学物理研究所 | Method for preparing low-carbon olefins from synthesis gas |
| CN114425411A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Supported Fe-based catalyst and preparation and application thereof |
-
1991
- 1991-06-22 CN CN 91106157 patent/CN1036131C/en not_active Expired - Lifetime
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065853C (en) * | 1996-05-24 | 2001-05-16 | 中国科学院大连化学物理研究所 | Preparation of ethylene, propylene and other low-carton olefine from methyl alcohol or dimethyl ether |
| CN101610835B (en) * | 2006-11-22 | 2013-03-27 | 英国石油化学品有限公司 | Process for producing alkenes from oxygenates by using supported heteropolyacid catalysts |
| CN101190415B (en) * | 2006-11-28 | 2011-05-11 | 韩国燃气公社 | Method of producing a catalyst used for synthesizing dimethylether from a synthesis gas containing carbon dioxide |
| CN104203885A (en) * | 2012-01-31 | 2014-12-10 | 巴斯夫欧洲公司 | Method for the conversion of synthesis gas into olefins |
| CN106311317B (en) * | 2015-07-02 | 2019-04-16 | 中国科学院大连化学物理研究所 | A kind of catalyst and the method that low-carbon alkene is directly prepared by one-step method from syngas |
| US10532961B2 (en) | 2015-07-02 | 2020-01-14 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Catalyst and method of preparing light olefin directly from synthesis gas by one-step process |
| CN106311317A (en) * | 2015-07-02 | 2017-01-11 | 中国科学院大连化学物理研究所 | Catalyst and method for directly preparing light olefins from synthesis gas by one-step process |
| CN107661774A (en) * | 2016-07-27 | 2018-02-06 | 中国科学院大连化学物理研究所 | The method that a kind of catalyst and synthesis gas directly convert producing light olefins |
| CN107661773A (en) * | 2016-07-29 | 2018-02-06 | 中国科学院大连化学物理研究所 | The method that a kind of catalyst and synthesis gas directly convert preparing liquid fuel co-producing light olefins |
| CN107661773B (en) * | 2016-07-29 | 2020-08-04 | 中国科学院大连化学物理研究所 | Method for preparing liquid fuel and co-producing low-carbon olefin by directly converting catalyst and synthesis gas |
| WO2018161670A1 (en) * | 2017-03-07 | 2018-09-13 | 中国科学院大连化学物理研究所 | Catalyst and process for producing ethylene by direct conversion of synthesis gas |
| CN109939669A (en) * | 2018-01-26 | 2019-06-28 | 中国科学院大连化学物理研究所 | A kind of method of base-modified composite catalyst and carbon monoxide hydrogenation ethylene |
| CN109939668A (en) * | 2018-01-26 | 2019-06-28 | 中国科学院大连化学物理研究所 | A method of the B acid catalyst of type containing LF and synthesis gas directly convert ethylene processed |
| CN109939668B (en) * | 2018-01-26 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for preparing ethylene by directly converting synthesis gas and catalyst containing LF type B acid |
| CN109939669B (en) * | 2018-01-26 | 2020-09-04 | 中国科学院大连化学物理研究所 | Alkali-modified composite catalyst and method for preparing ethylene through carbon monoxide hydrogenation reaction |
| WO2020073598A1 (en) * | 2018-10-11 | 2020-04-16 | 中国科学院大连化学物理研究所 | Method for preparing low-carbon olefins from synthesis gas |
| CN114425411A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Supported Fe-based catalyst and preparation and application thereof |
| CN114425411B (en) * | 2020-10-14 | 2023-08-29 | 中国石油化工股份有限公司 | Supported Fe-based catalyst and preparation and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1036131C (en) | 1997-10-15 |
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