CN1040397C - Iron manganese catalyst for preparation of low carbon olefines by synthetic gas and synthetic reaction - Google Patents
Iron manganese catalyst for preparation of low carbon olefines by synthetic gas and synthetic reaction Download PDFInfo
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Abstract
The present invention relates to a catalyst for preparing low-carbon olefin, such as ethene, propene, etc., from synthetic gas (CO and H2), with high selectivity, which is an iron-manganese catalyst system carried by alkaline earth oxide or silica-rich zeolite molecular sieves (or phosphorus-aluminum zeolite) of an IIA group, such as MgO, etc. The present invention has good low-carbon olefin synthesizing performance under the action of strong alkali (metal of the IA group) K<+> or a Cs ion assistant. The catalyst can be used for preparing low-carbon olefin from synthetic gas in high activity (namely the conversion rate of CO of more than 90 %) and high selectivity (namely the selectivity of the olefin of more than 66%) under the reaction conditions of the pressure of 1.0 to 5.0MPa and the temperature of 300 to 400 DEG C. The technological process of the present invention comprises: directly absorbing and separating CO2 by reacting tail gas through water, absorbing and separating C3 and C4 components through medium-pressure oil, and then producing ethylenzene by the reaction of benzene and low-concentration ethene in the tail gas. The present invention has the advantage of simple operating procedure, and is suitable for popularization and application.
Description
The present invention relates to a kind of by synthesis gas (CO+H
2) the directly new catalyst and the corresponding technical process of synthesizing low-carbon alkene.Specifically, Fe-Mn/MgO (CaO, SrO) or under the catalytic action of Fe-Mn/ silica-rich zeolite (phosphorus aluminium zeolite) and corresponding additive, synthesis gas can high activity, highly selective directly changes into low-carbon alkene (C
2～C
4).
Low-carbon alkene such as ethene, propylene is important basic Organic Chemicals, and is along with the development of chemical industry, more and more big to their demand.Up to now, the approach of producing low-carbon alkenes such as second, propylene because petroleum resources are limited, will be difficult to satisfy market to second, the growing demand of propylene mainly by the light oil cracking process.And, not only can reduce dependence, and some chemical industrial expansions in rich gas oil starvation area there is significance to petroleum resources from the technological development that synthesis gas (can be converted to by natural gas and coal) is directly produced second, propylene.The F-T synthesis reaction in past its objective is by synthesis gas synthetic fuel liquefied hydrocarbon, and the purpose of present carbon-chemical synthesis hydro carbons is with its low-carbon alkene as industrial chemicals, and especially ethene and propylene are the materials of present most worthy.And directly producing low-carbon alkene by synthesis gas is that single step reaction generates the purpose product, and its technological process is simpler than indirect method, and economic evaluation is also more worthwhile.By the direct synthesizing low-carbon alkene of synthesis gas is that last decade just begins one's study.For example, Ger.Pat.2536438, the Fe-Tl-Zn-K quaternary biscuit firing metallic catalyst that Ger.Pat. 2518964 is developed; Cobalt-containing catalyst that Fe-Cu-Zn-K catalyst that Get.Pat.2818308 developed and U.S.Pat.40393 02 are reported or the like is all obtained reasonable result.But these catalyst repeat performance in preparation, amplify the difficulty that runs in the preparation supervisor in various degree.Present inventors once put forward a kind of technology (CN91106157.6) and are directly produced low-carbon alkene reaction and provide industrial synthesizing methanol copper-based catalysts and solid acid oxide catalyst two component composite catalysts and molecular sieve zeolites catalyst for this reaction through two successive reaction steps by synthesis gas.
The purpose of this invention is to provide the supported catalyst of directly producing low-carbon alkenes such as ethylene, propylene by synthesis gas.This catalyst has the selectivity that good manufacturing repeats performance and very high active and generation low-carbon alkene.Simultaneously, the present invention also directly produces low-carbon alkene for synthesis gas corresponding, feasible technological process is provided, and this flow process ethene synthesizing ethyl benzene that can directly utilize reaction and generated.
Of the present invention by synthesis gas directly produce low-carbon alkene reaction usefulness to contain its active component of ferrimanganic supported catalyst be the Fe-Mn element, be supported on the alkaline earth oxide (MgO of IIA family, SrO or CaO), silica-rich zeolite molecular sieve (Silicalite-1, Silicalite-2, ZSM-12 or ZSM-48), on the carrier made of phosphate aluminium molecular sieve (APO-5) or their compound.Simultaneously, be the performance of regulating catalyst, in above-mentioned catalyst, add K or Cs ion and hydroxide or halide (OH
-1, Cl
-1, Br
-1, I
-1) make auxiliary agent.Cs wherein
+Ion and KOH make its catalytic effect the best of auxiliary agent.The weight ratio of each component is in the catalyst: (100) carrier: (5～20) Fe: (5～15) Mn: (3～20) K or CS.The weight ratio of its optimum range is (100) carrier: (5～15) Fe: (7～11) Mn: (3～15) K or CS.
Preparation of catalysts process of the present invention is pressed following step:
1, with carrier (IIA family alkaline earth oxide, silica-rich zeolite molecular sieve, phosphate aluminium molecular sieve or their compound) extrusion forming;
2, use alkali or the salt solution impregnation carrier that contains the inorganic salts of active component Fe, Mn and contain auxiliary agent K, Cs element, active component and auxiliary element are supported on carrier;
3, the carrier of dipping active component carries out roasting after drying under 400～750 ℃ of temperature;
4, the catalyst after the roasting reduces with hydrogen under 300～500 ℃ and makes finished catalyst.The reduction reaction of catalyst also can be carried out in reactor before catalytic reaction.The pressure of reducing gases hydrogen is 0.5～1.5MPa, and reduction reaction should be no less than 2 hours.The reduction temperature of above-mentioned the best is 400～480 ℃.
In above-mentioned Preparation of catalysts process, also can flood active component again with containing inorganic salts pressed powder and the evenly back extrusion forming of carrier powder of active component Fe or Mn.Its preferable preparation process is:
1, with carrier and contain Mn inorganic salts powder fully mix the back extrusion forming;
2, use alkali or the halide solution dipping carrier that contains the inorganic salts of Fe element and contain auxiliary agent K or Cs, active component and auxiliary element are supported on the carrier;
3, carry out roasting by above-mentioned 3,4 steps again and catalyst is made in reduction.
Catalyst of the present invention can be used for directly being produced by synthesis gas low-carbon alkenes such as ethene, propylene, and this reaction also can directly be carried out ethene and benzene alkylation reaction and obtains ethylbenzene.The present invention is directly produced low-carbon alkene by synthesis gas course of reaction is provided by accompanying drawing 1.Among Fig. 1: 1, raw material of synthetic gas (CO+H
2); 2, in the presence of catalyst, carry out catalytic reaction; 3, water absorbs operation; 4, C
3, C
4The component separation circuit; 5, low-carbon alkene preparation; 6 and benzene alkylation reaction; 7, unreacted gas repetitive cycling operation.By technological process shown in the accompanying drawing 1, specifically synthesis gas 1 raw material carries out synthetic reaction 2 in the presence of above-mentioned catalyst, and directly synthetic is the low-carbon alkene of primary product with ethene, propylene.Reaction back gas absorbs gas CO through operation 3 water
2After, again through separation circuit 4 with C
3, C
4The component separation obtains containing partial reaction gas CO, H
2And CH
4Rare ethylene gas.This contain the lower ethene mist of concentration can be directly as raw material and benzene carry out alkylated reaction and prepare ethylbenzene.The catalyst of its course of reaction and employing can be by patented technology CN87105054.4 number that present inventors in earlier stage once provided) carry out.
Catalyst of the present invention can be 320～500 ℃ of reaction temperatures, and 1.0～5.0MPa pressure is operation down, especially when using 3.0～4.0MPa pressure, and can direct and separation of C O
2And C
3, C
4Component system links, and operation is simple, thereby this flow process has its unique advantages.
Catalyst of the present invention can be in the operation of the field of activity of broad, when the conversion per pass that requires CO reaches 90% when above, the CO in the tail gas, H
2, CH
4Can no longer recycle, the gas that directly acts as a fuel uses.If require to improve olefine selective, can suitably reduce the CO activity of conversion of catalyst, the CO in the tail gas, H
2, CH
4Can proceed synthetic olefine reaction with unstripped gas by recirculation, in this case, methane gas can be used as the heat-obtaining medium, and catalyst performance is still unaffected.The characteristics of flow process of the present invention are can not only be directly and separation of C O
2, C
3, C
4Component system links, and can directly use rare ethene and benzene reaction in the tail gas to generate ethylbenzene, has improved the economic benefit of process.
Below by example content of the present invention is described in detail:
The preparation of embodiment 1 IIA family metal oxide supported catalyst A
With MgO (CaO, SrO) 10 gram powder and 2.6 gram KMnO
4Mechanical mixture is broken into 20～30 purpose particles behind 400 atmospheric pressure lower sheetings, after 600 ℃ of roasting a few hours, vacuumize dipping Fe (NO
3)
3Or Fe (NO
3)+KOH (Cs) mixed solution, 120 ℃ of bakings are 8 hours then, 540 ℃ of roastings 20 hours, the catalyst of gained is called catalyst A.Its composition (weight ratio) is: 100MgO: (5～20) Fe: (5～15) Mn: (5～15) K (or 3～20Cs).Catalyst sees Table 1 concrete the composition.
The preparation of embodiment 2 IIA family metal oxide supported catalyst B
(CaO, SrO) 10 gram powder are broken into 20～30 purpose particles again behind 400 atmospheric pressure lower sheetings, vacuumize dipping Fe (NO then with MgO
3)
3+ KMnO
4+ KOH (or Cs) mixed solution, 120 ℃ of bakings 10 hours, 540 ℃ of roastings 16 hours, the catalyst of gained is called catalyst B.Its composition (weight ratio) is: 100MgO: (5～20) Fe: (5～15) Mn: (5～15) K (or 3～20Cs).Catalyst sees Table 2 concrete the composition.
Embodiment 3 IIA family metal oxide supported catalyst C preparation
With MgO (CaO, SrO) 10 gram powder (or MgO and Si-2 mixed-powder) and Fe (NO
3)
3+ KMnO
4+ KOH (or Cs) solid phase mechanical mixture is broken into 20～30 purpose particles behind 400 atmospheric pressure lower sheetings, 600 ℃ of roastings 24 hours, and the gained catalyst is called catalyst C.Its composition (weight ratio) is: 100MgO: (5～20) Fe: (5～15) Mn: (5～15) K (or 3～15Cs).Catalyst sees Table 3 concrete the composition.
The preparation of embodiment 4 IIA family metal oxide supported catalyst D
Interpolation KX or CsX in the Fe-Mn catalyst system that MgO supports (X=Cl, Br, I) auxiliary agent, the gained catalyst is called catalyst D.Its composition (weight ratio) is: 100MgO: (5～20) Fe: (5～15) Mn: (5～15) K (or 5～15Cs): (1～5) X.Catalyst sees Table 4 concrete the composition.
The preparation of embodiment 5 high silicon (phosphorus aluminium) zeolite supported catalyst E
(Silicalite-1, ZSM-12 ZSM-48) or behind the APO-5 powder compacting, vacuumize dipping Fe (NO with Silicalite-2
3)
3+ KMnO
4+ KOH mixed solutions such as (or Cs), 120 ℃ of bakings are 8 hours then, 540 ℃ of roastings 15 hours, the gained catalyst is called catalyst E, and its composition (weight ratio) is: 100 molecular sieves: (5～20) Fe: (5～15) Mn: (5～15) K (or 5～15Cs).Catalyst sees Table 5 concrete the composition.
The preparation of embodiment 6 high silicon (phosphorus aluminium) zeolite supported catalyst F
With Silicalite-2 (Silicalite-1, ZSM-48, ZSM-12) or APO-5 powder and KMnO
4After the mechanical mixture moulding,, vacuumize dipping Fe (NO in 600 ℃ of roastings 5 hours
3)
3+ KOH (Cs) solution, 120 ℃ of bakings are 8 hours then, 540 ℃ of roastings 16 hours, the gained catalyst is called catalyst F.Its composition (weight ratio) is: 100 molecular sieves: (5～20) Fe: (5～5) Mn: (5～15) K (or 5～15Cs).Catalyst sees Table 6 concrete the composition.
Embodiment 7 synthesis gas system olefine reactions experiment 1
The catalyst A that the above-mentioned example 1 of filling 1ml is developed on continuous flow fixed bed reactor.At first at 400～500 ℃, the H of 0.5～1.5MPa
2Reduced in the atmosphere 5～15 hours, and cooled to 320～400 ℃ and switch CO/H
2=1/1～1/2 synthesis gas charging is at 1.0～5.0MPa, 500～2500h
-1React under the condition, the reaction result of catalyst A sees Table 1.C wherein
2～C
4Olefine selective is up to 66.1%, and the CO conversion ratio can reach 93.7%.
Embodiment 8 synthesis gas system olefine reactions experiment 2
Above-mentioned example 2 made catalyst B 1ml are seated on the continuous flow fixed bed reactor, adopt reducing condition and the reaction condition identical with above-mentioned example 7, the reaction result of catalyst B sees Table 2.Wherein the CO conversion ratio can reach 83.4%, C
2～C
4Olefine selective reaches 62.1%.
Embodiment 9 synthesis gas system olefine reactions experiment 3
With catalyst C 1ml on continuous flow fixed bed reactor, adopt the reducing condition identical to reduce with example 7 after, at 1.0～5.0MPa, 330 ℃, 800h
-1, CO/H
2Estimate under=1/2 the reaction condition, its reaction result sees Table 3.C wherein
2～C
4Olefine selective is 68.0%, and the CO conversion ratio is 83.3%.
Embodiment 10 synthesis gas system olefine reactions experiment 4
Adopt reducing condition identical and reaction condition CO/H to catalyst D with above-mentioned example 7
2Reactivity worth is estimated, and it the results are shown in Table 4.Wherein the CO conversion ratio reaches 77.3%, C
2～C
4Olefine selective is 64.7%.
Embodiment 11 synthesis gas system olefine reactions experiment 5
With molecular sieve supported type catalyst E after adopting loadings identical and reducing condition to reduce on the fixed-bed reactor with example 7, at 1.0～5.0MPa, 400 ℃, 2000h
-1, CO/H
2Carry out catalytic reaction under=1/2 the reaction condition, it the results are shown in Table 5.Wherein, the CO conversion ratio is up to 69.4%, C
2～C
4Olefine selective is 62.5%.
Embodiment 12 synthesis gas system olefine reactions experiment 6
Catalyst F1ml is seated on the fixed-bed reactor, adopt the reducing condition identical to reduce with example 7 after, at 1.0～5.0MPa, 400 ℃, 1500h
-1, CO/H
2React under=1/2 the condition, it the results are shown in Table 6, and its CO conversion ratio is 72.8%, C
2～C
4Olefine selective is 63.9%.
By above-mentioned example, it is that raw material is directly produced low-carbon alkene that catalyst provided by the invention can be used for by synthesis gas.In reaction pressure is 1.0～5.0MPa, and temperature is under 300～1000 ℃ the reaction condition, but high activity (the CO conversion ratio reaches more than 90%), and high selectivity is produced low-carbon alkene (olefine selective reaches more than 66%).Simultaneously this technical process can be directly by reaction end gas through water absorption and separation CO
2And the oily absorption and separation C of pressure in the warp
3, C
4Component is carried out alkylated reaction with the alkene concentration ethene in benzene and the tail gas then and is produced ethylbenzene.Its operating process is simple, is suitable for applying.
The CO hydrogenation system olefine reaction result of table 1. embodiment 1 catalyst A
| Catalyst | 100MgO∶12Fe ∶9Mn∶6K | 100MgO∶12Fe ∶9Mn∶6K∶4Cs | 100CaO∶10Fe ∶9Mn∶6K∶4Cs | 100SrO∶10Fe ∶9Mn∶6K∶4Cs | 100MgO∶12Fe ∶9Mn∶6K∶4Cs (*) | 100MgO∶15Fe ∶9Mn∶10K (*) |
| The CO conversion ratio | 78.9 | 85.6 | 80.9 | 82.3 | 76.1 | 74.4 |
| The selectivity of hydrocarbon (wt%) | ||||||
| CH4 C2H4 C2H6 C3H6 C3H8 C4H8 C4H10 | 23.3 24.7 3.2 24.5 2.7 19.7 1.9 | 23.2 25.1 4.4 24.3 4.1 17.7 1.2 | 26.5 22.3 3.6 24.2 3.0 18.4 2.0 | 25.9 21.1 4.1 24.7 4.8 17.6 1.8 | 23.1 27.4 2.9 23.1 3.6 17.8 2.1 | 23.0 28.1 3.1 22.4 4.4 16.9 2.1 |
| C2-4 alkene C2-4 alkane | 68.9 7.8 | 67.1 9.7 | 64.9 8.6 | 63.4 10.7 | 68.3 8.6 | 67.4 9.6 |
Reaction condition: 2.0MPa, 350 ℃, 900h
-1, CO/H2=1/2.(*) reaction condition: 1.0MPa, 350 ℃, 1000h
-1, CO/H2=1/1.
The CO hydrogenation system olefine reaction result of table 2. embodiment 2 catalyst B
Reaction condition: 2.0MPa, 330 ℃, 800h
-1, CO/H2=1/2.
| Catalyst | 100MgO∶10Fe ∶8Mn∶12K | 100MgO∶10Fe ∶8Mn∶8K | 100MgO∶10Fe ∶8Mn∶6K | 100MgO∶10Fe ∶8Mn∶6K∶6Cs | 100CaO∶10Fe ∶8Mn∶6K∶6Cs | 100SrO∶10Fe ∶8Mn∶6K∶6Cs |
| The CO conversion ratio | 79.4 | 76.8 | 74.3 | 83.4 | 79.6 | 80.0 |
| The selectivity of hydrocarbon (wt%) | ||||||
| CH4 C2H4 C2H6 C3H6 C3H8 C4H8 C4H10 | 27.2 23.5 7.2 22.1 3.6 15.3 1.1 | 31.9 22.2 4.5 21.4 3.3 15.2 1.5 | 31.0 20.4 8.5 22.6 5.4 10.0 2.1 | 26.4 23.3 6.4 23.1 3.8 15.7 1.3 | 28.1 19.2 3.7 23.7 4.0 19.4 1.9 | 27.4 20.0 4.7 23.0 3.9 18.4 2.6 |
| C2-C4 alkene C2-C4 alkane | 60.9 11.9 | 58.8 9.3 | 53.0 16.0 | 62.1 11.5 | 62.3 9.6 | 61.4 11.2 |
The CO hydrogenation system olefine reaction result of table 3. embodiment 3 catalyst C
| Catalyst | 100MgO∶10Fe ∶7Mn∶6K∶6Cs | 100MgO∶10Fe ∶7Mn∶12K | 100MgO∶10Fe ∶7Mn∶6K | 80MgO∶20Si-2 ∶15Fe∶9Mn ∶6Cs | 60MgO∶40Si-2 ∶12Fe∶8Mn∶6K |
| The CO conversion ratio | 69.4 | 64.3 | 55.4 | 83.3 | 80.2 |
| The selectivity of hydrocarbon (wt%) | |||||
| CH4 C2H4 C2H6 C3H6 C3H8 C4H8 C4H10 | 27.3 23.5 5.0 24.4 4.1 14.4 1.3 | 29.2 21.4 6.1 22.6 3.9 15.4 1.4 | 32.0 19.6 6.9 20.5 4.8 14.6 1.6 | 23.0 28.7 4.1 23.8 3.1 15.5 1.8 | 24.7 26.4 3.7 23.5 3.0 17.4 1.3 |
| C2-C4 alkene C2-C4 alkane | 62.3 10.4 | 59.4 11.4 | 54.7 13.3 | 68.0 9.0 | 67.3 8.0 |
Reaction condition: 2.0MPa, 335 ℃, 1200h
-1, CO/H2=1/2.
The CO hydrogenation system olefine reaction result of table 4. embodiment 4 catalyst D
| Catalyst | 100MgO∶10Fe ∶9Mn∶10K∶5Cl | 100MgO∶10Fe ∶9Mn∶6K∶4Cs ∶1Cl | 100MgO∶10Fe ∶9Mn∶6K∶4Cs ∶2Br | 100MgO∶10Fe ∶9Mn∶9K∶6Br |
| The CO conversion ratio | 76.4 | 77.3 | 64.3 | 64.1 |
| The selectivity of hydrocarbon (wt%) | ||||
| CH4 C2H4 C2H6 C3H6 C3H8 C4H8 C4H10 | 24.8 24.2 5.4 23.0 4.8 16.4 1.4 | 24.5 24.6 4.1 23.5 5.5 16.6 1.2 | 32.6 17.4 7.2 19.5 6.0 15.2 2.1 | 36.2 17.2 6.7 20.8 6.2 11.6 1.3 |
| C2-C4 alkene C2-C4 alkane | 63.6 11.6 | 64.7 10.8 | 52.1 15.3 | 49.6 14.2 |
Reaction condition: 2.0MPA, 360 ℃, 1100h
-1, CO/H2=1/2.
The CO hydrogenation system olefine reaction result of table 5. embodiment 5 catalyst E
| Catalyst | 100Si-2∶10Fe ∶8Mn∶10K | 100Si-1∶10Fe ∶8Mn∶10K | 100Si-2∶10Fe ∶8Mn∶5K∶5Cs | 100Si-1∶10Fe ∶8Mn∶5K∶5Cs | 100APO5∶10Fe ∶8Mn∶5K∶5Cs | 100ZSM-48 ∶10Fe∶8Mn ∶5K∶5Cs | 100ZSM-12 ∶10Mn∶8Mn ∶5K∶5Cs |
| The CO conversion ratio | 70.5 | 47.9 | 73.2 | 52.7 | 68.4 | 63.7 | 65.6 |
| The selectivity of hydrocarbon (wt%) | |||||||
| CH4 C2H4 C2H6 C3H6 C3H8 C4H8 C4H10 | 27.4 24.3 6.6 25.3 1.4 10.9 4.1 | 40.1 17.2 6.2 19.5 1.0 12.4 3.6 | 26.1 25.2 5.7 23.7 1.7 13.6 4.0 | 34.2 20.3 6.0 18.7 2.0 14.6 4.2 | 39.6 21.4 5.1 17.6 1.2 11.4 3.7 | 40.1 17.3 4.7 16.8 1.5 14.6 5.0 | 38.4 18.6 4.7 17.5 0.9 15.6 4.3 |
| C2-C4 alkene C2-4 alkane | 60.5 12.1 | 49.1 10.8 | 62.5 11.4 | 53.6 12.2 | 50.4 10.0 | 48.7 11.2 | 51.7 9.9 |
Reaction condition: 2.0MPA, 400 ℃, 2000h
-1, CO/H2=1/2.
Claims (1)
1. produce low-carbon alkene reaction by synthesis gas and use iron manganese catalyst for one kind, it is characterized in that:
(1) its active component Fe-Mn element is supported on IIA family alkaline earth oxide, on the carrier that silica-rich zeolite molecular sieve, phosphate aluminium molecular sieve or their compound are made; So-called silica-rich zeolite molecular sieve is Silicalite-1, Silicalite-2, and ZSM-12, ZSM-48 molecular sieve, phosphate aluminium molecular sieve are the APO-5 molecular sieve;
(2) cation of interpolation K or Cs element in above-mentioned catalyst, hydroxide or halide are made auxiliary agent;
(3) weight ratio of each component is in the catalyst: (100) carrier: (5～20) Fe: (5～15) Mn: (3～20) K or Cs;
(4) this Preparation of catalysts process is pressed following step:
1. with the carrier extrusion forming;
2. use the alkali or the halide solution dipping carrier that contain the inorganic salts of active component Fe, Mn and contain auxiliary agent K, Cs element;
3. flood the carrier of active component, under 400～750 ℃ of temperature, carry out roasting after drying.
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|---|---|---|---|
| CN92109866A CN1040397C (en) | 1992-09-03 | 1992-09-03 | Iron manganese catalyst for preparation of low carbon olefines by synthetic gas and synthetic reaction |
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|---|---|---|---|
| CN92109866A CN1040397C (en) | 1992-09-03 | 1992-09-03 | Iron manganese catalyst for preparation of low carbon olefines by synthetic gas and synthetic reaction |
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| CN1040397C true CN1040397C (en) | 1998-10-28 |
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| WO2014173229A1 (en) | 2013-04-25 | 2014-10-30 | 武汉凯迪工程技术研究总院有限公司 | Fischer-tropsch synthesis catalyst for syngas to low carbon olefins, modified molecular sieve carrier and preparation method thereof |
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| CN1083415A (en) | 1994-03-09 |
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