CN1040397C - Iron-manganese-containing catalyst for preparing low-carbon olefin from synthesis gas and synthesis reaction - Google Patents
Iron-manganese-containing catalyst for preparing low-carbon olefin from synthesis gas and synthesis reaction Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 28
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 28
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 25
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title claims abstract description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002808 molecular sieve Substances 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010457 zeolite Substances 0.000 claims abstract description 11
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 239000011572 manganese Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 7
- 229910002551 Fe-Mn Inorganic materials 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 18
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 abstract description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 11
- 150000001336 alkenes Chemical class 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003921 oil Substances 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- 239000005977 Ethylene Substances 0.000 abstract description 2
- 229910001417 caesium ion Inorganic materials 0.000 abstract description 2
- -1 ethylene, propylene Chemical group 0.000 abstract description 2
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 37
- 239000000203 mixture Substances 0.000 description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000010412 oxide-supported catalyst Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000320 mechanical mixture Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910007572 Zn-K Inorganic materials 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000015895 biscuits Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- YOPUATYREUZXIO-UHFFFAOYSA-N copper;methanol Chemical compound [Cu].OC YOPUATYREUZXIO-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011234 economic evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
From synthesis gas (CO + H)2) The catalyst for high-selectivity preparation of low-carbon olefin (such as ethylene, propylene, etc.) is an iron-manganese catalyst system carried by alkaline earth metal oxide of IIA group (such as MgO, etc.) or high-silicon zeolite molecular sieve (or phosphorus-aluminium zeolite), and is added in strong base (IA group metal) K+Or the Cs ion auxiliary agent has good performance of synthesizing low-carbon olefin, and the catalyst can be used for preparing the low-carbon olefin from the synthesis gas with high activity (the CO conversion rate is more than 90%) and high selectivity (the olefin selectivity is more than 66%) under the reaction conditions that the pressure is 1.0-5.0 MPa and the temperature is 300-400 ℃. The process flow of the invention can directly separate CO from the reaction tail gas through water absorption2And separating C by medium pressure oil absorption3、C4And then, reacting benzene with the ethylene with the alkene concentration in the tail gas to produce ethylbenzene. The operation process is simple 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-containing catalyst for preparing low-carbon olefin from synthesis gas and synthesis reaction |
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