CN104056627A - Catalyst for preparing low carbon olefin from synthetic gas and application thereof in Fischer-Tropsch reaction - Google Patents
Catalyst for preparing low carbon olefin from synthetic gas and application thereof in Fischer-Tropsch reaction Download PDFInfo
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- CN104056627A CN104056627A CN201310093228.5A CN201310093228A CN104056627A CN 104056627 A CN104056627 A CN 104056627A CN 201310093228 A CN201310093228 A CN 201310093228A CN 104056627 A CN104056627 A CN 104056627A
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Abstract
The invention discloses a preparation method of a catalyst for highly-selectively preparing low carbon olefin from synthetic gas. The method of the invention adopts an inert iron source precursor and an inert catalyst carrier, directly loads the carrier with the inert iron source, and thus obtains a catalyst with weak interaction between metal and the carrier. The catalyst is applicable to Fischer-Tropsch synthesis reaction, realizes highly-selective conversion of synthetic gas into low carbon olefin, can well inhibit the generation of methane, is simple in preparation method, and has very good application prospects.
Description
Technical field
The present invention relates to a kind of preparation of fischer-tropsch synthetic catalyst, being exactly specifically the source of iron of utilizing a kind of relative inertness loads on the fischer-tropsch catalysts of preparing high selectivity on the carrier of inertia and generate low-carbon alkene for presoma.
Background technology
Fischer-Tropsch(Fischer-Tropsch) synthetic be the important channel that obtains hydro carbons taking coal, natural gas and living beings as raw material, in the hydro carbons of gained, how the acquisition low-carbon alkene of high selectivity is a very important research direction in recent years.Directly obtain low-carbon alkene and not only can alleviate oil exhaustion and cause the present situation of low-carbon alkene raw materials for production shortage by synthesis gas, and with respect to the MTO process of rising at present, do not need through this step of synthesizing methanol, there is simpler technical process, thereby be of great immediate significance.But the synthetic product of Fischer-Tropsch is followed ASF and distributed, product is distributed in very wide carbon number range, only has methane and wax to have higher selective.Suppress methane and C
5+selective by the C that is controlled at of product high selectivity
2～C
4the scope of alkene remains a huge challenge of Fischer-Tropsch study on the synthesis.The body phase ferrum-based catalyst of having reported elements such as containing zinc, titanium, potassium in one section of Deutsche Bundespatent (DE2536488) of 1976 has well selective in preparation of low carbon olefines by synthetic gas, low-carbon alkene selectively reach 80%, methane selectively is nearly 10%, but this result does not obtain repetition.The catalyst of carbon load prepared by the presoma of the element such as Fe, Mn, K of the employings such as Venter can obtain 70% selectivity of light olefin under condition of normal pressure, but CO conversion ratio under this pressure condition is less than 1% conventionally.The research recently with breakthrough is report (Science, 2012,335, the 835-838 such as Dutch De jong; EP2314557A1) taking ferric citrate as presoma on carbon fiber and alpha-aluminium oxide the ferrum-based catalyst of load C in preparation of low carbon olefines by synthetic gas reaction
2～C
4alkene than weighing more than 50%, needs 25% iron load capacity and will obtain this result on alpha-aluminium oxide in hydrocarbon product.
Prepare fischer-tropsch catalysts taking the ferrous ammonium cyanide of relative inertness as presoma and have patent and reported in literature as far back as the eighties.One section of United States Patent (USP) (US4186112) of 1980 reported with the transition metal cyano compound precipitation method prepare a series of catalyst be applied to synthesis gas transform preparation C
1-C
4hydro carbons; Nineteen eighty-two one section of United States Patent (USP) (US4347164) has been reported molecular sieve carried transition metal cyano compound and has been applied to synthesis gas conversion reaction.One section of European patent (EP0447005A2) of 1991 reported transition metal cyano compound under oxidizing atmosphere, process be applied to synthesis gas transform and hydrodesulfurization; To sum up some patent reports mainly concentrate on the dispersion in multicomponent metal system and activated centre, and carrier concentrates on molecular sieve, silica and aluminium oxide.On silica and alumina support, iron is easy to and silicon or aluminium generation strong interaction, to such an extent as to gained catalyst is in preparation of low carbon olefines by synthetic gas reaction and fail effectively to suppress the generation of methane.On the carrier such as activated carbon, carbon black and carborundum of comparison inertia, be applied to preparation of low carbon olefines by synthetic gas and do not have document and patent report and load on for the ferrous ammonium cyanide of one-component inertia.
Summary of the invention
The present invention relates to a kind of simple, realize the preparation method of the iron-base fischer-tropsch catalyst of high-low carbon olefine selective, weak interaction (inertia source of iron loads on inert carrier), and apply in fischer-tropsch reaction.
Catalyst of the present invention is the preparation method of the ferrum-based catalyst of weak interaction, it is characterized in that, presoma prepared by described catalyst is inertia presoma: ferrous potassium cyanate, ferrocyanic acid ammonium, potassium ferricyanate, the one wherein such as fewrricyanic acid ammonium.
Described catalyst is the preparation method of the ferrum-based catalyst of weak interaction, it is characterized in that, the carrier of described catalyst is inert carrier: active carbon, carbon black, carborundum, zirconium dioxide, magnesia etc.
Described catalyst is the preparation method of the ferrum-based catalyst of weak interaction, it is characterized in that, preparation process comprises the preprocessing process of a carrier, comprises the passivation of carrier surface or functionalized, use acid as: hydrochloric acid, nitric acid, hydrofluoric acid, sulfuric acid; Use oxidant as oxygen, hydrogen peroxide.
Described catalyst is the preparation method of the ferrum-based catalyst of weak interaction, it is characterized in that, preparation method mainly comprises: infusion process, co-impregnation, the one wherein such as coprecipitation.
Described catalyst is the preparation method of the ferrum-based catalyst of weak interaction, it is characterized in that, preparation process comprises a drying course, and bake out temperature is 20～200 DEG C, time 1～24h, and pressure is 10～1 × 105Pa.
The application of the ferrum-based catalyst of weak interaction of the present invention in fischer-tropsch reaction, is characterized in that, this catalyst also comprises an original position preprocessing process.
The original position preprocessing process of the ferrum-based catalyst of described weak interaction, is characterized in that, Pretreatment atmosphere is argon gas, hydrogen, and helium or airborne one, pretreatment temperature is 200～700 DEG C, the time is 2～12h, 2 °/min of temperature programming speed.
The application of the ferrum-based catalyst of weak interaction of the present invention in fischer-tropsch reaction, is characterized in that, described CO and H
2ratio (CO/H
2) be 0.5～4 (mol ratio), preferably CO/H
2=0.5～2.
The application of the ferrum-based catalyst of described weak interaction in fischer-tropsch reaction, is characterized in that, 200～400 DEG C of reaction temperatures, preferably 320～380 DEG C; Reaction pressure 0.1～4Mpa, preferably 0.1～2Mpa; Air speed is 1000～40000h
-1, preferably 2000～15000h
-1.
Preparation method of the present invention comprises the steps:
Inertia source of iron presoma is mixed with to the certain density aqueous solution, the carrier of surface preparation is dried in certain temperature, after its cool to room temperature, the source of iron solution preparing is joined in above-mentioned carrier with the method for incipient impregnation, after stirring, dry under certain temperature and pressure.Make catalyst: wherein in catalyst, the mass percent of iron is 5%～20%.Fig. 1 is the XRD spectra after the iron catalyst of carbon black loadings 9.6% reduces.
The application conditions of catalyst of the present invention is: utilize pure H2 300～500 DEG C of in-situ reducing, reaction temperature is at 300～400 DEG C, reaction pressure 0.1～2Mpa, air speed 1000～20000h
-1, unstripped gas proportioning is H
2/ CO=1.
The present invention relates to a kind of simple, preparation method of realizing the iron-base fischer-tropsch catalyst of high-low carbon olefine selective, weak interaction, and application in fischer-tropsch reaction.The weak interaction here refers to the weak interaction between iron and carrier.
Advantage of the present invention is as follows:
Prepare aspect from catalyst: this catalytic component is single, and preparation method is simple, easy operating.
From fischer-tropsch reaction aspect: this catalyst selectivity of light olefin is high, well suppresses the generation of methane, has good machinery and chemical stability.
Brief description of the drawings
Fig. 1 is the XRD figure of sample.
Detailed description of the invention
Be described in further detail for whole process below by embodiment, but claim scope of the present invention is not subject to the restriction of these embodiment.Meanwhile, embodiment has just provided the partial condition of realizing this object, but and does not mean that must meet these conditions just can reach this object.
1. the ferrum-based catalyst catalyst of weak interaction preparation
Embodiment 1
Get the active carbon of 0.978g at 110 DEG C of baking 12h, (the NH that is 7wt% by 1.62g iron-holder
4)
4fe (CN)
6the aqueous solution joins in active carbon, stirs, and after room temperature vacuum drying 24h, catalyst is sieved at 6MPa compressing tablet, gets 40～60 object samples, obtains iron carrying capacity and be 11.6% AC1 catalyst.
Embodiment 2
By 5g carbon black in the hydrogen peroxide of 50ml15% 100 DEG C process 7h, washing suction filtration, after in 110 DEG C of baking ovens, dry.Get the carbon black of the above-mentioned oven dry of 0.315g, (the NH that is 7wt% by 0.375ml iron-holder
4)
4fe (CN)
6after aqueous solution dilution, incipient impregnation joins in carbon black at twice, room temperature vacuum drying 4h after at every turn stirring.Gained catalyst is sieved at 6MPa compressing tablet, get 40～60 object samples, obtain iron carrying capacity and be 9.6% BC1 catalyst.This catalyst is after hydrogen reducing, and the XRD of sample as shown in Figure 1.
Embodiment 3
Get the carbon black of 0.304g with above-mentioned processing, (the NH that is 7wt% by 0.525ml iron-holder
4)
4fe (CN)
6after the aqueous solution is diluted with water, equal-volume joins in carbon black at twice, room temperature vacuum drying 4h after at every turn stirring.Gained catalyst is sieved at 6MPa compressing tablet, get 40～60 order samples, obtain iron carrying capacity and be 13.9% BC2 catalyst.
Embodiment 4
Get the α carborundum that 1.0g is dried in 110 DEG C of baking ovens, (the NH that is 7wt% by 1.6ml iron-holder
4)
4fe (CN)
6the aqueous solution divides three equal-volumes to be impregnated in carborundum, front twice room temperature vacuum drying 4h, for the last time dry 12h.Catalyst is sieved at 6MPa compressing tablet, get 40～60 order samples, obtain iron carrying capacity and be 12.9% SC1 catalyst.
Embodiment 5
Get the α carborundum of the same processing of 1.0g, (the NH that is 7wt% by 2.5ml iron-holder
4)
4fe (CN)
6the aqueous solution divides five equal-volumes to be impregnated in carborundum, front twice room temperature vacuum drying 4h, last three dry 12h.Catalyst is sieved at 6MPa compressing tablet, get 40～60 order samples, obtain iron carrying capacity and be 20% SC2 catalyst.
2. the application of the ferrum-based catalyst of weak interaction in fischer-tropsch reaction
The example that responds all carries out in continuous-flow micro-reaction device, and this device is equipped with mass-flow gas meter and online product analysis chromatogram.Except specified otherwise, reaction gas is by 47.5vol.%H2 and 47.5vol.%CO composition, and Ar is as interior gas.Online product analysis uses Agilent7890A gas-chromatography, adopt one ten logical sample valve and two six direction changeover valves to realize full product analysis, wherein fid detector outfit FFAP post and the series connection of Plot Al2O3 post are switched respectively oxygenatedchemicals and hydro carbons are analyzed by six-way valve; TCD detector is equipped with Porapark Q post and 5A molecular sieve packed column series connection Analysis for CO
2, CO, Ar, CH4, carry out each product containing quantitative analysis with methane as the bridge between TCD and FID.
Embodiment 6
The catalytic evaluation of AC1 catalyst is tested in fixed bed reactor, with pure H
22 °/min is warmed up to 400 DEG C of reduction 12h, cools to 280 DEG C and passes into CO/H
2=1 synthesis gas, 0.5Mpa, air speed 15000h
-1, go out to react pipeline at 150 DEG C of constant temperature, detect all products of collecting.Be warmed up to 320 DEG C of reactions, result is as shown in table 1.
Embodiment 7
Catalyst B C1 is mixed taking volume ratio as 1:2 with the SiC with close particle diameter, and catalytic evaluation is tested in fixed bed reactor, with pure H
22 °/min is warmed up to 400 DEG C of reduction 12h, cools to 280 DEG C and passes into CO/H
2=1 synthesis gas, 0.5Mpa, air speed 10000h
-1, go out reaction tube in 150 DEG C of constant temperature, detect all products of collecting.Be warmed up to 360 DEG C of reactions, result is as shown in table 1.
Embodiment 8
Catalyst B C2 is mixed taking volume ratio as 1:2 with the SiC with close particle diameter, and catalytic evaluation is tested in fixed bed reactor, with pure H
22 °/min is warmed up to 400 DEG C of reduction 12h, cools to 280 DEG C and passes into CO/H
2=1 synthesis gas, 0.3Mpa, air speed 10000h
-1, go out reaction tube in 150 DEG C of constant temperature, detect all products of collecting.Be warmed up to 370 DEG C of reactions, result is as shown in table 1.
Embodiment 9
The catalytic evaluation of SC1 catalyst is tested in fixed bed reactor, with pure H
22 °/min is warmed up to 400 DEG C of reduction 12h, cools to 300 DEG C and passes into CO/H
2=1 synthesis gas, 0.5Mpa, air speed 5000h
-1, go out reaction tube in 150 DEG C of constant temperature, detect all products of collecting.Be warmed up to 340 DEG C of reactions, result is as shown in table 1.
Embodiment 10
The catalytic evaluation of SC2 catalyst is tested in fixed bed reactor, with pure H
22 °/min is warmed up to 400 DEG C of reduction 12h, cools to 300 DEG C and passes into CO/H
2=1 synthesis gas, 1.0Mpa, air speed 5000h
-1, go out reaction tube in 150 DEG C of constant temperature, detect all products of collecting.Be warmed up to 360 DEG C of reactions, result is as shown in table 1.
Table 1
* air speed: 5000h
-1;
#pressure: 1Mpa.
As can be seen from Table 1 under higher reaction temperature, all catalyst C
2 =-C
4 =selectively all up to more than 50%, and C
2 =-C
4=/C
2 0-C
4 0be greater than 8, be less than 20% taking carbon black and active carbon as the selective methane selectively of catalyst methane of the carrier of carrier, these catalyst all show good potential application foreground.
Claims (10)
1. a preparation of low carbon olefines by synthetic gas catalyst, is characterized in that:
It is ferrum-based catalyst, and in catalyst, the quality carrying capacity of iron is 5%～20%;
Adopt infusion process, co-impregnation or coprecipitation to prepare;
The presoma that its preparation process adopts is inertia presoma: ferrous potassium cyanate, ferrocyanic acid sodium, ferrocyanic acid ammonium, potassium ferricyanate, one or two or more kinds in fewrricyanic acid ammonium;
The carrier adopting is inert carrier, comprises active carbon, carbon black, carborundum, zirconium dioxide, one or two or more kinds in magnesia.
2. catalyst as claimed in claim 1, is characterized in that:
One of concrete preparation process is following:
Infusion process, is mixed with solution by one of described source of iron, is impregnated on described carrier with equal-volume or excess volume;
Co-impregnation, is mixed with solution by described two kinds or above source of iron presoma, is impregnated on described carrier with equal-volume or excess volume;
Coprecipitation, is mixed with solution by described a kind of or two kinds and above source of iron presoma, and described carrier is distributed in above-mentioned solution, add second component metallic solution, as ferric nitrate, ferric sulfate, iron chloride, manganese nitrate, one or two or more kinds in the solution such as manganese acetate carried out co-precipitation; Last suction filtration obtains the catalyst of fresh preparation.
3. catalyst as claimed in claim 1 or 2, is characterized in that:
Described carrier is pretreated carrier;
The preprocessing process of carrier, comprises the passivation of carrier surface and/or functionalized;
The acid that wherein passivation is used is as hydrochloric acid, nitric acid, hydrofluoric acid or sulfuric acid; By described carrier 20～120 DEG C of processing 1～8h in above-mentioned sour acid solution;
The oxidant of functionalized use is as oxygen, air, hydrogen peroxide, nitric acid; By described carrier 200～500 DEG C of processing 1～4h in described gaseous oxidant, gas space velocity is 500～10000h
- 1; Described carrier is distributed in described liquid oxidizer and is processed, and treatment temperature is 20～150 DEG C, and the processing time is 0.5～8h.
4. catalyst as claimed in claim 2, is characterized in that:
Drying course, bake out temperature is 20～200 DEG C, time 1～24h, pressure is 10～1 × 10
5pa.
5. the application of catalyst in fischer-tropsch reaction described in a claim 1.
6. application as claimed in claim 5, is characterized in that: this catalyst also comprises an original position preprocessing process before application;
Pretreatment atmosphere is argon gas, hydrogen, helium or airborne one;
Pretreatment temperature is 200～700 DEG C, and the time is 2～12h, and temperature programming is warmed up to pretreatment temperature, 2 °/min of speed from 20 DEG C.
7. the application as described in claim 5 or 6, is characterized in that: material synthesis gas CO and H
2mol ratio (CO/H
2) be 0.1～4, preferably CO/H
2=0.5～2.
8. the application as described in claim 5 or 6, is characterized in that: 200～400 DEG C of reaction temperatures, preferably 320～380 DEG C.
9. the application as described in claim 5 or 6, is characterized in that: reaction pressure 0.1～4Mpa, preferably 0.1～2Mpa.
10. the application as described in claim 5 or 6, is characterized in that: unstripped gas air speed is 1000～40000h
-1, preferably 2000～15000h
-1.
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| CN104785263A (en) * | 2015-03-18 | 2015-07-22 | 华东理工大学 | Loaded type iron-based catalyst, and preparation method and application thereof |
| WO2017000427A1 (en) * | 2015-07-02 | 2017-01-05 | 中国科学院大连化学物理研究所 | Catalyst and method of preparing light olefin directly from synthesis gas by one-step process |
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| 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 |
| CN109865515A (en) * | 2017-12-04 | 2019-06-11 | 中国科学院大连化学物理研究所 | A kind of synthesis gas producing linear alpha-olefin catalyst and its preparation and application |
| CN111889120A (en) * | 2019-05-05 | 2020-11-06 | 中国科学技术大学 | Fe core-shell nano catalyst, preparation method and application thereof |
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| CN113926478A (en) * | 2020-06-29 | 2022-01-14 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin by Fischer-Tropsch synthesis and preparation method and application thereof |
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| CN104785263A (en) * | 2015-03-18 | 2015-07-22 | 华东理工大学 | Loaded type iron-based catalyst, and preparation method and application thereof |
| RU2706241C2 (en) * | 2015-07-02 | 2019-11-15 | Далянь Инститьют Оф Кемикал Физикс, Чайниз Академи Оф Сайенсез | Catalyst and method of producing light olefins directly from synthesis gas as result of single-step process |
| WO2017000427A1 (en) * | 2015-07-02 | 2017-01-05 | 中国科学院大连化学物理研究所 | Catalyst and method of preparing light olefin directly from synthesis gas by one-step process |
| 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 |
| JP2018520862A (en) * | 2015-07-02 | 2018-08-02 | 中国科学院大▲連▼化学物理研究所Ｄａｌｉａｎ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｃｈｅｍｉｃａｌ Ｐｈｙｓｉｃｓ，Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ | Catalyst and process for the direct preparation of light olefins from synthesis gas by a 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 |
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| 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 |
| CN109865515A (en) * | 2017-12-04 | 2019-06-11 | 中国科学院大连化学物理研究所 | A kind of synthesis gas producing linear alpha-olefin catalyst and its preparation and application |
| CN113453798A (en) * | 2019-02-28 | 2021-09-28 | 埃克森美孚化学专利公司 | Catalyst composition and precursor, process for preparing the same and process for converting synthesis gas |
| CN111889120A (en) * | 2019-05-05 | 2020-11-06 | 中国科学技术大学 | Fe core-shell nano catalyst, preparation method and application thereof |
| CN111889120B (en) * | 2019-05-05 | 2023-04-21 | 中国科学技术大学 | Fe core-shell nano catalyst, and preparation method and application thereof |
| CN113926478A (en) * | 2020-06-29 | 2022-01-14 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin by Fischer-Tropsch synthesis and preparation method and application thereof |
| CN113926478B (en) * | 2020-06-29 | 2024-01-09 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin by Fischer-Tropsch synthesis, and preparation method and application thereof |
| CN113996301A (en) * | 2020-07-28 | 2022-02-01 | 中国科学院大连化学物理研究所 | Carbon material-supported cobalt-based catalyst and preparation and application thereof |
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