CN104056627B - A kind of preparation of low carbon olefines by synthetic gas catalyst and the application in fischer-tropsch reaction thereof - Google Patents
A kind of preparation of low carbon olefines by synthetic gas catalyst and the application in fischer-tropsch reaction thereof Download PDFInfo
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Abstract
The invention discloses a kind of preparation method being selectively produced light olefins catalyst by synthesis upward adverse flow of QI.The present invention utilizes inertia source of iron presoma and inert catalyst carrier, inertia source of iron is directly loaded on carrier, and the method has obtained the catalyst of metal and carrier weak interaction.This catalyst is applied to Fischer-Tropsch synthesis, it is achieved that synthesis upward adverse flow of QI selective conversion generation low-carbon alkene, and can preferably suppress the generation of methane, and preparation method is simple, has good application prospect.
Description
Technical field
The present invention relates to the preparation of a kind of fischer-tropsch synthetic catalyst, utilize the source of iron of a kind of relative inertness the most exactly
It is supported on inert carrier preparation height for presoma and selectively produces the fischer-tropsch catalysts of low-carbon alkene.
Background technology
Fischer-Tropsch(Fischer-Tropsch) synthesis be with coal, natural gas and biomass be raw material obtain hydro carbons important way
Footpath, in the hydro carbons of gained, the highest selective acquisition low-carbon alkene is a highly important research direction in recent years.By
Synthesis gas directly obtain low-carbon alkene be possible not only to alleviate oil exhaustion cause low-carbon alkene raw materials for production shortage present situation, and
Relative to the MTO process currently risen, it is not required to through synthesizing methanol the step for, there is simpler technique mistake
Journey, thus be of great immediate significance.But, the product of F-T synthesis follows ASF distribution, and products distribution is at the widest carbon number
Scope, only methane and wax have higher selectivity.Suppression methane and C5+Selectivity product height is optionally controlled
C2～C4The scope of alkene remains a huge challenge of F-T synthesis research.One Deutsche Bundespatent of 1976
(DE2536488) reported in, the body phase ferrum-based catalyst containing elements such as zinc, titanium, potassium has very in preparation of low carbon olefines by synthetic gas
Good selectivity, the selectivity of low-carbon alkene reaches 80%, methane selectively nearly 10%, but this result is not repeated.
The catalyst of carbon load prepared by the presoma of the elements such as Fe, Mn, K that Venter etc. use can obtain in atmospheric conditions
The selectivity of light olefin of 70%, but the CO conversion ratio under this pressure condition is typically smaller than 1%.There is breakthrough recently
Research be Holland De jong etc. report (Science, 2012,335,835-838;EP2314557A1) with ferric ammonium citrate
The ferrum-based catalyst C in preparation of low carbon olefines by synthetic gas reacts loaded on carbon fiber and alpha-aluminium oxide for presoma2～C4Alkene
Than weighing more than 50% in hydrocarbon product, and on alpha-aluminium oxide, to obtain this result need the ferrum load capacity of 25%.
Prepare fischer-tropsch catalysts with the ferrous ammonium cyanide of relative inertness for presoma and have patent and document as far back as the eighties
Report.A United States Patent (USP) (US4186112) in 1980 has been reported and has been prepared one by the transition metal cyano compound sedimentation method
Catalyst series is applied to synthesis gas and converts preparation C1-C4Hydro carbons；Nineteen eighty-two, one United States Patent (USP) (US4347164) was reported
Molecular sieve carried transition metal cyano compound is applied to synthesis gas conversion reaction.One European patent of 1991
(EP0447005A2) reported transition metal cyano compound to process under oxidizing atmosphere and be applied to synthesis gas and convert and hydrogenation is de-
Sulfur process；To sum up some patents report focuses primarily upon the dispersion in multicomponent metal system and active center, and carrier is concentrated
In molecular sieve, silicon dioxide and aluminium oxide.On silicon dioxide and alumina support, ferrum is prone to and silicon or aluminum generation strong interaction,
To such an extent as to gained catalyst fails to effectively suppress the generation of methane in preparation of low carbon olefines by synthetic gas reacts.And for single
The inert ferrous ammonium cyanide of component is supported on the carriers such as the inert activated carbon of comparison, white carbon black and carborundum and is applied to synthesis gas system
Low-carbon alkene does not have document and patent report.
Summary of the invention
The present invention relates to a kind of simple, realize high-low carbon olefine selective, (inertia source of iron is supported on inertia to weak interaction
On carrier) the preparation method of iron-base fischer-tropsch catalyst, 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 characterised in that described
Presoma prepared by catalyst is inertia presoma: ferrous potassium cyanate, ferrocyanic acid ammonium, potassium ferricyanate, and fewrricyanic acid ammonium etc. is wherein
One.
Described catalyst is the preparation method of the ferrum-based catalyst of weak interaction, it is characterised in that described catalyst
Carrier be inert carrier: activated carbon, white carbon black, carborundum, zirconium dioxide, magnesium oxide etc..
Described catalyst is the preparation method of the ferrum-based catalyst of weak interaction, it is characterised in that preparation process bag
Include the preprocessing process of a carrier, including passivation or the functionalization of carrier surface, use acid such as: hydrochloric acid, nitric acid, Fluohydric acid.,
Sulphuric acid；Use oxidant such as: oxygen, hydrogen peroxide.
Described catalyst is the preparation method of the ferrum-based catalyst of weak interaction, it is characterised in that preparation method master
Including: infusion process, co-impregnation, the one therein such as coprecipitation.
Described catalyst is the preparation method of the ferrum-based catalyst of weak interaction, it is characterised in that preparation process bag
Including a drying course, drying temperature is 20～200 DEG C, and the time 1～24h, pressure is 10～1 × 105Pa.
The ferrum-based catalyst of weak interaction of the present invention application in fischer-tropsch reaction, it is characterised in that this is urged
Agent also includes an in situ pretreatment process.
The in situ pretreatment process of the ferrum-based catalyst of described weak interaction, it is characterised in that Pretreatment atmosphere is
One in argon, hydrogen, helium or air, pretreatment temperature is 200～700 DEG C, and the time is 2～12h, programmed rate
2°/min。
The ferrum-based catalyst of weak interaction of the present invention application in fischer-tropsch reaction, it is characterised in that described
CO and H2Ratio (CO/H2) it is 0.5～4 (mol ratio), preferably CO/H2=0.5～2.
The ferrum-based catalyst of described weak interaction application in fischer-tropsch reaction, it is characterised in that reaction temperature 200
～400 DEG C, preferably 320～380 DEG C；Reaction pressure 0.1～4Mpa, preferably 0.1～2Mpa；Air speed is 1000～40000h-1, excellent
Select 2000～15000h-1。
The preparation method of the present invention comprises the steps:
Inertia source of iron presoma is configured to certain density aqueous solution, by the carrier of surface preparation in certain temperature
Dry, after it is cooled to room temperature, the source of iron solution prepared is joined in above-mentioned carrier with the method for incipient impregnation, stirs
After mixing uniformly, it is dried under certain temperature and pressure.I.e. prepare catalyst: wherein in catalyst, the mass percent of ferrum is 5%
～20%.Fig. 1 is the XRD spectra after the iron catalyst reduction of carbon black loadings 9.6%.
The application conditions of catalyst of the present invention is: utilize pure H2 300～500 DEG C of in-situ reducing, reaction temperature 300～
400 DEG C, reaction pressure 0.1～2Mpa, air speed 1000～20000h-1, unstripped gas proportioning is H2/CO=1。
The present invention relates to a kind of simple, realize the iron-base fischer-tropsch catalyst of high-low carbon olefine selective, weak interaction
Preparation method, and the application in fischer-tropsch reaction.Here weak interaction refers to the weak interaction between ferrum and carrier.
Advantages of the present invention is as follows:
In terms of prepared by catalyst: this catalytic component is single, and preparation method is simple, it is easy to operation.
In terms of fischer-tropsch reaction: this catalyst selectivity of light olefin is high, well suppress the generation of methane, have well
Mechanically and chemically stability.
Accompanying drawing explanation
Fig. 1 is the XRD figure of sample.
Detailed description of the invention
Below by embodiment, whole process is described in further detail, but scope of the presently claimed invention is not subject to
The restriction of these embodiments.Meanwhile, embodiment has been merely given as realizing the partial condition of this purpose, but is not meant to expire
These conditions of foot just can reach this purpose.
1. prepared by the ferrum-based catalyst catalyst of weak interaction
Embodiment 1
Take 0.978g and dry the activated carbon of 12h at 110 DEG C, be (the NH of 7wt% by 1.62g iron-holder4)4Fe(CN)6Aqueous solution
Join in activated carbon, stir, after room temperature in vacuo is dried 24h, catalyst is sieved at 6MPa tabletting, take 40～60 purposes
Sample, obtains the AC1 catalyst that ferrum carrying capacity is 11.6%.
Embodiment 2
By 5g white carbon black in the hydrogen peroxide of 50ml15% 100 DEG C process 7h, wash sucking filtration, after in 110 DEG C of baking ovens dry.
Take the white carbon black of the above-mentioned drying of 0.315g, be (the NH of 7wt% by 0.375ml iron-holder4)4Fe(CN)6After aqueous solution dilution at twice
Incipient impregnation joins in white carbon black, room temperature vacuum drying 4h after every time stirring.By gained catalyst in 6MPa tabletting mistake
Sieve, takes the sample of 40～60 mesh, obtains the BC1 catalyst that ferrum carrying capacity is 9.6%.This catalyst after hydrogen reducing, sample
XRD is as shown in Figure 1.
Embodiment 3
Take the 0.304g white carbon black with above-mentioned process, be (the NH of 7wt% by 0.525ml iron-holder4)4Fe(CN)6Aqueous solution adds
During after water dilution, equal-volume joins white carbon black at twice, room temperature vacuum drying 4h after every time stirring.Gained catalyst is existed
6MPa tabletting sieves, and takes 40～60 mesh samples, obtains the BC2 catalyst that ferrum carrying capacity is 13.9%.
Embodiment 4
Take the α carborundum that 1.0g is dried in 110 DEG C of baking ovens, be (the NH of 7wt% by 1.6ml iron-holder4)4Fe(CN)6Water
Solution incipient impregnation in three times is in carborundum, and front twice room temperature in vacuo is dried 4h, is dried 12h for the last time.By catalyst
Sieve at 6MPa tabletting, take 40～60 mesh samples, obtain the SC1 catalyst that ferrum carrying capacity is 12.9%.
Embodiment 5
Take the α carborundum that 1.0g ibid processes, be (the NH of 7wt% by 2.5ml iron-holder4)4Fe(CN)6Aqueous solution is in five times
Incipient impregnation is in carborundum, and front twice room temperature in vacuo is dried 4h, last three dry 12h.By catalyst at 6MPa tabletting
Sieve, take 40～60 mesh samples, obtain the SC2 catalyst that ferrum carrying capacity is 20%.
2. the ferrum-based catalyst of weak interaction application in fischer-tropsch reaction
Responded example is all carried out in continuously flowing micro-reaction device, this device be equipped with mass-flow gas meter and
Online product analysis chromatograph.In addition to specified otherwise, reaction gas is formed by 47.5vol.%H2 and 47.5vol.%CO, Ar conduct
Interior gas.Online product analysis uses Agilent7890A gas chromatogram, uses one ten logical sampling valve and two clematis stem switchings
Valve realizes full product analysis, and wherein fid detector is equipped with FFAP post and Plot Al2O3 post is connected in series through six-way valve switching point
Other oxygenatedchemicals and hydro carbons are analyzed；TCD detector is equipped with Porapark Q post and the series connection point of 5A molecular sieve packed column
Analysis CO2, CO, Ar, CH4, carry out the analysis of each product assay as the bridge between TCD and FID with methane.
Embodiment 6
The catalytic evaluation of AC1 catalyst is tested in fixed bed reactor, with pure H22 °/min is warmed up to 400 DEG C also
Former 12h, cools to 280 DEG C and is passed through CO/H2The synthesis gas of=1,0.5Mpa, air speed 15000h-1, go out to react pipeline 150 DEG C of perseverances
Temperature, detects all products collected.Being warmed up to 320 DEG C of reactions, result is as shown in table 1.
Embodiment 7
Being mixed with volume ratio for 1:2 by catalyst BC1 and the SiC with close particle diameter, catalytic evaluation experiment presses solidly adding
In fixed bed reactor, with pure H22 °/min is warmed up to 400 DEG C of reduction 12h, cools to 280 DEG C and is passed through CO/H2The synthesis gas of=1,
0.5Mpa, air speed 10000h-1, go out reaction tube in 150 DEG C of constant temperature, detect all products collected.It is warmed up to 360 DEG C of reactions,
Result is as shown in table 1.
Embodiment 8
Being mixed with volume ratio for 1:2 by catalyst BC2 and the SiC with close particle diameter, catalytic evaluation experiment presses solidly adding
In fixed bed reactor, with pure H22 °/min is warmed up to 400 DEG C of reduction 12h, cools to 280 DEG C and is passed through CO/H2The synthesis gas of=1,
0.3Mpa, air speed 10000h-1, go out reaction tube in 150 DEG C of constant temperature, detect all products collected.It is 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 H22 °/min is warmed up to 400 DEG C also
Former 12h, cools to 300 DEG C and is passed through CO/H2The synthesis gas of=1,0.5Mpa, air speed 5000h-1, go out reaction tube in 150 DEG C of constant temperature, inspection
Survey all products collected.Being 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 H22 °/min is warmed up to 400 DEG C also
Former 12h, cools to 300 DEG C and is passed through CO/H2The synthesis gas of=1,1.0Mpa, air speed 5000h-1, go out reaction tube in 150 DEG C of constant temperature, inspection
Survey all products collected.Being warmed up to 360 DEG C of reactions, result is as shown in table 1.
Table 1
* air speed: 5000h-1；#Pressure: 1Mpa.
The most in high reaction temperatures, all catalyst C2 =-C4 =Selectivity is all up to more than 50%,
And C2 =-C4=/C2 0-C4 0More than 8, with white carbon black and activated carbon, the catalyst methane selectivity methane selectively of the carrier as carrier is little
In 20%, these catalyst all show good potential application foreground.
Claims (12)
1. a preparation of low carbon olefines by synthetic gas catalyst, it is characterised in that:
It is ferrum-based catalyst, and in catalyst, the quality carrying capacity of ferrum is 5%～20%；
Infusion process, co-impregnation or coprecipitation is used to prepare；
The presoma that its preparation process uses is inertia presoma: ferrous potassium cyanate, ferrocyanic acid sodium, ferrocyanic acid ammonium, ferrum cyanogen
Acid potassium, one or two or more kinds in fewrricyanic acid ammonium；
The carrier used is inert carrier, including activated carbon, white carbon black, carborundum, zirconium dioxide, the one in magnesium oxide or two kinds
Above, described carrier is pretreated carrier；
The preprocessing process of carrier, including passivation and/or the functionalization of carrier surface；
Wherein being passivated the acid of use, acid is hydrochloric acid, nitric acid, Fluohydric acid. or sulphuric acid；By described carrier in above-mentioned acid solution
20～120 DEG C process 1～8h；
The oxidant that functionalization uses, oxidant is oxygen, air, hydrogen peroxide, nitric acid；By described carrier at described gas
In body oxidant, 200～500 DEG C process 1～4h, and gas space velocity is 500～10000h-1；By described support dispersion to described
Processing in liquid oxidizer, treatment temperature is 20～150 DEG C, and the process time is 0.5～8h.
2. catalyst as claimed in claim 1, it is characterised in that:
One of concrete preparation process is following:
Infusion process, is configured to solution by one of described source of iron, is impregnated on described carrier with equal-volume or excess volume；
Described two kinds or above source of iron presoma are configured to solution by co-impregnation, impregnate with equal-volume or excess volume
On described carrier；
Coprecipitation, is configured to solution by described a kind of or two kinds and above source of iron presoma, and by described support dispersion
In above-mentioned solution, adding second component metallic solution, metallic solution is ferric nitrate, iron sulfate, iron chloride, manganese nitrate, acetic acid
One or two or more kinds in the solution of manganese is co-precipitated；Last sucking filtration i.e. obtains the catalyst of fresh preparation.
3. catalyst application in fischer-tropsch reaction described in a claim 1.
Apply the most as claimed in claim 3, it is characterised in that: this catalyst the most also includes an in situ pretreatment mistake
Journey；
Pretreatment atmosphere is the one in argon, hydrogen, helium or air；
Pretreatment temperature is 200～700 DEG C, and the time is 2～12h, and temperature programming is warmed up to pretreatment temperature, speed from 20 DEG C
2°/min。
5. the application as described in claim 3 or 4, it is characterised in that: material synthesis gas CO and H2Mol ratio (CO/H2) it is 0.1
～4.
Apply the most as claimed in claim 5, it is characterised in that: material synthesis gas CO and H2Mol ratio (CO/H2) it is CO/H2
=0.5～2.
7. the application as described in claim 3 or 4, it is characterised in that: reaction temperature 200～400 DEG C.
Apply the most as claimed in claim 7, it is characterised in that: reaction temperature 320～380 DEG C.
9. the application as described in claim 3 or 4, it is characterised in that: reaction pressure 0.1～4Mpa.
Apply the most as claimed in claim 9, it is characterised in that: reaction pressure 0.1～2Mpa.
11. application as described in claim 3 or 4, it is characterised in that: unstripped gas air speed is 1000～40000h-1。
12. apply as claimed in claim 11, it is characterised in that: unstripped gas air speed is 2000～15000h-1。
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| WO2020176210A1 (en) * | 2019-02-28 | 2020-09-03 | Exxonmobil Chemical Patents Inc. | Catalyst compositions and precursors, processes for making the same and syngas conversion processes |
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| CN104785263B (en) * | 2015-03-18 | 2017-09-22 | 华东理工大学 | A kind of load-type iron-based catalyst and its production and use |
| EP3318327A4 (en) * | 2015-07-02 | 2019-02-27 | Dalian Institute Of Chemical Physics Chinese Academy of Sciences | Catalyst and method of preparing light olefin directly from synthesis gas by one-step process |
| CN107661774B (en) * | 2016-07-27 | 2020-11-03 | 中国科学院大连化学物理研究所 | Catalyst and method for preparing low-carbon olefin by directly converting synthesis gas |
| 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 |
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| 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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| WO2020176210A1 (en) * | 2019-02-28 | 2020-09-03 | Exxonmobil Chemical Patents Inc. | Catalyst compositions and precursors, processes for making the same and syngas conversion processes |
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