CN109908917A - A kind of nanometer iron-based fischer-tropsch synthetic catalyst and its preparation method and application - Google Patents
A kind of nanometer iron-based fischer-tropsch synthetic catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN109908917A CN109908917A CN201910288655.6A CN201910288655A CN109908917A CN 109908917 A CN109908917 A CN 109908917A CN 201910288655 A CN201910288655 A CN 201910288655A CN 109908917 A CN109908917 A CN 109908917A
- Authority
- CN
- China
- Prior art keywords
- tropsch synthetic
- nanometer iron
- synthetic catalyst
- based fischer
- iron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a kind of nanometer iron-based fischer-tropsch synthetic catalysts and its preparation method and application, molysite, manganese salt, urea homogeneous mixed solution are subjected to hydro-thermal reaction, hydrothermal synthesis product is separated by solid-liquid separation, pass through washing, drying and roasting, nanometer iron-based fischer-tropsch synthetic catalyst is prepared, is applied to F- T synthesis reaction for preparing light olefins.Compared with prior art, the present invention can obtain that particle size is uniform, catalytic reaction activity is high, the nanosized iron-based catalyst with excellent selectivity of light olefin.
Description
Technical field
The present invention relates to F- T synthesis fields, more particularly, to a kind of nanometer iron-based fischer-tropsch synthetic catalyst and its preparation side
Method and application.
Background technique
Low-carbon alkene (ethylene, propylene and butylene, C2 =-C4 =) it is that basic organic chemical industry important in chemical industry production is former
Material, is the foundation stone of modern chemical industry, and measures an important symbol of a national chemical industry industry development ability.They can
For multiple products such as synthetic polymer, solvent, drug, cosmetics, detergent.Traditional alkene production relies primarily on steam heat
It decomposes and naphtha catalytic cracking.
Currently, the production method of industrial alkene can be divided into petroleum path and Non oil-based route.Petroleum path passes through stone
Cerebrol cracking or the methods of dehydrating alkanes, however this production line height rely on petroleum and by oil price influence of fluctuations compared with
Greatly.With industrial continuous development, the mankind increasingly increase the demand of petroleum resources, and petroleum resources are increasingly deficient
Weary, this just gives traditional alkene production technology-petroleum path to bring stern challenge.
The fossil resource structure in China is " few oil has gas, more coals ", i.e., based on coal, the lasting health hair of national economy
Exhibition requires us that must change traditional energy development pattern, relies on national resource superiority development Elementary Chemical Industry raw material.According to China
The national conditions of coal and natural gas resource relative abundance develop the clean energy resource production technology based on coal and natural gas, can not only delay
Dependence of the solution to conventional petroleum resource, the demand to ever-increasing energy development, moreover it is possible to meet the environmental protection of continuous improvement
Policy meets the strategic requirement of national economy sustainable development steady in a long-term.It is wherein a weight by olefin production of coal
The technology path wanted, the route include direct method and indirect method.Indirect method route is coal through methanol-to-olefins, and core process is first
Alcohol olefin unit.From 2011, China's methanol-to-olefins project, which is such as emerged rapidly in large numbersBamboo shoots after a spring rain, went into operation successively, runs, and ended 2016 3
Month, it has gone into operation, the project that run is up to 13, production capacity is about 3,390,000 tons/year, it is contemplated that the year two thousand twenty, China's methanol-to-olefins production capacity
It will be up to 5,120,000 tons/year.And direct method route is alkene still in the experimental stage by synthesis gas direct catalytic conversion, apart from work
Industryization still has distance.
Fischer-tropsch synthesis process is an important Non oil-based route, i.e., contains carbon resource with coal, natural gas and biomass etc.
For raw material, via synthesis gas (with CO, H2Based on) it is catalytically conveted to clean fuel liquid alkene and oxygenatedchemicals etc., have
There are the advantages such as process is short, low energy consumption.In recent years, worsening shortages for Global Oil resource and to energy development strategy
Consider, F- T synthesis causes the concern of all circles again, it has also become the important goal in the national energy strategic decision of countries in the world.
It especially takes a long view, synthesis gas alkene directly processed is not necessarily to that investment can be greatly reduced by this pilot process of methanol.Institute
Directly to produce ethylene, propylene by F- T synthesis by synthesis gas compared to the traditional technology route for by methanol being intermediate
It is shorter that the technique of equal alkene can greatly reduce investment, process flow, investment cycle, more direct and economical.Pass through F- T synthesis
By synthesis gas, direct producing olefinic hydrocarbons technique is expected to replace conventional petroleum production line, and the pass of the technique in future with high selectivity
Key technology first is that the research and development of catalyst.
It is mainly iron-based catalysis that the synthesis gas direct catalytic conversion of research report, which is catalyst system used in alkene, at present
Agent, compared to other fischer-tropsch synthetic catalysts, ferrum-based catalyst is had the advantage that
1, rich reserves, it is cheap；
2, CO conversion reaction activity is high；
3, to selectivity of light olefin height；
4, when pyroreaction, methane selectively is lower.
Fischer-Tropsch synthesis occurs mainly in catalyst surface, is the highly sensitive reaction of a kind of pair of catalyst structure, i.e.,
The parameters such as Fischer-Tropsch performance and the morphology and size of catalyst are closely related.Currently, researcher generally believes in actually activation and anti-
During answering, the catalytic activity of ferrum-based catalyst is mainly by catalyst granules particle size, auxiliary agent and carriers affect.Traditional
Ferrum-based catalyst is based on precipitated iron catalyst, however the structures such as catalyst particle size, pattern prepared by coprecipitation have
Having can not control, it is difficult to realize the assembling etc. on molecular level or on nanoscale.Nanometer material science is quick in recent years
Development also provides possibility to regulate and control catalyst particle pattern on nanoscale.The experimental results show by changing oxygen
The pattern of compound, i.e., the active crystal face of selective exposure, can be obviously improved its catalytic perfomance.Based on crystal growth in solution
Mechanism, can Effective Regulation crystal morphology from the growth rate of dynamic (dynamical) angle modulation difference crystal face.Nanoparticle has uniqueness
Crystal structure and surface characteristic, catalytic activity and selectivity be better than traditional catalyst.Currently, novel nano catalysis material,
It has been widely used in many chemical reactions.However in Fischer-Tropsch synthesis, the application of nanotechnology mainly passes through leaching
Active component is supported on nano-carrier by stain method, would generally be generated between porous carrier and active phase or auxiliary agent stronger mutual
Effect, this interaction can hinder the influence of the reduction and auxiliary agent of active presoma to active phase.Therefore, design preparation is high
The new catalyst of activity, the carrier-free of morphology controllable and auxiliary agent interaction is the key that improve F- T synthesis technology.
Summary of the invention
It is an object of the invention to catalysis uneven, load-type iron-based for non-loading type nanosized iron-based catalyst appearance and size
The shortcomings that agent carrier and auxiliary agent strong interaction, a kind of surfactant-free is provided, it is at low cost, environmentally friendly, take in high temperature
The preparation method and application for the nanosized iron-based catalyst and the catalyst that catalytic activity is high, stability is good are held in the palm in synthetic reaction.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of nanometer iron-based fischer-tropsch synthetic catalyst mixes the aqueous solution of molysite, manganese salt, and urea is added
Solution carries out hydrothermal synthesis reaction after aged at room temperature, hydrothermal synthesis product is separated by solid-liquid separation, washs, dries and is roasted, and makes
It is standby to obtain nanometer iron-based fischer-tropsch synthetic catalyst.
The molysite is ferric nitrate or ferrous sulfate, and the manganese salt is manganese nitrate, and the molar ratio of molysite and manganese salt is 0-
0.4, urea is 2-4 with the molar ratio of molysite and the summation of manganese salt.
The hydrothermal synthesis reaction control reaction temperature is 100-180 DEG C, time 10-26h.
The drying control temperature is 100-120 DEG C, time 10-14h.
Blowing air roasts in Muffle furnace, controlled at 450-550 DEG C, time 2-6h.The Nanoscale Iron being prepared
Base fischer-tropsch synthetic catalyst can carry out high temperature fischer-tropsch synthesis in fixed bed reactors, and catalyst is placed in fixed bed reactors
In, then the 280-320 DEG C of reduction 8-24h in pure hydrogen is cooled to 180-220 DEG C again, and also Primordial Qi hydrogen is switched to original
Expect gas, unstripped gas proportion is H2/ CO=1-2, then for increasing temperature and pressure to 280-320 DEG C, 1.5-2.0MPa, control air speed carries out expense
Hold in the palm synthetic reaction.
Nanosized iron-based catalyst of the present invention decomposes the strategy of hydrothermal synthesis using urea and prepares, relative to traditional
Load and non-loading type ferrum-based catalyst and a small amount of reported nanosized iron-based catalyst prepared using urea as precipitating reagent
Synthetic technology has following substantive distinguishing features and progress:
(1) non-loading type nanosized iron-based catalyst made from the method for the present invention avoids due to carrier interacts with auxiliary agent
The shortcomings that activity reduces occurs, and the present invention to control the settling rate of iron, therefore is compared by regulation Hydrolysis rate of urea
In the catalyst of ordinary precipitation process preparation, nanosized iron-based catalyst particle size prepared by the present invention is small and distribution is uniform, can mention
The mass transfer of high unstrpped gas reduces diffusional resistance, improves catalytic activity.
(2) compared to other process for prepn. of urea, the present invention has investigated surfactant to catalyst morphology and reaction
Performance influences, it is found that these influence very little, from industrial cost's angle, surfactant or organic solvent can save completely
Slightly, overall flow is more simple and environmentally-friendly, Yi Fang great, saves the preparation cost and process waste liquor processing cost of catalyst.This hair
The bright influence for also having investigated different hydrolysis of urea temperature to nanosized iron-based catalyst Fischer-Tropsch synthesis performance, filters out optimal
Hydrolysis temperature.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Investigate different hydrothermal temperatures:
Embodiment 1
Weigh 20.00g ferric nitrate (Fe (NO3)3·9H2O), 9.3655g urea is dissolved in 80ml, 20ml respectively at room temperature
Deionized water and magnetic agitation 30min, weigh 0.8859g manganese nitrate solution (wt%=50%) and are added to above-mentioned iron nitrate solution
In.Then, with vigorous stirring, urea liquid is slowly dropped to iron, in manganese nitrate mixed solution.Aged at room temperature 1h.Aging
After, homogeneous phase solution is transferred in 200ml ptfe autoclave, 140 DEG C of hydro-thermal 18h.After reaction, it is down to room
Temperature is washed three times respectively with dehydrated alcohol, deionized water, is placed in 110 DEG C of baking oven after about 12h is dried, is transferred to
500 DEG C of roasting 4h of Muffle furnace blowing air.Nanosized iron-based catalyst can be obtained.
Embodiment 2
Weigh 20.00g ferric nitrate (Fe (NO3)3·9H2O), 9.3655g urea is dissolved in 80ml, 20ml respectively at room temperature
Deionized water and magnetic agitation 30min, weigh 0.8859g manganese nitrate solution (wt%=50%) and are added to above-mentioned iron nitrate solution
In.Then, with vigorous stirring, urea liquid is slowly dropped to iron, in manganese nitrate mixed solution.Aged at room temperature 1h.Aging
After, homogeneous phase solution is transferred in 200ml ptfe autoclave, 100 DEG C of hydro-thermal 18h.After reaction, it is down to room
Temperature is washed three times respectively with dehydrated alcohol, deionized water, is placed in 110 DEG C of baking oven after about 12h is dried, is transferred to
500 DEG C of roasting 4h of Muffle furnace blowing air.Nanosized iron-based catalyst can be obtained.
Embodiment 3
Weigh 20.00g ferric nitrate (Fe (NO3)3·9H2O), 9.3655g urea is dissolved in 80ml, 20ml respectively at room temperature
Deionized water and magnetic agitation 30min, weigh 0.8859g manganese nitrate solution (wt%=50%) and are added to above-mentioned iron nitrate solution
In.Then, with vigorous stirring, urea liquid is slowly dropped to iron, in manganese nitrate mixed solution.Aged at room temperature 1h.Aging
After, homogeneous phase solution is transferred in 200ml ptfe autoclave, 120 DEG C of hydro-thermal 18h.After reaction, it is down to room
Temperature is washed three times respectively with dehydrated alcohol, deionized water, is placed in 110 DEG C of baking oven after about 12h is dried, is transferred to
500 DEG C of roasting 4h of Muffle furnace blowing air.Nanosized iron-based catalyst can be obtained.
Embodiment 4
Weigh 20.00g ferric nitrate (Fe (NO3)3·9H2O), 9.3655g urea is dissolved in 80ml, 20ml respectively at room temperature
Deionized water and magnetic agitation 30min, weigh 0.8859g manganese nitrate solution (wt%=50%) and are added to above-mentioned iron nitrate solution
In.Then, with vigorous stirring, urea liquid is slowly dropped to iron, in manganese nitrate mixed solution.Aged at room temperature 1h.Aging
After, homogeneous phase solution is transferred in 200ml ptfe autoclave, 160 DEG C of hydro-thermal 18h.After reaction, it is down to room
Temperature is washed three times respectively with dehydrated alcohol, deionized water, is placed in 110 DEG C of baking oven after about 12h is dried, is transferred to
500 DEG C of roasting 4h of Muffle furnace blowing air.Nanosized iron-based catalyst can be obtained.
Embodiment 5
Weigh 20.00g ferric nitrate (Fe (NO3)3·9H2O), 9.3655g urea is dissolved in 80ml, 20ml respectively at room temperature
Deionized water and magnetic agitation 30min, weigh 0.8859g manganese nitrate solution (wt%=50%) and are added to above-mentioned iron nitrate solution
In.Then, with vigorous stirring, urea liquid is slowly dropped to iron, in manganese nitrate mixed solution.Aged at room temperature 1h.Aging
After, homogeneous phase solution is transferred in 200ml ptfe autoclave, 180 DEG C of hydro-thermal 18h.After reaction, it is down to room
Temperature is washed three times respectively with dehydrated alcohol, deionized water, is placed in 110 DEG C of baking oven after about 12h is dried, is transferred to
500 DEG C of roasting 4h of Muffle furnace blowing air.Nanosized iron-based catalyst can be obtained.
Investigate different Mn-Fe ratios:
Embodiment 6
Weigh 20.00g ferric nitrate (Fe (NO3)3·9H2O), 9.3655g urea is dissolved in 80ml, 20ml respectively at room temperature
Deionized water and magnetic agitation 30min, weigh 0.8859g manganese nitrate solution (wt%=50%) and are added to above-mentioned iron nitrate solution
In.Then, with vigorous stirring, urea liquid is slowly dropped to iron, in manganese nitrate mixed solution.Aged at room temperature 1h.Aging
After, homogeneous phase solution is transferred in 200ml ptfe autoclave, 180 DEG C of hydro-thermal 18h.After reaction, it is down to room
Temperature is washed three times respectively with dehydrated alcohol, deionized water, is placed in 110 DEG C of baking oven after about 12h is dried, is transferred to
500 DEG C of roasting 4h of Muffle furnace blowing air.Nanosized iron-based catalyst can be obtained.
Embodiment 7
Weigh 20.00g ferric nitrate (Fe (NO3)3·9H2O), 9.3655g urea is dissolved in 80ml, 20ml respectively at room temperature
Deionized water and magnetic agitation 30min, weigh 1.7718g manganese nitrate solution (wt%=50%) and are added to above-mentioned iron nitrate solution
In.Then, with vigorous stirring, urea liquid is slowly dropped to iron, in manganese nitrate mixed solution.Aged at room temperature 1h.Aging
After, homogeneous phase solution is transferred in 200ml ptfe autoclave, 180 DEG C of hydro-thermal 18h.After reaction, it is down to room
Temperature is washed three times respectively with dehydrated alcohol, deionized water, is placed in 110 DEG C of baking oven after about 12h is dried, is transferred to
500 DEG C of roasting 4h of Muffle furnace blowing air.Nanosized iron-based catalyst can be obtained.
Embodiment 8
Weigh 20.00g ferric nitrate (Fe (NO3)3·9H2O), 9.3655g urea is dissolved in 80ml, 20ml respectively at room temperature
Deionized water and magnetic agitation 30min, weigh 3.5436g manganese nitrate solution (wt%=50%) and are added to above-mentioned iron nitrate solution
In.Then, with vigorous stirring, urea liquid is slowly dropped to iron, in manganese nitrate mixed solution.Aged at room temperature 1h.Aging
After, homogeneous phase solution is transferred in 200ml ptfe autoclave, 180 DEG C of hydro-thermal 18h.After reaction, it is down to room
Temperature is washed three times respectively with dehydrated alcohol, deionized water, is placed in 110 DEG C of baking oven after about 12h is dried, is transferred to
500 DEG C of roasting 4h of Muffle furnace blowing air.Nanosized iron-based catalyst can be obtained.
Embodiment 9
Weigh 20.00g ferric nitrate (Fe (NO3)3·9H2O), 9.3655g urea is dissolved in 80ml, 20ml respectively at room temperature
Deionized water and magnetic agitation 30min, weigh 5.3153g manganese nitrate solution (wt%=50%) and are added to above-mentioned iron nitrate solution
In.Then, with vigorous stirring, urea liquid is slowly dropped to iron, in manganese nitrate mixed solution.Aged at room temperature 1h.Aging
After, homogeneous phase solution is transferred in 200ml ptfe autoclave, 180 DEG C of hydro-thermal 18h.After reaction, it is down to room
Temperature is washed three times respectively with dehydrated alcohol, deionized water, is placed in 110 DEG C of baking oven after about 12h is dried, is transferred to
500 DEG C of roasting 4h of Muffle furnace blowing air.Nanosized iron-based catalyst can be obtained.
Investigate the different hydro-thermal times:
Embodiment 10
Weigh 20.00g ferric nitrate (Fe (NO3)3·9H2O), 9.3655g urea is dissolved in 80ml, 20ml respectively at room temperature
Deionized water and magnetic agitation 30min, weigh 0.8859g manganese nitrate solution (wt%=50%) and are added to above-mentioned iron nitrate solution
In.Then, with vigorous stirring, urea liquid is slowly dropped to iron, in manganese nitrate mixed solution.Aged at room temperature 1h.Aging
After, homogeneous phase solution is transferred in 200ml ptfe autoclave, 140 DEG C of hydro-thermal 10h.After reaction, it is down to room
Temperature is washed three times respectively with dehydrated alcohol, deionized water, is placed in 110 DEG C of baking oven after about 12h is dried, is transferred to
500 DEG C of roasting 4h of Muffle furnace blowing air.Nanosized iron-based catalyst can be obtained.
Embodiment 11
Weigh 20.00g ferric nitrate (Fe (NO3)3·9H2O), 9.3655g urea is dissolved in 80ml, 20ml respectively at room temperature
Deionized water and magnetic agitation 30min, weigh 0.8859g manganese nitrate solution (wt%=50%) and are added to above-mentioned iron nitrate solution
In.Then, with vigorous stirring, urea liquid is slowly dropped to iron, in manganese nitrate mixed solution.Aged at room temperature 1h.Aging
After, homogeneous phase solution is transferred in 200ml ptfe autoclave, 140 DEG C of hydro-thermal 18h.After reaction, it is down to room
Temperature is washed three times respectively with dehydrated alcohol, deionized water, is placed in 110 DEG C of baking oven after about 12h is dried, is transferred to
500 DEG C of roasting 4h of Muffle furnace blowing air.Nanosized iron-based catalyst can be obtained.
Embodiment 10
Weigh 20.00g ferric nitrate (Fe (NO3)3·9H2O), 9.3655g urea is dissolved in 80ml, 20ml respectively at room temperature
Deionized water and magnetic agitation 30min, weigh 0.8859g manganese nitrate solution (wt%=50%) and are added to above-mentioned iron nitrate solution
In.Then, with vigorous stirring, urea liquid is slowly dropped to iron, in manganese nitrate mixed solution.Aged at room temperature 1h.Aging
After, homogeneous phase solution is transferred in 200ml ptfe autoclave, 140 DEG C of hydro-thermal 26h.After reaction, it is down to room
Temperature is washed three times respectively with dehydrated alcohol, deionized water, is placed in 110 DEG C of baking oven after about 12h is dried, is transferred to
500 DEG C of roasting 4h of Muffle furnace blowing air.Nanosized iron-based catalyst can be obtained.
Embodiment 11
A kind of preparation method of nanometer iron-based fischer-tropsch synthetic catalyst, urea liquid is added into ferrous sulfate aqueous solution,
Carry out hydrothermal synthesis reaction after aged at room temperature, reaction temperature control at 180 DEG C, time control in 12h, urea and ferrous sulfate
Molar ratio is 2, and hydrothermal synthesis product is separated by solid-liquid separation, is washed, 100 DEG C of dry 14h, the blowing air control temperature in Muffle furnace
Degree is 450 DEG C of roasting 6h, and nanometer iron-based fischer-tropsch synthetic catalyst is prepared.
Embodiment 12
A kind of preparation method of nanometer iron-based fischer-tropsch synthetic catalyst, it is roughly the same with embodiment 11, the difference is that,
Urea liquid is added in the mixed aqueous solution of ferrous sulfate and manganese nitrate, and the molar ratio of molysite and manganese salt is 0.2, remaining technique
Parameter is consistent.
Embodiment 13
A kind of preparation method of nanometer iron-based fischer-tropsch synthetic catalyst, it is roughly the same with embodiment 11, the difference is that,
Urea liquid is added in the mixed aqueous solution of ferrous sulfate and manganese nitrate, and the molar ratio of molysite and manganese salt is 0.1, remaining technique
Parameter is consistent.
Embodiment 14
A kind of preparation method of nanometer iron-based fischer-tropsch synthetic catalyst, it is roughly the same with embodiment 11, the difference is that,
Urea liquid is added in the mixed aqueous solution of ferrous sulfate and manganese nitrate, and the molar ratio of molysite and manganese salt is 0.05, remaining work
Skill parameter is consistent.
Embodiment 15
A kind of preparation method of nanometer iron-based fischer-tropsch synthetic catalyst, it is roughly the same with embodiment 11, the difference is that,
Urea liquid is added in the mixed aqueous solution of ferrous sulfate and manganese nitrate, and the molar ratio of molysite and manganese salt is 1/30, remaining work
Skill parameter is consistent.
Embodiment 16
A kind of preparation method of nanometer iron-based fischer-tropsch synthetic catalyst, it is roughly the same with embodiment 12, the difference is that,
The hydro-thermal reaction time control is in 10h in the present embodiment.
Embodiment 17
A kind of preparation method of nanometer iron-based fischer-tropsch synthetic catalyst, it is roughly the same with embodiment 16, the difference is that,
The hydro-thermal reaction time control is in 18h in the present embodiment.
Embodiment 18
A kind of preparation method of nanometer iron-based fischer-tropsch synthetic catalyst, it is roughly the same with embodiment 16, the difference is that,
The hydro-thermal reaction time control is in 26h in the present embodiment.
The application for the high temperature fischer-tropsch synthesis that nanometer iron based catalyst prepared in use for Fischer-Tropsch synthesis under high temperature carries out in fixed bed reactors, is answered
With method and optimal technique for applying Parameter Conditions are as follows: then 300 DEG C of reduction 10h first in pure hydrogen are cooled to 200 again
DEG C, and will also switch to unstripped gas by Primordial Qi hydrogen, unstripped gas proportion is H2: CO:N2=60:30:10, then increasing temperature and pressure to 320
DEG C, 1.5MPa carries out Fischer-Tropsch synthesis under certain space velocities.
Above-mentioned catalyst see the table below in the evaluation condition and evaluation result of synthesis gas high temperature fischer-tropsch synthesis producing light olefins.
Table 1 investigates different hydrothermal temperatures
Table 2 investigates different Mn-Fe ratios
Table 3 investigates the different hydro-thermal times
Through data in table it is found that under the even higher air speed of equal conditions, it is anti-that catalyst of the present invention is applied to fixed bed
It answers and carries out high-temperature Fischer-Tropsch synthesis reaction in device, each group Catalyst Conversion is all larger than 80%, shows that catalyst of the present invention is living
Property it is high.By the comparison of each group reactivity worth it can be concluded that, the hydro-thermal time reactivity worth is influenced it is smaller, in addition, manganese content with
And hydrothermal temperature has a major impact the selectivity of catalyst activity and low-carbon alkene.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (9)
1. a kind of preparation method of nanometer iron-based fischer-tropsch synthetic catalyst, which is characterized in that this method is by molysite, manganese salt, urea
Homogeneous mixed solution carries out hydro-thermal reaction, and hydrothermal synthesis product is separated by solid-liquid separation, and passes through washing, drying and roasting, preparation
Obtain nanometer iron-based fischer-tropsch synthetic catalyst.
2. a kind of preparation method of nanometer iron-based fischer-tropsch synthetic catalyst according to claim 1, which is characterized in that the party
Method mixes the aqueous solution of molysite, manganese salt, and urea liquid is added, hydrothermal synthesis reaction is carried out after aged at room temperature, by hydrothermal synthesis
Product is separated by solid-liquid separation, is washed, is dried and is roasted, and nanometer iron-based fischer-tropsch synthetic catalyst is prepared.
3. a kind of preparation method of nanometer iron-based fischer-tropsch synthetic catalyst according to claim 1 or 2, which is characterized in that
The molysite is ferric nitrate or ferrous sulfate, and the manganese salt is manganese nitrate, and the molar ratio of molysite and manganese salt is 0-0.4, urea with
The molar ratio of the summation of molysite and manganese salt is 2-4.
4. a kind of preparation method of nanometer iron-based fischer-tropsch synthetic catalyst according to claim 1 or 2, which is characterized in that
The hydrothermal synthesis reaction control reaction temperature is 100-180 DEG C, time 10-26h.
5. a kind of preparation method of nanometer iron-based fischer-tropsch synthetic catalyst according to claim 1 or 2, which is characterized in that
The drying control temperature is 100-120 DEG C, time 10-14h.
6. a kind of preparation method of nanometer iron-based fischer-tropsch synthetic catalyst according to claim 1 or 2, which is characterized in that
Blowing air roasts in Muffle furnace, controlled at 450-550 DEG C, time 2-6h.
7. the nanometer iron-based fischer-tropsch synthetic catalyst being prepared such as method of any of claims 1-6.
8. the nanometer iron-based fischer-tropsch synthetic catalyst that such as method of any of claims 1-6 is prepared is in fixed bed
The application of the high temperature fischer-tropsch synthesis carried out in reactor.
9. the application of nanometer iron-based fischer-tropsch synthetic catalyst according to claim 8, which is characterized in that be placed in catalyst solid
In fixed bed reactor, then the 280-320 DEG C of reduction 8-24h in pure hydrogen is cooled to 180-220 DEG C again, and will go back Primordial Qi hydrogen
Autogenous cutting changes unstripped gas into, and unstripped gas proportion is H2/ CO=1-2, then increasing temperature and pressure is to 280-320 DEG C, 1.5-2.0MPa, control
Air speed carries out Fischer-Tropsch synthesis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910288655.6A CN109908917A (en) | 2019-04-11 | 2019-04-11 | A kind of nanometer iron-based fischer-tropsch synthetic catalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910288655.6A CN109908917A (en) | 2019-04-11 | 2019-04-11 | A kind of nanometer iron-based fischer-tropsch synthetic catalyst and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109908917A true CN109908917A (en) | 2019-06-21 |
Family
ID=66969508
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910288655.6A Pending CN109908917A (en) | 2019-04-11 | 2019-04-11 | A kind of nanometer iron-based fischer-tropsch synthetic catalyst and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109908917A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111659395A (en) * | 2020-05-26 | 2020-09-15 | 北京化工大学 | Preparation method and application of foamed iron-based catalyst with high all-olefin selectivity |
| CN116237075A (en) * | 2023-03-15 | 2023-06-09 | 宁夏大学 | Preparation method and application of modified carbon nitride loaded iron Fischer-Tropsch synthesis catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105013503A (en) * | 2015-06-29 | 2015-11-04 | 中国科学院广州能源研究所 | Preparation method and applications of Fe-based catalyst used for Fischer-Tropsch synthesis |
| CN105013486A (en) * | 2015-06-29 | 2015-11-04 | 中国科学院广州能源研究所 | Preparation method and applications of core-shell structured Fe3O4@C catalyst used for Fischer-Tropsch synthesis |
| CN106890650A (en) * | 2015-12-18 | 2017-06-27 | 中国石油天然气股份有限公司 | Catalyst for Fischer-Tropsch synthesis and preparation method thereof |
-
2019
- 2019-04-11 CN CN201910288655.6A patent/CN109908917A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105013503A (en) * | 2015-06-29 | 2015-11-04 | 中国科学院广州能源研究所 | Preparation method and applications of Fe-based catalyst used for Fischer-Tropsch synthesis |
| CN105013486A (en) * | 2015-06-29 | 2015-11-04 | 中国科学院广州能源研究所 | Preparation method and applications of core-shell structured Fe3O4@C catalyst used for Fischer-Tropsch synthesis |
| CN106890650A (en) * | 2015-12-18 | 2017-06-27 | 中国石油天然气股份有限公司 | Catalyst for Fischer-Tropsch synthesis and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111659395A (en) * | 2020-05-26 | 2020-09-15 | 北京化工大学 | Preparation method and application of foamed iron-based catalyst with high all-olefin selectivity |
| CN116237075A (en) * | 2023-03-15 | 2023-06-09 | 宁夏大学 | Preparation method and application of modified carbon nitride loaded iron Fischer-Tropsch synthesis catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107486234B (en) | Catalyst for preparing light aromatic hydrocarbon by directly converting synthesis gas and preparation method thereof | |
| CN106031871A (en) | Iron-based catalyst for low-carbon olefin production through CO2 hydrogenation, and preparation and applications thereof | |
| CN105056952B (en) | Preparation method and application of nickel-based photocatalyst for preparing high-carbon hydrocarbon above carbon dioxide by photocatalytic carbon monoxide hydrogenation | |
| CN104437504B (en) | A kind of CO2The catalyst of Efficient Conversion producing light olefins | |
| CN107051461B (en) | Graphene modified iron-based catalyst, preparation thereof and application thereof in Fischer-Tropsch reaction | |
| CN106607037B (en) | GTO catalyst for fluid bed and preparation method thereof | |
| CN101293206B (en) | Iron base catalyst for fischer-tropsch synthesis and preparation method thereof | |
| CN104801304A (en) | Iron-based catalyst for preparation of low carbon olefin from synthetic gas, and preparation method and application thereof | |
| CN104226329B (en) | Catalyst for direct preparation of low carbon olefin from synthesis gas and preparation method thereof | |
| CN107971026A (en) | Combination catalyst for producing light olefins | |
| CN103666518B (en) | A kind of method of Fischer-Tropsch process exhaust higher value application | |
| CN105126894B (en) | A kind of GaN catalyst and preparation method thereof and the application in catalysis n butane oxidation dehydrogenation reaction | |
| CN106311310B (en) | A kind of load-type iron-based composite metal catalyst and its preparation method and application | |
| CN105817254A (en) | Application of iron-based catalyst with porous film structure in Fischer-Tropsch reaction | |
| CN103611540B (en) | A kind of Catalysts and its preparation method for CO hydrogenation and application | |
| CN107362802A (en) | A kind of synthesis gas is converted into catalyst of alkene and its preparation method and application | |
| CN102872875A (en) | Slurry bed methanation catalyst, preparing method and application | |
| CN102698764B (en) | Catalyst, the preparation method and its usage of preparation of low carbon olefines by synthetic gas | |
| CN106607053B (en) | Synthesis gas directly prepares Fe-Mn series catalysts of low-carbon alkene and preparation method thereof | |
| CN105597772A (en) | Cobalt-based catalyst having core-shell structure, and preparation method thereof | |
| CN105964263A (en) | Catalyst for preparing graphene-loaded low-carbon olefin by efficient iron-based Fischer-Tropsch synthesis, and preparation method of catalyst | |
| CN106607050B (en) | The fluid catalyst and preparation method thereof of one-step method from syngas producing light olefins | |
| CN106607061B (en) | The fluid catalyst and preparation method thereof of one-step method from syngas producing light olefins | |
| CN106607058B (en) | Iron-based catalyst for directly preparing low-carbon olefin from synthesis gas and preparation method thereof | |
| CN109908917A (en) | A kind of nanometer iron-based fischer-tropsch synthetic catalyst and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190621 |
|
| RJ01 | Rejection of invention patent application after publication |