CN101099931A - Nanometer iron-series catalyst and preparation method and device thereof - Google Patents
Nanometer iron-series catalyst and preparation method and device thereof Download PDFInfo
- Publication number
- CN101099931A CN101099931A CNA2007100228183A CN200710022818A CN101099931A CN 101099931 A CN101099931 A CN 101099931A CN A2007100228183 A CNA2007100228183 A CN A2007100228183A CN 200710022818 A CN200710022818 A CN 200710022818A CN 101099931 A CN101099931 A CN 101099931A
- Authority
- CN
- China
- Prior art keywords
- iron
- expansion chamber
- reative cell
- particle
- liquid
- 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.)
- Granted
Links
Images
Landscapes
- Catalysts (AREA)
Abstract
The present invention discloses one kind of nanometer iron catalyst and its preparation process and apparatus. The nanometer iron catalyst comprising iron particles smaller than 100 nm suspended in isolating liquid medium is prepared through the following steps: heating high purity nitrogen or inert gas to temperature higher than the critical temperature of iron pentacarbonyl inside the reactor, and introducing iron pentacarbonyl liquid or vapor to decompose iron pentacarbonyl to obtain iron particle; and pumping the iron particle from the reactor to the isolating liquid medium in a settling chamber. The present invention utilizes liquid medium to block the aggregation of iron particle for obtain nanometer iron particle. The nanometer iron catalyst has simple preparation process and high catalytic activity, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of Fe-series catalyst and preparation method thereof and device, be specifically related to a kind ofly utilize the iron pentacarbonyl steam heat to decompose to obtain homodisperse highly active nanometer iron-series catalyst and preparation method thereof and device.
Background technology
Transition element iron is because of having special d electron orbit, to H
2, N
2, NH
3, C
2H
2, C
2H
4Deng producing chemisorbed, generate the surface intermediate kind, make to be adsorbed molecule activation and to be dissociated into atom, offering reactant carries out various chemical reactions, thereby is a kind of good chemical catalyst.Fe-series catalyst is used widely at Coal Chemical Industry, petroleum refining, ammonia synthesis and decomposition catalytic field.
Fe-series catalyst commonly used at present mainly contains natural pyrite, troilite and various melting waste slag.Its particle generally several microns to tens of micron, difficulties in dispersion, catalytic effect is restricted.Studies show that catalyst particle is thin more, its dispersion in coal slurry or oil product is good more, and catalytic effect is also good more.Use the high dispersive Ultra-fine Particle Catalysts, can improve hydrogenation conversion, reduce catalyst amount, reduce cost, reduce environmental pollution.From existing report, adopt the mechanical lapping means to reduce catalyst particle size, reaching micron order has been the limit.
For reducing iron series hydrocatalyst particle diameter, the various countries researcher develops the kinds of artificial synthetic method.
In the west, particularly the scientist of European and American countries is devoted to the exploitation of dispersed catalysts always.Current research at most, the most popular be that the Fe series catalysts is made particle diameter at the ultrafine particle below 1 micron, particularly (1～100nm) particle, the preparation method who has proposed has nanoscale: the Rapid Thermal solution of laser cracking process, solution, the coprecipitation of metal salt solution and reversed phase micelle microemulsion method etc.The U.S. mainly adopts trivalent iron salt as the catalyst raw material, is prepared into nano particle, but trivalent iron salt price height, cost is big; Germany adopts aluminium making residue, and this technology does not need independent grinding, has reduced cost, but does not meet the low national conditions of China's bauxite resource iron content.
Japan's New Energy Development Organization (NEDO) with ferric sulfate and sulphur as raw material, 480-500 ℃ of synthetic iron sulfide (SIS) in the continuous fluid bed bioreactor.The primary particle of catalyst is 50-200nm, owing to reunite, the particle mean size of catalyst offspring is 108um, needs to be dispersed into submicron-scale by ultrasonic vibrations.Japan brown coal liquefaction company is a raw material with ferrous sulfate and ammoniacal liquor, add ammonium hydrogen phosphate after making ferrous hydroxide, 40 ℃ of air oxidations 20 hours, make γ-FeOOH ultrafine particle, γ-FeOOH powder is dry down at 100 ℃, γ-FeOOH reunites easily, needs to be crushed to the submicron order particle diameter by ultra-fine mill in process solvent.
The nearest achievement in research of China's 863 Program shows, divalent iron salt as base stock synthesis of nano grade particles, can be played good catalytic effect, but the nanocatalyst precursor that generates in the preparation process is a kind of metastable solids thing, as untimely dispersion, secondary agglomeration can take place; When the precursor oxidation generates catalyst prod, also the phenomenon that particle is grown up can take place, the specific area that reduces Fe-series catalyst is with active.
Summary of the invention
The objective of the invention is to: a kind of nanometer iron-series catalyst and preparation method thereof and device are provided, adopt the catalytic activity height of the nanometer iron-series catalyst of this preparation method and device production, preparation technology is simple, is easy to amplify carry out industrialization production.
To be this nanometer iron-series catalyst by particle diameter be suspended in the liquid spacer medium less than the iron particle of 100nm technical solution of the present invention forms.
The preparation method of nanometer iron-series catalyst of the present invention is made up of following steps:
1. in expansion chamber, inject liquid spacer medium, vacuumize or with the air in high pure nitrogen or other inert gas replacement reative cell and the expansion chamber, vacuumize or replace and make high pure nitrogen or other inert gas in reative cell, keep certain pressure after finishing;
2. start the heater of reative cell, make the reaction indoor temperature be higher than the critical-temperature of iron pentacarbonyl, open the iron pentacarbonyl inlet, in reative cell, feed iron pentacarbonyl liquid or steam, iron pentacarbonyl decomposes in the high pure nitrogen of heat or other inert gas, obtains iron particle;
3. open the expansion chamber gas outlet, the vavuum pump that startup links to each other with the gas outlet, open the valve that connects iron particle outlet and iron particle inlet simultaneously, iron particle in the reative cell feeds in the liquid spacer medium of expansion chamber through iron particle outlet and iron particle inlet, be dispersed in liquid spacer medium in gas rising diffusion process, gas remaining or that produce is evacuated to exhaust treatment system by vavuum pump;
4. open the expansion chamber discharging opening, the suspension injection closed container of nano-iron particle and liquid spacer medium composition is preserved.
Among the preparation method of nanometer iron-series catalyst of the present invention, high pure nitrogen or other inert gas are 0.1-5Mpa in the reative cell internal pressure.
Among the preparation method of nanometer iron-series catalyst of the present invention, the reative cell heating-up temperature is higher than the iron pentacarbonyl critical-temperature, is lower than 500 ℃, when adding iron pentacarbonyl steam, feeding amount and reaction chamber volume volume ratio 0.2 :-5: 1 when adding iron pentacarbonyl liquid, account for the 0.05-0.5 of reaction chamber volume.
Among the preparation method of nanometer iron-series catalyst of the present invention, the liquid medium addition accounts for the 0.5-0.8 of expansion chamber volume in the expansion chamber.
Among the preparation method of nanometer iron-series catalyst of the present invention, liquid spacer medium is at least a in oil, fat, naphthalene, anthracene, phenanthrene, phenol, benzene, alcohols or the water.
The invention provides a kind of used device of above-mentioned preparation method of implementing; it is characterized in that: device is made up of reative cell and expansion chamber; reative cell is provided with iron pentacarbonyl liquid or steam inlet, nano-iron particle outlet and protection gas air inlet; expansion chamber is provided with nano-iron particle import, gas vent, liquid spacer medium inlet and discharging opening; wherein the nano-iron particle inlet stretches in the liquid spacer medium of expansion chamber; gas vent links to each other with vavuum pump, and the iron particle outlet of reative cell is connected by high pressure valve with the iron particle inlet of expansion chamber.
The present invention has the following advantages: after 1. pyrolytical condition reaches, and Fe (CO)
5The nascent state iron that decomposition generates is compared with the nanometer molysite and is had more activity, again because it is transported to evenly dispersion in the liquid spacer medium rapidly, and its dispersiveness, good stability, particle is difficult to secondary agglomeration, therefore can remedy the deficiency of various catalyst; 2. preparation technology is simple, is easy to amplify carry out industrialization production.
Description of drawings
Fig. 1 is a structural representation of implementing preparation method's equipment therefor of the present invention.
Among the figure: 1. reative cell, 2. expansion chamber, 3. iron pentacarbonyl inlet, 4. protection gas air inlet, 5. iron particle outlet, 6. iron particle inlet, 7. expansion chamber gas outlet, 8. liquid spacer medium inlet, 9. high pressure valve, 10. discharging opening, 11. vavuum pumps.
The specific embodiment
Fe-series catalyst of the present invention is suspended in the liquid spacer medium less than the iron particle of 100nm by particle diameter to be formed.
The used device of preparation nanometer iron-series catalyst of the present invention is made up of reative cell 1 and expansion chamber 2; reative cell 1 is provided with iron pentacarbonyl liquid or steam inlet 3, iron particle outlet 5 and protection gas air inlet 4; expansion chamber is provided with iron particle inlet 6, gas vent 7, liquid spacer medium inlet 8 and discharging opening 10; wherein nano-iron particle inlet 6 stretches in the liquid spacer medium of expansion chamber; gas vent 7 links to each other with vavuum pump 11, and reative cell iron particle outlet 5 and expansion chamber iron particle inlet 6 link to each other by high pressure valve 9.
The preparation method of nanometer iron-series catalyst of the present invention is made up of following steps:
1. in expansion chamber 2, inject liquid medium, vacuumize or with the air in high pure nitrogen or other inert gas replacement reative cell 1 and the expansion chamber 2, vacuumize or replace and make high pure nitrogen or other inert gas in reative cell 1, keep certain pressure after finishing;
2. start the heater of reative cell 1, make the reaction indoor temperature reach certain temperature, open the valve of iron pentacarbonyl inlet 3, feed iron pentacarbonyl liquid or steam in reative cell, iron pentacarbonyl decomposes in the high pure nitrogen of heat or other inert gas, obtains iron particle;
3. open expansion chamber gas outlet 7, the vavuum pump 11 that startup links to each other with expansion chamber gas outlet 7, open the valve 9 of coupled reaction chamber 1 and expansion chamber 2 simultaneously, iron particle in the reative cell feeds in the liquid spacer medium of expansion chamber 2 through iron particle outlet 5 and iron particle inlet 6, be scattered in liquid medium in gas rising diffusion process, gas is by vavuum pump 11 suction exhaust treatment systems;
4. open expansion chamber discharging opening 10, the suspension injection airtight container of nano-iron particle and liquid spacer medium composition is preserved.
Among the preparation method of nanometer iron-series catalyst of the present invention, high pure nitrogen or other inert gas are 0.1-5Mpa in the reative cell internal pressure.
Among the preparation method of nanometer iron-series catalyst of the present invention, the reative cell heating-up temperature is higher than the iron pentacarbonyl critical-temperature, be lower than 500 ℃, when adding iron pentacarbonyl steam, the volume ratio of feeding amount and reaction chamber volume 1: 5 :-5: 1, when adding iron pentacarbonyl liquid, account for the 0.05-0.5 of reaction chamber volume.
Among the preparation method of nanometer iron-series catalyst of the present invention, the liquid medium addition accounts for the 0.5-0.8 of expansion chamber volume in the expansion chamber.
Among the preparation method of nanometer iron-series catalyst of the present invention, liquid spacer medium is at least a in oil, fat, naphthalene, anthracene, phenanthrene, phenol, benzene, alcohols or the water.
The present invention is further illustrated below in conjunction with Fig. 1 and embodiment.
In the expansion chamber 1 of 2L, inject heavy oil to volume and account for expansion chamber 1L, opening protection gas inlet 4 and high pressure valve 9, is reaction under high pressure chamber 1 and the expansion chamber 2 interior air of 2L with the high pure nitrogen displaced volume, after displacement is finished, valve-off 9 continues to feed high pure nitrogen to 0.1MPa in reative cell 1; Start heater and be warming up to 285 ℃, open iron pentacarbonyl inlet 3 and feed 0.4L iron pentacarbonyl steam, iron pentacarbonyl enters reative cell and decomposes, and makes nano-iron particle; Open high pressure valve 9 and expansion chamber gas outlet 7, start vavuum pump simultaneously, nano-iron particle enters expansion chamber 2 and is scattered in the heavy oil through iron particle outlet 5 and iron particle inlet 6; Opening heavy oil that discharging opening 10 will be dispersed with nano-iron particle packs into and preserves in the closed container.
Above-mentioned nanometer iron-series catalyst is applied to the DCL/Direct coal liquefaction experiment: use Huo Lin river brown coal, with the hydrogenated residue is solvent, 350 ℃ of reaction temperatures, initial hydrogen pressure 6MPa, catalyst addition 5%, press Fe: the S mass ratio adds Cosan, reaction time 1.5 hour at 2: 3, coal conversion ratio 86.3%, oil-collecting ratio 57.2%.
Adopt preparation method and the device identical with embodiment 1 to produce Fe-series catalyst, wherein, liquid spacer medium is a phenol, and reative cell is warming up to 400 ℃, and feeding high pure nitrogen pressure is 2.5Mpa, iron pentacarbonyl steam 5L.Coal is changed to Shenhua east victory brown coal carries out coal liquefaction experiment, coal conversion ratio 89.5%, oil-collecting ratio 57%.
Adopt preparation method and the device identical with embodiment 1 to produce Fe-series catalyst, wherein, liquid spacer medium is a naphthane, and reative cell is warming up to 500 ℃, and feeding high pure nitrogen pressure is 5Mpa, iron pentacarbonyl steam 10L.Huo Lin river brown coal are carried out coal liquefaction experiment, coal conversion ratio 94.5%, oil-collecting ratio 58.4%.
Adopt preparation method and the device identical with embodiment 3 to produce Fe-series catalyst, wherein, liquid spacer medium is an ethanol, and reative cell is warming up to 300 ℃, and feeding high pure nitrogen pressure is 0.1Mpa, iron pentacarbonyl liquid 0.1L.Coal is changed to Shenhua east victory brown coal carries out coal liquefaction experiment, coal conversion ratio 91.6%, oil-collecting ratio 62%.
Adopt preparation method and the device production Fe-series catalyst identical with embodiment 3, wherein, liquid spacer medium is a water, and reative cell is warming up to 350 ℃, and pressure is 1Mpa, iron pentacarbonyl liquid 0.5L.Coal is changed to Shenhua east wins brown coal, carry out the coal liquefaction experiment, coal conversion ratio 85.6%, oil-collecting ratio 62.8%.
Adopt preparation method and the device production Fe-series catalyst identical with embodiment 3, wherein, liquid spacer medium is a carbolineum, and reative cell is warming up to 350 ℃, and pressure is 1Mpa, iron pentacarbonyl liquid 1L.Coal is changed to Shenhua east wins brown coal, carry out the coal liquefaction experiment, coal conversion ratio 86.7%, oil-collecting ratio 61.4%.
Claims (7)
1. nanometer iron-series catalyst is characterized in that: it is suspended in the liquid spacer medium less than the iron particle of 100nm by particle diameter forms.
2. the preparation method of the described nanometer iron-series catalyst of claim 1 is characterized in that this method is made up of following steps:
1. in expansion chamber, inject liquid spacer medium, vacuumize or with the air in high pure nitrogen or other inert gas replacement reative cell and the expansion chamber, vacuumize or replace and make high pure nitrogen or other inert gas in reative cell, keep certain pressure after finishing;
2. start the heater of reative cell, the reaction indoor temperature is higher than the critical-temperature of iron pentacarbonyl, opens the iron pentacarbonyl inlet, feeds iron pentacarbonyl liquid or steam in reative cell, iron pentacarbonyl decomposes in the high pure nitrogen of heat or other inert gas, obtains iron particle;
3. open the expansion chamber gas outlet, the vavuum pump that startup links to each other with the gas outlet, open simultaneously and connect iron particle outlet and the valve that enters the mouth, iron particle in the reative cell feeds in the liquid spacer medium of expansion chamber through iron particle outlet and inlet, be dispersed in liquid spacer medium in gas rising diffusion process, gas remaining or that produce is evacuated to exhaust treatment system by vavuum pump;
4. open the expansion chamber discharging opening, the suspension injection closed container of nano-iron particle and liquid spacer medium composition is preserved.
3. the preparation method of nanometer iron-series catalyst according to claim 2, it is characterized in that: the reative cell heating-up temperature is higher than the iron pentacarbonyl critical-temperature, be lower than 500 ℃, when adding iron pentacarbonyl steam, feeding amount and reaction chamber volume volume ratio 0.2 :-5: 1, when adding iron pentacarbonyl liquid, account for the 0.05-0.5 of reaction chamber volume.
4. the preparation method of nanometer iron-series catalyst according to claim 2, it is characterized in that: high pure nitrogen or other inert gas are 0.1-5Mpa in the reative cell internal pressure.
The preparation method of 5 nanometer iron-series catalysts according to claim 2 is characterized in that: the liquid medium addition accounts for the 0.5-0.8 of expansion chamber volume in the expansion chamber.
6. the preparation method of nanometer iron-series catalyst according to claim 2 is characterized in that: at least a in oil, fat, naphthalene, anthracene, phenanthrene, phenol, benzene, alcohols or the water of liquid barrier medium.
7. device of implementing the described nanometer iron-series catalyst preparation method of claim 2; it is characterized in that: this device is made up of reative cell (1) and expansion chamber (2); reative cell (1) is provided with iron pentacarbonyl liquid or steam inlet (3); iron particle outlet (5) and protection gas air inlet (4); expansion chamber (2) is provided with iron particle inlet (6); gas outlet (7); liquid medium inlet (8) and discharging opening (10); wherein iron particle inlet (6) stretches in the liquid state obstruct medium of expansion chamber (2); gas outlet (7) links to each other with vavuum pump (11), and the iron particle outlet (5) of reative cell (1) is connected by high pressure valve (9) with the iron particle inlet (6) of expansion chamber (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710022818A CN101099931B (en) | 2007-05-23 | 2007-05-23 | Nanometer iron-series catalyst and preparation method and device thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710022818A CN101099931B (en) | 2007-05-23 | 2007-05-23 | Nanometer iron-series catalyst and preparation method and device thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101099931A true CN101099931A (en) | 2008-01-09 |
| CN101099931B CN101099931B (en) | 2010-05-19 |
Family
ID=39034474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710022818A Expired - Fee Related CN101099931B (en) | 2007-05-23 | 2007-05-23 | Nanometer iron-series catalyst and preparation method and device thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101099931B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102666693A (en) * | 2009-10-27 | 2012-09-12 | 巴斯夫欧洲公司 | Heat aging-resistant polyamides with flame retardancy |
| CN110302807A (en) * | 2019-07-01 | 2019-10-08 | 山东大学 | A kind of preparation method and application of modified Zero-valent Iron liquid catalyst |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3428121A1 (en) * | 1984-07-31 | 1986-02-13 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING IRON POWDER |
| CN1049996C (en) * | 1995-09-04 | 2000-03-01 | 冶金工业部钢铁研究总院 | Manufacture method and device for metal magnetic liquid |
| CN1219303C (en) * | 2003-05-15 | 2005-09-14 | 中国科学院化学研究所 | Method for preparing magnetic nano microparticles with biological compatibility |
| CN100348501C (en) * | 2006-01-10 | 2007-11-14 | 江苏天一超细金属粉末有限公司 | Production and producer for nanometer ferric oxide |
-
2007
- 2007-05-23 CN CN200710022818A patent/CN101099931B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102666693A (en) * | 2009-10-27 | 2012-09-12 | 巴斯夫欧洲公司 | Heat aging-resistant polyamides with flame retardancy |
| CN110302807A (en) * | 2019-07-01 | 2019-10-08 | 山东大学 | A kind of preparation method and application of modified Zero-valent Iron liquid catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101099931B (en) | 2010-05-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9272920B2 (en) | System and method for ammonia synthesis | |
| CN102942971B (en) | Application of raney nickel as slurry reactor to synthesize methane catalyst | |
| CN101099932B (en) | High-efficient iron-series catalyst and its preparation method | |
| CN103949654A (en) | Supercritical hydro-thermal synthesis preparation system of nano particles | |
| JPS63146989A (en) | Hydrogeneration of heavy oil and residual oil | |
| CN106732606B (en) | A kind of kerosene co grinding method ferrum-based catalyst | |
| CA2472607A1 (en) | Catalyst enhancement | |
| CN103289722B (en) | Recycling method of iron-based waste catalyst for Fischer-Tropsch synthesis and direct coal liquefaction reaction catalyst | |
| CN104045569B (en) | By the dinitrotoluene (DNT) low-voltage hydrogenation synthesis technique of tolylene diamine and the method for making of catalyzer and catalyzer | |
| CN101099931B (en) | Nanometer iron-series catalyst and preparation method and device thereof | |
| US20090202417A1 (en) | System and method for ammonia synthesis | |
| WO2008008076A1 (en) | Improved method for activating an iron-based fischer-tropsch catalyst | |
| Gao et al. | Preparation of supported Mo2C-based catalysts from organic–inorganic hybrid precursor for hydrogen production from methanol decomposition | |
| CN107474875A (en) | A kind of method of hypergravity diesel oil and gasoline hydrofinishing | |
| CN101279260B (en) | Iron nickel Fischer-Tropsch synthetic catalyst and preparation thereof | |
| CN201042666Y (en) | Device for producing nano-iron catalyzer | |
| CN106810419A (en) | For graphene-supported metal composite in acetic acid preparation of ethanol through hydrogenation catalyst and preparation method thereof | |
| CN104058971B (en) | The dinitrotoluene (DNT) low-voltage hydrogenation synthesis continuous production processes of tolylene diamine and the method for making of catalyzer and catalyzer | |
| CN101190412B (en) | Fe catalyst for preparing hydrocarbons with synthesis gas and preparation method thereof | |
| CN102464299A (en) | Method for producing hydrogen through fluidized-bed methane steam reforming | |
| CN101099930B (en) | Nanometer iron-series catalyst and preparation method thereof | |
| US8092672B2 (en) | Method and apparatus for hydroprocessing low-volatile hydrocarbon materials into volatile liquids | |
| CN104058974B (en) | Dinitrotoluene (DNT) low-voltage hydrogenation produces the technique of tolylene diamine and the method for making of catalyzer and catalyzer | |
| CN111905791B (en) | Catalyst for preparing high-carbon alcohol from synthesis gas and preparation method thereof | |
| CN106635160A (en) | Coal-coal tar mixed hydrogenation system and process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100519 Termination date: 20160523 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |