CN102309966B - Preparation method for cobalt-based Fischer-Tropsch synthesis catalyst - Google Patents
Preparation method for cobalt-based Fischer-Tropsch synthesis catalyst Download PDFInfo
- Publication number
- CN102309966B CN102309966B CN 201010220846 CN201010220846A CN102309966B CN 102309966 B CN102309966 B CN 102309966B CN 201010220846 CN201010220846 CN 201010220846 CN 201010220846 A CN201010220846 A CN 201010220846A CN 102309966 B CN102309966 B CN 102309966B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- cobalt
- tropsch synthesis
- based fischer
- hours
- 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.)
- Active
Links
Abstract
The invention discloses a preparation method for a cobalt-based Fischer-Tropsch synthesis catalyst. The method comprises the processes of extracting, drying and roasting an inactivated cobalt-based Fischer-Tropsch synthesis catalyst and loading an active ingredient Co by the treated inactivated cobalt-based Fischer-Tropsch synthesis catalyst. The method has the advantages of low cost, simplicity in operation and the like; the prepared catalyst has good stability and high activity; and meanwhile, a new path is provided for reutilization of the inactivated cobalt-based Fischer-Tropsch synthesis catalyst.
Description
Affiliated field
The present invention relates to a kind of preparation method of Co based Fischer-Tropsch synthesis catalyst.
Background technology
Synthetic synthesis gas (the CO+H that refers to of Fischer-Tropsch
2) catalyze and synthesize the reaction of liquid hydrocarbon fuel on catalyst.Exhaustion day by day along with petroleum resources, be subject to the attention of countries in the world more with the Fischer-Tropsch synthesis prepare liquid fuel.In the research of the fischer-tropsch catalysts of nearly 80 years, people have found that Fe, Co and Ru etc. are the effective active components of fischer-tropsch catalysts, the various auxiliary elements such as Zr, K and Pt play an important role to activity, the stability of fischer-tropsch catalysts, and the carrier of catalyst is generally with unformed SiO
2, TiO
2, ZrO
2and Al
2o
3be main.Cobalt-base catalyst can not only generate heavy hydrocarbon to greatest extent, and cobalt-base catalyst carbon deposit tendency is low, active high.
CN1401736A has reported a kind of with ZrO
2preparation method for carrier, La or the Ce high-activity cobalt-based Fischer-Tropsch synthetic catalyst that is auxiliary agent.The catalyst weight percentage composition is: Co 5%-30%; La or Ce 0-5%; ZrO
270%-90%.In reaction temperature, be 220 ℃, under reaction pressure 2.5MPa, the conversion ratio of CO is 89.4%, C
1be selectively 6.5%, C
5 +be selectively 89.9%.Petrole et Technique.1988, introduced the Co catalysts used in the synthetic intermediate distillates technique (SMDS) of Shell Co. Ltd's Fischer-Tropsch in P415, it consists of 25Co:0.9Zr, Ti or Cr:100SiO
2(wt), cobalt is supported on silica gel by the method for dipping or kneading.At 220 ℃, 2.0MPa and 500h
-1under condition, the total conversion (CO+H of catalyst
2) be 75%, C
5 +be selectively 82%.The preparation method of the Co based Fischer-Tropsch synthesis catalyst of CN1454714A report be take sol-gal process and is made silica gel as carrier, adopts the ammonia spirit of 1%-25% to carry out surface modification to carrier, has improved the activity of catalyst.At 220 ℃, under 2MPa, conversion ratio is 90.1%, C
5 +be selectively 85.7%.
Co based Fischer-Tropsch synthesis catalyst is in the long time running process, and the active component cobalt easily reacts and generates cobaltous silicate, cobalt titanate and cobalt aluminate compounds and make catalysqt deactivation with carrier, the service life of reduction catalyst.The active component cobalt is buried or reclaimed to the existing processing mode of the Co based Fischer-Tropsch synthesis catalyst of inactivation.CN101270420A has introduced the recovery method of cobalt in a kind of Co based Fischer-Tropsch synthesis catalyst, the method is by deionized water and is to add in reactor at 1～5: 1 by weight containing cobalt Fischer-Tropsch decaying catalyst, the gas of CO is passed in reactor, its minute is pressed between 0.5MPa～5MPa, under the condition that low whipping speed is 50～700 rev/mins and 50～200 ℃ heating, constant temperature 0.5～12h; Cooling is emitted CO from reactor, from reactor, water being discharged, adds alkali lye solution in water, and cobalt is precipitated as cobalt hydroxide; Add nitric acid dissolve in precipitation, evaporative crystallization, obtain cobalt nitrate.
From said method, in order to improve the performance of Co based Fischer-Tropsch synthesis catalyst, not only need catalyst carrier is carried out to pretreatment and/or carried metal auxiliary agent, and the content of active component cobalt is also higher.This makes the cost of catalyst be much higher than Fischer-Tropsch synthetic iron-based catalyst.Hydrothermal strong due to cobalt, easily make catalysqt deactivation affect the life-span of catalyst in addition.To decaying catalyst, adopt the simple process mode of burying or reclaim the active component cobalt big for environment pollution.Above factor makes Co based Fischer-Tropsch synthesis catalyst be subject to certain restriction in industrial application.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of Co based Fischer-Tropsch synthesis catalyst.The method has that cost is low, simple operation and other advantages, also for the recycling of inactivation Co based Fischer-Tropsch synthesis catalyst, provides a kind of new way simultaneously.
The preparation method of Co based Fischer-Tropsch synthesis catalyst of the present invention comprises the process of inactivation Co based Fischer-Tropsch synthesis catalyst surface hydrocarbon product being carried out to separation process, drying and roasting process and inactivation Co based Fischer-Tropsch synthesis catalyst load active component Co.
Describedly inactivation Co based Fischer-Tropsch synthesis catalyst surface hydrocarbon product is carried out to separation process can adopt the way of distillation or solvent extraction process, the preferred solvent extraction process.Described extraction solvent is benzinum, benzene, toluene, normal octane and ethanol etc., preferably adopts normal octane and ethanol to carry out extracting.Extractive process can be carried out under the condition stirred, and also can be heated extractor system, and general temperature is controlled at 40-50 ℃.Carry out drying and roasting process after extracting, baking temperature is 80-100 ℃, and be 5-10h drying time, and sintering temperature is 300-400 ℃, and roasting time is 2-8 hour.
The process of inactivation Co based Fischer-Tropsch synthesis catalyst load active component Co after described processing comprises following content: inactivation Co based Fischer-Tropsch synthesis catalyst after processing dipping 2wt%-10wt% active metal component Co comprises aging, drying steps and calcination steps after dipping.Aging 2-150 hour, preferably 5-20 hour.Drying steps is dry 8-24 hour under 50-150 ℃, and calcination steps is at 280-600 ℃ of lower roasting 2-10 hour.
Described inactivation Co based Fischer-Tropsch synthesis catalyst comprise take silica, alundum (Al2O3), titanium dioxide and zirconium dioxide one or more be carrier, take metallic cobalt as active component, it is arbitrary inactivation Co based Fischer-Tropsch synthesis catalyst of auxiliary agent that a kind of or youngster of take in Re, Zr, Hf, Ce and Th plants, the inactivation Co based Fischer-Tropsch synthesis catalyst that the silica of preferably take is auxiliary agent as carrier, zirconium.
A kind of Co based Fischer-Tropsch synthesis catalyst adopts the method preparation of load active component cobalt on the inactivation Co based Fischer-Tropsch synthesis catalyst after processing.
Compared with prior art, the preparation method of Co based Fischer-Tropsch synthesis catalyst of the present invention has following advantage: the activity that is hydrothermal generation cobaltous silicate, cobalt titanate and the cobalt aluminate compounds rear catalyst of active component cobalt and carrier according to the Co based Fischer-Tropsch synthesis catalyst deactivation cause does not reach instructions for use.According to experimental studies have found that, after the Co based Fischer-Tropsch synthesis catalyst inactivation, be not that all active components have all lost catalytic performance, existing processing method is not fully examined or check the inactivation Co based Fischer-Tropsch synthesis catalyst, does not consider how effectively to utilize in the inactivation Co based Fischer-Tropsch synthesis catalyst this part component that still has certain catalytic activity.The inventive method adopts the methods such as solvent extraction, drying, roasting to be processed the cobalt-based decaying catalyst, and then on the cobalt-based decaying catalyst after processing, the supported active cobalt is prepared the Co based Fischer-Tropsch synthesis catalyst that is applicable to application again.The inventive method makes carrier, auxiliary agent and the active component cobalt of decaying catalyst obtain again utilizing, again the consumption of the active component cobalt of load is few, greatly reduce the cost of Co based Fischer-Tropsch synthesis catalyst, be conducive to the commercial Application of Co based Fischer-Tropsch synthesis catalyst.The preparation method of Co based Fischer-Tropsch synthesis catalyst of the present invention is also a kind of processing method of inactivation Co based Fischer-Tropsch synthesis catalyst simultaneously, compared with prior art has that cost is low, advantages of environment protection.The cobaltous silicate generated on the inactivation Co based Fischer-Tropsch synthesis catalyst in addition, cobalt titanate and cobalt aluminate compounds also can play the twice-modified effect to carrier, the hydro-thermal reaction of the Co based Fischer-Tropsch synthesis catalyst that inhibition is prepared again, the life-span of improving catalyst.In a word, the inventive method cost is low, simple to operate, has industrial application value.
The specific embodiment
Further illustrate process and the effect of the inventive method below in conjunction with embodiment.
Example 1
Get inactivation CoZr/SiO
2catalyst 50g, results of elemental analyses is zirconium content 2.85wt%, cobalt content 18.6wt%.At first adopt normal octane to separate 1-2 time with the catalyst mix extracting, then separate 1-3 time with the ethanol extracting, the extracting time is 5h, then carries out drying and roasting.Baking temperature is 90 ℃, and be 8h drying time, and roasting was 350 ℃ of lower roastings 4 hours.Finally take 20g, the amount dipping according to increasing 5wt%Co, take cobalt nitrate hexahydrate 4.94g solution in 27.06g distilled water, in the decaying catalyst dissolved fully after adding processing, be stirred to evenly, aging 5h, 50 ℃ of dryings 24 hours, in 280 ℃, roasting is 10 hours.The gained catalyst is designated as CFT-1.
Evaluating catalyst test, in the high pressure CSTR, is usingd paraffin as solvent, and with reduction under 350 ℃ of pure hydrogen 12 hours, pressure was 1.0MPa.After cooling, the switching synthesis gas is reacted.Reaction effluent is collected by hot trap, cold-trap respectively.Reaction condition is 180-250 ℃, 1000h
-1, 2.0MPa, H
2/ CO=2 (mol ratio).Turn round after 100 hours, CFT-1 catalyst Fischer-Tropsch synthesis result is as shown in table 1.
Example 2
Get inactivation CoZr/SiO
2catalyst 50g, results of elemental analyses is zirconium content 2.85wt%, cobalt content 18.6wt%.At first adopt normal octane to separate 1-2 time with the catalyst mix extracting, then separate 2-3 time with extracting under alcohol at normal temperature, the extracting time is 2h, and extraction temperature is controlled as 40-50 ℃, then carries out drying and roasting.Baking temperature is 80 ℃, and be 10h drying time.Roasting was 300 ℃ of lower roastings 8 hours.Then take 20g, the amount according to increasing dipping 7.5wt%Co, take cobalt nitrate hexahydrate 7.41g solution in 17.18g distilled water, treat to dissolve fully to add in above-mentioned dead catalyst and be stirred to evenly, aging 20h, 150 ℃ of dryings 8 hours, in 600 ℃, roasting is 2 hours.The gained catalyst is designated as CFT-2, and catalyst activity evaluation experimental condition is with embodiment 1.Turn round after 100 hours, CFT-2 catalyst Fischer-Tropsch synthesis result is as shown in table 1.
Example 3
Get inactivation CoZr/SiO
2catalyst 50g, results of elemental analyses is zirconium content 2.85wt%, cobalt content 18.6wt%.At first adopt normal octane to separate 2-3 time with catalyst mix extracting under stirring condition, then separate 1-3 time with the ethanol extracting, the extracting time is 8h, and extraction temperature is controlled as 40-50 ℃, then carries out drying and roasting.Baking temperature is 100 ℃, and be 5h drying time.Roasting was 400 ℃ of lower roastings 2 hours.Finally take 20g, the amount according to increasing dipping 10wt%Co, take cobalt nitrate hexahydrate 9.88g solution in 22.12g distilled water, treat to dissolve fully to add in above-mentioned dead catalyst to be stirred to evenly, and aging 10h, 80 ℃ of dryings 6 hours, in 400 ℃, roasting is 6 hours.The gained catalyst is designated as CFT-3, and catalyst activity evaluation experimental condition is with embodiment 1.Turn round after 100 hours, CFT-3 catalyst Fischer-Tropsch synthesis result is as shown in table 1.
Example 4
Get inactivation CoZr/TiO
2catalyst 50g, results of elemental analyses is zirconium content 2.68wt%, cobalt content 17.2wt%.At first adopt normal octane to separate 1-2 time with the catalyst mix extracting, then separate 1-3 time with the ethanol extracting, the extracting time is 5h, and extraction temperature is controlled as 40-50 ℃, then carries out drying and roasting.Baking temperature is 90 ℃, and be 8h drying time, and roasting was 350 ℃ of lower roastings 4 hours.Finally take 20g, the amount according to dipping 5wt%Co, take cobalt nitrate hexahydrate 4.94g solution in 15.08g distilled water, treat to dissolve fully to add in above-mentioned dead catalyst to be stirred to evenly, and aging 10h, 80 ℃ of dryings 6 hours, in 400 ℃, roasting is 6 hours.The gained catalyst is designated as CFT-4, and catalyst activity evaluation experimental condition is with embodiment 1.Turn round after 100 hours, CFT-4 catalyst Fischer-Tropsch synthesis result is as shown in table 1.
Example 5
Get inactivation CoZr/ γ-Al
2o
3catalyst 50g, results of elemental analyses is zirconium content 2.91wt%, cobalt content 19.3wt%.At first adopt normal octane to separate 1-2 time with the catalyst mix extracting, then separate 1-3 time with the ethanol extracting, the extracting time is 5h, and extraction temperature is controlled as 40-50 ℃, then carries out drying and roasting.Baking temperature is 90 ℃, and be 8h drying time, and roasting was 350 ℃ of lower roastings 4 hours.Finally take 20g, the amount according to dipping 5wt%Co, take cobalt nitrate hexahydrate 4.94g solution in 15.08g distilled water, treat to dissolve fully to add in above-mentioned dead catalyst to be stirred to evenly, and aging 10h, 80 ℃ of dryings 6 hours, in 400 ℃, roasting is 6 hours.The gained catalyst is designated as CFT-5, and catalyst activity evaluation experimental condition is with embodiment 1.Turn round after 100 hours, CFT-5 catalyst Fischer-Tropsch synthesis result is as shown in table 1.
Comparative example 1
Take commercially available silica gel 30g, by final catalyst zirconium content 3wt%, take nitrate trihydrate zirconium 4.24g and add water 43.76g and dissolve, treat to dissolve fully to add in carrier silica gel and be stirred to evenly, aging 12 hours, 80 ℃ of dryings 8 hours, in 350 ℃, roasting is 4 hours.By final catalyst cobalt content 20wt%, take cobalt nitrate hexahydrate 29.63g and be dissolved in 18.39g distilled water, add in the sample after above-mentioned dipping zirconium and be stirred to evenly, aging 12 hours, 80 ℃ of dryings 8 hours, in 350 ℃, roasting is 4 hours.The gained catalyst is designated as CFT-6 catalyst activity evaluation experimental condition with embodiment 1.Turn round after 100 hours, CFT-6 catalyst Fischer-Tropsch synthesis result is as shown in table 1.
The reactivity worth of table 1 catalyst
Claims (1)
1. the preparation method of a Co based Fischer-Tropsch synthesis catalyst, is characterized in that comprising being prepared as follows step: get inactivation CoZr/ γ-Al
2o
3catalyst 50g, results of elemental analyses is zirconium content 2.91wt%, cobalt content 19.3wt%, at first adopt normal octane to separate 1-2 time with the catalyst mix extracting, with the ethanol extracting, separate 1-3 time again, the extracting time is 5h, extraction temperature is controlled as 40-50 ℃, then carry out drying and roasting, baking temperature is 90 ℃, be 8h drying time, roasting was 350 ℃ of lower roastings 4 hours, finally take 20g, amount according to dipping 5wt%Co, taking cobalt nitrate hexahydrate 4.94g is dissolved in 15.08g distilled water, treat to dissolve fully to add in dead catalyst and be stirred to evenly, aging 10h, 80 ℃ of dryings 6 hours, in 400 ℃, roasting is 6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010220846 CN102309966B (en) | 2010-07-07 | 2010-07-07 | Preparation method for cobalt-based Fischer-Tropsch synthesis catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010220846 CN102309966B (en) | 2010-07-07 | 2010-07-07 | Preparation method for cobalt-based Fischer-Tropsch synthesis catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102309966A CN102309966A (en) | 2012-01-11 |
| CN102309966B true CN102309966B (en) | 2013-06-19 |
Family
ID=45423756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010220846 Active CN102309966B (en) | 2010-07-07 | 2010-07-07 | Preparation method for cobalt-based Fischer-Tropsch synthesis catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102309966B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105727978B (en) * | 2014-12-06 | 2018-01-16 | 中国石油化工股份有限公司 | A kind of method for preparing catalyst for making ethylene from ethane oxidative dehydrogenation |
| CN105727977B (en) * | 2014-12-06 | 2017-12-22 | 中国石油化工股份有限公司 | A kind of synthesis gas methanation substitutes the method for preparing catalyst of natural gas |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1750876A (en) * | 2002-01-29 | 2006-03-22 | 埃克森美孚研究工程公司 | Catalyst regeneration |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6869978B2 (en) * | 1999-11-17 | 2005-03-22 | Conocophillips Company | Pressure swing catalyst regeneration procedure for Fischer-Tropsch catalyst |
-
2010
- 2010-07-07 CN CN 201010220846 patent/CN102309966B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1750876A (en) * | 2002-01-29 | 2006-03-22 | 埃克森美孚研究工程公司 | Catalyst regeneration |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102309966A (en) | 2012-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103055928A (en) | Catalyst for preparing arene via direct methanol conversion and preparation method thereof | |
| CN110152663A (en) | It is a kind of for the catalyst of preparation by furfural gas phase hydrogenation furfuryl alcohol and its preparation and application | |
| CN102441386B (en) | Novel Fischer Tropsch synthesis method | |
| JP2021520992A (en) | A method for producing a catalyst used when synthesizing aviation kerosene from syngas, a catalyst obtained by the method, and its use. | |
| CN102309966B (en) | Preparation method for cobalt-based Fischer-Tropsch synthesis catalyst | |
| CN102029166B (en) | Catalyst for preparing low-carbon mixed alcohol by using synthesis gas and preparation method thereof | |
| CN112973718B (en) | Kerosene co-hydrogenation catalyst and preparation method thereof | |
| CN101920204B (en) | Preparation method of cobalt-based Fischer-Tropsch synthesis catalyst | |
| CN102861581B (en) | Preparation method for cobalt-based Fischer-Tropasch synthetic catalyst | |
| CN111167484B (en) | Hydrodeoxygenation catalyst for oxygen-containing derivatives of benzene, preparation method thereof and application of hydrodeoxygenation catalyst in preparation of cycloparaffins | |
| CN110129084B (en) | Biomass hydrogen supply-catalytic liquefaction coupling method and supported biomass liquefaction catalyst | |
| CN101518738A (en) | Dolomite catalyst for preparing hydrogen-rich gas from coke oven gas and method for preparing same | |
| CN103769101B (en) | A kind of Co based Fischer-Tropsch synthesis catalyst and its preparation method and application | |
| CN102441388B (en) | Preparation method for cobalt-base Fischer Tropsch synthetic catalyst with high stability | |
| CN112062673B (en) | Method for directionally synthesizing methyl lactate by catalytically converting fructose by one-pot method | |
| CN101524644B (en) | Cobalt-based catalyst for the oil-wax co-production of synthetic natural gas, preparation method and application thereof | |
| CN110093179A (en) | A kind of method that the upgrading of lignin mink cell focus prepares biological oxygenated fuel | |
| CN101920203A (en) | Method for preparing cobalt-based Fischer-Tropsch synthesis catalyst | |
| CN103769109B (en) | A kind of syngas conversion catalyst and its preparation method and application | |
| CN103769098B (en) | A kind of syngas conversion catalyst and its preparation method and application | |
| CN103769102B (en) | A kind of cobalt-base catalyst and its preparation method and application | |
| CN103769097B (en) | A kind of preparation method of Co based Fischer-Tropsch synthesis catalyst | |
| CN114797878B (en) | Method for preparing tar catalytic cracking reforming hydrogen production and carbon dioxide adsorption dual-function catalyst by using biomass ash | |
| CN103769099B (en) | A kind of Co based Fischer-Tropsch synthesis catalyst and its preparation method and application | |
| CN102441389B (en) | Preparation method of cobalt-based catalyst for Fischer Tropsch synthesis |
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 |