CN106582658A - Preparation method of Fischer-Tropsch synthesis iron-based catalyst - Google Patents

Preparation method of Fischer-Tropsch synthesis iron-based catalyst Download PDF

Info

Publication number
CN106582658A
CN106582658A CN201510680014.7A CN201510680014A CN106582658A CN 106582658 A CN106582658 A CN 106582658A CN 201510680014 A CN201510680014 A CN 201510680014A CN 106582658 A CN106582658 A CN 106582658A
Authority
CN
China
Prior art keywords
precipitation
iron
ageing
fischer
container
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
Application number
CN201510680014.7A
Other languages
Chinese (zh)
Inventor
朱加清
常海
刘庆华
程萌
武鹏
张魁
罗明生
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenhua Group Corp Ltd
National Institute of Clean and Low Carbon Energy
Original Assignee
Shenhua Group Corp Ltd
National Institute of Clean and Low Carbon Energy
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shenhua Group Corp Ltd, National Institute of Clean and Low Carbon Energy filed Critical Shenhua Group Corp Ltd
Priority to CN201510680014.7A priority Critical patent/CN106582658A/en
Publication of CN106582658A publication Critical patent/CN106582658A/en
Pending legal-status Critical Current

Links

Abstract

The invention discloses a preparation method of a precipitating catalyst precursor and a preparation method of Fischer-Tropsch synthesis iron-based catalyst. The method comprises the steps that 1, a precipitator solution and a metal salt solution containing iron salt perform precipitation reaction in a precipitation container to produce iron-based precipitate coarse slurry; 2, the iron-based precipitate coarse slurry is aged in an ageing container; 3, the aged iron-based precipitate is washed and filtered to remove impurities, and then slurry is prepared; 4, the slurry is mixed with a silicon source, a pH value is regulated, and a Fischer-Tropsch synthesis iron-based catalyst precursor is obtained through filtration and optimal drying, wherein the precipitation reaction and the ageing process are sequentially performed in the precipitation container and the ageing container which are different and are serially connected mutually so as to perform the precipitation reaction and the ageing process. By the adoption of the method, continuous production of the prepared Fischer-Tropsch synthesis iron-based catalyst precursor can be achieved, and the quality and the performance of the catalyst can be also improved.

Description

A kind of preparation method of Fischer-Tropsch synthetic iron-based catalyst
Technical field
The present invention relates to a kind of preparation method of sedimentation type catalyst precursor and Fischer-Tropsch synthetic iron-based catalysis The preparation method of agent.
Background technology
F- T synthesis are by synthesis gas (CO+H2) in the presence of catalyst synthetic liquid fuel and other The course of reaction of chemicals.The conventional catalyst of business has ferrum-based catalyst, wherein prepare precipitation iron-based urging The method of agent is different, by the pattern of appreciable impact catalyst, thing phase, surface texture and intensity, finally Affect the reactivity worth of catalyst.Therefore, develop the ferrum of the industrialized unit for being suitable for coal liquefaction technology Base catalyst is very important.
CN201061758Y discloses a kind of continuous hybrid reaction of pipeline for blood plasma precipitates reaction Device, including reaction tube, the reaction tube are externally provided with coolant chuck and shell, are provided between coolant chuck and shell Cold-keeping Layer, between coolant chuck and reaction tube constitute coolant sandwich passage, two sections of coolant sandwich passage respectively with The turnover adapter of one coolant is connected.
CN1404920A discloses a kind of catalyst for by synthesis gas liquid hydrocarbon, constitutes weight ratio For ferrum oxide:Copper oxide:Potassium oxide:Silicon dioxide=100:0.0876-8.76:0.084-12.64:7.5-29.94. The preparation method for specifically disclosing the catalyst is:The slaine for being first respectively configured ferric nitrate and copper nitrate is molten Liquid, and the precipitant solution of ammonia and potassium silicate;Metal salt solution and precipitant solution cocurrent are entered In the bottom of continuous precipitation reactor, and holding reactor, the flow regime of solution is piston flow, and it is heavy to prepare Form sediment;Precipitation is filtered, pH value is adjusted in slurrying and dry cake is used as catalyst precursor;Finally with carbonic acid Potassium solution impregnated catalyst precursor, and dry, roasting is obtained catalyst.
CN102658148A discloses a kind of Fischer-Tropsch synthetic iron-based catalyst and preparation method thereof, including: 1) iron salt, mantoquita, the aqueous solution of cobalt salt and wet chemical coprecipitation reaction are precipitated into slurry; 2) by precipitate slurry Jing after burin-in process, add water after stirring, concentration removes part moisture content;3) will Potassium silicate water glass or Ludox are added in the precipitate slurry after concentration, are stirred, and stand 0-180 Minute;4) step 3) obtained by slurry is spray-dried, after roasting, obtain Fischer-Tropsch synthetic iron-based catalysis Agent, catalyst consist of Fe2O3:Cu:K:SiO2:Co=100:(1-10):(1-10):(5-30): (0.5-20)。
But, prior art is prepared in the method for precipitated iron-based catalyst, is usually taken with agitator Tank reactor in intermittently carry out, wherein, precipitation and ageing process usually hold in same reaction Carry out in device, so cause to realize the continuous prodution of catalyst preparation, and material is anti-in autoclave Answer the flowing in device to there is Concentraton gradient, thermograde and pH value gradient, affect the matter of final catalyst Amount.
Therefore, in order to improve the production efficiency of Fischer-Tropsch synthesis catalyst, prepare the precipitation of better quality Ferrum-based catalyst, needs to develop the preparation expense of a kind of new be carried out continuously precipitation and ageing process The method of support synthesis iron base catalyst precursor.
The content of the invention
The invention aims to continuously produce Fischer-Tropsch synthetic iron-based catalyst precursor and improve catalyst Quality and performance, there is provided a kind of preparation method of Fischer-Tropsch synthetic iron-based catalyst precursor, meanwhile, this Invention also provides a kind of preparation method of sedimentation type catalyst precursor.
According to the first aspect of the invention, there is provided a kind of preparation method of sedimentation type catalyst precursor, Including:(1) by precipitant solution and the front body comprising sedimentation type catalyst active component in precipitation vessel The solution of body is sufficiently mixed, so as to Jing precipitation produces the precursor of the active component of catalyst containing sedimentation type Precipitate unscreened stock liquid;(2) above-mentioned precipitate unscreened stock liquid is aged in ageing container, is made small Precipitate particles gradually reunite or assemble, so as to further improve the physical arrangement of precipitate, wherein, The precipitation vessel and the ageing container are different, but the container that is serially connected, so that the precipitation Reaction and ageing process are continuously carried out in the precipitation vessel and ageing container successively.
According to the second aspect of the invention, there is provided a kind of preparation of Fischer-Tropsch synthetic iron-based catalyst precursor Method, including:(1) precipitant solution is sunk in precipitation vessel with the metal salt solution containing iron salt Form sediment and react, produce the iron-based precipitate unscreened stock of the precursor containing Fischer-Tropsch synthetic iron-based catalyst active component Liquid;(2) above-mentioned iron-based precipitate unscreened stock liquid is aged in ageing container, to realize the iron-based The reunion or aggregation of precipitation finely particulate, further improves the physical arrangement of the iron-based precipitate;(3) Iron-based precipitate after ageing is carried out washing, filtered, after removing wherein impurity, ferrum containing F- T synthesis is made The serosity of the precursor of base catalyst active component;(4) by the serosity and silicon source in step (3) Mix and adjust pH value, then Jing is filtered and is optionally dried, and obtains body before Fischer-Tropsch synthetic iron-based catalyst Body;Wherein, the precipitation and ageing process are successively in different, but the precipitation that is serially connected Carry out in container and ageing container, continuously to carry out the precipitation and ageing process.
The inventive method is by sedimentation type catalyst precursor or the shape of Fischer-Tropsch synthetic iron-based catalyst precursor It is divided in different, but the precipitation vessel that is serially connected and the precipitation carried out in ageing container into process Process and ageing two stages of (aging) process, it is achieved thereby that precipitation process and ageing (aging) mistake The tight linking of journey and continuous operation, wherein, first paragraph is precipitation section, can tubular type it is static or Carry out in dynamic mixing reactor;Second segment is ageing section, can carry out in tubular type digestion tank;It is so real The consecutive production of sedimentation type catalyst precursor or Fischer-Tropsch synthetic iron-based catalyst precursor is prepared now, also Quantity, size and the uniformity of the crystal seed of the catalyst precursor of preparation can be better controled over, is thus urged Fischer-Tropsch synthetic iron-based catalyst prepared by agent precursor has more preferable pore structure and tear strength, more excellent Different catalyst quality and performance, the stability of Fischer-Tropsch synthesis become more preferable.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of description, with Detailed description below is used for explaining the present invention together, but is not construed as limiting the invention. In accompanying drawing:
Fig. 1 is a kind of preparation of the Fischer-Tropsch synthetic iron-based catalyst precursor of embodiment that the present invention is provided The flow chart of method.
Description of reference numerals
1st, the metal salt solution 2 containing iron salt, precipitant solution 3, the first feed pump
4th, the second feed pump 5, static mixer 6, online pH detectors
7th, tubular type ageing reactor 8, ageing product
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place is retouched The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of sedimentation type catalyst precursor, including:(1) in precipitation Solution in container by precipitant solution with the precursor comprising sedimentation type catalyst active component is fully mixed Close, so as to Jing precipitation produces the precipitate unscreened stock of the precursor of the active component of catalyst containing sedimentation type Liquid;(2) above-mentioned precipitate unscreened stock liquid is aged in ageing container, makes small precipitate particles Gradually reunite or assemble, so as to further improve the physical arrangement of precipitate, wherein, the precipitation vessel It is different, but the container that is serially connected with the ageing container, so as to the precipitation and be aged Cheng Yici is continuously carried out in the precipitation vessel and ageing container.
The invention provides a kind of preparation method of Fischer-Tropsch synthetic iron-based catalyst precursor, as shown in figure 1, Including:(1) precipitant solution is carried out into precipitation in precipitation vessel with the metal salt solution containing iron salt, Produce the iron-based precipitate unscreened stock liquid of the precursor containing Fischer-Tropsch synthetic iron-based catalyst active component;(2) exist Above-mentioned iron-based iron-based precipitate unscreened stock liquid is aged in ageing container, to realize the iron-based precipitation The reunion or aggregation of finely particulate, further improves the physical arrangement of the iron-based precipitate;(3) it is right Iron-based precipitate after ageing is carried out washing, is filtered, and is made containing Fischer-Tropsch synthetic iron-based after removing wherein impurity The serosity of the precursor of catalyst active component;(4) serosity in step (3) is mixed with silicon source Merge and adjust pH value, then Jing is filtered and is optionally dried, and obtains Fischer-Tropsch synthetic iron-based catalyst precursor; Wherein, the precipitation and ageing process are in different, but the precipitation vessel that is serially connected and old Carry out in changing container, continuously to carry out the precipitation and ageing process.
The inventive method is by sedimentation type catalyst precursor or the shape of Fischer-Tropsch synthetic iron-based catalyst precursor It is divided into precipitation section and ageing two stages of section into process, the two stages are serially connected different Implement in container, the process in above-mentioned two stage can be made each individually to carry out, i.e., be closely connected again mutually not Affect, so as to overcome in prior art, successively carry out precipitation and ageing process in a vessel It is had to face exchange because precipitating and being aged two processes, and caused precipitation and ageing process The technical problem that intermittently must be carried out;The inventive method is made containing effective group of Fischer-Tropsch synthetic iron-based catalyst The iron-based precipitate unscreened stock liquid of the precursor for dividing enters during ageing container is directly entered from after precipitation vessel discharge Row ageing, it is possible to achieve sedimentation type catalyst precursor or Fischer-Tropsch synthetic iron-based catalyst precursor it is continuous Metaplasia is produced, and can better control over the number of the crystal seed of the Fischer-Tropsch synthetic iron-based catalyst precursor of preparation Amount, size and uniformity, further improve the Fischer-Tropsch synthetic iron-based catalysis that thus prepared by catalyst precursor The pore structure and tear strength of agent, improves the quality and performance of catalyst.
, according to the invention it is preferred in the case of, the precipitation vessel is static mixer or dynamic mixer. For precipitation reaction, expect to participate in the raw material of the precipitation:Precipitant solution and containing iron salt There can be violent mixing between metal salt solution.Precipitated in static mixer or dynamic mixer The stage of reaction, using the teaching of the invention it is possible to provide have sufficient back-mixing in the flow regime of material, promotes precipitant solution and contains Efficiently mixed between the metal salt solution of iron salt, be conducive to thoroughly carrying out for precipitation.
In the present invention, static mixer or dynamic mixer can be conventional use of such blender, As long as meeting the time of staying of the material of stage of reaction requirement in blender.For example, static mixing The length of device or dynamic mixer can be the length of 0.5-200m, static mixer or dynamic mixer Degree is 1-200 with the ratio of diameter.The static mixer or dynamic that for example can be provided for the positive sky in Beijing is mixed Clutch.
Preferably, the temperature of the precipitation is 30-90 DEG C, and the pH value of the precipitation is 5-10.
PH meter probe 6 can be set in the end of the precipitation vessel in the present invention, be examined with on-line continuous Survey the iron-based precipitate of the precursor containing Fischer-Tropsch synthetic iron-based catalyst active component that precipitation is obtained The pH value of unscreened stock liquid.
Preferably, the time of the precipitation can be material in static mixer or dynamic mixer The time of staying.It is possible to further pass through to control precipitant solution and the metal salt solution containing iron salt Charging rate, meets the time of staying of needs.The time of the precipitation is 15-60min.
, according to the invention it is preferred in the case of, also contain mantoquita, cobalt salt, rare earth in the metal salt solution At least one in slaine, manganese salt and potassium salt.
, according to the invention it is preferred in the case of, the concentration of the slaine contained in the metal salt solution is big In 0 weight % and less than or equal to 50 weight %.It is each that the concentration contains in referring to the metal salt solution The respective concentration of slaine.Specifically, the concentration of iron nitrate solution is 1-40 weight %, and copper nitrate is molten The concentration of liquid is 0.01-5 weight %, and the concentration of manganese nitrate solution is 0.01-5 weight %, cobalt nitrate solution Concentration be 0.01-5 weight %.
, according to the invention it is preferred in the case of, water of the slaine contained in the metal salt solution for metal Soluble, for example, can be the halogenide of the nitrate and/or metal of metal;Specifically, as ferric nitrate, Copper nitrate, manganese nitrate, cobalt nitrate.
Preferably, the temperature of the metal salt solution is 0-70 DEG C.
, according to the invention it is preferred in the case of, the concentration of the precipitant contained in the precipitant solution is 1-50 weight %.The concentration is the respective concentration of precipitant contained in the precipitant solution.
Preferably, the precipitant is carbonate and/or ammonia.Specifically, the carbonate can be Sodium carbonate or potassium carbonate.
In the present invention, the active component potassium contained in Fischer-Tropsch synthetic iron-based catalyst can pass through preparation process In number of ways add, for example can be containing potassium salt, or the precipitant in the metal salt solution Contain potassium element in containing potassium salt, or the silicon source in solution.The inventive method can also be included to roasting Potassium-containing compound is introduced in burning product, the introducing of component of potassium is realized.Generally, the catalyst active component Incorporation way be preferably infusion process or the sedimentation method.Preferably, the introducing potassium unit during silicon source is introduced Element, for example, add the compound containing potassium element, such as potassium silicate.
, according to the invention it is preferred in the case of, the ageing container is tubular type digestion tank.Ageing stage is to thing The requirement of material flow regime is different from precipitation reaction:Now precipitant solution and the slaine containing iron salt Precipitation between solution is completed, but the iron-based precipitation of formation is reacted in needing reasonable control material The growth of the crystal seed of thing, realizes the gradually reunion or aggregation of the iron-based precipitate fine particle, enters one Step improves the physical arrangement of the iron-based precipitate.The present invention distinguishes both different Flow of Goods and Materials shapes State, respectively operational control, to realize the continuous prodution of Fischer-Tropsch synthetic iron-based catalyst precursor, and has Beneficial to the quality and performance that improve the Fischer-Tropsch ferrum-based catalyst for further preparing.
In the present invention, tubular type ageing reactor can be shell-and-tube reactor.Tubular type is aged the selection of reactor As long as satisfaction prepares the time of the ageing of Fischer-Tropsch synthetic iron-based catalyst precursor needs, i.e., material is in tubular type The time of staying in ageing reactor.For example, the ratio of the length and diameter of tubular type ageing reactor can Think 1-1000, the diameter of tubular type ageing reactor can be 0.001-10m.
In the present invention, the precipitation vessel and the ageing container can be one, or multiple, Precipitation vessel and the respective particular number of the ageing container can determine according to actual needs, for example, two After individual precipitation vessel and two ageing containers are each connected, the precipitation vessel of two series connection is connected with two again Ageing container series connection.
Preferably, the temperature of the ageing is 30-90 DEG C.
Preferably, the time of the ageing can be the iron-based precipitate unscreened stock liquid that the precipitation is obtained The time of staying in reactor is aged in tubular type.Preferably, the time of the ageing is 0.01-6h.
Washing and filtration in the step (3) of the present invention can be method conventional in the art, washing Temperature can be 20-90 DEG C.
, according to the invention it is preferred in the case of, contain Fe in the serosity in step (3)2O3, which is dense Spend for 1-40 weight %.
According to the present invention, step (4) is for adding silicon components, and adjusts the pH value of serosity.It is preferred that feelings Under condition, the silicon source is potassium silicate solution and/or Ludox.
Preferably, the modulus of potassium silicate solution is 0.5-10, and the concentration of solution is 5-50 weight %.
Preferably, SiO in Ludox2Content be 5-50 weight %, pH value be 1-5 or 8-12.
Preferably, it is 4-8 the slurry pH value to be adjusted in step (4).Wherein can be by adding acid It is adjusted pH value, such as nitric acid, acetic acid or oxalic acid.
The Fischer-Tropsch synthetic iron-based catalyst precursor prepared using the inventive method, can further prepare expense Support synthesis iron base catalyst.Concrete grammar can be:By the Fischer-Tropsch synthetic iron-based catalyst precursor and water Spraying slurry is mixed to prepare, the spraying slurry is carried out into spray drying forming and roasting, Fischer-Tropsch conjunction is obtained Into ferrum-based catalyst.
Wherein, the solid content of the spraying slurry is 10-50 weight %.
The hot blast temperature of the spray drying is 200-500 DEG C, and leaving air temp is 90-250 DEG C.
The condition of the roasting can include:Point two-stage roasting, first stage under air atmosphere:Temperature For 70-200 DEG C, the time is 1-12 hours;Second stage:Temperature is 300-800 DEG C, and the time is 1-10 Hour.
Flow chart with reference to shown in Fig. 1, exemplarily further illustrates the inventive method.
By the metal salt solution 1 containing iron salt by the first feed pump 3, while precipitant solution 2 is passed through Feed pump 4 carries out precipitation in adding static mixer 5 (precipitation vessel).In static mixer 5 The outlet of (precipitation vessel) determines the pH value of the slurry that precipitation is obtained with online pH detectors 6, See and whether meet requirement, and slurry is aged into tubular type digestion tank 7 (ageing container). Agitator can be provided with tubular type digestion tank 7 (ageing container) as needed, to be conducive to control old The crystal seed quantity of the precipitate that precipitation is obtained during change, size and uniformity, it is described heavy to realize The gradually reunion of starch molecule or aggregation, further improve the physical arrangement of the precipitate;In pipe The outlet of formula digestion tank 7 (ageing container) obtains being aged serosity 8.
Ageing serosity 8 is sequentially entered into follow-up washing, filtration step and removes impurity therein, Ran Houzai The product for obtaining is made into serosity;To in serosity, add silicon source to be mixed, and acid adding is adjusted pH Step, eventually passes through filter and is optionally dried, obtain Fischer-Tropsch synthetic iron-based catalyst precursor.
Further, by Fischer-Tropsch synthetic iron-based catalyst precursor be made as spray slurry, it is spray-dried into Type step and calcination stepses, obtain Fischer-Tropsch synthetic iron-based catalyst.
Hereinafter will be described the present invention by embodiment.
In following examples and comparative example, the component analyses of the Fischer-Tropsch synthetic iron-based catalyst of preparation pass through XRF methods are measured;
The pore structure of Fischer-Tropsch synthetic iron-based catalyst is measured by BET methods;
The abrasion index of Fischer-Tropsch synthetic iron-based catalyst is measured by gas jet method.
Embodiment 1
This example demonstrates that the preparation method of Fischer-Tropsch synthetic iron-based catalyst precursor of the present invention and catalyst.
(1) precipitation reaction:By nine water ferric nitrates of 25kg, 0.77kg copper nitrates, six water of 0.77kg Cobalt nitrate dissolves in deionized water, and (metal salt concentrations are 16.59 weights to be made into 160 liters of metal salt solutions Amount %);12.5kg sodium carbonate deionized water is dissolved, 140 liters of precipitant solution (sodium carbonate are made into Concentration is 8.9 weight %);
By metal salt solution and precipitant solution by corresponding feed pump, static mixer is separately added into (precipitation vessel) (a diameter of 250mm, draw ratio be 10) in carry out precipitation, precipitation Temperature is 90 DEG C, and it is 8.5 that on-line pH value detector controls the pH value of precipitation, the precipitation time For 20min;
(2) ageing stage:The coarse particles that precipitation reaction is obtained are continuously flowed into into tubular type digestion tank (straight Footpath is 250mm, and draw ratio is that Aging Temperature is 90 DEG C, digestion time 25) in (ageing container) For 15min;
(3) washing and filtering:Ageing product is gone after the removal of impurity Jing band filter washing, by filter cake system Into serosity, wherein Fe2O3Concentration is 18 weight %;
(4) add silicon source:By SiO2Content is that the Ludox that 20 weight %, pH are 9 adds step (3) Made by serosity, stir at 60 DEG C 30 minutes and mix, and to add nitric acid to adjust slurry pH value be 5, Jing is filtered and is obtained Fischer-Tropsch synthetic iron-based catalyst precursor again;
(5) catalyst processed:Fischer-Tropsch synthetic iron-based catalyst precursor and water are mixed to prepare into spraying slurry, Solid content is 40 weight %;Spraying slurry is sent into spray dryer carries out molding, and hot blast temperature is 250 DEG C, leaving air temp is 90 DEG C;Molding materials are carried out under air atmosphere roasting, first stage temperature is 200 DEG C, the time is 1 hour;Second stage temperature is 600 DEG C, and the time is 2 hours.Obtain Fischer-Tropsch conjunction Into ferrum-based catalyst FTC-1.
Catalyst FTC-1 is tested, 1 is the results are shown in Table.
Catalyst FTC-1 composition analysis are:Fe2O3:Cu:K:SiO2:Co=100:4.1:1.8: 15:3.
Embodiment 2
This example demonstrates that the preparation method of Fischer-Tropsch synthetic iron-based catalyst precursor of the present invention and catalyst.
(1) precipitation reaction:By nine water ferric nitrates of 25kg, 0.20kg copper nitrates, 2.15kg nitric acid Manganese solution dissolves in deionized water, is made into 50 liters of metal salt solutions (metal salt concentrations are 51 weight %); 12.5kg potassium carbonate deionized water is dissolved, (concentration of potassium carbonate is 63 to be made into 20 liters of precipitant solutions Weight %);
By metal salt solution and precipitant solution by corresponding feed pump, static mixer is separately added into (precipitation vessel) (diameter 500mm, draw ratio be 5) in carry out precipitation, precipitation reaction temperature For 30 DEG C, it is 10 that on-line pH value detector controls the pH value of precipitation, and the precipitation time is 60min;
(2) ageing stage:The coarse particles that precipitation reaction is obtained are continuously flowed into into tubular type digestion tank (straight Footpath is 500mm, and draw ratio is that Aging Temperature is 30 DEG C, digestion time 100) in (ageing container) For 60min;
(3) washing and filtering:Ageing product is gone after the removal of impurity Jing band filter washing, by filter cake system Into serosity, wherein Fe2O3Concentration is 18 weight %;
(4) add silicon source:By SiO2Content is that the Ludox that 20 weight %, pH are 11 adds step (3) Made by serosity, stir at 60 DEG C 30 minutes and mix, and to add acetic acid to adjust slurry pH value be 5, Jing is filtered and is obtained Fischer-Tropsch synthetic iron-based catalyst precursor again;
(5) catalyst processed:Fischer-Tropsch synthetic iron-based catalyst precursor and water are mixed to prepare into spraying slurry, Solid content is 40 weight %;Spraying slurry is sent into spray dryer carries out molding, and hot blast temperature is 250 DEG C, leaving air temp is 90 DEG C;Molding materials are carried out under air atmosphere roasting, first stage temperature is 200 DEG C, the time is 1 hour;Second stage temperature is 500 DEG C, and the time is 3 hours.Obtain Fischer-Tropsch conjunction Into ferrum-based catalyst FTC-2.
Catalyst FTC-2 is tested, 1 is the results are shown in Table.
Catalyst FTC-2 composition analysis are:Fe2O3:Cu:K:SiO2:Mn=100:1:10:5: 6.5。
Embodiment 3
This example demonstrates that the preparation method of Fischer-Tropsch synthetic iron-based catalyst precursor of the present invention and catalyst.
(1) precipitation reaction:By nine water ferric nitrates of 25kg, 0.20kg copper nitrates, six water of 0.14kg Cobalt nitrate dissolves in deionized water, is made into 50 liters of metal salt solutions (metal salt concentrations are 51 weight %); 12.5kg potassium carbonate deionized water is dissolved, (concentration of potassium carbonate is 63 to be made into 20 liters of precipitant solutions Weight %);
By metal salt solution and precipitant solution by corresponding feed pump, dynamic mixer is separately added into (a diameter of 500mm, draw ratio are 10) to carry out precipitation, precipitation temperature in (precipitation vessel) Spend for 90 DEG C, it is 5 that on-line pH value detector controls the pH value of precipitation, the precipitation time is 40min;
(2) ageing stage:The slurry that the stage of reaction is obtained is continuously flowed into into tubular type ageing reactor (straight Footpath is 500mm, and draw ratio is that 200), Aging Temperature is 30 DEG C, and digestion time is 120min;
(3) washing and filtering:Ageing product is gone after the removal of impurity Jing band filter washing, by filter cake system Into serosity, wherein Fe2O3Concentration be 18 weight %;
(4) add silicon source:It is 20 weight % by silica concentration, pH is that 8 Ludox adds step Suddenly in serosity made by (3), stir at 60 DEG C 30 minutes and mix, and add nitric acid to adjust serosity PH value is 5, then Jing is filtered and obtained Fischer-Tropsch synthetic iron-based catalyst precursor;
(5) catalyst processed:Fischer-Tropsch synthetic iron-based catalyst precursor and water are mixed to prepare into spraying slurry, Solid content is 20 weight %;Spraying slurry is sent into spray dryer carries out molding, and hot blast temperature is 250 DEG C, leaving air temp is 90 DEG C;Molding materials are carried out under air atmosphere roasting, first stage temperature is 200 DEG C, the time is 1 hour;Second stage temperature is 500 DEG C, and the time is 3 hours.Obtain Fischer-Tropsch conjunction Into ferrum-based catalyst FTC-3.
Catalyst FTC-3 is tested, 1 is the results are shown in Table.
Catalyst FTC-3 composition analysis are:Fe2O3:Cu:K:SiO2:Co=100:1:10:5: 0.5。
Comparative example 1
Method according to CN102658148A disclosed embodiments 4 prepares comparative catalyst DC-1.
The component of catalyst DC-1 is:Fe2O3:Cu:K:SiO2:Co=100:4.1:1.8:15: 3。
The result tested is as shown in table 1.
Comparative example 2
Method according to CN102658148A disclosed embodiments 6 prepares comparative catalyst DC-2.
The component of catalyst DC-1 is:Fe2O3:Cu:K:SiO2:Co=100:1:10:5:0.5.
The result tested is as shown in table 1.
Test case 1
Catalyst FTC-1 is carried out into the performance evaluation of Fischer-Tropsch synthesis, evaluation methodology is commented for fixed bed Valency, appreciation condition are H2/ CO (volume ratio)=1.5, T=235 DEG C, P=1.6MPa, SV=3000ml/ (hg), t=500h.Evaluation test the results are shown in Table 2.
The composition in product is measured by chromatographic apparatuss, and following reaction evaluating parameter is calculated (see row Mark HG/T 4677-2014):
XCOFor the conversion ratio of carbon monoxide, calculating formula is
SCH4For methane selectively, calculating formula is
SCO2For carbon dioxide selectivity, calculating formula is
The calculating formula of deactivation rate is
Wherein, n1:The numerical value of the molal quantity of carbon monoxide in unstripped gas, unit are mole (mol);
n2:The numerical value of the molal quantity of carbon monoxide in tail gas, unit are mole (mol);
n3:The numerical value of the molal quantity of methane in tail gas, unit are mole (mol);
n4:The numerical value of the molal quantity of carbon dioxide in tail gas, unit are mole (mol);
E300:During 300h, the numerical value of the conversion ratio of carbon monoxide, is represented with %;
E500:During 500h, the numerical value of the conversion ratio of carbon monoxide, is represented with %.
Test case 2-5
According to the method for test case 1, except for the difference that, respectively with FTC-2, FTC-3, DC-1 and DC-2 FTC-1 is substituted, evaluation test the results are shown in Table 2.
Table 1
Numbering FTC-1 FTC-2 FTC-3 DC-1 DC-2
BET(m2/g) 201 136 163 175 165
Pore volume (cm3/g) 0.62 0.31 0.43 0.33 0.32
Abrasion index (h-1) 0.8 0.7 0.7 0.8 1.2
Table 2
Numbering FTC-1 FTC-2 FTC-3 DC-1 DC-2
XCO(%) 67 63 66 66 61
SCH4(%) 1.5 2.0 1.3 2.4 1.7
SCO2(%) 23 21 21 24 22
Deactivation rate (%/day) 0.09 0.10 0.08 0.13 0.11
The method that the present invention is provided can carry out the continuous production of Fischer-Tropsch synthetic iron-based catalyst precursor.By Above-described embodiment and comparative example, and the data of table 1-2 can be seen that by the method prepare Fischer-Tropsch close The Fischer-Tropsch synthetic iron-based catalyst further obtained into ferrum-based catalyst precursor has more preferable pore structure, Higher specific surface area and pore volume;Wear strength is higher, and abrasion index is lower, is carrying out F- T synthesis During reaction, more preferable catalytic performance is shown, CO conversion ratios are higher, methane and CO2Selectivity more It is low, while the deactivation rate of catalyst is lower, illustrate the F- T synthesis prepared in the method that the present invention is provided The Fischer-Tropsch synthetic iron-based catalyst that ferrum-based catalyst precursor is further obtained is carrying out Fischer-Tropsch synthesis When, the stability of course of reaction is more preferable.

Claims (10)

1. a kind of preparation method of sedimentation type catalyst precursor, including:
(1) by precipitant solution and the front body comprising sedimentation type catalyst active component in precipitation vessel The solution of body is sufficiently mixed, so as to Jing precipitation produces the precursor of the active component of catalyst containing sedimentation type Precipitate unscreened stock liquid;
(2) above-mentioned precipitate unscreened stock liquid is aged in ageing container, makes small precipitate Grain is gradually reunited or is assembled, so as to further improve the physical arrangement of precipitate,
Wherein, the precipitation vessel and the ageing container are different, but the container that is serially connected, with The precipitation and ageing process is made continuously to carry out in the precipitation vessel and ageing container successively.
2. a kind of preparation method of Fischer-Tropsch synthetic iron-based catalyst precursor, including:
(1) precipitant solution is carried out into precipitation in precipitation vessel with the metal salt solution containing iron salt, Produce the iron-based precipitate unscreened stock liquid of the precursor containing Fischer-Tropsch synthetic iron-based catalyst active component;
(2) above-mentioned iron-based precipitate unscreened stock liquid is aged in ageing container, to realize the ferrum The reunion or aggregation of base precipitation finely particulate, further improves the physical arrangement of the iron-based precipitate;
(3) iron-based precipitate after ageing is carried out washing, is filtered, made after removing wherein impurity and contain The serosity of the precursor of Fischer-Tropsch synthetic iron-based catalyst active component;
(4) serosity in step (3) is mixed and is adjusted pH value with silicon source, then Jing filter and Optionally it is dried, obtains Fischer-Tropsch synthetic iron-based catalyst precursor;
Wherein, the precipitation and ageing process are successively in different, but the precipitation that is serially connected Carry out in container and ageing container, continuously to carry out the precipitation and ageing process.
3. method according to claim 1 and 2, wherein, the precipitation vessel is static mixing Device or dynamic mixer.
4. method according to claim 1 and 2, wherein, the temperature of the precipitation is 30-90 DEG C, the pH value of the precipitation is 5-10.
5. method according to claim 2, wherein, the metal contained in the metal salt solution The concentration of salt is more than 0 weight % and less than or equal to 50 weight %.
6. the method according to claim 2 or 5, wherein, also contain in the metal salt solution At least one in mantoquita, cobalt salt, rare earth metal salt, manganese salt and potassium salt.
7. method according to claim 1 and 2, wherein, contain in the precipitant solution The concentration of precipitant is 1-50 weight %;The precipitant is carbonate and/or ammonia.
8. method according to claim 1 and 2, wherein, the ageing container is tubular type ageing Device;Aging Temperature is 30-90 DEG C, and the digestion time is 0.01-6h.
9. method according to claim 2, wherein, contain in the serosity in step (3) Fe2O3, its concentration is 1-40 weight %.
10. method according to claim 2, wherein, the silicon source be potassium silicate solution and/or Ludox;The slurry pH value is adjusted for 4-8.
CN201510680014.7A 2015-10-19 2015-10-19 Preparation method of Fischer-Tropsch synthesis iron-based catalyst Pending CN106582658A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510680014.7A CN106582658A (en) 2015-10-19 2015-10-19 Preparation method of Fischer-Tropsch synthesis iron-based catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510680014.7A CN106582658A (en) 2015-10-19 2015-10-19 Preparation method of Fischer-Tropsch synthesis iron-based catalyst

Publications (1)

Publication Number Publication Date
CN106582658A true CN106582658A (en) 2017-04-26

Family

ID=58554960

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510680014.7A Pending CN106582658A (en) 2015-10-19 2015-10-19 Preparation method of Fischer-Tropsch synthesis iron-based catalyst

Country Status (1)

Country Link
CN (1) CN106582658A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101035616A (en) * 2004-08-25 2007-09-12 约翰森·马瑟公开有限公司 High cobalt content , high cobalt surface area catalysts, preparation and use thereof
WO2014070116A1 (en) * 2012-11-01 2014-05-08 Agency For Science, Technology And Research Encapsulated Nanoparticles
CN103816945A (en) * 2014-01-29 2014-05-28 上海摩醇动力技术有限公司 Continuous catalyst production process and equipment

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101035616A (en) * 2004-08-25 2007-09-12 约翰森·马瑟公开有限公司 High cobalt content , high cobalt surface area catalysts, preparation and use thereof
WO2014070116A1 (en) * 2012-11-01 2014-05-08 Agency For Science, Technology And Research Encapsulated Nanoparticles
CN103816945A (en) * 2014-01-29 2014-05-28 上海摩醇动力技术有限公司 Continuous catalyst production process and equipment

Similar Documents

Publication Publication Date Title
EP2261172B1 (en) Process for producing liquid hydrocarbon from natural gas
CN107285334A (en) The method and catalyst of a kind of synthesis in solid state AEI type molecular sieves
CN107376922A (en) The method of a kind of iron-base fischer-tropsch synthesis catalyst and its preparation method and application and synthesis gas through F- T synthesis hydrocarbon compound
CN104772031B (en) Directly produce urea for vehicle solution containment and its production method
CA2530702A1 (en) Catalyst for oxidation of methanol to formaldehyde
CN106925274A (en) A kind of preparation method of load type metal Co catalysts
CN107537548A (en) A kind of carbon-containing molecules sieve catalyst and its preparation method and application
CN106916315A (en) Metal porous organic framework material, its preparation method and its application
CN107597130A (en) Different scale high-specific surface area cerium oxide cupric oxide composite mesopore ball and preparation method
CN100594061C (en) Nickelic Fischer-Tropsch synthetic iron-based catalyst and preparation thereof
CN108067234A (en) A kind of precipitation iron-base fischer-tropsch synthesis catalyst and preparation method thereof
Zhou et al. NH3 treatment of CeO2 nanorods catalyst for improving NH3-SCR of NO
CN108033475A (en) A kind of method that micro- reaction prepares nano-calcium carbonate
CN103240091B (en) Recycle method of precipitate iron Fischer-Tropsch catalyst precursor formation fine powder
CN106582658A (en) Preparation method of Fischer-Tropsch synthesis iron-based catalyst
CN107011107A (en) A kind of method that use load type metal catalyst prepares alcohol
CN106925333A (en) A kind of fluid catalyst of synthesis gas methanation and preparation method thereof
CN103157486A (en) Preparation method for oxide catalyst, and oxide catalyst prepared by same
CN103230800B (en) A kind of containing gallium iron-base fischer-tropsch Catalysts and its preparation method
CN105713657B (en) Hydrocracking method
CN103521217B (en) For acrylonitrile fluid bed Catalysts and its preparation method
CN106582798A (en) Catalyst for MTP (methanol-to-propylene) through conversion and preparation method of catalyst
CN204911210U (en) Directly produce automobile -used urea solution device
CN107519880B (en) Iron-based Fischer-Tropsch synthesis catalyst, preparation method and application thereof, and Fischer-Tropsch synthesis method of synthesis gas
CN110065959A (en) A kind of η-Al2O3Microballoon 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
RJ01 Rejection of invention patent application after publication

Application publication date: 20170426