CN107617442A

CN107617442A - The method that F- T synthesis precipitated iron-based catalyst and its preparation method and application and synthesis gas synthesize hydrocarbon compound processed through syrup state bed Fischer Tropsch

Info

Publication number: CN107617442A
Application number: CN201610560019.0A
Authority: CN
Inventors: 常海; 王鹏; 张魁; 吕毅军; 郭秀盈; 程萌; 王涛; 罗熙
Original assignee: Shenhua Group Corp Ltd; National Institute of Clean and Low Carbon Energy
Current assignee: China Energy Investment Corp Ltd; National Institute of Clean and Low Carbon Energy
Priority date: 2016-07-15
Filing date: 2016-07-15
Publication date: 2018-01-23
Anticipated expiration: 2036-07-15
Also published as: CN107617442B

Abstract

The present invention relates to F- T synthesis precipitated iron-based catalyst field, discloses the method that a kind of F- T synthesis precipitated iron-based catalyst and its preparation method and application and synthesis gas synthesize hydrocarbon compound processed through syrup state bed Fischer Tropsch.The composition weight ratio of the catalyst is Fe:Cu:K:Co:Mn:SiO₂=100:(0.1~6):(0.6~6):(0.01~0.6)：(0.01~10):(5~27)；The catalyst is through low temperature N₂The pore structure of physisorphtion measure has following characteristics：In bore dia≤80nm total pore volume, bore dia ＜ 12nm aperture accounting is less than 35%；12~80nm of bore dia mesopore accounting is more than 65%.The catalyst has the good performance for resisting physics and chemical abrasion, and simulated experiment is carried out using stirred tank evaluating apparatus, can continuously run 2000h or so and non-inactivation, and Fischer-Tropsch synthesis result C₅ ⁺The selectivity of product improves.

Description

F- T synthesis precipitated iron-based catalyst and its preparation method and application and synthesis gas are through slurry The method of state bed F- T synthesis hydrocarbon compound

Technical field

The present invention relates to F- T synthesis precipitated iron-based catalyst field, in particular it relates to which a kind of F- T synthesis precipitates iron-based The method that catalyst and its preparation method and application and synthesis gas synthesize hydrocarbon compound processed through syrup state bed Fischer Tropsch.

Background technology

In the presence of the fischer-tropsch synthetic catalyst such as precipitated iron or Supported Co, by synthesis gas (CO and H₂) be catalyzed instead Should, slurry bubble column reactor for the purpose of synthesizing liquid hydro carbons/wax class hydrocarbon products and its artificial oil technique to match, more To get over attention and the favor by researcher and developer.

It is whole anti-in slurry bubble column reactor different from the gas-solid reaction system carried out using fixed bed reactors System is answered to be carried out in the environment of atoleine.From the angle of catalyst, either reactant (CO and H₂) infiltration, expand Dissipate and adsorb, or the desorption of reaction product and interior external diffusion, it will all be influenceed by reaction medium.

In syrup state bed Fischer Tropsch artificial oil art production process, the wear strength of catalyst how is improved, and simultaneously can Ensure good catalytic performance, be the key link of the artificial oil technique, and still unsolved problem so far.Catalyst Intensity it is unqualified, be prone to wear out or broken etc., substantial amounts of fine powder (particle diameter is less than about 20 μm) can be caused, and then cause filter Blocking, technological operation load aggravate, pollution subsequent product, or even be forced parking with a series of intractable difficulty such as processing filters Topic.

The catalytic reaction operation stability of catalyst also directly influences the long-term operation life-span of catalyst, and weighs The important indicator of catalytic reaction production efficiency.In slurry reactor technological operation, if the stability of catalyst is poor, it would be desirable to no Stop more catalyst changeout, fresh makeup catalyst, with maintain smoothly operation operation and keep product qualification rate.

CN1270822C discloses a kind of preparation method of ferrimanganic fischer-tropsch synthetic catalyst, by Ludox (acid or alkalescence) It is added in the mixed solution of iron, manganese, calcium that total concentration of metal ions is 0.05-10.0 mol/Ls, is then rubbed with 0.1-5.0 You/liter ammonia spirit mixing；Or Ludox is added in the ammonia spirit of 0.1-5.0 mol/Ls, then with total metal Ion concentration is the iron of 0.05-10.0 mol/Ls, the mixed solution mixing of manganese, calcium；At 30-98 DEG C, pH value is 7.0-11.5 bars Precipitated under part, it is 10-50 weight % filter cakes to be washed after precipitation, be filtrated to get solid content, and water and sylvite (carbon are added in filter cake Sour potassium, tumer, saleratus) mashing, the catalyst pulp that solid content is 5-45 weight % is obtained, catalyst pulp is sprayed Microballoon is dried to, then 2-12h is calcined at 300-750 DEG C, obtains syrup state bed Fischer Tropsch synthesis Iron-Manganese Catalyst, forms and is：Fe: Mn:Ca:K:SiO₂=100:(4-100):(1-40):(0.5-10):(3-50).The present invention emphasizes, because settling step directly draws Ludox is entered, the good calcium-silicate of intensity can be formed, so as to improve the mechanical strength of catalyst.The patent, which does not refer to, appoints The information of what catalyst pore structure.In addition also studies have found that, it is (any to introduce that excessive silica is introduced in settling step Silicon source), it can cause the pore structure of last resulting catalyst to be offset to aperture direction.And (the Rong such as Rong Zhao Zhao,James G.Goodwin,Jr.,K.Jothimurugesan,Santosh K.Gangwal,and James J.Spivey, Ind.Eng.Chem.Res.2001,40,1065-1075) research conclusion thinks, with the silicon introduced in settling step The increase of content, the mechanical strength of catalyst can reduce.

CN1203920C discloses a kind of iron/manganese catalyst for F- T synthesis, Fe in catalyst:Mn:Ca:K:SiO₂ =100:(4-100):(2-50):(0.2-10), wherein SiO₂Percentage by weight in the catalyst is 1-45 weight %；Catalysis Active component Fe, Mn, Ca, K exist in the form of an oxide respectively in agent.Specifically disclosed preparation method includes：(1) catalyst is pressed Composition, compound concentration is the ferric nitrate of 0.05-2.0 mol/Ls, the mixing salt solution of calcium nitrate, manganese nitrate or manganese acetate；(2) It is the ammonia spirit of 0.1-5.0 mol/Ls by the mixing salt solution and concentration, is 30-90 DEG C in temperature, pH=7.0-11.5's Under the conditions of stir, precipitated, after precipitation stand 5-48 hours, filtering, obtain filter cake；(3) it is 0.1- potassium carbonate to be made into concentration The solution of potassium carbonate of 1.5 mol/Ls；(4) silica aqueous solution is added to filter cake by silicone content in catalyst (to contain SiO₂25wt%), and solution of potassium carbonate, and add deionized water and be mixed with beating, water：Preformed catalyst weight ratio=5-9：1； (5) slurries are dried 5-60 hours in 40-95 DEG C of water-bath, are dried and are dried 6-42 hours, Ran Houyu again after 80-150 DEG C 1-12 hours, cooling, compression molding are calcined at 300-650 DEG C.Though the patent highlights the high specific surface area of gained catalyst With high mechanical strength, but any specific achievement data is not provided.It is conventional compression molding in preparation method.For Fischer-Tropsch Synthetic reaction, its CO₂Selective % is 27.12-43.25%, CH₄Selective % is 5.69-12.11%, C₅ ⁺Selective % is 55.77-76.43%.

(the A new and direct preparation method of iron-based bimodal such as Yi Zhang catalyst and its application in Fischer–Tropsch synthesis,Applied Catalysis A:General 352 (2009) 277-281) ferrum-based catalyst with structure of double peak holes is have studied, by using in carrier The active material that aperture is established inside macropore is directly prepared.Carrier is molten with the mixing of ferric nitrate, copper nitrate and potassium nitrate Liquid carries out equi-volume impregnating, then is air-dried 12h by 120 DEG C, and 2h is calcined at 400 DEG C, load active component, load is made Type ferrum-based catalyst, iron load capacity are 20 weight %, Fe：Cu：K is 200：30：5.Carrier is the silica gel (Q-50) being obtained commercially, Macropore with aperture 50-60nm, 5-7nm aperture is formed between the active component particles on dipping.But only 700 DEG C heat treatments Aperture disappears afterwards.The disclosed catalyst with diplopore distribution of this text, because establishing on macropore carrier, CO activity of conversion reaches To 89.5%, but it is load-type iron-based catalyst (iron oxide load capacity is 30wt%) after all, chain growth probability a values very low Have 0.60, it is seen that its C₅₊Hydrocarbon product selectivity is very low.And the wear resistance of this non-Study of Catalyst of text.

As can be seen here, it is desirable to provide can solve the skill of the wear-resistant defect of catalyst of syrup state bed Fischer Tropsch synthesis technique production Art.

The content of the invention

The invention aims to solve in syrup state bed Fischer Tropsch synthesis technique, the intensity deficiency of catalyst, abrasion be present Or the problem of broken, there is provided a kind of F- T synthesis precipitated iron-based catalyst and its preparation method and application and synthesis gas are through slurry The method of bed F- T synthesis hydrocarbon compound.

The present inventor has found when studying catalyst abrasion during the course of the reaction or crushing reasons, excludes Catalyst is mutually collided etc. outside physical abrasion caused by factor, chemical abrasion that catalyst granules is subjected to or it is broken be to cause to urge Agent intensity declines, produces abrasion or broken more main cause, specifically includes, the endoporus knot of catalyst in pre-reduction Structure changes, and aperture collapses, and then the wear strength of catalyst in itself changes or died down；In catalytic reaction process In, the accumulation of long chain hydrocarbons heavy product of Fischer-Tropsch synthesis generation, plug-hole, Carbon deposition etc. cause the stifled of the duct of catalyst Fill in, rack, influence the intensity of catalyst.Thus it was recognized by the inventor that fischer-tropsch catalysts to be solved are anti-in syrup state bed Fischer Tropsch synthesis Should during abrasion or it is broken the problem of, just must be from endoporus knot more accurately first from the improvement of the internal structure of catalyst The modulation of structure and improvement are started with, and are possible to efficiently solve the intensity of catalyst, wear problem, and catalyst is made and provides slurry The operation steady in a long-term of bed Fischer-Tropsch synthesis.

To achieve these goals, the present invention provides a kind of F- T synthesis precipitated iron-based catalyst, the composition of the catalyst Weight ratio is Fe:Cu:K:Co:Mn:SiO₂=100:(0.1~6):(0.6~6):(0.01~0.6)：(0.01~10):(5~ 27)；The catalyst is through low temperature N₂The pore structure of physisorphtion measure has following characteristics：In bore dia≤80nm total hole body In product, bore dia ＜ 12nm aperture accounting is less than 35%；The mesopore accounting that bore dia is 12~80nm is more than 65%.

Present invention also offers a kind of preparation method of F- T synthesis precipitated iron-based catalyst, including：(1) by molysite, copper Salt, cobalt salt and manganese salt are dissolved in the water to obtain aqueous metal salt, and the electrical conductivity of the water is below 60 μ s/cm；By precipitating reagent, Silicon-containing compound and water are mixed to get the precipitating reagent aqueous solution, and the precipitating reagent is selected from sodium carbonate, potassium carbonate, saleratus and ammoniacal liquor At least one of, the mol ratio of the precipitating reagent and the silicon-containing compound is 100：(1~3)；(2) by the metal salt solution Solution is added in the precipitating reagent aqueous solution, carries out coprecipitation reaction at being 55~90 DEG C in temperature, obtained coprecipitated product The pH of slurries is 5.5~8.5；(3) the coprecipitated product slurries are cooled down, makes the temperature of the coprecipitated product slurries Less than 20 DEG C are reduced in 15min, and dilutes the coprecipitated product slurries, obtains slurry I；(4) the slurry I is carried out Filter and wash, obtain the precipitated filter cakes a that solid content is 15~70 weight %；(5) by Ludox or potassium silicate, potassium carbonate, water It is mixed with beating with the precipitated filter cakes a, and adds acid solution, the slurry II that pH is less than 7 is made；The slurry II is carried out quiet Put, and filter cake b is obtained through filtering；The filter cake b is added into water and carries out high shear agitation, it is 10~50 weights to obtain solid content Measure % catalyst precursor slurry III；(6) the catalyst precursor slurry III is spray-dried and is calcined；Wherein, iron Salt, mantoquita, cobalt salt, manganese salt, precipitating reagent, potassium carbonate, the addition of potassium silicate or Ludox, meet Fe:Cu:K:Co:Mn:SiO₂ Weight ratio be=100:(0.1~6):(0.6~6):(0.01~0.6)：(0.01~10):(5~27).

Preferably, above-mentioned cooling is that ice cube is added into the coprecipitated product slurries, ice cube and the coprecipitated product The weight ratio of slurries is 1：Less than 1.

Present invention also offers F- T synthesis precipitated iron-based catalyst made from a kind of method of the invention.

Present invention also offers a kind of F- T synthesis precipitated iron-based catalyst of the invention to be carried out in paste state bed reactor Fischer-Tropsch synthesis prepares the application in hydrocarbon compound.

Present invention also offers a kind of method of synthesis gas through syrup state bed Fischer Tropsch synthetic reaction hydrocarbon compound, including：(a) In the presence of reducing atmosphere and diluent media, by the present invention F- T synthesis precipitated iron-based catalyst temperature be 230~320 DEG C, pressure be 0.1~2.8MPa, H in the reducing atmosphere₂Mol ratio with CO is (0.2~35)：Under conditions of 1, gone back Original 1~48h of reaction, obtains reduction-state activated catalyst；(b) in the presence of the reduction-state activated catalyst, will contain CO and H₂Synthesis gas under conditions of temperature is 210~300 DEG C, pressure is 1.2~2.8MPa, expense is carried out in paste state bed reactor Synthetic reaction is held in the palm, obtains hydrocarbon compound；Wherein, H in the synthesis gas₂Mol ratio with CO is (0.5~3.5)：1, the conjunction Air speed into gas is 5~16NL/g-cath.

F- T synthesis precipitated iron-based catalyst provided by the invention has through low temperature N₂Physical absorption measure with lower opening knot Structure feature, it is specially：In bore dia≤80nm total pore volume, bore dia ＜ 12nm aperture accounting is less than 35%；Kong Zhi The mesopore accounting that footpath is 12~80nm is more than 65%.The catalyst pore structure with reference to made from the embodiment 1 that Fig. 1 is shown is distributed Figure, it is shown that the appearance and a peak of winding up of two more obvious pore diameter distributions.It can be seen that provided by the invention urge Agent has two sections of pore size distributions more concentrated, wherein, it is much more obvious and present that mesopore (bore dia is 12~80nm) occupies ratio Go out normal state broad feature.Such pore structure makes catalyst provided by the invention have good physics wear resistance, uses The abrasion index of ASTM D5757-00 air gunite test is below 4.0%.

In addition, the wear resistance of catalyst provided by the invention improves, can be urged in paste state bed reactor using this Agent, which carries out Fischer-Tropsch synthesis, can carry out long-term operation.Simulated experiment, the catalyst are carried out using stirred tank evaluating apparatus 2000h or so can be continuously run, carrying out Fischer-Tropsch synthesis still has compared with high reaction activity.Urged using provided by the invention Agent can avoid or reduce the online replacing number of catalyst, reduce overall operation cost.

In the syrup state bed Fischer Tropsch synthetic reaction using the catalyst of the present invention, CO high conversion rates, methane selection is reduced Property and C₂-C₄Light hydrocarbon selectivity of product, improves C₅ ⁺The selectivity of product.

Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.

Brief description of the drawings

Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：

Fig. 1 is the SEM electromicroscopic photographs that F- T synthesis precipitated iron-based catalyst is made in embodiment 1；

Fig. 2 is the pore size distribution$ figure that F- T synthesis precipitated iron-based catalyst is made in embodiment 1；

Fig. 3 is the pore size distribution$ figure that F- T synthesis precipitated iron-based catalyst is made in comparative example 2；

Fig. 4 is the CO conversion ratio changing trend diagrams of syrup state bed Fischer Tropsch synthetic reaction long-term operation in evaluation and test example 1.

Embodiment

The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.

The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more New number range, these number ranges should be considered as specific open herein.

The present invention provides a kind of F- T synthesis precipitated iron-based catalyst, and the composition weight ratio of the catalyst is Fe:Cu:K: Co:Mn:SiO₂=100:(0.1~6):(0.6~6):(0.01~0.6)：(0.01~10):(5~27)；Wherein, the catalysis Agent is through low temperature N₂The pore structure of physisorphtion measure has following characteristics：In bore dia≤80nm total pore volume, Kong Zhi Footpath ＜ 12nm aperture accounting is less than 35%；The mesopore accounting that bore dia is 12~80nm is more than 65%.

It is preferred that the composition weight ratio of the catalyst is Fe:Cu:K:Co:Mn:SiO₂=100:(0.6~5):(2.5~ 5.5):(0.1~0.3)：(1.0~9.6):(17~24).

The pore structure of F- T synthesis precipitated iron-based catalyst provided by the invention has diapsid distribution, such as shown in Fig. 2 Embodiment 1 obtain catalyst pore size distribution$ figure in, it is shown that the appearance of two more obvious pore diameter distributions with An and peak of winding up.It can be seen that catalyst has two sections of pore diameter distributions more concentrated.F- T synthesis provided by the invention Precipitated iron-based catalyst is as characterized above can to have improved wear resistance.

According to the present invention, in the diplopore distribution characteristics of the catalyst, aperture and mesopore are respective in total pore volume Accounting is different, is mainly presented that the accounting of the aperture is small, and the accounting of the mesopore is big, and can aid in improves the strong of catalyst Degree, improve polishing machine.Under preferable case, in bore dia≤80nm total pore volume, bore dia ＜ 12nm aperture accounting Less than 30% and more than 0%.It is preferred that aperture accounting is 15~28%.

In the case of, according to the invention it is preferred to, in bore dia≤80nm total pore volume, bore dia is in 12~80nm Hole accounting is 65% less than 99%.It is preferred that mesopore accounting is 72~85%.

Preferably, the total pore volume of catalyst of the invention is 0.55~0.7cm³/ g, preferably 0.58~0.68cm³/g。

In the present invention, when limiting the structure in the hole that the catalyst has, bore dia and pore volume are by low temperature N₂Thing Numerical value obtained by determination of adsorption method is managed, bore dia is the average diameter of finger-hole.Further, the embodiment of the present invention 1 is observed to be made Catalyst pore size distribution$ figure, as shown in Fig. 2 wherein, bore dia is that the appearance curve of 12~80nm mesopore is in normal state The broad peak of distribution.Show catalyst provided by the invention can be Fischer-Tropsch synthesis during raw material absorption and diffusion, The desorption of product and diffusion, there is provided the guarantee in space in enough holes, can effectively slow down the catalyst caused by chemical factor Abrasion, intensity decline.

In the present invention, it is preferable that the specific surface area of the catalyst is 120~260cm²/g；Preferably 142~239cm²/ g。

According to the present invention, catalyst provided by the invention has a more preferable wear resistance, under preferable case, according to ASTM D5757-00 air gunitees, the abrasion index for testing the catalyst are less than 4.0%.Preferably 2.5~4%, more preferably For 2.8~3.9%.

Present invention also offers a kind of preparation method of F- T synthesis precipitated iron-based catalyst, including：

(1) molysite, mantoquita, cobalt salt and manganese salt are dissolved in the water to obtain aqueous metal salt, the electrical conductivity of the water is Below 60 μ s/cm；Precipitating reagent, silicon-containing compound and water are mixed to get the precipitating reagent aqueous solution, the precipitating reagent be selected from sodium carbonate, The mol ratio of at least one of potassium carbonate, saleratus and ammoniacal liquor, the precipitating reagent and the silicon-containing compound is 100：(1 ~3)；

(2) aqueous metal salt is added in the precipitating reagent aqueous solution, be total at being 55~90 DEG C in temperature Precipitation reaction, the pH of obtained coprecipitated product slurries is 5.5~8.5；

(3) the coprecipitated product slurries are cooled down, the temperature of the coprecipitated product slurries is dropped in 15min As little as less than 20 DEG C, and the coprecipitated product slurries are diluted, obtain slurry I；

(4) the slurry I is filtered and washed, obtain the precipitated filter cakes a that solid content is 15~70 weight %；

(5) Ludox or potassium silicate, potassium carbonate, water are mixed with beating with the precipitated filter cakes a, and add acid solution, be made PH is less than 7 slurry II, and preferably slurry II pH is less than 6；The slurry II is stood, and again through being filtered Cake b；The filter cake b is added into water and carries out high shear agitation, the catalyst precarsor that solid content is 10~50 weight % is obtained and starches Expect III；

(6) the catalyst precursor slurry III is spray-dried and is calcined；

Wherein, the addition of molysite, mantoquita, cobalt salt, manganese salt, precipitating reagent, potassium carbonate, potassium silicate or Ludox, meets Fe: Cu:K:Co:Mn:SiO₂Weight ratio be=100:(0.1~6):(0.6~6):(0.01~0.6)：(0.01~10):(5~ 27)。

The present invention F- T synthesis precipitated iron-based catalyst preparation method in, step (1) preparing metal saline solution and The precipitating reagent aqueous solution is as reaction raw materials solution.Wherein, in the aqueous metal salt, molysite using the concentration that Fe is counted as 1.0~ 6.0 weight %, mantoquita is using the concentration that Cu is counted as 0.05~0.36 weight %, and cobalt salt is using the concentration that Co is counted as 0.00001~0.06 Weight %, manganese salt is using the concentration that Mn is counted as 0.001~0.6 weight %.

Preferably, molysite can be ferric nitrate, the hydrate of ferric nitrate, ferric sulfate, the hydrate of ferric sulfate, iron chloride and The hydrate of at least one of iron oxide, preferably ferric nitrate and/or ferric nitrate.

Preferably, mantoquita can be copper nitrate, the hydrate of copper nitrate, copper sulphate and copper sulphate hydrate at least The hydrate of one kind, preferably copper nitrate and/or copper nitrate.

Preferably, cobalt salt can be cobalt nitrate, the hydrate of cobalt nitrate and organic acid cobalt such as at least one of cobalt acetate, The preferably hydrate of cobalt nitrate and/or cobalt nitrate.

Preferably, manganese salt can be at least one of manganese nitrate, the hydrate of manganese nitrate and manganese nitrate aqueous solution, preferably For the aqueous solution of manganese nitrate.

In above-mentioned raw materials, the raw material without hydrate can be the phase that respective metal material is directly obtained with sour dissolution process Answering compound, such as ferric nitrate can be, the metal containing iron is dissolved into obtained ferric nitrate with nitric acid.

In the present invention, the content of precipitating reagent can meet that the pH of the precipitating reagent aqueous solution is in the precipitating reagent aqueous solution 10~14, preferably 12~13.

In the present invention, the precipitating reagent can be sodium carbonate, optional potassium carbonate and/or saleratus, optional ammoniacal liquor. During using sodium carbonate, potassium carbonate and/or saleratus, sodium or potassium may be incorporated into.

According to the present invention, silicon-containing compound is preferably added in the precipitating reagent aqueous solution, under preferable case, the silicide-comprising Compound includes solid silicic acid potassium, liquid silicic acid potassium, Ludox, Ludox containing potassium, water soluble silica and sodium metasilicate at least It is a kind of.

In the present invention, the mol ratio of the precipitating reagent and the silicon-containing compound is 100：(1~3), such as the precipitation Agent is sodium carbonate, when the silicon-containing compound is potassium silicate, sodium carbonate：The mol ratio of potassium silicate is 100：(1~3).

In the preparation method of the F- T synthesis precipitated iron-based catalyst of the present invention, step (2) carries out the coprecipitation reaction. A kind of preferred embodiment, the precipitating reagent aqueous solution is put into precipitation reactor, then added the aqueous metal salt Enter in the precipitation reactor, the addition of all aqueous metal salts is completed preferably in 15min, makes the metal salt solution Solution mixes with the precipitating reagent aqueous solution completes the coprecipitation reaction.In the present invention, the aqueous metal salt is completed to add After entering, i.e., described coprecipitation reaction stops.In the present invention, control the coprecipitation reaction to implement in a manner of as above, limiting Complete that the pore structure for obtaining catalyst of the invention can be more beneficial in time.

In the present invention, the temperature for carrying out the coprecipitation reaction can be by by the precipitating reagent aqueous solution and the metal Saline solution is separately heated to 55~90 DEG C to realize.

In the preparation method of the F- T synthesis precipitated iron-based catalyst of the present invention, step (3) is entered to coprecipitated product slurries Row processing, it can aid in and control the growth that particle is precipitated in the slurries and disperse, be advantageous to through the follow-up of the preparation method Step obtains the double-pore structure distribution of catalyst.The control of cooling and the dilution coprecipitated product slurry can be realized by adding ice cube Liquid.The temperature of more preferably described coprecipitated product slurries is reduced to less than 15 DEG C.Meanwhile the temperature of the coprecipitated product slurries More than 0 DEG C is maintained at, is not frozen.

In the preparation method of the F- T synthesis precipitated iron-based catalyst of the present invention, the washing of step (4) can be multiple, institute The electrical conductivity for stating the last filtrate that washing obtains is below 1.2ms/cm.Now, Na ion concentrations can in precipitated filter cakes a To ignore.

In the preparation method of the F- T synthesis precipitated iron-based catalyst of the present invention, step (5) prepares slurry II, Ludox or Potassium silicate, potassium carbonate, water, the precipitated filter cakes a be mixed with beating can according to first by the precipitated filter cakes a with it is a certain amount of Water is mixed into slurry, then Ludox or potassium silicate, potassium carbonate are added into the slurries to be formed and are mixed with beating.Wherein, Ludox or Potassium silicate, potassium carbonate, water, the respective inventory of the precipitated filter cakes a can meet that weight ratio is water：Ludox or potassium silicate： Potassium carbonate：Precipitated filter cakes a=1：(0.02~0.08)：(0.005~0.03)：(0.2~0.5).Beating time is preferably 20~ 30min.It can be hydrochloric acid or nitric acid to add acid solution.

In the preparation method of the F- T synthesis precipitated iron-based catalyst of the present invention, slurry II is carried out described quiet in step (5) Processing is put, the growth for the particle that can aid in the slurry II and scattered advantageously forms the hole knot of the catalyst of acquisition Structure.Under preferable case, when the slurry II is stood, dwell temperature is 20~65 DEG C, and time of repose is 30~90min.

In the preparation method of the F- T synthesis precipitated iron-based catalyst of the present invention, filter cake b carries out high speed shear in step (5) The time of stirring is 20~30min, and stir speed (S.S.) is 80~450rpm.It is preferred that in the high speed that speed of agitator is 350~450rpm Carried out in cutter.

In the case of, according to the invention it is preferred to, the spray drying is carried out, entrance wind-warm syndrome is 200~340 DEG C, exports wind-warm syndrome For 95~145 DEG C.Spray pattern can be pressure type or atomizer drying means.

In the case of, according to the invention it is preferred to, the roasting is carried out, is calcined 10~14h at 100~120 DEG C in atmosphere, with 300~340 DEG C/h is warming up to 500~550 DEG C of 2~8h of constant temperature.

According to the present invention, in the multiple steps for the preparation method for implementing F- T synthesis precipitated iron-based catalyst, it is required for making Medium is used as by the use of water, it is generally the case that the electrical conductivity of the water is below 60 μ s/cm, and preferably electrical conductivity is below 35 μ s/cm. There can be the effect for the pore structure for preferably obtaining catalyst.The measure of electrical conductivity can be surveyed automatically by commercially available conductivity meter It is fixed.The ice cube added in step (3) is also formed by meeting that the water-ice of above-mentioned electrical conductivity freezes.

In the present invention, the composition weight ratio of obtained F- T synthesis precipitated iron-based catalyst is Fe:Cu:K:Co:Mn:SiO₂ =100:(0.1~6):(0.6~6):(0.01~0.6)：(0.01~10):(5~27)；The catalyst is through low temperature N₂Physics is inhaled The pore structure of attached method measure has following characteristics：In bore dia≤80nm total pore volume, bore dia ＜ 12nm aperture accounts for Than less than 35%；The mesopore accounting that bore dia is 12~80nm is more than 65%.

Preferably, in obtained F- T synthesis precipitated iron-based catalyst, in bore dia≤80nm total pore volume, Kong Zhi Footpath ＜ 12nm aperture accounting is less than 30% and more than 0%.It is preferred that aperture accounting is 15~28%.

Preferably, in obtained F- T synthesis precipitated iron-based catalyst, in bore dia≤80nm total pore volume, Kong Zhi The mesopore accounting that footpath is 12~80nm is 65% less than 99%.It is preferred that mesopore accounting is 72~85%.

Obtained F- T synthesis precipitated iron-based catalyst, according to ASTM D5757-00 air gunitees, test the catalysis The abrasion index of agent is less than 4.0%.Preferably 2.5~4%, more preferably 2.8~3.9%.

Preferably, the specific surface area of the catalyst is 120~260cm²/g；Preferably 142~239cm²/g。

A kind of method for synthesizing hydrocarbon compound processed through syrup state bed Fischer Tropsch present invention also offers synthesis gas, including：(a) also In the presence of Primordial Qi atmosphere and diluent media, the F- T synthesis precipitated iron-based catalyst of the present invention is 230~320 DEG C, pressed in temperature Power is H in 0.1~2.8MPa, the reducing atmosphere₂Mol ratio with CO is (0.2~35)：Under conditions of 1, reduce instead 1~48h is answered, obtains reduction-state activated catalyst；(b) in the presence of the reduction-state activated catalyst, CO and H will be contained₂'s Synthesis gas carries out Fischer-Tropsch conjunction under conditions of temperature is 210~300 DEG C, pressure is 1.2~2.8MPa in paste state bed reactor Into reaction, hydrocarbon compound is obtained；Wherein, H in the synthesis gas₂Mol ratio with CO is (0.5~3.5)：1, the synthesis gas Air speed be 5~16NL/g-cath.

In the present invention, the diluent media can be atoleine, such as the atoleine that commercial grade is KX 11.It is preferred that The usage amount of the diluent media makes the concentration of F- T synthesis precipitated iron-based catalyst be 5~30 weight %.

Method of the synthesis gas of the present invention through syrup state bed Fischer Tropsch synthetic reaction hydrocarbon compound, in step (a), the reduction Reaction can also be carried out in the paste state bed reactor of Fischer-Tropsch synthesis of step (b) is carried out.A kind of preferred embodiment, can To carry out the Fischer-Tropsch synthesis of the reduction reaction of step (a) and step (b) in paste state bed reactor, as long as from step (a) It is transformed into and carries out step (b), changes H in reducing atmosphere₂Pressure, temperature and the air speed of molar ratio, reaction system with CO (GHSV) condition of step (b) is met.

In method of the synthesis gas through syrup state bed Fischer Tropsch synthetic reaction hydrocarbon compound of the present invention, reduced in step (a) Atmosphere can be to contain CO and H₂Mixed gas, wherein, H₂Mol ratio with CO is 1：(3~40).

In step (b), CO concentration is 15~65 volume % in the synthesis gas.

In the present invention, the paste state bed reactor can be commonly used in the art various is suitable in a manner of slurry bed system Carry out the reactor of Fischer-Tropsch synthesis.Present invention also offers a kind of embodiment, carries out growing week using slurry bed system stirred tank Phase Fischer-Tropsch synthesis, verify that F- T synthesis precipitated iron-based catalyst provided by the invention has more preferable stability.The present invention The F- T synthesis precipitated iron-based catalyst of offer can continuously run more than 2000h on slurry bed system stirred tank, wherein, the present invention The weight ratio of reduction-state catalyst and diluent of the F- T synthesis precipitated iron-based catalyst of offer after reduction reaction is 1：(2 ~35), containing CO and H₂Synthesis gas carry out Fischer-Tropsch synthesis condition be：Temperature be 210~300 DEG C, pressure be 1.2~ 2.8MPa, H in the synthesis gas₂Molar ratio with CO is 0.5~3.5, and the air speed of the synthesis gas is 5~16NL/g- cat·h。

In the present invention, it is gauge pressure to be related to pressure.

The present invention will be described in detail by way of examples below.

In following examples, the diluent for carrying out Fischer-Tropsch synthesis is the board of Jiangsu Yonghua Fine Chemical Co., Ltd. Number be KX11 atoleine；

The specific surface area and pore volume of obtained F- T synthesis precipitated iron-based catalyst are determined using low-temperature nitrogen adsorption method, than Surface area is BET specific surface area；

The grain graininess of obtained F- T synthesis precipitated iron-based catalyst uses laser particle analyzer (Malvern Mastersizer 2000) measurement Size Distribution, make dispersant with water；

The constituent content of obtained F- T synthesis precipitated iron-based catalyst uses XRF component analysis instrument (XRF) (island Tianjin XRF-1800) analyzed；

The wear strength of obtained F- T synthesis precipitated iron-based catalyst uses air gunite (ASTM D5757-00) Tested, specially each test sample amount is catalyst granules sample of the 50g particle size range at 50~150 μm.Experiment When, sample balances first through drying under 35% humidity.1h abrasion fine powders are first collected, then change another fines collection Device carries out 4h wear tests again.Result of the test is provided with air jet mill damage index (AJI)；

The electrical conductivity of the water used in embodiment passes through conductivity meter (Shanghai Rong Han instrument and meter for automations Co., Ltd, model LRS-D23) automatically determine.

Embodiment 1

This example demonstrates that the preparation method of the F- T synthesis precipitated iron-based catalyst of the present invention.

The electrical conductivity of the water used in the present embodiment is 34 μ s/cm.

(1) 22.0kg Fe (NO are weighed₃)₃·9H₂O, 0.58kg Cu (NO₃)₂·3H₂O and 0.045kg Co (NO₃)₂·6H₂O, add 100L water stirring and dissolvings；Again toward the Mn that addition 1.35kg concentration is 50 weight % in the solution that stirred (NO₃)₂The aqueous solution, fully stir evenly, obtain aqueous metal salt；

Weigh 12.0kg Na₂CO₃, 63.0L water stirring and dissolvings are added, add 0.47kg potassium silicate (Na₂CO₃With silicon The mol ratio of sour potassium is 100：2.1), stirring and dissolving obtains the precipitating reagent aqueous solution, tests its pH value as 12.7；

(2) the above-mentioned precipitating reagent aqueous solution is heated to 65 DEG C, aqueous metal salt is heated to 63 by coil pipe preheater ℃；Aqueous metal salt is added in 15min in the precipitating reagent aqueous solution being stirred vigorously, carries out and complete co-precipitation instead Should；The temperature for monitoring coprecipitation reaction on-line is 63 DEG C, and the pH of coprecipitated product slurries is 7.3；

(3) to addition 90kg ice cubes in obtained 190kg coprecipitated product slurries, coprecipitated product is starched in 10min The temperature of liquid is reduced to 19 DEG C or so, obtains slurries I；

(4) slurries I is immediately transferred into Suction filtration device and filtered, discarded to be washed with water after filtrate and wash filter cake.Instead After backwashing is washed until the electrical conductivity of last filtrate is below 1.2ms/cm, obtains precipitated filter cakes a, solid content is 35 weight %；

(5) by 12.8kg precipitated filter cakes a according to precipitated filter cakes a：The mass ratio of water is 3：1 is mixed into slurry, and adds (modulus 2.01, potassium content are 13.67 weight %, SiO to 1.38kg potassium silicate water glass₂Content is 27.54 weight %) with (weight of potassium silicate water glass and potassium carbonate ratio is 2.9 to potassium carbonate (Chinese medicines group)：1) carry out being mixed with beating 25min；Add 10kg concentration is 13.6 weight % dust technology, obtains the slurry II that pH value is 6；Slurry II is stood at 55 DEG C 45min, then by filtering again, obtain filter cake b；Filter cake b is added into water and carries out high shear agitation (360rpm, 25min) Obtain catalyst pulp III of the solid content for 21 weight % or so；

(6) catalyst pulp III is inputted into spray-drying installation, is 280 DEG C in entrance wind-warm syndrome, outlet wind-warm syndrome is 102 DEG C It is spray-dried under conditions of left and right, being sprayed after about 8min finishes；Gained catalyst granules is put into Muffle furnace, in air In be calcined 12h at 110 DEG C, be then warming up to 520 DEG C with 320 DEG C/h heating rates, be calcined 4h at such a temperature, that is, obtain final Catalyst about 4.1kg.

The catalyst as obtained by SEM electron microscope observations, SEM electron micrographs are shown in Fig. 1, show the catalyst The sphericity and surface gloss of particle are good.

The catalyst carries out component analysis, Fe:Cu:K:Co:Mn:SiO₂Weight ratio be=100:5.0:2.5:0.3: 6.5:19.0。

The pore size distribution$ of catalyst low-temperature nitrogen adsorption method measure is shown in Fig. 2.

Specific surface area, total pore volume and abrasion index data are shown in Table 1.

Embodiment 2

The electrical conductivity of the water used in the present embodiment is 32 μ s/cm.

(1) 22.0kg Fe (NO are weighed₃)₃·9H₂O, 0.46kg Cu (NO₃)₂·3H₂O and 0.075kg Co (NO₃)₂·6H₂O, add 100L water stirring and dissolvings；Again toward the Mn that addition 1.45kg concentration is 50 weight % in the solution that stirred (NO₃)₂The aqueous solution, fully stir evenly, obtain aqueous metal salt；

Weigh 14.0kg Na₂CO₃, 63.0L water stirring and dissolvings are added, add 0.51kg potassium silicate (Na₂CO₃With silicon The mol ratio of sour potassium is 100：2.5), stirring and dissolving obtains the precipitating reagent aqueous solution, tests its pH value as 12.8；

(2) the above-mentioned precipitating reagent aqueous solution is heated to 85 DEG C；Also aqueous metal salt is heated to by coil pipe preheater 87℃；Aqueous metal salt is added in 15min in the precipitating reagent aqueous solution being stirred vigorously, carries out and complete to be co-precipitated Reaction；The temperature for monitoring coprecipitation reaction on-line is 83 DEG C, and the pH of coprecipitated product slurries is 7.8；

(3) to addition 130kg ice cubes in obtained 195kg coprecipitated product slurries, coprecipitated product is starched in 9min The temperature of liquid is reduced to 17 DEG C or so, obtains slurries I；

(4) slurries I is immediately transferred into Suction filtration device and filtered, discarded to be washed with water after filtrate and wash filter cake.Instead After backwashing is washed until the electrical conductivity of last filtrate is below 1.2ms/cm, obtains precipitated filter cakes a, solid content is 33 weight %；

(5) by 13.4kg precipitated filter cakes a according to precipitated filter cakes a：The mass ratio of water is 3.5：1 is mixed into slurry, and adds (modulus 0.7, potassium content are 35.28 weight %, SiO to 2.15kg Ludox containing potassium₂Content is 25.24 weight %) and carbonic acid (weight of Ludox and potassium carbonate ratio is 15 to potassium (Beijing modern times east fine chemicals)：1), carry out being mixed with beating 20min；Again The dust technology that 12kg concentration is 15.0 weight % is added, obtains the slurry II that pH value is 5；Slurry II is stood at 65 DEG C 80min, then by filtering again, obtain filter cake b；Filter cake b is added into water and carries out high shear agitation (380rpm, 30min) Obtain catalyst pulp III of the solid content for 22 weight % or so；

(6) catalyst pulp III is inputted into spray-drying installation, is 290 DEG C in entrance wind-warm syndrome, outlet wind-warm syndrome is 105 DEG C It is spray-dried under conditions of left and right, being sprayed after about 8min finishes；Gained catalyst granules is put into Muffle furnace, in air In be calcined 12h at 110 DEG C, be then warming up to 520 DEG C with 320 DEG C/h heating rates, be calcined 5h at such a temperature, that is, obtain final Catalyst about 4.1kg.

The catalyst as obtained by SEM electron microscope observations, the sphericity and table of the particle of the catalyst similar to Fig. 1 Face glossiness is good.

The catalyst carries out component analysis, Fe:Cu:K:Co:Mn:SiO₂Weight ratio be=100:4.0:5.1:0.5: 7.0:24.0。

Embodiment 3

The electrical conductivity of the water used in the present embodiment is 33 μ s/cm.

(1) 22.0kg Fe (NO are weighed₃)₃·9H₂O, 0.174kg Cu (NO₃)₂·3H₂O and 0.06kg Co (NO₃)₂·6H₂O, add 100L water stirring and dissolvings；Again toward the Mn that addition 1.0kg concentration is 50 weight % in the solution that stirred (NO₃)₂The aqueous solution, fully stir evenly, obtain aqueous metal salt；

Weigh 15.0kg Na₂CO₃, 63.0L water stirring and dissolvings are added, add 0.47kg potassium silicate (Na₂CO₃With silicon The mol ratio of sour potassium is 100：2.5), stirring and dissolving obtains the precipitating reagent aqueous solution, tests its pH value as 12.9；

(2) the above-mentioned precipitating reagent aqueous solution is heated to 57 DEG C, aqueous metal salt is heated to 58 by coil pipe preheater ℃；Aqueous metal salt is added in 15min in the precipitating reagent aqueous solution being stirred vigorously, carries out and complete co-precipitation instead Should；The temperature for monitoring coprecipitation reaction on-line is 55 DEG C, and the pH of coprecipitated product slurries is 8.5；

(3) to addition 133kg ice cubes in obtained 197kg coprecipitated product slurries, coprecipitated product is starched in 10min The temperature of liquid is reduced to 17 DEG C or so, obtains slurries I；

(4) slurries I is immediately transferred into Suction filtration device and filtered, discarded to be washed with water after filtrate and wash filter cake.Instead After backwashing is washed until the electrical conductivity of last filtrate is below 1.2ms/cm, obtains precipitated filter cakes a, solid content is 36 weight %；

(5) by 11.7kg precipitated filter cakes a according to precipitated filter cakes a：The mass ratio of water is 5：1 is mixed into slurry, and adds (potassium content is 47.1 weight %, SiO to 1.41kg potassium silicate₂Content is 30.0 weight %) and the weight of precipitated filter cakes a weight 20 % water is measured, carries out being mixed with beating 25min；The dust technology that 10kg concentration is 12.0 weight % is added, it is 5.7 to obtain pH value Slurry II；Slurry II is subjected to standing 60min at 20 DEG C, then by filtering again, obtains filter cake b；Filter cake b is added into water Carry out high shear agitation (420rpm, 25min) and obtain catalyst pulp III of the solid content for 24 weight % or so；

(6) catalyst pulp III is inputted into spray-drying installation, is 310 DEG C in entrance wind-warm syndrome, outlet wind-warm syndrome is 108 DEG C It is spray-dried under conditions of left and right, being sprayed after about 8min finishes；Gained catalyst granules is put into Muffle furnace, in air In be calcined 12h at 110 DEG C, be then warming up to 450 DEG C with 320 DEG C/h heating rates, be calcined 7h at such a temperature, that is, obtain final Catalyst about 4.1kg.

The catalyst carries out component analysis, Fe:Cu:K:Co:Mn:SiO₂Weight ratio be=100:1.5:5.5:0.4: 5.0:20.0。

Embodiment 4

The electrical conductivity of the water used in the present embodiment is 35 μ s/cm.

(1) 22.0kg Fe (NO are weighed₃)₃·9H₂O, 0.69kg Cu (NO₃)₂·3H₂O and 0.105kg Co (NO₃)₂·6H₂O, add 100L water stirring and dissolvings；Again toward the Mn that addition 0.53kg concentration is 50 weight % in the solution that stirred (NO₃)₂The aqueous solution, fully stir evenly, obtain aqueous metal salt；

Weigh 13.0kg Na₂CO₃, 63.0L water stirring and dissolvings are added, add 0.47kg potassium silicate (Na₂CO₃With silicon The mol ratio of sour potassium is 100：2.5), stirring and dissolving obtains the precipitating reagent aqueous solution, tests its pH value as 12.7；

(2) the above-mentioned precipitating reagent aqueous solution is heated to 70 DEG C, aqueous metal salt is heated to 70 by coil pipe preheater ℃；Aqueous metal salt is added in 15min in the precipitating reagent aqueous solution being stirred vigorously, carries out and complete co-precipitation instead Should；The temperature for monitoring coprecipitation reaction on-line is 68 DEG C, and the pH of coprecipitated product slurries is 7.5；

(3) to addition 125kg ice cubes in obtained 193kg coprecipitated product slurries, coprecipitated product is starched in 5min The temperature of liquid is reduced to 15 DEG C or so, obtains slurries I；

(5) by 12.7kg precipitated filter cakes a according to precipitated filter cakes a：The mass ratio of water is 3：1 is mixed into slurry, and adds (modulus 2.01, potassium content are 13.67 weight %, SiO to 1.38kg potassium silicate water glass₂Content is 27.54 weight %) with (weight of potassium silicate water glass and potassium carbonate ratio is 2.9 to potassium carbonate (Chinese medicines group)：1), carry out being mixed with beating 25min；Again plus Enter the dust technology that 10kg concentration is 13.6 weight %, obtain the slurry II that pH value is 6；Slurry II is stood at 45 DEG C 45min, then by filtering again, obtain filter cake b；Filter cake b is added into water and carries out high shear agitation (360rpm, 25min) Obtain catalyst pulp III of the solid content for 21 weight % or so；

The catalyst as obtained by SEM electron microscope observations, it is similar to Fig. 1, show the sphericity of the particle of the catalyst It is good with surface gloss.

Embodiment 5

The electrical conductivity of the water used in the present embodiment is 33.6 μ s/cm.

(1) 22.0kg Fe (NO are weighed₃)₃·9H₂O, 0.069kg Cu (NO₃)₂·3H₂O and 0.035kg Co (NO₃)₂·6H₂O, add 85L water stirring and dissolvings；Again toward the Mn that addition 1.92kg concentration is 50 weight % in the solution that stirred (NO₃)₂The aqueous solution, fully stir evenly, obtain aqueous metal salt；

Weigh 12.0kg Na₂CO₃, 63.0L water stirring and dissolvings are added, add 0.3kg potassium silicate (Na₂CO₃With silicon The mol ratio of sour potassium is 100：1.7), stirring and dissolving obtains the precipitating reagent aqueous solution, tests its pH value as 12.6；

(2) the above-mentioned precipitating reagent aqueous solution is heated to 60 DEG C, aqueous metal salt is heated to 63 by coil pipe preheater ℃；Aqueous metal salt is added in 15min in the precipitating reagent aqueous solution being stirred vigorously, carries out and complete co-precipitation instead Should；The temperature for monitoring coprecipitation reaction on-line is 60 DEG C, and the pH of coprecipitated product slurries is 7.0；

(3) to addition 108kg ice cubes in obtained 192kg coprecipitated product slurries, coprecipitated product is starched in 12min The temperature of liquid is reduced to 18 DEG C or so, obtains slurries I；

(5) by 13.0kg precipitated filter cakes a according to precipitated filter cakes a：The mass ratio of water is 3.5：1 addition water is mixed into slurry, And add 1.42kg potassium silicate water glass (modulus 2.01, potassium content are 13.67 weight %, SiO₂Content is 27.54 weights Measure %) (weight of potassium silicate water glass and potassium carbonate ratio is 2 with potassium carbonate (Beijing modern times east fine chemicals)：1), carry out It is mixed with beating 25min；The dust technology that 12kg concentration is 10.0 weight % is added, obtains the slurry II that pH value is 6.3；By slurry II carries out standing 40min at 45 DEG C, then by filtering again, obtains filter cake b；Filter cake b is added into water and carries out high speed shear Stirring (350rpm, 25min) obtains catalyst pulp III of the solid content for 20 weight % or so；

The catalyst carries out component analysis, Fe:Cu:K:Co:Mn:SiO₂Weight ratio be=100:0.6:4.8:0.1: 9.6:17.0。

Embodiment 6

(1) 22.0kg Fe (NO are weighed₃)₃·9H₂O, 0.50kg Cu (NO₃)₂·3H₂O and 0.135kg Co (NO₃)₂·6H₂O, add 90L water stirring and dissolvings；Again toward the Mn that addition 0.2kg concentration is 50 weight % in the solution that stirred (NO₃)₂The aqueous solution, fully stir evenly, obtain aqueous metal salt；

Weigh 13.0kg Na₂CO₃, 63.0L water stirring and dissolvings are added, add 0.55kg potassium silicate (Na₂CO₃With silicon The mol ratio of sour potassium is 100：2.9), stirring and dissolving obtains the precipitating reagent aqueous solution, tests its pH value as 12.8；

(2) the above-mentioned precipitating reagent aqueous solution is heated to 77 DEG C；Aqueous metal salt is heated to 79 by coil pipe preheater ℃；Aqueous metal salt is added in 15min in the precipitating reagent aqueous solution being stirred vigorously, carries out and complete co-precipitation instead Should；The temperature for monitoring coprecipitation reaction on-line is 77 DEG C, and the pH of coprecipitated product slurries is 7.5；

(3) to addition 115kg ice cubes in obtained 196kg coprecipitated product slurries, coprecipitated product is starched in 13min The temperature of liquid is reduced to 20 DEG C or so, obtains slurries I；

(4) slurries I is immediately transferred into Suction filtration device and filtered, discarded filtrate and filter is washed with deionized again afterwards Cake.Washing obtains precipitated filter cakes a, solid content is 35 weight % until the electrical conductivity of last filtrate is below 1.2ms/cm repeatedly；

(5) by 12.3kg precipitated filter cakes a according to precipitated filter cakes a：The mass ratio of water is 3：1 addition water is mixed into slurry, and (modulus 2.01, potassium content are 13.67 weight %, SiO to addition 1.7kg potassium silicate water glass₂Content is 27.54 weight %) (weight of potassium silicate water glass and potassium carbonate ratio is 1.8 with potassium carbonate (Chinese medicines group)：1), carry out being mixed with beating 25min；Again The dust technology that 10kg concentration is 8.5 weight % is added, obtains the slurry II that pH value is 6；Slurry II is stood at 45 DEG C 45min, then by filtering again, obtain filter cake b；Filter cake b is added into water and carries out high shear agitation (380rpm, 25min) Obtain catalyst pulp III of the solid content for 21 weight % or so；

The catalyst carries out component analysis, Fe:Cu:K:Co:Mn:SiO₂Weight ratio be=100:5.0:2.5:0.3: 1.0:19.0。

Comparative example 1

The electrical conductivity of the water used in comparative example 1 is 112 μ s/cm.

(1) 22.0kg Fe (NO are weighed₃)₃·9H₂O, 0.59kg Cu (NO₃)₂·3H₂O and 0.03kg Co (NO₃)₂· 6H₂O, add 100L water stirring and dissolvings；Again toward the Mn (NO that addition 1.2kg concentration is 50 weight % in the solution that stirred₃)₂Water Solution, fully stir evenly, obtain aqueous metal salt；

Weigh 13.0kg Na₂CO₃, 63.0L water stirring and dissolvings are added, add 0.47kg potassium silicate (Na₂CO₃With silicon The mol ratio of sour potassium is 100：2.5), stirring and dissolving obtains the precipitating reagent aqueous solution, tests its pH value as 12.6；

(2) aqueous metal salt and the precipitating reagent aqueous solution are heated to 75 DEG C by coil pipe preheater respectively, by metal salt The aqueous solution is added in 15min in the precipitating reagent aqueous solution being stirred vigorously, and is carried out and is completed coprecipitation reaction；On-line monitoring The temperature of coprecipitation reaction is 73 DEG C, and the pH of coprecipitated product slurries is 7.3；

(3) to addition 118kg ice cubes in obtained 190kg coprecipitated product slurries, coprecipitated product is starched in 5min The temperature of liquid is reduced to 18 DEG C or so, obtains slurries I；

(4) coprecipitated product slurries I is transferred in Suction filtration device and filtered, discarded to be washed with water after filtrate and wash filter Cake.Washing obtains precipitated filter cakes a, solid content is 36 weight % until the electrical conductivity of last filtrate is below 1.2ms/cm repeatedly；

(5) by 12.8kg precipitated filter cakes a according to precipitated filter cakes a：The mass ratio of water is 4：1 addition water is mixed into slurry, and (potassium content is 47.1 weight %, SiO to addition 1.41kg potassium silicate₂Content is 30.0 weight %) and precipitated filter cakes a weight 20 weight % water, carry out being mixed with beating 25min；The dust technology that 10kg concentration is 12.0 weight % is added, obtains pH value For 6.7 slurry II；Slurry II is subjected to standing 30min at 45 DEG C, then by filtering again, obtains filter cake b；By filter cake B adds water progress high shear agitation (380rpm, 25min) and obtains catalyst pulp III of the solid content for 22 weight % or so；

The catalyst carries out component analysis, Fe:Cu:K:Co:Mn:SiO₂Weight ratio be=100:5.1:2.7:0.2: 6.0:18.0。

Comparative example 2

The electrical conductivity of the water used in comparative example 2 is 38 μ s/cm.

(1) 22.0kg Fe (NO are weighed₃)₃·9H₂O, 0.50kg Cu (NO₃)₂·3H₂O and 0.06kg Co (NO₃)₂· 6H₂O, add 100L water stirring and dissolvings；Again toward the Mn (NO that addition 1.36kg concentration is 50 weight % in the solution that stirred₃)₂Water Solution, fully stir evenly, obtain aqueous metal salt；

(2) 15.0kg Na is weighed₂CO₃, 63.0L water stirring and dissolvings are added, add 0.51kg potassium silicate (Na₂CO₃ Mol ratio with potassium silicate is 100：2.5), stirring and dissolving obtains the precipitating reagent aqueous solution, tests its pH value as 12.8；

(3) the precipitating reagent aqueous solution is heated to 85 DEG C, aqueous metal salt is heated to 87 DEG C by coil pipe preheater, will Aqueous metal salt is added in 15min in the precipitating reagent aqueous solution being stirred vigorously, and is carried out and is completed coprecipitation reaction； The temperature of line monitoring coprecipitation reaction is 83 DEG C, and the pH of coprecipitated product slurries is 7.8；

(4) coprecipitated product slurries are stood into 5min at 45 DEG C, transfers in Suction filtration device and filtered, discard filter It is washed with water after liquid and washs filter cake.Washing obtains precipitated filter cakes until the electrical conductivity of last filtrate is below 1.2ms/cm repeatedly A, solid content are 35 weight %；

(5) by precipitated filter cakes a according to precipitated filter cakes a：The mass ratio of water is 3.5：1 addition water is mixed into slurry, and adds (modulus 0.7, potassium content are 35.28 weight %, SiO to 2.15kg Ludox containing potassium₂Content is 25.24 weight %) and carbonic acid (weight of Ludox and potassium carbonate ratio is 15 to potassium (Beijing modern times east fine chemicals)：1), carry out being mixed with beating 25min；Again The dust technology that 12kg concentration is 15.0 weight % is added, obtains the slurry II that pH value is 7；Slurry II is stood at 45 DEG C 80min, then by filtering again, obtain filter cake b；Filter cake b is added into water and carries out high shear agitation (385rpm, 25min) Obtain catalyst pulp III of the solid content for 24 weight % or so；

The catalyst carries out component analysis, Fe:Cu:K:Co:Mn:SiO₂Weight ratio be=100:4.3:5.0:0.4: 6.8:25.0。

The pore size distribution$ of catalyst low-temperature nitrogen adsorption method measure is shown in Fig. 3.

Table 1

Note：Aperture：Bore dia ＜ 12nm；Mesopore：Bore dia is 12~80nm.

Abrasion index is determined using fresh catalyst as sample, and the test sample that each embodiment and comparative example are selected uses particle diameter Close particle, specific particle diameter are shown in Table 2.

F- T synthesis precipitated iron provided by the invention is can be seen that from the data of above-described embodiment and comparative example, and table 1 Base catalyst has a specified pore structure, such as the pore size distribution$ of catalyst that the embodiments 1 that show of Fig. 2 obtain, and shows two The individual appearance for significantly corresponding to different bore dia regions.The data of table 1 show each of pore volume corresponding to two bore dia regions From accounting, it can be seen that the accounting of aperture is low, and the accounting of mesopore is high.The pattern sphericity and table for the catalyst that Fig. 1 is shown simultaneously Face glossiness is good.Catalyst provided by the invention has improved polishing machine, ASTM D5757-00 air injection measure Abrasion index be less than 4.0%.

In the method for preparing the F- T synthesis precipitated iron-based catalyst of the present invention, the conductance of the water used in comparative example 1 Rate is higher than 60 μ s/cm, and aperture accounting is higher than 35% in the pore structure of the catalyst of acquisition, and mesopore accounting is less than 65%, thus grinds It is high to damage index, the wear resistance of catalyst is poor.In comparative example 2 not by coprecipitated product slurries addition ice cube cooled and Dilution, thus the pore structure of catalyst is obtained as shown in figure 3, and aperture substantially less than normal with reference to the data total pore volume that table 1 is shown Accounting is 51.1%, and mesopore accounting is 48.9%, poor different from embodiment 1-6, wear resistance.

Evaluate and test example 1

This evaluation and test example illustrates that the catalyst of the embodiment of the present invention 1 carries out syrup state bed Fischer Tropsch synthetic reaction.

Evaluating apparatus is laboratory 2L slurry bed system stirred tanks.

Loaded catalyst is：About 700g atoleine is by F- T synthesis precipitated iron-based catalyst made from embodiment 1 By 20 weight % concentration dilution, then it is loaded into slurry bed system stirred tank.

(a) reduction reaction：With containing CO and H₂Reducing atmosphere (CO and H₂Mol ratio be 0.1：1) in 270 DEG C and pressure Reduction reaction 24h is carried out under 0.1MPa；

(b) F- T synthesis：It is passed through synthesis gas (H₂Mol ratio with CO is 1.9：1), under 260 DEG C, pressure 2.2MPa, close It is 5.0NL/g-cath into gas air speed, carries out Fischer-Tropsch synthesis.

The reactivity worth for carrying out the catalyst of successive reaction the results are shown in Table 2.

The catalyst as obtained by SEM electron microscope observations, it can be seen that catalyst after it experienced 1803h reaction, Wear small, still catalyst granules has good sphericity and surface gloss.

The catalyst is carried out to CO conversion ratios, the CO of on-line determination during long-term operation₂Selectivity, CH₄Selectivity is made Figure, as shown in Figure 4, it can be seen that the catalyst is in prolonged course of reaction, CO conversion ratios, CO₂Selectivity, CH₄Selectivity Curve it is steady, still have higher CO conversion ratios and relatively low CO after it experienced 1803h₂Selectivity and CH₄Selectivity, display The catalyst has stable catalyzed conversion activity.

Evaluate and test example 2

The catalyst of embodiment 2 is carried out syrup state bed Fischer Tropsch synthetic reaction by the method according to evaluation example 1, unlike, use " synthesis gas air speed is 8NL/g-cath ", and " synthesis gas air speed is 5.0NL/g-cath " to replacement.

Evaluate and test example 3

This evaluation and test example illustrates that the catalyst of the embodiment of the present invention 3 carries out syrup state bed Fischer Tropsch synthetic reaction.

Evaluating apparatus is laboratory 2L slurry bed system stirred tanks.

Loaded catalyst is：About 700g atoleine is by F- T synthesis precipitated iron-based catalyst made from embodiment 3 By 10 weight % concentration dilution, then it is loaded into slurry bed system stirred tank.

(b) F- T synthesis：It is passed through synthesis gas (H₂Mol ratio with CO is 1.9：1), under 260 DEG C, pressure 2.2MPa, close It is 7NL/g-cath into gas air speed, carries out Fischer-Tropsch synthesis.

Evaluate and test example 4-6

According to the method for evaluation example 3, the catalyst of embodiment 4-6 catalyst alternative embodiment 3 is subjected to slurry bed system and taken Hold in the palm synthetic reaction.

Evaluate and test example 7-8

The catalyst of comparative example 1-2 catalyst alternative embodiment 3 is carried out syrup state bed Fischer Tropsch by the method according to evaluation example 3 Synthetic reaction.

Table 2

Note：D (0.5) is that the cumulative particle sizes percentile of fresh catalyst reaches particle diameter corresponding when 50%, is used Laser particle analyzer determines.

The catalyst that the present invention is can be seen that from the result of above-mentioned evaluation and test example and table 2 is carrying out syrup state bed Fischer Tropsch synthesis instead At once long-term operation can be continued, the reactivity worth of catalyst still keeps stable.And in Fischer-Tropsch synthesis result, C₅ ⁺Choosing Selecting property is improved, more than 89.4%；And 85.77% is only up in comparative example 1,2.

In the catalyst preparation process of comparative example 1, aqueous metal salt and the precipitating reagent aqueous solution are using the molten of high conductivity Xie Shui, so the aperture ratio of obtained catalyst substantially increases, wear resistance is poor.Carry out the long-term fortune of Fischer-Tropsch synthesis Row effect is poor.

In the catalyst preparation process of comparative example 2, after coprecipitation reaction terminates, coprecipitated product slurries are not carried out fast Prompt drop gently dilutes, so the aperture accounting of obtained catalyst further increases, wear resistance is poor.It is anti-to carry out F- T synthesis The longtime running effect answered is poor.

Claims

1. a kind of F- T synthesis precipitated iron-based catalyst, the composition weight ratio of the catalyst is Fe:Cu:K:Co:Mn:SiO₂= 100:(0.1~6):(0.6~6):(0.01~0.6)：(0.01~10):(5~27)；The catalyst is through low temperature N₂Physical absorption The pore structure of method measure has following characteristics：In bore dia≤80nm total pore volume, bore dia ＜ 12nm aperture accounting Less than 35%；The mesopore accounting that bore dia is 12~80nm is more than 65%.

2. catalyst according to claim 1, wherein, in bore dia≤80nm total pore volume, bore dia ＜ 12nm Aperture accounting be less than 30% and more than 0%.

3. catalyst according to claim 1 or 2, wherein, in bore dia≤80nm total pore volume, bore dia 12 ~80nm mesopore accounting is 65% less than 99%.

4. according to the catalyst described in any one in claim 1-3, wherein, according to ASTMD5757-00 air gunitees, The abrasion index for testing the catalyst is less than 4.0%.

5. a kind of preparation method of F- T synthesis precipitated iron-based catalyst, including：

(1) molysite, mantoquita, cobalt salt and manganese salt are dissolved in the water to obtain aqueous metal salt, the electrical conductivity of the water is 60 μ s/ Below cm；Precipitating reagent, silicon-containing compound and water are mixed to get the precipitating reagent aqueous solution, the precipitating reagent is selected from sodium carbonate, carbonic acid The mol ratio of at least one of potassium, saleratus and ammoniacal liquor, the precipitating reagent and the silicon-containing compound is 100：(1~3)；

(2) aqueous metal salt is added in the precipitating reagent aqueous solution, be co-precipitated at being 55~90 DEG C in temperature Reaction, the pH of obtained coprecipitated product slurries is 5.5~8.5；

(3) the coprecipitated product slurries are cooled down, the temperature of the coprecipitated product slurries is reduced in 15min Less than 20 DEG C, and the coprecipitated product slurries are diluted, obtain slurry I；

(5) Ludox or potassium silicate, potassium carbonate, water are mixed with beating with the precipitated filter cakes a, and add acid solution, it is 7 that pH, which is made, Following slurry II；The slurry II is stood, and filter cake b is obtained through filtering；The filter cake b is added into water and carried out at a high speed Shear agitation, obtain the catalyst precursor slurry III that solid content is 10~50 weight %；

(6) the catalyst precursor slurry III is spray-dried and is calcined；

Wherein, the addition of molysite, mantoquita, cobalt salt, manganese salt, precipitating reagent, potassium carbonate, potassium silicate or Ludox, meets Fe:Cu: K:Co:Mn:SiO₂Weight ratio be=100:(0.1~6):(0.6~6):(0.01~0.6)：(0.01~10):(5~27).

6. according to the method for claim 5, wherein, the cooling is to add ice cube into the coprecipitated product slurries, The weight ratio of ice cube and the coprecipitated product slurries is 1：Less than 1.

7. according to the method for claim 5, wherein, the silicon-containing compound includes solid silicic acid potassium, liquid silicic acid potassium, silicon At least one of colloidal sol, Ludox containing potassium, water soluble silica and sodium metasilicate.

8. according to the method for claim 5, wherein, in step (2), the aqueous metal salt is added in 15min Enter the precipitating reagent aqueous solution.

9. the method according to claim 11, wherein, in step (5), when the slurry II is stood, dwell temperature For 20~65 DEG C, time of repose is 30~90min.

10. according to the method described in any one in claim 5-9, wherein, the electrical conductivity of the water is below 35 μ s/cm.

11. F- T synthesis precipitated iron-based catalyst made from a kind of method in 5-10 as claim described in any one.

12. the F- T synthesis precipitated iron-based catalyst in a kind of claim 1-4 and 11 described in any one is in slurry reactor Progress Fischer-Tropsch synthesis prepares the application in hydrocarbon compound in device.

13. a kind of method of synthesis gas through syrup state bed Fischer Tropsch synthetic reaction hydrocarbon compound, including：

(a) in the presence of reducing atmosphere and diluent media, the F- T synthesis described in any one in claim 1-4 and 11 is sunk Shallow lake ferrum-based catalyst temperature be 230~320 DEG C, pressure is 0.1~2.8MPa, H in the reducing atmosphere₂With CO mol ratio For (0.2~35)：Under conditions of 1,1~48h of reduction reaction is carried out, obtains reduction-state activated catalyst；

(b) in the presence of the reduction-state activated catalyst, CO and H will be contained₂Synthesis gas temperature be 210~300 DEG C, pressure Under conditions of power is 1.2~2.8MPa, Fischer-Tropsch synthesis is carried out in paste state bed reactor, obtains hydrocarbon compound；Wherein, institute State H in synthesis gas₂Mol ratio with CO is (0.5~3.5)：1, the air speed of the synthesis gas is 5~16NL/g-cath.