CN104707620B - A kind of fischer-tropsch synthetic catalyst and preparation method and application - Google Patents
A kind of fischer-tropsch synthetic catalyst and preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of fischer-tropsch synthetic catalyst and preparation method and application.The present invention is using silicate solutions as raw material, silicate solution is obtained by cation exchange treatment, the silicate solution is removed into anionic impurity such as Cl therein through anion exchange processing again, obtain active silicic acid solution, replace business Ludox to prepare fischer-tropsch synthetic catalyst as silicon source using the active silicic acid, can effectively solve iron species and SiO2Between mix uneven problem, so as to increase the surface area of catalyst, improve the mechanical strength of catalyst.This method is easy to operate, with low cost, is highly suitable for being commercialized the preparation of fischer-tropsch synthetic catalyst.
Description
Technical field
The invention belongs to catalyst preparation technical field, and in particular to a kind of fischer-tropsch synthetic catalyst and preparation method thereof with
Using.
Background technology
Fischer-Tropsch synthesis refers to the synthesis gas that the gasification containing carbon resource such as coal, natural gas, biomass is obtained being converted into
The process of hydro carbons and chemicals.Due to the increasingly depleted of petroleum resources, F- T synthesis technology is by more extensive pass in recent years
Note.The conventional catalyst of Fischer-Tropsch synthesis is including Fe, Co, Ru etc..Wherein Ru is not suitable for industry due to its expensive price
Change application.Fe and Co are only to be suitable for industrialized two kinds of fischer-tropsch synthetic catalysts.
SiO2It is most commonly seen a kind of carrier in F- T synthesis iron catalyst, its addition can significantly improve catalyst
Degree of scatter so that active component is in high degree of dispersion state, is conducive to improving the activity of catalyst.In addition, SiO2Presence
More solid skeleton structure is provided for catalyst, the intensity of catalyst is improved so that catalyst has certain operation
Stability.The SiO that current industrial catalyst is added when preparing2Typically using commercially available business Ludox as presoma, such as China is special
Business Ludox is all used to be SiO in sharp CN1297343C, CN1287895C, CN1270822C, CN1260007C2Presoma.
Generally with sedimentation type SiO2With binder-type SiO2Form be added in catalyst.The former is to enter source of iron and Ludox first
Row is sufficiently mixed, and then carries out coprecipitation process, and binding agent SiO2Iron filter cake carries out reslurry after usually precipitating,
Ludox is added in slurry.Which kind of feed postition all there is SiO with2The drawbacks of mixing uneven between iron species, from
And be difficult to embody SiO to greatest extent2It is used as the advantage of carrier.Problem above occur has its source in commercially available business Ludox
Middle micelle average-size is too big, is not suitable for the preparation of fischer-tropsch synthetic catalyst.Using organosilicon (such as tetraethyl orthosilicate) generation
It can be solved the above problems to a certain extent for business Ludox, but organosilicon cost is too high, is not suitable for large-scale production.
The content of the invention
The technical problems to be solved by the invention are the suitable SiO of selection2Presoma replaces business Ludox, to solve to lead to
Cross SiO made from business Ludox2The problem of mixing uneven between iron species, increases the surface area of catalyst, and raising is urged
The mechanical strength of agent, so as to significantly provide the activity and reaction stability of catalyst.
In order to solve the above-mentioned technical problem, the invention provides a kind of fischer-tropsch synthetic catalyst and preparation method thereof.
Fischer-tropsch synthetic catalyst provided by the present invention is prepared by the method comprising the following steps：
(1) silicate solutions are obtained into silicate solution through cation exchange treatment；The silicate solution is handed over through anion
Change processing and remove anionic impurity therein, obtain active silicic acid solution；
(2) iron nitrate solution and the active silicic acid solution are mixed to get mixed solution 1, the mixed solution 1 is entered
Row aging, obtains the aging activity silicate solution containing Fe；The iron nitrate solution is once addition or adds in two times, the nitre
When sour ferrous solution is added in two times, the addition of first time is the 0.1%-1% of whole iron nitrate solutions, the ferric nitrate of surplus
Solution is added after weathering；
(3) the aging activity silicate solution containing Fe is mixed with the nitrate solution of transition metal M, obtains mixing molten
Liquid 2；
(4) in the presence of precipitating reagent so that iron and transition metal M co-precipitation in the mixed solution 2, precipitated
Slurry；
(5) precipitate slurry is filtered, obtains filter cake, the filter cake is mixed with water and potassium promoter presoma and beaten
Slurry, obtains slurry；Catalyst precursor is obtained after the slurry drying is molded；
(6) catalyst precursor roasting is obtained into fischer-tropsch synthetic catalyst.
In above method step (1), the silicate concretely commercially available KP1 or commercial sodium water glass.
In the silicate solutions, the mass concentration of silicate is 0.5%-10%, concretely 10%.
The cation exchange treatment is：By the silicate solutions with 1mL/min-100mL/min (such as 25mL/min)
Flow velocity pass through pH be 2-7 (such as 6-7) cationic ion-exchange resin.
The cationic ion-exchange resin can be polystyrene highly acidic resin, and such as commercially available 001 × 7 strongly acidic styrene is sun
Ion exchange resin.
The pH value of the silicate solution is 3-6, such as 5-6.
The anion exchange is processed as：By the silicate solution with 1mL/min-100mL/min (such as 20mL/min)
Flow velocity passes through anion exchange resin of the pH for 7-9 (such as 8-9).
The anion exchange resin can be styrene series anion exchange resin, such as commercially available 201 × 7 strong-basicity styrene
Series anion exchange resin.
The pH of the active silicic acid solution is 5-6.
The active silicic acid solution is with SiO2Its mass concentration is counted for 0.5%-5%, such as 5%.
Preferably, in the preparation process of above-mentioned active silicic acid solution, source of iron is first added in the silicate solutions, then
Follow-up cation exchange treatment and anion exchange processing is carried out successively, obtains the stable active silicic acid solution of Fe.
The source of iron concretely Fe (OH)3Or ferric nitrate.
The source of iron is Fe (OH)3When, the SiO in the silicate solutions2With the Fe (OH) of addition3The mass ratio of middle iron
For 100:0.5-10.
When the source of iron is ferric nitrate, the SiO in the silicate solutions2Mass ratio with iron in the ferric nitrate of addition is
100:0.5-5。
In above method step (2), Fe and SiO in the mixed solution 12Mass ratio be 100:1-60, such as 100:20.
The temperature of the aging is 25 DEG C -80 DEG C, and such as 30 DEG C, 50 DEG C, 80 DEG C, the time is 1h-36h, such as 2h, 3h, 5h.
In above method step (3), the nitrate of the transition metal M is the nitric acid of following at least one transition metal
Salt：Mn, Cr, V, Mo, W, Ni and Cu.
In the mixed solution 2, Fe and M mass ratio are 100:1-45.
In above method step (4), the precipitating reagent concretely ammoniacal liquor.
The mass concentration of the ammoniacal liquor is 1-25%.
The amount of the precipitating reagent is to cause the pH value of reaction system at the end of precipitating to be advisable as 6-9.
The feed postition of the precipitating reagent is following a, b or c：
A, the precipitating reagent is added in the mixed solution 2, the ascending change of pH value, final ph during this
It is maintained at pH=6-9, such as pH=8；
B, the mixed solution 2 is added in the precipitating reagent, the descending change of pH value, final ph during this
It is maintained at pH=6-9, such as pH=8；
C, the mixed solution 2 and the precipitating reagent be subjected to co-precipitation, pH value is constant in pH=6- during this
9, such as pH=8.
The temperature of the co-precipitation is 35 DEG C -80 DEG C.
In above method step (5), the solid holdup of the filter cake is 6wt%-50wt%.
The potassium promoter presoma is soluble potassium salt.
The potassium promoter presoma may be selected from following at least one：Potassium nitrate, potassium carbonate, saleratus and organic sylvite.
In the slurry, the mass ratio of Fe and potassium in the potassium promoter presoma is 100:1-8.
Adjusted before roasting is dried to the slurry, in addition to by the pH value of the slurry to 4-10 operation.
The solid holdup of the slurry is 5-40wt%.
The drying and moulding is carried out in adding pressure type spray drying Tower System.
The condition of the drying is：150-350 DEG C of EAT, 90-205 DEG C of leaving air temp.
In above method step (6), the roasting is carried out in air atmosphere or inert atmosphere.
The temperature of the roasting is 300 DEG C -700 DEG C, and the time is -8 hours 2 hours.
The surface area of the fischer-tropsch synthetic catalyst prepared is 201m2/g-220m2/ g, wear rate is 8%-12%, Cl
Content is less than 1ppm.
The fischer-tropsch synthetic catalyst prepared by the above method falls within protection scope of the present invention.
The main active component of the fischer-tropsch synthetic catalyst is Fe, simultaneously containing transition metal promoter M, potassium promoter and carrier
SiO2。
Wherein, Fe and transition metal promoter M, potassium and carrier S iO2Mass ratio be followed successively by 100:1-50:1-8:1-60, tool
Body can be 100：24.9：8.0：20.
The transition metal promoter M may be selected from following at least one：Mn, Cr, V, Mo, W, Ni and Cu.
The surface area of the fischer-tropsch synthetic catalyst is 201m2/g-220m2/ g, wear rate is 8%-12%, and Cl contents are small
In 1ppm.
Application of the above-mentioned fischer-tropsch synthetic catalyst in Fischer-Tropsch synthesis falls within protection scope of the present invention.
When the fischer-tropsch synthetic catalyst is used for fixed bed Fischer-Tropsch synthesis, fixed bed reaction condition is：Temperature is
230 DEG C -300 DEG C, air speed is 1000-20000h-1, pressure is 0.1-5.5MPa, unstripped gas H2/ CO=1.5-2.5, circulation of tail gas
Than for 2.
When the fischer-tropsch synthetic catalyst is used for syrup state bed Fischer Tropsch synthetic reaction, slurry reactor condition is：Temperature is
230 DEG C -280 DEG C, air speed is 1000-20000h-1, pressure is 0.1-5.5MPa, unstripped gas H2/ CO=1.5-2.5, circulation of tail gas
Than for 2.
The fischer-tropsch synthetic catalyst is before for fixed bed or syrup state bed Fischer Tropsch synthetic reaction, in addition it is also necessary to carry out pre-activated
Processing.
The condition of the activating pretreatment is：Temperature is 230-450 DEG C, and air speed is 1000-8000h-1, pressure is 0.1-
5.5MPa, synthesis gas H2/ CO=0-1000 (being not 0), the time is 10h-60h.
Ferrum-based catalyst provided by the present invention has high reactivity under 230~300 DEG C of reaction temperature, excellent
Stability, and good wear resistance.Prepared catalyst has extensive adaptability, can be used as fixed bed, slurry
The fischer-tropsch synthetic catalyst of state bed reactor (but being not limited only to).
Compared with prior art, the invention has the advantages that：
(1) SiO that the present invention is provided2The production method of presoma is novel, and technique is simple, it is easy to mass produce；
(2) preparation method for the catalyst that the present invention is provided is practical, and traditional Ludox is replaced as silicon using active silicic acid
It is presoma steady quality, controllable during source, the quality stability of catalyst can be obviously improved, during large-scale industrial production, it is to avoid
Because raw material SiO2The change of property causes the quality dissatisfaction of catalyst；
(3) SiO produced by the invention2Impurity Cl ion concentrations are controllable in presoma, are significantly less than miscellaneous in business Ludox
The content of matter Cl ions；
(4) present invention passes through SiO made from active silicic acid2Mixed with iron species fully, gained catalyst dispersity is good, than
Surface area is high, it is to avoid because the negative effect that colloid size is brought greatly very much in Ludox；
(5) catalyst that the present invention is provided can significantly improve reactivity during slurry bed system and fixed bed reaction；
(6) catalyst provided by the present invention has very high mechanical strength, be particularly suitable under higher temperature (230~
300 DEG C) Fischer-Tropsch synthesis.
(7) catalyst that the present invention is provided is in slurry bed system or fixed bed reactors operating process, and reaction hydrocarbon products are obvious
To medium carbon number C5More than) skew, but methane selectively is lower than existing low temperature slurry bed process, can be controlled within 3wt%,
Catalyst is separated easily with product.
The present invention replaces business Ludox as silicon source to prepare catalyst using active silicic acid, can effectively solve iron species with
SiO2Between mix uneven problem, this method is easy to operate, with low cost, be highly suitable for commercialization F- T synthesis catalysis
The preparation of agent.
Embodiment
Below by specific embodiment, the present invention will be described, but the invention is not limited in this.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., unless otherwise specified, are commercially obtained.
Embodiment 1
Weigh 19.8 kilograms of potassium silicates and prepare the potassium silicate solution for obtaining 10wt%, under conditions of flow velocity is 25mL/min
By 001 × 7 strongly acidic styrene type cation exchange resin that pH value is 6-7, pH=5-6 silicate solution is made, by this
Silicate solution is exchanged under conditions of flow velocity is 20mL/min by 201 × 7 strong-basicity styrene series anions that pH value is 8-9
Resin, obtains SiO2Concentration is 5% 112 kilograms of active silicic acid solution；0.85 kilogram is added into the active silicic acid solution
Fe(NO3)39H2O (SiO2Mass ratio with Fe is 100:1.97), fully dissolving, the aging 5h at 80 DEG C, by 211.75 kilograms
Added after Fe(NO3)39H2O dissolving, obtain the aging activity silicate solution containing Fe；Then it is then added to mixed nitrate solution
(weigh 5.7 kilograms of Gerhardite, 35.8 kilograms of 50wt% manganese nitrate solutions to be dissolved in deionized water, obtained concentration is
25.92wt% mixed nitrate solutions, consisting of：Mn:Cu=19.64:5.35) in, stir；The concentration is taken to be
19.6wt% ammonia spirit, is preheated to 20 DEG C, under stirring in 50 DEG C, pH value be 9.0 under continuous co-precipitation；It is heavy
Aging 120 minutes behind shallow lake, it is 51.2wt%'s that washing ammonium nitrate content into slurries, which is less than 0.5wt%, is filtrated to get solid holdup,
Filter cake；5L deionized water and 5.66 kilograms of potassium acetate is added into filter cake；Fully after mashing, regulation slurry pH is 5.2, admittedly
It is 38.20wt% containing rate, spray drying, to control EAT be 180 DEG C, leaving air temp is 90 DEG C.By dried catalyst
Presoma is calcined 4 hours at 550 DEG C, obtains fischer-tropsch synthetic catalyst, and weight composition is Fe：M(Mn：Cu=19.6：5.3)：
K：SiO2=100：24.9：8.0：20, the catalyst is designated as B.
Comparative example
Weigh 212.6 kilograms of Fe(NO3)39H2O (iron is 27.99 kilograms), (copper is 1.5 to 5.7 kilograms of Gerhardite
Kilogram), 35.8 kilograms of 50wt% manganese nitrate solutions (manganese be 5.5 kilograms) be dissolved in deionized water, it is 25.92wt% that concentration, which is made,
Mixed nitrate solution is standby, consisting of：Fe：Mn：Cu=100：19.6：5.3；Weigh 30.0wt% commercially available Ludox
18.6 kilograms of (Qingdao Marine Chemical Co., Ltd.), is added in above-mentioned nitrate solution, stirs；Take a certain amount of dense
The ammonia spirit for 19.6wt% is spent, 20 DEG C are preheated to, continuous cocurrent is coprecipitated under 50 DEG C, pH value is 9.0 under stirring
Form sediment；Aging 120 minutes after precipitation, washing ammonium nitrate content into slurries, which is less than 0.5wt%, is filtrated to get solid holdup, is
51.2wt% filter cake；5L deionized waters and 5.66 kilograms of potassium acetate are added into filter cake (potassium is 2.25 kilograms)；Fully beat
After slurry, regulation slurry pH is that 5.2, solid holdup is 38.20wt%, spray drying, and it is 180 DEG C, leaving air temp to control EAT
For 90 DEG C.Take dried catalyst to be calcined 4 hours at 550 DEG C, obtain fischer-tropsch synthetic catalyst, weight composition is Fe：M
(Mn：Cu=19.6：5.3)：K：SiO2=100：24.9：8.0：20 catalyst are designated as A.
Embodiment 2
Weigh 19.8 kilograms of potassium silicates and prepare the potassium silicate solution for obtaining 10wt%, under conditions of flow velocity is 25mL/min
By 001 × 7 strongly acidic styrene type cation exchange resin that pH value is 6-7, pH=5-6 silicate solution is made, by this
Silicate solution is exchanged under conditions of flow velocity is 20mL/min by 201 × 7 strong-basicity styrene series anions that pH value is 8-9
Resin, obtains SiO2Concentration is 5% 112 kilograms of active silicic acid solution；It will be added after 212.6 kilograms of Fe(NO3)39H2O dissolvings
Obtain mixed solution 1 into the active silicic acid solution, by the mixed solution 1 at 30 DEG C aging 2h, obtain containing the old of Fe
Change active silicic acid solution (SiO2Mass ratio with Fe is 20:100)；Added in the aging activity silicate solution containing Fe pre-
First ready mixed nitrate solution (weighs 5.7 kilograms of Gerhardite, 35.8 kilograms of 50wt% manganese nitrate solutions to be dissolved in
In deionized water, it is 25.92wt% mixed nitrate solutions that concentration, which is made, consisting of：Mn:Cu=19.6:5.3), fully stir
Mix uniform；The ammonia spirit for taking a certain amount of concentration to be 19.6wt%, is preheated to 20 DEG C, is in 50 DEG C, pH value under stirring
Continuous co-precipitation under 9.0；Aging 120 minutes after precipitation, washing ammonium nitrate content into slurries is less than 0.5wt%, filtering
Obtain the filter cake that solid holdup is 51.2wt%；5L deionized water and 5.66 kilograms of potassium acetate is added into filter cake；Fully beat
After slurry, regulation slurry pH is that 5.2, solid holdup is 38.20wt%, spray drying, and it is 180 DEG C, leaving air temp to control EAT
For 90 DEG C.Take dried catalyst precursor to be calcined 4 hours at 550 DEG C, obtain fischer-tropsch synthetic catalyst, constitute as Fe：M
(Mn：Cu=19.6：5.3)：K：SiO2=100：24.9：8.0：20, the catalyst is designated as C.
Embodiment 3
Weigh 19.8 kilograms of potassium silicates and prepare the potassium silicate solution for obtaining 10wt%, under conditions of flow velocity is 25mL/min
By 001 × 7 strongly acidic styrene's cationic ion-exchange resin that pH value is 6-7, pH=5-6 silicate solution is made, by this silicon
Acid solution is exchanged by 201 × 7 strong-basicity styrene series anions that pH value is 8-9 under conditions of flow velocity is 20mL/min and set
Fat, obtains SiO2Concentration is 5% 112 kilograms of active silicic acid solution；8.5 kilogram of nine hydration nitre is added into active silicic acid solution
Sour iron (SiO2Mass ratio with Fe is 100:20), fully dissolve, aging 3h at 50 DEG C, by 204.09 kilograms of Fe(NO3)39H2Os
Added after dissolving, obtain the aging activity silicate solution containing Fe；Then it is then added to mixed nitrate solution and (weighs three hydration nitre
Sour 5.7 kilograms of copper, 35.8 kilograms of 50wt% manganese nitrate solutions are dissolved in deionized water, and it is 25.92wt% mixing nitre that concentration, which is made,
Acid salt solution, consisting of：Mn:Cu=19.6:5.3) in, stir；The ammoniacal liquor for taking a concentration to be 19.6wt% is molten
Liquid, is preheated to 20 DEG C, under stirring in 50 DEG C, pH value be 9.0 under continuous co-precipitation；Aging 120 minutes after precipitation,
Ammonium nitrate content is washed into slurries to be less than 0.5wt%, be filtrated to get the filter cake that solid holdup is 51.2wt%；Added into filter cake
5L deionized water and 5.66 kilograms of potassium acetate；Fully after mashing, regulation slurry pH is that 5.2, solid holdup is 38.20wt%,
Spray drying, to control EAT be 180 DEG C, leaving air temp is 90 DEG C.Dried spherical catalyst is taken to be calcined at 550 DEG C
4 hours, fischer-tropsch synthetic catalyst is obtained, weight composition is Fe：M(Mn：Cu=19.6：5.3)：K：SiO2=100：24.9：
8.0：20, the catalyst is designated as D.
Embodiment 4
It is sufficiently mixed uniformly after weighing 19.8 kilograms of potassium silicates, 0.85 kilogram of Fe(NO3)39H2O dissolving, preparation is obtained
10wt% potassium silicate solution, by 001 × 7 strongly acidic styrene that pH value is 6-7 under conditions of flow velocity is 25mL/min
Cation exchanger resin, is made pH=5-6 silicate solution, and this silicate solution is led under conditions of flow velocity is 20mL/min
201 × 7 strong-basicity styrene series anion exchange resins that pH value is 8-9 are crossed, SiO is obtained2Concentration is the stable work of 5%, Fe
112 kilograms of silicate solution of property；In the active silicic acid solution stable by above-mentioned Fe is added to after 211.75 kilograms of nitric acid dissolved ferric irons,
Aging 8h at 80 DEG C, is then then added to mixed nitrate solution and (weighs 5.7 kilograms of Gerhardite, 50wt% manganese nitrates
35.8 kilograms of solution is dissolved in deionized water, and it is 25.92wt% mixed nitrate solutions that concentration, which is made, consisting of：Mn:Cu=
19.6:5.3) in, stir；Take concentration be 19.6wt% ammonia spirit, be preheated to 20 DEG C, under stirring in
50 DEG C, pH value be 9.0 under continuous co-precipitation；Aging 120 minutes after precipitation, washing ammonium nitrate content into slurries is less than
0.5wt%, be filtrated to get solid holdup be 51.2wt% filter cake；A certain amount of deionized water and 5.66 kilograms are added into filter cake
Potassium acetate；Fully after mashing, regulation slurry pH is that 5.2, solid holdup is 38.20wt%, and spray drying controls the EAT to be
180 DEG C, leaving air temp be 90 DEG C.Take dried catalyst precursor to be calcined 4 hours at 550 DEG C, obtain F- T synthesis and urge
Agent, weight composition is Fe：M(Mn:Cu=19.6:5.3)：K：SiO2=100：24.9：8.0：20, the catalyst is designated as E.
The catalyst A-E of table 1 some test results
a：Wear rate test process meets U.S.'s ASTMD5757 standards, and sample is sieved first before test, removes
Fine-powder below 200 mesh, weighs sample 50g after screening and is laid on surface plate, and surface plate is placed in into top saturation chlorine
The electrostatic produced to weaken in follow-up test is humidified in the drier for changing calcium solution.It is m by the weight handled wellsSample
Add in abrasion pipe, top insertion weight is m0Collection trap, start humidity is passed through as 20% sky using 10L/min speed
Gas, catalyst is blown into expansion chamber, smaller catalyst in the collision of abrasion Guan Zhongyu tube walls and mutually collision, the fragment of generation
Dust rises in expansion chamber, is finally collected trap collection.Collection trap is removed after 1 hour to weigh, and is designated as m1, insert collection trap
(weight is designated as m0') continue to wear away 4h, the weight for weighing collection trap is designated as m2, finally wear away taking-up catalyst weight in pipe and be designated as
mr.The calculating of fine loss (Fine loss) finally, abrasion loss (Attrition loss) and the rate of recovery (Recovery)
Formula is as follows.Fine loss=(m1-m0)/ms* 100, Attrition loss=(m1-m0+m2-m0’)/ms* 100,
Recovery=(mr+m1-m0+m2-m0’)/ms*100
The Cl contents for the fischer-tropsch synthetic catalyst that the method provided as shown in Table 1 using the present invention is prepared are significantly
Reduction, the specific surface area of catalyst is increased substantially, while the intensity of catalyst also increases.
The catalyst A-E of table 2 fixed bed evaluation result
b:Inactivation rate refers under conditions of keeping reaction condition constant, continuously runs 1000h, initial CO conversion rate with
The difference of 1000h CO conversion ratios, then divided by initial CO conversion rate, be shown below：Inactivation rate (%)=%* (initial CO conversions
Rate -1000h CO conversion ratios)/initial CO conversion rate
As shown in Table 2：Catalyst prepared by the method provided using the present invention has good reactivity worth, from fixed bed
From the point of view of reaction result, CH can be significantly reduced4Selectivity, while improving the operation stability of catalyst.
The catalyst A-E of table 3 slurry bed system evaluation result
b:Inactivation rate refers under conditions of keeping reaction condition constant, continuously runs 1000h, initial CO conversion rate with
The difference of 1000h CO conversion ratios, then divided by initial CO conversion rate, be shown below：Inactivation rate (%)=%* (initial CO conversions
Rate -1000h CO conversion ratios)/initial CO conversion rate
As shown in Table 3：Catalyst prepared by the method provided using the present invention has good reactivity worth, from slurry bed system
From the point of view of reaction result, CH can be significantly reduced4Selectivity, while improving the operation stability of catalyst.
Claims (9)
1. a kind of method for preparing fischer-tropsch synthetic catalyst, comprises the steps：
(1) silicate solutions are obtained into silicate solution through cation exchange treatment；By the silicate solution through anion exchange at
Reason removes anionic impurity therein, obtains active silicic acid solution；
The active silicic acid solution is with SiO2Its mass concentration is counted for 0.5%-5%；
(2) iron nitrate solution and the active silicic acid solution are mixed to get mixed solution 1, the mixed solution 1 is carried out always
Change, obtain the aging activity silicate solution containing Fe；The iron nitrate solution is once addition or adds in two times, the ferric nitrate
When solution is added in two times, the addition of first time is the 0.1%-1% of whole iron nitrate solutions, the iron nitrate solution of surplus
Add after weathering；
Fe and SiO in the mixed solution 12Mass ratio be 100:1-60；
The temperature of the aging is 25 DEG C -80 DEG C, and the time is 1h-36h；
(3) the aging activity silicate solution containing Fe is mixed with the nitrate solution of transition metal M, obtains mixed solution 2；
(4) in the presence of precipitating reagent so that iron and transition metal M co-precipitation in the mixed solution 2, precipitation slurry is obtained
Material；
(5) precipitate slurry is filtered, obtains filter cake, the filter cake is mixed into mashing with water and potassium promoter presoma,
Obtain slurry；Catalyst precursor is obtained after the slurry drying is molded；
(6) catalyst precursor roasting is obtained into fischer-tropsch synthetic catalyst.
2. according to the method described in claim 1, it is characterised in that：In methods described step (1), the silicate is potassium water glass
Glass or sodium silicate；
In the silicate solutions, the mass concentration of silicate is 0.5%-10%；
The cation exchange treatment is：By the silicate solutions using 1mL/min-100mL/min flow velocity by pH as 2-7
Cationic ion-exchange resin；
The cationic ion-exchange resin is polystyrene highly acidic resin；
The pH value of the silicate solution is 3-6；
The anion exchange is processed as：By the silicate solution using 1mL/min-100mL/min flow velocity by pH as 7-9's
Anion exchange resin；
The anion exchange resin is styrene series anion exchange resin；
The pH of the active silicic acid solution is 5-6.
3. method according to claim 1 or 2, it is characterised in that：In methods described step (1), in the active silicic acid
In the preparation process of solution, source of iron is first added in the silicate solutions, then carry out follow-up cation exchange treatment successively
With anion exchange processing, the stable active silicic acid solution of Fe is obtained；
The source of iron is Fe (OH)3Or ferric nitrate；
The source of iron is Fe (OH)3, the SiO in the silicate solutions2With the Fe (OH) of addition3The mass ratio of middle iron is 100:
0.5-10；
The source of iron is the SiO in ferric nitrate, the silicate solutions2Mass ratio with iron in the ferric nitrate of addition is 100:
0.5-5。
4. method according to claim 1 or 2, it is characterised in that：The nitrate of the transition metal M is following at least one
Plant the nitrate of transition metal：Mn, Cr, V, Mo, W, Ni and Cu；
In the mixed solution 2, Fe and M mass ratio are 100:1-45.
5. method according to claim 1 or 2, it is characterised in that：In the step (4), the precipitating reagent is ammoniacal liquor；
The temperature of the co-precipitation is 35 DEG C -80 DEG C.
6. method according to claim 1 or 2, it is characterised in that：In the step (5), the potassium promoter presoma is
Soluble potassium salt；
In the slurry, the mass ratio of Fe and potassium in the potassium promoter presoma is 100:1-8.
7. method according to claim 1 or 2, it is characterised in that：In the step (6), the temperature of the roasting is 300
DEG C -700 DEG C, the time is -8 hours 2 hours.
8. the fischer-tropsch synthetic catalyst that method any one of claim 1-7 is prepared, the fischer-tropsch synthetic catalyst
Surface area be 201m2/g-220m2/ g, wear rate is 8%-12%, and Cl contents are less than 1ppm.
9. a kind of Fischer-Tropsch synthesis method, it is characterised in that：The Fischer-Tropsch synthesis method is using the F- T synthesis described in claim 8
Catalyst；
The F- T synthesis is carried out in fixed bed, and the fixed bed reaction condition is：Temperature is 230 DEG C -300 DEG C, and air speed is
1000-20000h-1, pressure is 0.1-5.5MPa, unstripped gas H2/ CO=1.5-2.5, circulation of tail gas ratio is 2；
The F- T synthesis is carried out in slurry bed system, and the slurry reactor condition is：Temperature is 230 DEG C -280 DEG C, and air speed is
1000-20000h-1, pressure is 0.1-5.5MPa, unstripped gas H2/ CO=1.5-2.5, circulation of tail gas ratio is 2.
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Address after: 101407 No.1, south 2nd Yueyuan street, C District, Yanqi Economic Development Zone, Huairou District, Beijing Patentee after: Zhongke synthetic oil Technology Co.,Ltd. Address before: 101407 No.1, south 2nd Yueyuan street, C District, Yanqi Economic Development Zone, Huairou District, Beijing Patentee before: SYNFUELS CHINA TECHNOLOGY Co.,Ltd. |