CN108620077B - Low-temperature Fischer-Tropsch synthesis catalyst and preparation method and application thereof - Google Patents

Low-temperature Fischer-Tropsch synthesis catalyst and preparation method and application thereof Download PDF

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CN108620077B
CN108620077B CN201710161306.9A CN201710161306A CN108620077B CN 108620077 B CN108620077 B CN 108620077B CN 201710161306 A CN201710161306 A CN 201710161306A CN 108620077 B CN108620077 B CN 108620077B
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salt
potassium
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CN108620077A (en
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林泉
王鹏
程萌
张魁
常海
朱加清
吕毅军
门卓武
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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Shenhua Group Corp Ltd
National Institute of Clean and Low Carbon Energy
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    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
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Abstract

The invention relates to the field of Fischer-Tropsch synthesis, in particular to a low-temperature Fischer-Tropsch synthesis catalyst, and a preparation method and application thereof. The preparation method of the low-temperature Fischer-Tropsch synthesis catalyst comprises the following steps: (1) providing an aqueous solution containing iron salt, copper salt and auxiliary agent metal M salt, namely a first solution; providing an aqueous solution containing a precipitating agent and a silicon source, i.e. a second solution; carrying out coprecipitation reaction on the first solution and the second solution, then carrying out solid-liquid separation and washing the obtained solid phase; (2) pulping the washed solid phase with water to obtain slurry, introducing a potassium-containing silicon source, and adjusting the pH value of the obtained mixture to acidity for aging; (3) and carrying out solid-liquid separation on the aged slurry, pulping the obtained solid phase and water, and carrying out spray drying and roasting on the obtained slurry. The method can obtain high activity, low byproduct selectivity, and high C5+A low-temperature Fischer-Tropsch synthesis catalyst with product selectivity, high stability and high abrasion resistance.

Description

Low-temperature Fischer-Tropsch synthesis catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of Fischer-Tropsch synthesis, in particular to a low-temperature Fischer-Tropsch synthesis catalyst, and a preparation method and application thereof.
Background
The Fischer-Tropsch synthesis reaction refers to synthesis gas (H)2+ CO) is converted to hydrocarbons and other chemicals over a catalyst at a temperature and pressure. The development of the Fischer-Tropsch synthesis technology has practical significance for realizing crude oil substitution, guaranteeing the energy safety of China and converting and utilizing clean coal. The Fischer-Tropsch synthesis can be realized only under the action of a proper catalyst. In the last 50 th century, the SASOL company in south Africa adopted the German luer company's patent technology to realize the commercial application of low-temperature Fischer-Tropsch synthesis technology and high-temperature Fischer-Tropsch synthesis technology. The reaction temperature of the low-temperature Fischer-Tropsch synthesis technology is between 210 ℃ and 280 ℃, the catalyst comprises a precipitated iron catalyst and a cobalt-based catalyst, and the reactor is a fixed bed reactor and a slurry bed reactor. The reaction temperature of the high-temperature Fischer-Tropsch synthesis technology is between 300 and 350 ℃, and the reactors are in the forms of a fixed fluidized bed and a circulating fluidized bed reactor. Compared with cobalt catalyst, the precipitated iron catalyst has the characteristics of low cost, wide application range to reaction conditions and synthesis gas components, and high alpha-olefin selectivity in the synthesized product.
After decades of development, technical developers all over the world continuously improve the formula and the preparation method of the catalyst, and a plurality of new useful auxiliary agents are added into Fe-Cu-K-SiO2The performance of the catalyst is improved in the system. Representative Fe-Mn-Cu-K-SiO developed by Chinese synthetic oil2Yan Fe-Cu-K-SiO developed from mine2Fe-Co-Cu-K-SiO developed by-Na, Shenhua2And the like.
However, the existing low-temperature Fischer-Tropsch synthesis iron-based catalyst still has the improvement on the properties such as activity, selectivity of byproducts, selectivity of C5+ products, stability and abrasion resistance.
Disclosure of Invention
The invention aims to provide a catalyst with high activity, low byproduct selectivity and high C5+A low-temperature Fischer-Tropsch synthesis catalyst with product selectivity, high stability and high abrasion resistance, a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a low temperature fischer-tropsch synthesis catalyst, the method comprising:
(1) providing an aqueous solution containing iron salt, copper salt and auxiliary agent metal M salt, namely a first solution; providing an aqueous solution containing a precipitating agent and a silicon source, i.e. a second solution; carrying out coprecipitation reaction on the first solution and the second solution, then carrying out solid-liquid separation and washing the obtained solid phase; the temperature is 5-35 deg.C, pH is 4.5-9.5, and the time is 5-60 min; defining the pH value of the coprecipitation reaction as a value n, and defining the temperature of the coprecipitation reaction as a value T, wherein the temperature and the pH value of the coprecipitation reaction satisfy the following formula: n +0.16T ═ 9-14; the auxiliary metal M is lanthanide metal;
(2) pulping the washed solid phase with water to obtain slurry, introducing a potassium-containing silicon source, and adjusting the pH value of the obtained mixture to acidity for aging;
(3) carrying out solid-liquid separation on the aged slurry, pulping the obtained solid phase and water, and carrying out spray drying and roasting on the obtained slurry;
wherein the iron salt, the copper salt, the auxiliary metal M salt, the silicon source and the potassium-containing silicon source are used in amounts such that the weight percentage of Fe in the obtained catalyst is2O3：Cu：K：M：SiO2＝100：1-8：1-8：1-8：10-30。
In a second aspect the invention provides a low temperature fischer-tropsch synthesis catalyst obtainable by the above process.
The invention also provides a method for preparing hydrocarbon compounds by the slurry bed Fischer-Tropsch synthesis reaction of the synthesis gas, which comprises the following steps: in the presence of the reduced Fischer-Tropsch synthesis catalyst, the catalyst contains CO and H2The synthesis gas is subjected to Fischer-Tropsch synthesis reaction in a slurry bed reactor at the temperature of 210-280 ℃ and the pressure of 1.0-5.0 MPa; wherein the reduced Fischer-Tropsch synthesis catalyst is obtained by reducing the low-temperature Fischer-Tropsch synthesis catalyst.
The preparation method of the low-temperature Fischer-Tropsch synthesis catalyst can obtain high activity, low byproduct selectivity and high C5+A low-temperature Fischer-Tropsch synthesis catalyst with product selectivity, high stability and high abrasion resistance.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect of the invention, there is provided a process for the preparation of a low temperature fischer-tropsch synthesis catalyst, the process comprising:
(1) providing an aqueous solution containing iron salt, copper salt and auxiliary agent metal M salt, namely a first solution; providing an aqueous solution containing a precipitating agent and a silicon source, i.e. a second solution; carrying out coprecipitation reaction on the first solution and the second solution, then carrying out solid-liquid separation and washing the obtained solid phase; the temperature is 5-35 deg.C, pH is 4.5-9.5, and the time is 5-60 min; defining the pH value of the coprecipitation reaction as a value n, and defining the temperature of the coprecipitation reaction as a value T, wherein the temperature and the pH value of the coprecipitation reaction satisfy the following formula: n +0.16T ═ 9-14; the auxiliary metal M is lanthanide metal;
(2) pulping the washed solid phase with water to obtain slurry, introducing a potassium-containing silicon source, and adjusting the pH value of the obtained mixture to acidity for aging;
(3) carrying out solid-liquid separation on the aged slurry, pulping the obtained solid phase and water, and carrying out spray drying and roasting on the obtained slurry;
wherein the iron salt, the copper salt, the auxiliary metal M salt, the silicon source and the potassium-containing silicon source are used in amounts such that the weight percentage of Fe in the obtained catalyst is2O3：Cu：K：M：SiO2＝100：1-8：1-8：1-8：10-30。
According to the present invention, in step (1), a coprecipitation reaction of a first solution containing a metal salt and a second solution containing a precipitant can be performed to obtain a precursor for preparing a subsequent catalyst. It will be understood by those skilled in the art that Fe3+The products formed by precipitation are very complex, the precipitation process is very sensitive to conditions, the fluctuation of pH value (such as forward and reverse precipitation) and the temperatureThe fluctuation and the aging time of the catalyst can affect the species of the generated precipitation particles, and even if hydrated iron oxide is generated during precipitation, the hydrated iron oxide can be continuously converted into other iron species, so that iron grains generated during precipitation are not single species, and different species and grain sizes affect the performance of the final catalyst. Wherein, when the conditions of the coprecipitation reaction are controlled to meet the conditions that the temperature is 5-35 ℃, the pH value is 4.5-9.5, the time is 5-60min and the formula n +0.16T is 9-14 (preferably n +0.16T is 10-13), the catalyst precursor which has the characteristics of hydrated iron oxide as a crystal phase and is characterized by multimodal pore channel distribution and excellent performance can be obtained, thereby being beneficial to obtaining the catalyst with high activity and high wear resistance. Particularly, under the condition that the coprecipitation reaction is controlled to be in the range and the formula is satisfied, the growth speed of hydrated iron oxide grains at low temperature is low, the hydrated iron oxide grains are not easy to dehydrate, meanwhile, the more hydroxyl groups on the surface of the hydrated iron oxide grains are, the more agglomeration among the hydrated iron oxide grains is facilitated, a multi-scale pore channel structure is formed, the bonding strength among the grains is enhanced, and the important contribution is made to the active surface structure, the pore distribution structure and the abrasion resistance of the catalyst. Preferably, in step (1), the conditions of the coprecipitation reaction include: the temperature is 5-30 deg.C, pH is 5-9, and the time is 10-50 min. More preferably, the temperature of the coprecipitation reaction is 8 to 20 ℃.
According to the invention, the amounts of iron salt, copper salt, auxiliary metal M salt, silicon source and potassium-containing silicon source are controlled such that the resulting catalyst contains Fe by weight2O3：Cu：K：M：SiO2100: 1-8: 1-8: 1-8: 10 to 30, the catalyst which can achieve the desired effect of the present invention can be obtained, but in order to obtain a catalyst having higher activity and lower selectivity for by-products, C5+A low temperature fischer-tropsch catalyst having a higher product selectivity, higher stability and higher attrition resistance, preferably the iron salt, the copper salt, the promoter metal M salt, the silicon source and the potassium-containing silicon source are used in amounts such that in the resulting catalyst, Fe is present in the amount by weight2O3：Cu：K：M：SiO2100: 1-5: 1-5: 1-5: 10-25, preferably Fe2O3：Cu：K：M：SiO2＝100：1-4：1.5-4：2-5：10-23。
The iron salt is not particularly limited in the present invention, and various soluble iron salts conventionally used in the art can be used, and specific examples of the iron salt may be one or more of iron nitrate, iron sulfate and iron chloride, and preferably iron nitrate.
The copper salt is not particularly limited in the present invention, and various soluble copper salts conventionally used in the art can be used, and specific examples of the copper salt may be one or more of copper nitrate, copper sulfate and copper chloride.
The auxiliary metal M is preferably one or more of La, Ce and Nd, and more preferably, the auxiliary metal M salt is one or more of lanthanum nitrate, cerium nitrate, neodymium nitrate, lanthanum sulfate, cerium sulfate, neodymium sulfate, lanthanum chloride, cerium chloride and neodymium chloride.
The silicon source may be any silicon-containing silicon source conventionally used in the art, and may be one or more of potassium silicate, sodium silicate, silica sol, and potassium-containing silica sol. Wherein the potassium-containing silica sol may be a silica sol and/or a mixture of potassium silicate and a potassium salt (e.g. one or more of potassium carbonate, potassium sulfate, potassium chloride and potassium nitrate), such as K2O：SiO2Is 50-200: 100 silica sol and/or a mixture of potassium silicate and potassium salt. The silicon source may be provided in solid form or may be provided in the form of an aqueous solution, and when provided in the form of an aqueous solution, it is provided as SiO2The calculated concentration is, for example, 5 to 25% by weight.
As the potassium-containing silicon source, various potassium-containing silicon sources conventionally used in the art can be used, and examples thereof include potassium silicate and/or potassium-containing silica sol. The potassium-containing silica sol is described above and will not be described in detail herein.
According to the present invention, the concentration of the first solution may vary within a wide range, and the inventors of the present invention have found that when the concentration of Fe in the first solution is controlled2O3The measured concentration of the ferric salt is 20-120g/L, particularly 30-100g/L, the low-temperature Fischer-Tropsch synthesis catalyst with more excellent performance can be obtainedThe reason for this is presumed to be that this concentration range is suitable for the growth of hydrated iron oxide nuclei, and the concentration is too high, the nucleation rate is too high, and the crystal grains are too small, which affects the stability of the catalyst; if the concentration is too low, a large amount of aqueous solution is consumed, and the hydrated iron oxide nuclei are not easily formed. Most preferably, the first solution is in Fe2O3The concentration of the ferric salt is 30-60 g/L.
Similarly, the concentration of the second solution can also vary within a wide range, but the inventor of the present invention has found that when the concentration of the precipitant in the second solution is controlled to be 100-300g/L, especially 110-250g/L, a low-temperature Fischer-Tropsch synthesis catalyst with better performance can be obtained, and the inventor of the present invention speculates that the reason is that the concentration of the precipitant is related to the formation of hydrated iron oxide crystal grains, and when the concentration is too high, the nucleation speed is too high, and the crystal grains are too small, which affects the stability of the catalyst; if the concentration is too low, a large amount of aqueous solution is consumed, and the hydrated iron oxide nuclei are not easily formed. Most preferably, the concentration of the precipitant in the second solution is 120-200 g/L.
Among them, various precipitants conventionally used in the art may be used, and preferably, the precipitant is one or more of sodium carbonate, sodium bicarbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, ammonium carbonate, ammonium bicarbonate and aqueous ammonia. The concentration of the aqueous ammonia may be, for example, 20 to 28% by weight, and when aqueous ammonia is used as the precipitant, the aqueous ammonia is generally calculated as the precipitant as a whole, and water is not removed therefrom.
According to the invention, it should be noted that the silicon source containing potassium is divided into two parts (namely the silicon source and the silicon source containing potassium) and is introduced into the catalyst step by step, so that the metal in the obtained low-temperature Fischer-Tropsch synthesis catalyst microsphere can be in layered distribution, particularly, part of potassium and adhesive silicon dioxide are introduced in the subsequent step 2, so that the potassium and the silicon dioxide are formed into the outer layer of the low-temperature Fischer-Tropsch synthesis catalyst microsphere, a stable and wear-resistant low-temperature iron-based catalyst for low-temperature Fischer-Tropsch synthesis can be obtained, and the low temperature is adopted in the coprecipitation process, the potassium-containing silicon source is introduced and then aged in an acidic environment, and iron and copper can also be agedAnd M is uniformly distributed in the catalyst of the inner core and forms a passage allowing the entrance and exit of reactants and products at low temperature, thereby endowing the catalyst with high activity, low selectivity of byproducts and high C5+And (4) product selectivity. Preferably in SiO2The silicon source is calculated by SiO2The weight ratio of the silicon source containing potassium is 1: 2-10, preferably 1: 3-7.
According to the present invention, in the step (1), the system after the coprecipitation reaction may be subjected to solid-liquid separation by filtration (e.g., suction filtration, pressure filtration, etc.), and the obtained solid phase may be washed, for example, to a filtrate conductivity of 1500. mu.s/cm or less.
According to the invention, the washed solid phase is beaten with water in step (2) and the slurry thus obtained is ready for subsequent treatment, preferably in such an amount that the concentration of the slurry obtained is 4 to 9% by weight, i.e. the proportion of solid phase in the slurry is 4 to 9% by weight, preferably 4.5 to 8% by weight, in order to be able to obtain a catalyst having higher stability and attrition resistance.
According to the present invention, a silicon source containing potassium is introduced into the slurry obtained by the beating in the step (2), thereby further supplying potassium and silica to the catalyst. Wherein the potassium-containing silicon source may be introduced as a solid of the potassium-containing silicon source or as a solution of the potassium-containing silicon source (e.g., as SiO)2In concentrations of from 10 to 25% by weight), the latter preferably being employed. After introduction, stirring is carried out for uniform mixing, for example at a stirring speed of 10-500rpm for 5-120 min.
According to the invention, the pH needs to be adjusted to acidity before aging, which facilitates impregnation of the precipitate with a source of silicon containing potassium, and also facilitates impregnation of the precipitate with a certain amount of acid, thereby enabling the formation of microspheres having a porous structure in subsequent processing, forming channels in contact with the active metal of the core. Preferably, in step (2), the pH is adjusted to 4 to 6.5, more preferably to 4.5 to 6 before aging, so that not only a moderate pore structure but also a moderate attrition resistance and stability of the catalyst can be maintained. The acid used for adjusting the system to acidity may be an inorganic acid conventionally used in the art, such as hydrochloric acid, sulfuric acid, nitric acid, etc., and the concentration of the acid may be, for example, 3 to 15% by weight.
According to the present invention, in order to match the coprecipitation conditions of the present invention, the aging conditions of the present invention are also relatively mild, which facilitates obtaining a catalyst having the desired properties of the present invention. Preferably, in step (2), the aging conditions include: the temperature is 5-60 deg.C, and the time is 30-150 min. More preferably, in step (2), the aging conditions include: the temperature is 15-55 deg.C, and the time is 50-120 min. According to the present invention, the aged system in the step (3) may be subjected to solid-liquid separation by filtration (e.g., suction filtration, pressure filtration, etc.), and the obtained solid phase is subjected to beating to obtain a slurry. The slurry preferably has a concentration of 12 to 25 wt%, preferably 12 to 20 wt%, and such slurry is employed for subsequent spray drying and calcination to obtain low temperature fischer-tropsch catalyst microspheres of the desired morphology.
According to the present invention, preferably, the spray drying conditions include: the inlet air temperature is 180-380 deg.C, and the outlet air temperature is 70-180 deg.C. More preferably, the conditions of the spray drying include: the inlet air temperature is 220-380 ℃, and the outlet air temperature is 100-140 ℃.
According to the present invention, preferably, the firing conditions include: the temperature is 350-600 ℃, and the time is 1-15 h. More preferably, the conditions of the calcination include: the temperature is 350-550 ℃, and the time is 3-12h (more preferably 5-12 h).
The invention also provides the low-temperature Fischer-Tropsch synthesis catalyst prepared by the method.
In the catalyst, Fe by weight2O3：Cu：K：M：SiO2100: 1-8: 1-8: 1-8: 10-30, preferably Fe by weight2O3：Cu：K：M：SiO2100: 1-5: 1-5: 1-5: 10-25, more preferably, Fe by weight2O3：Cu：K：M：SiO2＝100：1-4：1.5-4：2-5：10-23。
The catalyst is microspherical, for example, microspheres with a particle size of 30-150 μm. The microspheres have moderate pore channel structures, and the total specific surface area of the catalyst is preferably 60-185m2A/g, preferably of 70-170m2(ii)/g; the average pore diameter is preferably 10-25 nm; the pore volume is preferably 0.2-0.8cm3Per g, more preferably 0.2 to 0.7cm3/g。
The invention also provides a method for preparing hydrocarbon compounds by the slurry bed Fischer-Tropsch synthesis reaction of the synthesis gas, which comprises the following steps: in the presence of the reduced Fischer-Tropsch synthesis catalyst, the catalyst contains CO and H2The synthesis gas is subjected to Fischer-Tropsch synthesis reaction in a slurry bed reactor at the temperature of 210-280 ℃ and the pressure of 1.0-5.0 MPa; wherein the reduced Fischer-Tropsch synthesis catalyst is obtained by reducing the low-temperature Fischer-Tropsch synthesis catalyst.
The method for reducing the low-temperature Fischer-Tropsch synthesis catalyst can be carried out by a method conventional in the art, and for example, H can be used2CO or H in any proportion2And CO mixed gas is used as a reducing agent. The conditions for the reduction may include: the temperature is 200-300 ℃ (preferably 220-270 ℃), the pressure is 0.1-3MPa (preferably 0.1-2.9MPa), and the time is 8-60h (preferably 16-48 h).
Wherein the Fischer-Tropsch synthesis conditions may comprise: the temperature is 210 ℃ and 280 ℃ (preferably 240 ℃ and 270 ℃), and H in the synthesis gas2The molar ratio to CO is 1-5: 1. the fischer-tropsch synthesis conditions may further comprise: the pressure is 0.5-6MPa (preferably 1.5-5 MPa).
The low-temperature Fischer-Tropsch synthesis catalyst has higher activity, stability and abrasion resistance, and can obtain lower by-products and higher yield of C in the preparation of hydrocarbon compounds by the slurry bed Fischer-Tropsch synthesis reaction of synthesis gas5+And (3) obtaining the product.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
the BET method was used to determine the total specific surface area, average pore size and pore volume of the catalyst.
The mole number of CO in the feeding material is determined and analyzed at the feeding port of the reactor for carrying out the Fischer-Tropsch synthesis reaction, and the CO and CO in the discharging material are determined and analyzed at the discharging port of the reactor2、CH4Mole number of (2), percent conversion to CO,% CO2Selectivity% CH4The% selectivity was calculated by the following formula:
percent CO conversion ═ mole of CO in feed-mole of CO in discharge/mole of CO in feed ] × 100%;
CO2selectivity%2Mole number/(moles of CO in feed-moles of CO in discharge)]×100％；
CH4Selectivity%4Mole number/(moles of CO in feed-moles of CO in discharge)]×100％。
Selectivity% of C5 ═ 100% x [ moles of C5+ in the discharge/(moles of CO in the feed-moles of CO in the discharge) ].
Catalyst attrition resistance is measured by ASTM D5757-95 air sparging.
The catalyst stability was measured by measuring the rate of decrease in CO conversion of the catalyst over a period of 100-500 hours under Fischer-Tropsch synthesis reaction conditions in%/100 hours.
Example 1
This example illustrates a low temperature Fischer-Tropsch synthesis catalyst and a method of making the same according to the present invention.
(1) 303g of Fe (NO)3)3·9H2O, 7.95g of Cu (NO)3)2·3H2O and 3.7g of Nd (NO)3)3·6H2O was added to 1700g of deionized water and dissolved by stirring to obtain a first solution. 251gNa2CO3And 30g of an aqueous potassium silicate solution (in SiO)2Calculated concentration of 5 wt.%) was added to 2000g of deionized water and dissolved with stirring to give a second solution. Then the two materials are in parallel flow and enter a stirred reaction kettle to carry out coprecipitation reaction, and the coprecipitation reaction conditions are as follows: the temperature is 20 ℃, the pH value is 8.5, and the reaction time is 40 min. And after the precipitation is finished, carrying out pressure filtration on the precipitation slurry, and repeatedly washing and carrying out pressure filtration by using deionized water until the conductivity of the filtrate is about 1400 mu S/cm, and finishing the washing.
(2) The washed filter cake was slurried with 1600g of deionized water (the resulting slurry had a solids content of 5% by weight), followed by addition of 96g of an aqueous potassium silicate solution (in SiO2Calculated concentration of 5 wt%) and stirred until homogeneous. At the same time, 5 weight portions of the mixture are preparedAmount% dilute nitric acid. Enabling the potassium silicate-containing slurry and dilute nitric acid to flow into a reactor in parallel, and mixing for 40min at the temperature of 20 ℃ and the pH value of 5.5; then standing and aging for 120min at the temperature of 20 ℃;
(3) performing filter pressing on the aged slurry to obtain a filter cake, and repulping the filter cake with deionized water to obtain catalyst slurry (the solid content is 20 wt%); the obtained catalyst slurry was fed into a spray dryer and spray-dried (pelletized) at an inlet air temperature of 290 ℃ and an outlet air temperature of 115 ℃. And (3) putting the obtained microspherical catalyst into a roasting furnace, and keeping the temperature at 500 ℃ for 6 hours to obtain the final catalyst C1.
In the catalyst, Fe by weight is determined by elemental analysis2O3：Cu：K：Nd：SiO2100: 3.5: 1.8: 2: 10.5. the catalyst is spherical, has good sphericity and surface appearance, particle size of 120 μm and total specific surface area of 148m2Per g, pore volume of 0.66cm3In terms of/g, the mean pore diameter is 21 nm.
Example 2
This example illustrates a low temperature Fischer-Tropsch synthesis catalyst and a method of making the same according to the present invention.
(1) 303g of Fe (NO)3)3·9H2O, 2.3g of Cu (NO)3)2·3H2O and 7.3g of Nd (NO)3)3·6H2O was added to 1700g of deionized water and dissolved by stirring to obtain a first solution. 251gNa2CO3And 7.5g of potassium silicate solution (in SiO)2Calculated concentration of 24 wt.%) was added to 2000g of deionized water and dissolved with stirring to give a second solution. Then the two materials are in parallel flow and enter a stirred reaction kettle to carry out coprecipitation reaction, and the coprecipitation reaction conditions are as follows: the temperature is 8 ℃, the pH value is 9, and the reaction time is 30 min. And after the precipitation is finished, carrying out pressure filtration on the precipitation slurry, and repeatedly washing and carrying out pressure filtration by using deionized water until the conductivity of the filtrate is about 1000 mu S/cm, and finishing the washing.
(2) The washed filter cake was slurried with 1000g of deionized water (the resulting slurry had a solids content of 7% by weight), followed by addition of 48.8g of an aqueous potassium silicate solution (in SiO2Calculated concentration of 24% by weight) and 40g of K2CO3Aqueous solution (K) of (A)2CO3Concentration 20 wt.%) and stirred until homogeneous. At the same time, 10 wt% of dilute nitric acid is prepared. Enabling the potassium silicate-containing slurry and dilute nitric acid to flow into a reactor in parallel, and mixing for 15min at the temperature of 55 ℃ and the pH value of 6; then standing and aging for 90min at the temperature of 55 ℃;
(3) performing filter pressing on the aged slurry to obtain a filter cake, and repulping the filter cake with deionized water to obtain catalyst slurry (the solid content is 15 wt%); the obtained catalyst slurry was fed into a spray dryer, and spray-dried and molded (pelletized) under conditions of an inlet air temperature of 350 ℃ and an outlet air temperature of 130 ℃. And (3) putting the obtained microspherical catalyst into a roasting furnace, and keeping the temperature at 400 ℃ for 12 hours to obtain the final catalyst C2.
In the catalyst, Fe by weight is determined by elemental analysis2O3：Cu：K：Nd：SiO2100: 1: 4: 4: 22.5. the catalyst is spherical, has good sphericity and surface appearance, and has a total specific surface area of 91m2Per g, pore volume of 0.33cm3In g, the mean pore diameter is 22 nm.
Example 3
This example illustrates a low temperature Fischer-Tropsch synthesis catalyst and a method of making the same according to the present invention.
(1) 303g of Fe (NO)3)3·9H2O, 6.8g of Cu (NO)3)2·3H2O and 11g of Nd (NO)3)3·6H2O was added to 1200g of deionized water and dissolved by stirring to obtain a first solution. 180g of ammonium carbonate and 15g of silica sol (in SiO)2Calculated concentration of 10 wt.%) was added to 1000g of deionized water and dissolved with stirring to give a second solution. Then the two materials are in parallel flow and enter a stirred reaction kettle to carry out coprecipitation reaction, and the coprecipitation reaction conditions are as follows: the temperature is 18 ℃, the pH value is 8, and the reaction time is 50 min. And after the precipitation is finished, carrying out pressure filtration on the precipitation slurry, and repeatedly washing and carrying out pressure filtration by using deionized water until the conductivity of the filtrate is about 1400 mu S/cm, and finishing the washing.
(2) The washed filter cake was slurried with 1600g of deionized water (solids content of the resulting slurry was 4.5 wt.%) followed by the addition of 75g of siliconSol solution (in SiO)210% by weight) and 60g of K2CO3Aqueous solution (K) of (A)2CO3Concentration 20 wt%) and stirred until homogeneous. At the same time, 15 wt% of dilute nitric acid is prepared. Feeding the slurry and dilute nitric acid into a reactor in parallel, and mixing for 30min at the temperature of 35 ℃ and the pH value of 5.5; then standing and aging for 60min at the temperature of 35 ℃;
(3) performing filter pressing on the aged slurry to obtain a filter cake, and repulping the filter cake with deionized water to obtain catalyst slurry (the solid content is 20 wt%); the obtained catalyst slurry was fed into a spray dryer, and spray-dried and molded (pelletized) at an inlet air temperature of 300 ℃ and an outlet air temperature of 120 ℃. And (3) putting the obtained microspherical catalyst into a roasting furnace, and keeping the temperature of the microspherical catalyst at 350 ℃ for 12 hours to obtain the final catalyst C3.
In the catalyst, Fe by weight is determined by elemental analysis2O3：Cu：K：Nd：SiO2100: 3: 3: 6: 15. the catalyst is spherical, has good sphericity and surface appearance, and has a total specific surface area of 125m2Per g, pore volume of 0.34cm3In g, the mean pore diameter is 16 nm.
Example 4
This example illustrates a low temperature Fischer-Tropsch synthesis catalyst and a method of making the same according to the present invention.
The process of example 1, except that the temperature of the coprecipitation reaction in step (1) is 35 ℃ and the pH is 5.5; thus, a final catalyst C4 was obtained. In the catalyst, Fe by weight is determined by elemental analysis2O3：Cu：K：Nd：SiO2100: 3.5: 1.8: 2: 10.5. the catalyst is spherical, has good sphericity and surface appearance, and has a total specific surface area of 164m2Per g, pore volume of 0.79cm3In terms of/g, the mean pore diameter is 11 nm.
Example 5
This example illustrates a low temperature Fischer-Tropsch synthesis catalyst and a method of making the same according to the present invention.
The process of example 1, except that the temperature of the coprecipitation reaction in step (1) is 25 ℃ and the pH is 6; thereby obtainingTo final catalyst C5. In the catalyst, Fe by weight is determined by elemental analysis2O3：Cu：K：Nd：SiO2100: 3.5: 1.8: 2: 10.5. the catalyst is spherical, has good sphericity and surface appearance, and has a total specific surface area of 155m2Per g, pore volume of 0.61cm3G, average pore diameter of 17 nm.
Example 6
This example illustrates a low temperature Fischer-Tropsch synthesis catalyst and a method of making the same according to the present invention.
The method of example 1, except that the first solution was prepared in step (1) using an amount of 600g of deionized water; thus, a final catalyst C6 was obtained. In the catalyst, Fe by weight is determined by elemental analysis2O3：Cu：K：Nd：SiO2100: 3.5: 1.8: 2: 10.5. the catalyst is spherical, has good sphericity and surface appearance, and has a total specific surface area of 78m2Per g, pore volume of 0.26cm3In g, the mean pore diameter is 15 nm.
Example 7
This example illustrates a low temperature Fischer-Tropsch synthesis catalyst and a method of making the same according to the present invention.
The method of example 1, except that the amount of deionized water used to formulate the first solution in step (1) was 2500 g; thus, a final catalyst C7 was obtained. In the catalyst, Fe by weight is determined by elemental analysis2O3：Cu：K：Nd：SiO2100: 3.5: 1.8: 2: 10.5. the catalyst is spherical, has good sphericity and surface appearance, and has a total specific surface area of 185m2Per g, pore volume of 0.7cm3In g, the mean pore diameter is 14 nm.
Example 8
This example illustrates a low temperature Fischer-Tropsch synthesis catalyst and a method of making the same according to the present invention.
The process of example 1 was followed except that in step (2) the washed cake was slurried with 800g of deionized water (resulting slurry having a solids content of 10% by weight) prior to introduction of the aqueous potassium silicate solution; thereby obtaining the final catalysisAgent C8. In the catalyst, Fe by weight is determined by elemental analysis2O3：Cu：K：Nd：SiO2100: 3.5: 1.8: 2: 10.5. the catalyst is spherical, has good sphericity and surface appearance, and has total specific surface area of 156m2Per g, pore volume of 0.65cm3In terms of/g, the mean pore diameter is 19 nm.
Example 9
This example illustrates a low temperature Fischer-Tropsch synthesis catalyst and a method of making the same according to the present invention.
According to the process described in example 1, except that 2.4g of Ce (NO) were used in step (1)3)3·6H2O instead of Nd (NO)3)3·6H2O; thus, a final catalyst C9 was obtained. In the catalyst, Fe by weight is determined by elemental analysis2O3：Cu：K：Ce：SiO2100: 3.5: 1.8: 2: 10.5. the catalyst is spherical, has good sphericity and surface appearance, and has a total specific surface area of 143m2Per g, pore volume of 0.59cm3In terms of/g, the mean pore diameter is 19 nm.
Example 10
This example illustrates a low temperature Fischer-Tropsch synthesis catalyst and a method of making the same according to the present invention.
The process as described in example 1, except that 3.2g of La (NO) was used in step (1)3)3·6H2O instead of Nd (NO)3)3·6H2O; thus, a final catalyst C10 was obtained. In the catalyst, Fe by weight is determined by elemental analysis2O3：Cu：K：Ce：SiO2100: 3.5: 1.8: 2: 10.5. the catalyst is spherical, has good sphericity and surface appearance, and has a total specific surface area of 144m2Per g, pore volume of 0.63cm3In g, the mean pore diameter is 20 nm.
Comparative example 1
The process as described in example 1, except that the temperature of the coprecipitation reaction in step (1) is 40 ℃; thus, the final catalyst DC1 was obtained. In the catalyst, Fe by weight is determined by elemental analysis2O3：Cu：K：Nd：SiO2100: 3.5: 1.8: 2: 10.5. the catalyst is spherical, has good sphericity and surface appearance, and has a total specific surface area of 150m2Per g, pore volume of 0.38cm3In g, the mean pore diameter is 12 nm.
Comparative example 2
The process as described in example 1, except that the temperature of the coprecipitation reaction in step (1) is 90 ℃; thus, the final catalyst DC2 was obtained. In the catalyst, Fe by weight is determined by elemental analysis2O3：Cu：K：Nd：SiO2100: 3.5: 1.8: 2: 10.5. the catalyst is spherical, has good sphericity and surface appearance, and has a total specific surface area of 105m2Per g, pore volume of 0.31cm3(ii)/g, average pore diameter 13 nm.
Comparative example 3
The process of example 1, except that in step (1), the temperature of the coprecipitation reaction is 60 ℃ and the pH of the coprecipitation reaction is 6; thus, the final catalyst DC3 was obtained. In the catalyst, Fe by weight is determined by elemental analysis2O3：Cu：K：Nd：SiO2100: 3.5: 1.8: 2: 10.5. the catalyst is spherical, has good sphericity and surface appearance, and has a total specific surface area of 169m2Per g, pore volume of 0.5cm3In g, the mean pore diameter is 10 nm.
Comparative example 4
The process of example 1 except that in step (2) the pH was not adjusted prior to aging, which was 7.8; thus, the final catalyst DC4 was obtained. In the catalyst, Fe by weight is determined by elemental analysis2O3：Cu：K：Nd：SiO2100: 3.5: 1.8: 2: 10.5. the catalyst is spherical, has good sphericity and surface appearance, and has a total specific surface area of 107m2Per g, pore volume of 0.39cm3In g, the mean pore diameter is 12 nm.
Comparative example 5
The method of example 1, except that in step (1), Cu (NO)3)2·3H2The amount of O used was 1.2g, Nd (NO)3)3·6H2The amount of O used was 0.9g, thereby obtaining a final catalyst DC 5. In the catalyst, Fe by weight is determined by elemental analysis2O3：Cu：K：Nd：SiO2100: 0.5: 1: 0.5: 15. the catalyst is spherical, has good sphericity and surface appearance, and has a total specific surface area of 117m2Per g, pore volume of 0.43cm3(ii)/g, average pore diameter 13 nm.
Comparative example 6
The method of example 1, except that in step (1), Cu (NO)3)2·3H2O in an amount of 22.7g, Nd (NO)3)3·6H2The amount of O is 18.2g, K2CO3The amount of the solution was 159g, thereby obtaining a final catalyst DC 6. In the catalyst, Fe by weight is determined by elemental analysis2O3：Cu：K：Nd：SiO2100: 10: 10: 10: 10.5. the catalyst is spherical, has good sphericity and surface appearance, and has a total specific surface area of 158m2Per g, pore volume of 0.61cm3In g, the mean pore diameter is 17 nm.
Comparative example 7
The process of example 1, except that the second solution in step (1) was not charged with the aqueous potassium silicate solution, and the part of the aqueous potassium silicate solution was introduced in step (2), i.e., 126g of the aqueous potassium silicate solution in step (2); thus, the final catalyst DC7 was obtained. In the catalyst, Fe by weight is determined by elemental analysis2O3：Cu：K：Nd：SiO2100: 3.5: 1.8: 2: 10.5. the catalyst is spherical, the sphericity and the surface appearance are common, and the total specific surface area is 121m2Per g, pore volume of 0.36cm3In g, the mean pore diameter is 14 nm.
Comparative example 8
The process as described in example 1, except that the temperature of the coprecipitation reaction in step (1) is 35 ℃ and the pH is 9; thus, the final catalyst DC8 was obtained. In the catalyst, Fe by weight is determined by elemental analysis2O3：Cu：K：Nd：SiO2100: 3.5: 1.8: 2: 10.5. the catalyst is a ballGood shape, sphericity and surface appearance, and total specific surface area of 147m2Per g, pore volume of 0.65cm3In g, the mean pore diameter is 16 nm.
Comparative example 9
According to the method described in example 1, except that Nd (NO) is not used in step (1)3)3·6H2O to obtain the final catalyst DC 9. In the catalyst, Fe by weight is determined by elemental analysis2O3：Cu：K：SiO2100: 3.5: 1.8: 10.5. the catalyst is spherical, has good sphericity and surface appearance, and has a total specific surface area of 145m2Per g, pore volume of 0.62cm3In terms of/g, the mean pore diameter is 19 nm.
Comparative example 10
The process of example 2, except that the temperature of the coprecipitation reaction in step (1) was 35 ℃ and the pH was 9.0; thus, the final catalyst DC10 was obtained. In the catalyst, Fe by weight is determined by elemental analysis2O3：Cu：K：Nd：SiO2100: 1: 4: 4: 22.5. the catalyst is spherical, has good sphericity and surface appearance, and has a total specific surface area of 151m2Per g, pore volume of 0.58cm3In g, the mean pore diameter is 16 nm.
Comparative example 11
The process of example 2, except that the temperature of the coprecipitation reaction in step (1) is 15 ℃ and the pH is 6; thus, the final catalyst DC11 was obtained. In the catalyst, Fe by weight is determined by elemental analysis2O3：Cu：K：Nd：SiO2100: 1: 4: 4: 22.5. the catalyst is spherical, has good sphericity and surface appearance, and has a total specific surface area of 135m2Per g, pore volume of 0.47cm3In g, the mean pore diameter is 14 nm.
Test example 1
The catalyst reaction performance was evaluated in a 1L stirred tank evaluation apparatus.
(a) Reduction reaction: with a gas containing CO and H2Reducing atmosphere (CO and H)2In a molar ratio of 0.2: 1) respectively subjecting the above to reaction at 260 ℃ and a pressure of 0.1MPaCarrying out reduction reaction for 24 hours by catalysts C1-C10 and DC1-DC 11;
(b) Fischer-Tropsch synthesis: introduction of synthesis gas (H)2The molar ratio to CO was 2: 1) the Fischer-Tropsch synthesis reaction is carried out at 250 ℃ and 2.3MPa, and the gas hourly space velocity is 4000 mL/(g.h).
The results of the reaction performance of the catalyst for carrying out the continuous reaction are shown in Table 1.
TABLE 1
Figure BDA0001248612820000181
As can be seen from Table 1, the low-temperature Fischer-Tropsch synthesis catalyst obtained by the method can obtain higher CO conversion rate and lower CO2Lower selectivity CH4Higher C of5+And (4) selectivity.
Test example 2
The catalysts C1-C10, DC1-DC8, and DC10-DC11 were tested for stability and abrasion resistance, and the results are shown in Table 2:
TABLE 2
Catalyst and process for preparing same Reduction rate of CO conversion,%/100 h Abrasion resistance
C1 0.42 1.2
C2 0.55 1.4
C3 0.67 1.6
C4 0.98 2.1
C5 0.89 2.2
C6 1.1 2.0
C7 0.93 1.9
C8 1.21 2.2
C9 0.68 1.6
C10 0.72 1.8
DC1 3.14 4.3
DC2 2.21 5.9
DC3 1.82 4.8
DC4 1.54 3.6
DC5 1.64 3.7
DC6 3.23 2.6
DC7 1.67 2.7
DC8 1.71 3.2
DC10 1.52 2.5
DC11 1.47 2.4
As can be seen from Table 2, the low temperature Fischer-Tropsch synthesis catalyst obtained by the method of the present application has higher stability and abrasion resistance.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (29)

1. A preparation method of a low-temperature Fischer-Tropsch synthesis catalyst is characterized by comprising the following steps:
(1) providing an aqueous solution containing iron salt, copper salt and auxiliary agent metal M salt, namely a first solution; providing an aqueous solution containing a precipitating agent and a silicon source, i.e. a second solution; carrying out coprecipitation reaction on the first solution and the second solution, then carrying out solid-liquid separation and washing the obtained solid phase; the conditions of the coprecipitation reaction include: the temperature is 5-35 deg.C, pH is 4.5-9.5, and the time is 5-60 min; defining the pH value of the coprecipitation reaction as a value n, and defining the temperature of the coprecipitation reaction as a value T, wherein the temperature and the pH value of the coprecipitation reaction satisfy the following formula: n +0.16T ═ 9-14; the auxiliary metal M is lanthanide metal;
(2) pulping the washed solid phase with water to obtain slurry, introducing a potassium-containing silicon source, and adjusting the pH value of the obtained mixture to acidity for aging;
(3) carrying out solid-liquid separation on the aged slurry, pulping the obtained solid phase and water, and carrying out spray drying and roasting on the obtained slurry;
wherein the iron salt, the copper salt, the auxiliary metal M salt, the silicon source and the potassium-containing silicon source are used in amounts such that the weight percentage of Fe in the obtained catalyst is2O3：Cu：K：M：SiO2＝100：1-8：1-8：1-8：10-30。
2. The method of claim 1In which the iron salt, the copper salt, the auxiliary metal M salt, the silicon source and the potassium-containing silicon source are used in amounts such that the resulting catalyst contains Fe by weight2O3：Cu：K：M：SiO2＝100：1-5：1-5：1-5：10-25。
3. The process of claim 2 wherein the iron, copper, promoter metal M salt, silicon and potassium-containing silicon salts are used in amounts such that the resulting catalyst contains Fe by weight2O3：Cu：K：M：SiO2＝100：1-4：1.5-4：2-5：10-23。
4. The method of any one of claims 1-3, wherein the iron salt is one or more of ferric nitrate, ferric sulfate, and ferric chloride;
the copper salt is one or more of copper nitrate, copper sulfate and copper chloride;
the auxiliary metal M is one or more of La, Ce and Nd;
the silicon source is one or more of potassium silicate, sodium silicate, silica sol and silica sol containing potassium;
the potassium-containing silicon source is potassium silicate and/or potassium-containing silica sol.
5. The method of claim 4, wherein the iron salt is ferric nitrate;
the auxiliary metal M salt is one or more of lanthanum nitrate, cerium nitrate, neodymium nitrate, lanthanum sulfate, cerium sulfate, neodymium sulfate, lanthanum chloride, cerium chloride and neodymium chloride.
6. The method of any one of claims 1-3 and 5, wherein the first solution is in Fe2O3The concentration of the ferric salt is 20-120 g/L.
7. The method of claim 6, wherein the first solution is in Fe2O3The concentration of the ferric salt is 30-100 g/L.
8. The method of claim 7, wherein the first solution is in Fe2O3The concentration of the ferric salt is 30-60 g/L.
9. The method as claimed in claim 6, wherein the concentration of the precipitant in the second solution is 100-300 g/L.
10. The method as claimed in claim 9, wherein the concentration of the precipitant in the second solution is 110-250 g/L.
11. The method as claimed in claim 10, wherein the concentration of the precipitant in the second solution is 120-200 g/L.
12. The method of claim 6, wherein the precipitant is one or more of sodium carbonate, sodium bicarbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, ammonium carbonate, ammonium bicarbonate, and aqueous ammonia.
13. The method of claim 6, wherein the SiO is used2The silicon source is calculated by SiO2The weight ratio of the silicon source containing potassium is 1: 2-10.
14. The method of claim 13, wherein the SiO is used2The silicon source is calculated by SiO2The weight ratio of the silicon source containing potassium is 1: 3-7.
15. The method according to any one of claims 1 to 3, 5 and 7 to 14, wherein in step (1), the conditions of the co-precipitation reaction comprise: the temperature is 5-30 deg.C, pH is 5-9, and the time is 10-50 min.
16. The method according to claim 15, wherein the temperature of the coprecipitation reaction in step (1) is 8-20 ℃.
17. The method according to any one of claims 1 to 3, 5, 7 to 14 and 16, wherein in step (2), the pH is adjusted to 4 to 6.5 before aging.
18. The method of claim 17, wherein in step (2), the pH is adjusted to 4.5-6 before aging.
19. The method of claim 17, wherein the aging condition comprises: the temperature is 5-60 deg.C, and the time is 30-150 min.
20. The method of claim 19, wherein the aging condition comprises: the temperature is 15-55 deg.C, and the time is 50-120 min.
21. The process of any one of claims 1-3, 5, 7-14, 16, and 18-20, wherein the concentration of the resulting slurry in step (3) is 12-25 wt% before the spray drying is performed.
22. The method of claim 21, wherein the conditions of the spray drying comprise: the inlet air temperature is 180-380 deg.C, and the outlet air temperature is 70-180 deg.C.
23. The method of claim 22, wherein the conditions of the spray drying comprise: the inlet air temperature is 220-380 ℃, and the outlet air temperature is 100-140 ℃.
24. The method of claim 21, wherein the firing conditions comprise: the temperature is 350-600 ℃, and the time is 1-15 h.
25. The method of claim 24, wherein the firing conditions include: the temperature is 350-550 ℃, and the time is 3-12 h.
26. A low temperature fischer-tropsch synthesis catalyst made by the process of any one of claims 1 to 25.
27. The low temperature fischer-tropsch synthesis catalyst of claim 26, wherein the catalyst is microspheroidal and has a total specific surface area of from 60 to 185m2/g；
The average pore diameter is 10-25 nm;
the pore volume is 0.2-0.8cm3/g。
28. The low temperature Fischer-Tropsch synthesis catalyst of claim 27, wherein the total specific surface area of the catalyst is 100-165m2(ii)/g; the pore volume is 0.2-0.7cm3/g。
29. A process for producing hydrocarbons from synthesis gas by a slurry Fischer-Tropsch synthesis reaction, the process comprising: in the presence of a reduced Fischer-Tropsch synthesis catalyst, the catalyst contains CO and H2The synthesis gas is subjected to Fischer-Tropsch synthesis reaction in a slurry bed reactor at the temperature of 210-280 ℃ and the pressure of 1.0-5.0 MPa; wherein the reduced fischer-tropsch catalyst is obtained by reduction of a low temperature fischer-tropsch catalyst as claimed in any one of claims 26 to 28.
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