CN109908912B - Catalyst for preparing low-carbon olefin from synthesis gas and preparation method thereof - Google Patents

Catalyst for preparing low-carbon olefin from synthesis gas and preparation method thereof Download PDF

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CN109908912B
CN109908912B CN201711325714.XA CN201711325714A CN109908912B CN 109908912 B CN109908912 B CN 109908912B CN 201711325714 A CN201711325714 A CN 201711325714A CN 109908912 B CN109908912 B CN 109908912B
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potassium
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CN109908912A (en
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张舒冬
孙晓丹
张庆军
宋永一
刘继华
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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Abstract

The invention provides a catalyst for preparing low-carbon olefin from synthesis gas and a preparation method thereof, wherein the catalyst comprises an active component, an electronic assistant, a structural assistant, a second structural assistant and a carrier; the preparation method comprises the steps of mixing petroleum coke, a compound containing active metal, a compound containing structural auxiliary agent, a compound containing secondary structural auxiliary agent and an activating agent, uniformly mixing and activating; and treating the obtained sample by using an acid solution, washing until the washing liquid is neutral, drying the washed solid sample, introducing an electronic assistant to the solid sample, drying, roasting and forming to obtain the low-carbon olefin catalyst prepared from the synthesis gas.

Description

Catalyst for preparing low-carbon olefin from synthesis gas and preparation method thereof
Technical Field
The invention relates to a catalyst for preparing low-carbon olefin from synthesis gas and a preparation method thereof, in particular to a catalyst for preparing low-carbon olefin from synthesis gas by using activated carbon as a carrier and a preparation method thereof.
Background
Low carbon olefin (C2)=-C4=) The method is the most basic raw material for petrochemical production, is the basis for producing other organic chemical products, can be used for producing organic compounds such as polyethylene, polypropylene, acrylonitrile, ethylene oxide or ethylene glycol, and plays an important role in national economy, and the development level and the market supply and demand balance condition of the industry directly influence the development level and the industrial scale of the whole petrochemical industry.
The methods for preparing low-carbon olefins generally fall into two main categories: one is the petroleum route; the second is a non-petroleum route. The petroleum route is to prepare products such as ethylene, propylene and the like by using crude oil derivatives as raw materials and using ethylene cracking and other traditional methods. In order to relieve the dependence on petroleum resources, researchers at home and abroad are dedicated to developing the technology for producing low-carbon olefin by taking coal-based, natural gas-based and biomass-based synthetic gas as raw materials. Currently, the mainstream process is to prepare methanol from synthesis gas, and then convert the methanol into olefin products (i.e. MTO and MTP processes). The technology has long process flow and complex process. If the synthesis gas can be used for directly preparing the low-carbon olefin, the flow can be greatly shortened, and the investment and operation cost can be reduced.
In the catalyst system for preparing the low-carbon olefin by directly converting the synthesis gas, the iron-based catalyst has the advantages of low methane selectivity, high low-carbon olefin selectivity and low cost, and is a research focus for directly preparing the low-carbon olefin catalyst system by the synthesis gas. Kreitman et al (K.M. Kreitman, M. Baerns and J.B. Butt. J.Catal., 1987, 105: 319) prepared iron-based catalysts with MnO as a carrier showed higher selectivity to low carbon olefins, but manganese strongly interacted with iron oxide, inhibiting reduction and carbonization of the catalyst, and having low reactivity. CN104549354A discloses a preparation method of a Fe-Mn-K catalyst with a carbon material as a carrier, which comprises the steps of treating activated carbon with a potassium permanganate solution, and then impregnating an active component Fe to obtain the catalyst with active metal dispersibility, wherein the catalyst has good activity of preparing low-carbon olefin from synthesis gas. CN1537674A discloses a Fe/AC catalyst, which adopts a vacuum impregnation method to load Fe on an activated carbon carrier for the reaction of preparing low-carbon olefin from synthesis gas, C2 in hydrocarbon products=-C4=The selectivity is above 68%. Both of these patents use carbon material as carrier and active metal is loaded by impregnation method, in order to find a catalyst with good dispersibility and weak interaction between metal and carrier. However, when the carbon material is used as a carrier to load metals, the surface of the carbon material needs to be modified first, and the number of oxygen-containing groups is increased to increase the dispersion degree of the active metals, but under the high-temperature reaction condition, the active metals are aggregated due to dehydration condensation of the oxygen-containing groups, and the stability is poor.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a catalyst for preparing low-carbon olefin from synthesis gas and a preparation method thereof, the catalyst takes petroleum coke-based active carbon as a carrier, the problem of high-temperature aggregation of active metal of the existing active carbon carrier catalyst is solved, and the prepared catalyst has the advantages of good dispersion of active components, sintering resistance, high activity, good low-carbon olefin selectivity and the like.
The invention provides a catalyst for preparing low-carbon olefin from synthesis gas, which comprises an active component, an electronic assistant, a structural assistant, a second structural assistant and a carrier; the active component is Fe; the electron auxiliary agent is K; the structural auxiliary agent is Mn; the second structural auxiliary agent is selected from one or more of Si, Zr and Ti, and Si or Ti is preferred; the carrier is petroleum coke-based activated carbon.
In the catalyst for preparing low-carbon olefin from synthesis gas, the mass content of active components calculated by elements is 5wt% -30 wt%, preferably 10wt% -20 wt%; the mass content of the electronic assistant K calculated by elements is 1wt% -10 wt%, preferably 2wt% -5 wt%; the mass content of the structural auxiliary Mn calculated by elements is 1wt% -20 wt%, preferably 5wt% -10 wt%; the mass content of the second structural auxiliary agent is 1wt% -10 wt%, preferably 2wt% -4 wt%, and the mass content of the carrier is 40wt% -80 wt%, preferably 50wt% -70 wt%, calculated by element.
The specific surface of the catalyst for preparing low-carbon olefin from synthesis gas is 200-1000 m2Preferably 400 to 800 m/g2(ii)/g; the pore size distribution is such that the pores smaller than 2nm are larger than 60%, preferably larger than 80%.
In the catalyst for preparing low-carbon olefin from synthesis gas, active components and auxiliaries (including electronic auxiliaries, structural auxiliaries and secondary structural auxiliaries) are embedded into an amorphous defect of petroleum coke-based activated carbon and an activated carbon graphite microchip layer, and the size of active metal crystal grains is 0.5-5 nm, preferably 1-3 nm.
The second aspect of the present invention provides a preparation method of a catalyst for preparing low carbon olefins from synthesis gas, wherein the preparation method comprises the following steps:
(1) mixing petroleum coke, a compound containing active metal, a compound containing a structural assistant, a compound containing a secondary structural assistant and an activating agent, and activating after uniformly mixing;
(2) treating the sample obtained in the step (1) by using an acid solution, then washing until the washing liquid is neutral, and drying the washed solid sample;
(3) and (3) introducing the electronic assistant to the solid sample obtained in the step (2), and then drying and roasting to obtain the catalyst for preparing the low-carbon olefin from the synthesis gas.
In the preparation method of the catalyst for preparing low-carbon olefin from synthesis gas, the active metal-containing compound in the step (1) is selected from any one of potassium ferrate, sodium ferrate and lithium ferrate, and potassium ferrate is preferred.
In the preparation method of the invention, the structural assistant compound in the step (1) is potassium permanganate or sodium permanganate, preferably potassium permanganate.
In the preparation method of the catalyst for preparing low-carbon olefin from synthesis gas, the compound containing the second structural auxiliary in the step (1) is one of a sodium salt containing a second auxiliary acid radical, a potassium salt containing the second auxiliary acid radical or a second auxiliary oxide, specifically potassium silicate, sodium silicate, potassium titanate, sodium titanate, potassium zirconate, sodium zirconate, silicon dioxide, titanium dioxide and zirconium dioxide, and preferably one of potassium silicate, silicon dioxide, potassium titanate and titanium dioxide.
In the preparation method of the catalyst for preparing low-carbon olefin from the synthesis gas, the activating agent in the step (1) is one or more of potassium hydroxide, sodium hydroxide, potassium bicarbonate and sodium bicarbonate, and the activating agent is preferably potassium hydroxide.
In the preparation method of the synthesis gas methanation catalyst, in the step (1), the mass ratio of the petroleum coke, the active metal-containing compound (calculated by the mass of the active metal element), the structure-containing auxiliary agent compound (calculated by the mass of the structure-containing auxiliary agent element), the second structure-containing auxiliary agent compound (calculated by the mass of the second structure-containing auxiliary agent element) and the activating agent is 1: 0.01-0.3: 0.01-0.15: 0.005-0.1: 1-5, preferably 1: 0.05-0.15: 0.03-0.06: 0.01-0.05: 2 to 4.
In the preparation method of the catalyst for preparing low-carbon olefin from synthesis gas, the activation process in the step (1) is as follows: grinding petroleum coke into powder, uniformly mixing the powder with an active metal-containing compound, a structural assistant-containing compound, a secondary structural assistant-containing compound and an activating agent, heating to an activation temperature, cooling to room temperature after activation is completed, and performing subsequent treatment, wherein the activation temperature is 600-1000 ℃, preferably 700-900 ℃, and the activation time is 5-240 min, preferably 10-120 min. The activation process is further preferably carried out under microwave irradiation conditions, the microwave frequency being 2450MHz or 915 MHz; the microwave power is 1-10 kw per kg of petroleum coke, and preferably 2-4 kw. When the activation is carried out under the microwave radiation condition, the activation is further preferably carried out in two sections, the first section is activated for 10-60 min at 400-600 ℃ under the vacuum condition, inert gas or nitrogen is introduced to the atmosphere under the constant temperature condition, and the temperature is continuously increased to 700-900 ℃ under the microwave radiation condition for activation for 10-30 min.
In the preparation method of the catalyst for preparing low-carbon olefin from synthesis gas, the specific process in the step (2) is as follows: and (2) mixing the sample obtained in the step (1) with an acid solution, preferably grinding the sample obtained in the step (1) into powder, mixing with the acid solution, uniformly mixing, performing solid-liquid separation, and washing the obtained solid with deionized water until the pH value of the filtrate is neutral.
In the preparation method of the catalyst for preparing low-carbon olefin from synthesis gas, the acid solution in the step (2) is a hydrochloric acid solution, a sulfuric acid solution or a nitric acid solution, preferably a hydrochloric acid solution, the concentration of the acid solution is 1-10 wt%, preferably 2-5 wt%, and the mass ratio of the sample obtained in the step (1) to the acid solution is 1: 5-1: 30, preferably 1: 10-1: 20.
in the preparation method of the catalyst for preparing the low-carbon olefin from the synthesis gas, the drying temperature in the step (2) is 80-200 ℃, the preferred drying temperature is 120-180 ℃, the drying time is 2-10 hours, and the preferred drying time is 4-8 hours. The drying is preferably carried out under vacuum.
In the preparation method of the catalyst for preparing low-carbon olefin from synthesis gas, the specific process in the step (3) is as follows: and (3) dipping the solid sample obtained in the step (2) by adopting a precursor aqueous solution containing an electronic auxiliary agent, and then drying and roasting to obtain the low-carbon olefin catalyst prepared from the synthesis gas. The precursor containing the electronic assistant is a soluble potassium-containing compound, such as one or more of potassium nitrate, potassium chloride, potassium sulfate, potassium hydroxide, potassium acetate and potassium citrate, and preferably potassium nitrate. The impregnation method is a method known in the art, such as equal volume impregnation, supersaturated impregnation, preferably equal volume impregnation.
In the preparation method of the catalyst for preparing the low-carbon olefin from the synthesis gas, the drying temperature in the step (3) is 60-160 ℃, the preferred drying temperature is 80-120 ℃, the drying time is 2-10 hours, and the preferred drying time is 4-8 hours. The drying is further preferably carried out under vacuum conditions.
In the preparation method of the catalyst for preparing the low-carbon olefin from the synthesis gas, the roasting in the step (3) is carried out in an inert atmosphere or a nitrogen atmosphere, the roasting temperature is 300-700 ℃, the preferred roasting temperature is 400-600 ℃, the roasting time is 2-10 hours, and the preferred roasting time is 4-8 hours.
In the preparation method of the catalyst for preparing low-carbon olefin from the synthesis gas, the calcined catalyst in the step (3) can be further molded, and the molding is carried out according to the general technical method in the field, such as extrusion, tabletting and the like, and the catalyst can be prepared or selected into proper particle forms, such as strips, tablets and the like, according to the use requirements.
The catalyst for preparing the low-carbon olefin from the synthesis gas, which is prepared by the method, can be applied to the reaction for preparing the low-carbon olefin from the synthesis gas.
Compared with the prior art, the catalyst for preparing the low-carbon olefin from the synthesis gas and the preparation method thereof have the following advantages:
1. the catalyst for preparing low-carbon olefin from synthesis gas has the advantages of large specific surface area, good dispersion of active metal, high reaction activity, good selectivity of low-carbon olefin, sintering resistance and the like, and the preparation method is simple.
2. According to the preparation method of the catalyst, the Fe, Mn, Si, Ti and other auxiliaries are introduced in the petroleum coke activation process, the activator enters a diffusion path generated by the petroleum coke bulk phase, and is tightly combined with amorphous carbon defects and graphite carbon lamella under the action of microwave catalysis to obtain the catalyst with high dispersion and high temperature stability, so that the problems of active metal aggregation and activity loss caused by dehydration and condensation of oxygen-containing groups at high temperature when the metal catalyst with the active carbon as a carrier is applied to high-temperature reaction are solved.
3. The catalyst takes the activated carbon as a carrier, and improves the carbon deposition resistance of the catalyst by utilizing the intermiscibility of the activated carbon in the carrier and carbon deposition generated in the application process and abundant micropores.
4. According to the preparation method of the catalyst, the active metal and the auxiliary agent precursor introduced in the petroleum coke activation process exist in the form of acid radicals, and can more easily enter the petroleum coke-based active carbon. The reason is that under the action of an activator, active sites of petroleum coke react to generate positive charged cavities, and acid radical anions are more easily combined and intercalated.
Detailed Description
The technical contents and effects of the present invention will be further described with reference to examples, but the present invention is not limited thereto.
In the following examples and comparative examples, low-temperature N was used for the specific surface area and pore size distribution of the catalyst2Measuring by an adsorption method; the grain size of the active component of the catalyst is measured by an X-ray broadening method; catalyst composition was determined using XRF analysis techniques.
Example 1
Grinding 100g of petroleum coke into powder, uniformly mixing with 36g of potassium ferrate, 15g of potassium permanganate, 11g of potassium silicate and 300g of potassium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, introducing nitrogen to the normal pressure, and continuously heating to 800 ℃ under the condition that the microwave power is 0.3kw for activation for 20 min. And after the activation is finished, cooling to normal temperature, and taking out the obtained sample.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: and 15, adding the mixture into a hydrochloric acid solution with the concentration of 3wt%, fully stirring, uniformly mixing, carrying out solid-liquid separation, washing the obtained solid by deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying for 6 hours at 150 ℃ under a vacuum condition.
Weighing 20g of the sample, weighing a proper amount of potassium nitrate according to the final catalyst K content of 3%, dissolving the potassium nitrate into a proper amount of deionized water, fixing the volume to 26mL, loading the potassium nitrate into the sample by adopting an isometric immersion method, stirring uniformly, and aging for 2 hours; and then placing the sample in a vacuum drying oven, drying for 6h at 100 ℃ under a vacuum condition, and roasting for 6h at 500 ℃ under a nitrogen atmosphere to obtain the catalyst which comprises 15% of Fe, 8% of Mn, 3% of Si and 3% of K in percentage by mass of elements and is marked as C-1.
Example 2
Grinding 100g of petroleum coke into powder, uniformly mixing with 22g of potassium ferrate, 18g of potassium permanganate, 7g of potassium silicate and 300g of potassium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 600 ℃ under the condition that the microwave power is 0.2kw, keeping the temperature constant for 20min, introducing nitrogen to the normal pressure, and continuously heating to 900 ℃ under the condition that the microwave power is 0.2kw for activation for 10 min. And after the activation is finished, cooling to normal temperature, and taking out the obtained sample.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: and 10, adding the mixture into a hydrochloric acid solution with the concentration of 5wt%, fully stirring, uniformly mixing, carrying out solid-liquid separation, washing the obtained solid by deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying for 8 hours at 120 ℃ under a vacuum condition.
Weighing 20g of the sample, weighing a proper amount of potassium nitrate according to 5% of the final catalyst K content, dissolving the potassium nitrate into a proper amount of deionized water, fixing the volume to 26mL, loading the potassium nitrate into the sample by adopting an isometric immersion method, stirring uniformly, and aging for 2 hours; and then placing the sample in a vacuum drying oven, drying the sample for 8 hours at 80 ℃ under a vacuum condition, and roasting the sample for 4 hours at 600 ℃ under a nitrogen atmosphere to obtain the catalyst which comprises 10 percent of Fe, 10 percent of Mn, 2 percent of Si and 5 percent of K in terms of element mass and is marked as C-2.
Example 3
Grinding 100g of petroleum coke into powder, uniformly mixing with 49g of potassium ferrate, 10g of potassium permanganate, 15g of potassium silicate and 300g of potassium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 400 ℃ under the condition that the microwave power is 0.4kw, keeping the temperature constant for 60min, introducing nitrogen to the normal pressure, and continuously heating to 700 ℃ under the condition that the microwave power is 0.4kw for activation for 30 min. And after the activation is finished, cooling to normal temperature, and taking out the obtained sample.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 20, adding the mixture into a hydrochloric acid solution with the concentration of 2wt%, fully stirring, uniformly mixing, then carrying out solid-liquid separation, washing the obtained solid by deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying for 4 hours at 180 ℃ under a vacuum condition.
Weighing 20g of the sample, weighing a proper amount of potassium nitrate according to the final catalyst K content of 2%, dissolving the potassium nitrate into a proper amount of deionized water, fixing the volume to 26mL, loading the potassium nitrate into the sample by adopting an isometric immersion method, stirring uniformly, and aging for 2 hours; and then placing the sample in a vacuum drying oven, drying at 120 ℃ for 4h under a vacuum condition, and roasting at 400 ℃ for 8h under a nitrogen atmosphere to obtain the catalyst which comprises 20% of Fe, 5% of Mn, 4% of Si and 2% of K in percentage by mass of elements and is marked as C-3.
Example 4
Grinding 100g of petroleum coke into powder, uniformly mixing with 43g of potassium ferrate, 14g of potassium permanganate, 18g of potassium silicate and 200g of potassium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, introducing nitrogen to the normal pressure, and continuously heating to 800 ℃ under the condition that the microwave power is 0.3kw for activation for 20 min. And after the activation is finished, cooling to normal temperature, and taking out the obtained sample.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: and 15, adding the mixture into a hydrochloric acid solution with the concentration of 3wt%, fully stirring, uniformly mixing, carrying out solid-liquid separation, washing the obtained solid by deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying for 6 hours at 150 ℃ under a vacuum condition.
Weighing 20g of the sample, weighing a proper amount of potassium nitrate according to the final catalyst K content of 3%, dissolving the potassium nitrate into a proper amount of deionized water, fixing the volume to 26mL, loading the potassium nitrate into the sample by adopting an isometric immersion method, stirring uniformly, and aging for 2 hours; and then placing the sample in a vacuum drying oven, drying for 6h at 100 ℃ under a vacuum condition, and roasting for 6h at 500 ℃ under a nitrogen atmosphere to obtain the catalyst which comprises 15% of Fe, 6% of Mn, 4% of Si and 3% of K in percentage by mass of elements and is marked as C-4.
Example 5
Grinding 100g of petroleum coke into powder, uniformly mixing with 28g of potassium ferrate, 12g of potassium permanganate, 9g of potassium silicate and 400g of potassium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, introducing nitrogen to the normal pressure, and continuously heating to 800 ℃ under the condition that the microwave power is 0.3kw for activation for 20 min. And after the activation is finished, cooling to normal temperature, and taking out the obtained sample.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: and 15, adding the mixture into a hydrochloric acid solution with the concentration of 3wt%, fully stirring, uniformly mixing, carrying out solid-liquid separation, washing the obtained solid by deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying for 6 hours at 150 ℃ under a vacuum condition.
Weighing 20g of the sample, weighing a proper amount of potassium nitrate according to the final catalyst K content of 2%, dissolving the potassium nitrate into a proper amount of deionized water, fixing the volume to 26mL, loading the potassium nitrate into the sample by adopting an isometric immersion method, stirring uniformly, and aging for 2 hours; and then placing the sample in a vacuum drying oven, drying for 6h at 100 ℃ under a vacuum condition, and roasting for 6h at 500 ℃ under a nitrogen atmosphere to obtain the catalyst which comprises 15% of Fe, 8% of Mn, 3% of Si and 2% of K in percentage by mass of elements and is marked as C-5.
Example 6
Grinding 100g of petroleum coke into powder, uniformly mixing with 35g of potassium ferrate, 15g of potassium permanganate, 11g of potassium titanate and 300g of potassium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, introducing nitrogen to the normal pressure, and continuously heating to 800 ℃ under the condition that the microwave power is 0.3kw for activation for 20 min. And after the activation is finished, cooling to normal temperature, and taking out the obtained sample.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: and 15, adding the mixture into a hydrochloric acid solution with the concentration of 3wt%, fully stirring, uniformly mixing, carrying out solid-liquid separation, washing the obtained solid by deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying for 6 hours at 150 ℃ under a vacuum condition.
Weighing 20g of the sample, weighing a proper amount of potassium nitrate according to the final catalyst K content of 3%, dissolving the potassium nitrate into a proper amount of deionized water, fixing the volume to 26mL, loading the potassium nitrate into the sample by adopting an isometric immersion method, stirring uniformly, and aging for 2 hours; and then placing the sample in a vacuum drying oven, drying for 6h at 100 ℃ under a vacuum condition, and roasting for 6h at 500 ℃ under a nitrogen atmosphere to obtain the catalyst which comprises 15% of Fe, 8% of Mn, 3% of Ti and 3% of K in percentage by mass of elements, and marking as C-6.
Example 7
Grinding 100g of petroleum coke into powder, uniformly mixing with 11g of sodium ferrate, 37g of sodium permanganate, 3g of sodium silicate and 300g of sodium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, introducing nitrogen to the normal pressure, and continuously heating to 800 ℃ under the condition that the microwave power is 0.3kw for activation for 20 min. And after the activation is finished, cooling to normal temperature, and taking out the obtained sample.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 30, adding the mixture into a hydrochloric acid solution with the concentration of 1wt%, fully stirring, uniformly mixing, then carrying out solid-liquid separation, washing the obtained solid by deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying for 6 hours at 150 ℃ under a vacuum condition.
Weighing 20g of the sample, weighing a proper amount of potassium chloride according to the content of the final catalyst K of 3%, dissolving the potassium chloride in a proper amount of deionized water, fixing the volume to 26mL, loading the potassium chloride in the sample by adopting an isometric immersion method, stirring uniformly, and aging for 2 h; and then placing the sample in a vacuum drying oven, drying for 6h at 100 ℃ under a vacuum condition, and roasting for 6h at 500 ℃ under a nitrogen atmosphere to obtain the catalyst which comprises 5% of Fe, 20% of Mn, 1% of Si and 3% of K in percentage by mass of elements and is marked as C-7.
Example 8
Grinding 100g of petroleum coke into powder, uniformly mixing with 76g of potassium ferrate, 2g of potassium permanganate, 12g of potassium silicate and 300g of potassium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, introducing nitrogen to the normal pressure, and continuously heating to 800 ℃ under the condition that the microwave power is 0.3kw for activation for 20 min. And after the activation is finished, cooling to normal temperature, and taking out the obtained sample.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: and 5, adding the mixture into a hydrochloric acid solution with the concentration of 10wt%, fully stirring, uniformly mixing, carrying out solid-liquid separation, washing the obtained solid by deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying for 6 hours at 150 ℃ under a vacuum condition.
Weighing 20g of the sample, weighing a proper amount of potassium nitrate according to the final catalyst K content of 10%, dissolving the potassium nitrate into a proper amount of deionized water, fixing the volume to 26mL, loading the potassium nitrate into the sample by adopting an isometric immersion method, stirring uniformly, and aging for 2 hours; and then placing the sample in a vacuum drying oven, drying for 6h at 100 ℃ under a vacuum condition, and roasting for 6h at 500 ℃ under a nitrogen atmosphere to obtain the catalyst which comprises 30% of Fe, 1% of Mn, 3% of Si and 10% of K in percentage by mass of elements and is marked as C-8.
Example 9
Grinding 100g of petroleum coke into powder, uniformly mixing with 34g of potassium ferrate, 15g of potassium permanganate, 3g of potassium silicate and 300g of potassium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, introducing nitrogen to the normal pressure, and continuously heating to 800 ℃ under the condition that the microwave power is 0.3kw for activation for 20 min. And after the activation is finished, cooling to normal temperature, and taking out the obtained sample.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: and 15, adding the mixture into a hydrochloric acid solution with the concentration of 3wt%, fully stirring, uniformly mixing, carrying out solid-liquid separation, washing the obtained solid by deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying for 6 hours at 150 ℃ under a vacuum condition.
Weighing 20g of the sample, weighing a proper amount of potassium chloride according to the content of the final catalyst K of 1%, dissolving the potassium chloride in a proper amount of deionized water, fixing the volume to 26mL, loading the potassium chloride in the sample by adopting an isometric immersion method, stirring uniformly, and aging for 2 h; and then placing the sample in a vacuum drying oven, drying for 6h at 100 ℃ under a vacuum condition, and roasting for 6h at 500 ℃ under a nitrogen atmosphere to obtain the catalyst which comprises 15% of Fe, 8% of Mn, 1% of Si and 1% of K in percentage by mass of elements and is marked as C-9.
Example 10
Grinding 100g of petroleum coke into powder, uniformly mixing with 36g of potassium ferrate, 2g of potassium permanganate, 39g of potassium silicate and 300g of potassium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 500 ℃ under the condition that the microwave power is 0.3kw, keeping the temperature constant for 40min, introducing nitrogen to the normal pressure, and continuously heating to 800 ℃ under the condition that the microwave power is 0.3kw for activation for 20 min. And after the activation is finished, cooling to normal temperature, and taking out the obtained sample.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: and 15, adding the mixture into a hydrochloric acid solution with the concentration of 3wt%, fully stirring, uniformly mixing, carrying out solid-liquid separation, washing the obtained solid by deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying for 6 hours at 150 ℃ under a vacuum condition.
Weighing 20g of the sample, weighing a proper amount of potassium nitrate according to the final catalyst K content of 3%, dissolving the potassium nitrate into a proper amount of deionized water, fixing the volume to 26mL, loading the potassium nitrate into the sample by adopting an isometric immersion method, stirring uniformly, and aging for 2 hours; and then placing the sample in a vacuum drying oven, drying for 6h at 100 ℃ under a vacuum condition, and roasting for 6h at 500 ℃ under a nitrogen atmosphere to obtain the catalyst which comprises 15% of Fe, 1% of Mn, 10% of Si and 3% of K in percentage by mass of elements, and marking as C-10.
Example 11
Grinding 100g of petroleum coke into powder, then uniformly mixing with 32g of potassium ferrate, 14g of potassium permanganate, 10g of potassium silicate and 300g of potassium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 800 ℃ under the condition that the microwave power is 0.3kw, and keeping constant for 60 min. And after the activation is finished, cooling to normal temperature, and taking out the obtained sample.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: and 15, adding the mixture into a hydrochloric acid solution with the concentration of 3wt%, fully stirring, uniformly mixing, carrying out solid-liquid separation, washing the obtained solid by deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying for 6 hours at 150 ℃ under a vacuum condition.
Weighing 20g of the sample, weighing a proper amount of potassium nitrate according to the final catalyst K content of 3%, dissolving the potassium nitrate into a proper amount of deionized water, fixing the volume to 26mL, loading the potassium nitrate into the sample by adopting an isometric immersion method, stirring uniformly, and aging for 2 hours; and then placing the sample in a vacuum drying oven, drying for 6h at 100 ℃ under a vacuum condition, and roasting for 6h at 500 ℃ under a nitrogen atmosphere to obtain the catalyst which comprises 15% of Fe, 8% of Mn, 3% of Si and 3% of K in percentage by mass of elements and is marked as C-11.
Example 12
Grinding 100g of petroleum coke into powder, then uniformly mixing with 40g of potassium ferrate, 17g of potassium permanganate, 12g of potassium silicate and 300g of potassium hydroxide, placing in a high-temperature vacuum roasting furnace, heating to 800 ℃ under a vacuum condition, and activating for 60 min. And after the activation is finished, cooling to normal temperature, and taking out the obtained sample.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: and 15, adding the mixture into a hydrochloric acid solution with the concentration of 3wt%, fully stirring, uniformly mixing, carrying out solid-liquid separation, washing the obtained solid by deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying for 6 hours at 150 ℃ under a vacuum condition.
Weighing 20g of the sample, weighing a proper amount of potassium nitrate according to the final catalyst K content of 3%, dissolving the potassium nitrate into a proper amount of deionized water, fixing the volume to 26mL, loading the potassium nitrate into the sample by adopting an isometric immersion method, stirring uniformly, and aging for 2 hours; and then placing the sample in a vacuum drying oven, drying for 6h at 100 ℃ under a vacuum condition, and roasting for 6h at 500 ℃ under a nitrogen atmosphere to obtain the catalyst which comprises 15% of Fe, 8% of Mn, 3% of Si and 3% of K in percentage by mass of elements and is marked as C-12.
Comparative example 1
Grinding 100g of petroleum coke into powder, then uniformly mixing with 300g of potassium hydroxide, and heating to 800 ℃ for activation for 120min under the nitrogen atmosphere.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 15, adding the mixture into a hydrochloric acid solution with the concentration of 3wt%, fully stirring, then carrying out solid-liquid separation, washing the obtained solid with deionized water until the pH value of the filtrate is neutral, placing the obtained fixed sample in a vacuum drying oven, and drying for 6 hours at 150 ℃ under the vacuum condition.
Weighing 20g of an active carbon carrier, weighing a proper amount of sodium silicate according to the final catalyst Si content of 3%, dissolving the sodium silicate in a proper amount of deionized water, fixing the volume to 22mL, loading the active carbon carrier by an isometric impregnation method, uniformly stirring, aging for 2h, then placing a sample in a vacuum drying oven, drying for 6h at 100 ℃ under a vacuum condition, and roasting for 6h at 600 ℃ under a nitrogen atmosphere; weighing a proper amount of ferric nitrate nonahydrate, manganese nitrate hexahydrate and potassium nitrate according to the Fe content of 15%, the Mn content of 8% and the K content of 3%, dissolving in a proper amount of deionized water, fixing the volume to 22mL, loading on a silicon-containing activated carbon carrier by adopting an isometric immersion method, stirring uniformly, and aging for 2 h; and then placing the sample in a vacuum drying oven, drying for 6h at 100 ℃ under a vacuum condition, and roasting for 6h at 600 ℃ under a nitrogen atmosphere to obtain the catalyst which comprises 15% of Fe, 8% of Mn, 3% of Si and 3% of K in percentage by mass of elements, and marking as D-1.
Evaluation of catalyst reaction Performance: the reaction performance was examined with samples of the catalysts prepared in examples 1 to 12 and comparative example 1, respectively, and the reaction was carried out in a continuous flow fixed bed reactor with a catalyst loading of 3g, H2The reaction temperature is 270 ℃, the reaction pressure is 2MPa, and the volume space velocity is 2000h-1(ii) a Product ofThe results of the reaction are shown in Table 1, by gas chromatography on-line analysis.
TABLE 1 catalyst Properties and reaction Performance
Figure DEST_PATH_IMAGE001

Claims (41)

1. A catalyst for preparing low-carbon olefin from synthesis gas comprises an active component, an electronic assistant, a structural assistant, a second structural assistant and a carrier; the active component is Fe; the electron auxiliary agent is K; the structural auxiliary agent is Mn; the second structural auxiliary agent is selected from one or more of Si, Zr and Ti, the carrier is petroleum coke-based activated carbon, wherein the active component accounts for 5-30 wt% of the element by mass, the electronic auxiliary agent K accounts for 1-10 wt% of the element by mass, the structural auxiliary agent Mn accounts for 1-20 wt% of the element by mass, the second structural auxiliary agent accounts for 1-10 wt% of the element by mass, and the carrier accounts for 40-80 wt%;
the preparation method of the catalyst for preparing the low-carbon olefin from the synthesis gas comprises the following steps:
(1) mixing petroleum coke, a compound containing active metal, a compound containing a structural assistant, a compound containing a secondary structural assistant and an activating agent, and activating after uniformly mixing;
(2) treating the sample obtained in the step (1) by using an acid solution, then washing until the washing liquid is neutral, and drying the washed solid sample;
(3) and (3) introducing the electronic assistant to the solid sample obtained in the step (2), and then drying and roasting to obtain the catalyst for preparing the low-carbon olefin from the synthesis gas.
2. The catalyst for preparing low-carbon olefin from synthesis gas according to claim 1, which is characterized in that: the catalyst comprises an active component, an electronic assistant, a structural assistant, a second structural assistant and a carrier; the active component is Fe; the electron auxiliary agent is K; the structural auxiliary agent is Mn; the second structural auxiliary agent is Si or Ti; the carrier is petroleum coke-based activated carbon, wherein the mass content of the active component is 10-20 wt% calculated by element; the mass content of the electronic additive K is 2wt% -5 wt% in terms of elements; the mass content of the structural auxiliary Mn is 5wt% -10 wt% calculated by elements; the mass content of the second structural auxiliary agent is 2wt% -4 wt% and the carrier content is 50wt% -70 wt% in terms of elements.
3. The catalyst for preparing low-carbon olefin from synthesis gas according to claim 1, which is characterized in that: the specific surface area of the catalyst is 200-1000 m2/g。
4. The catalyst for preparing low-carbon olefin from synthesis gas according to claim 1, which is characterized in that: the specific surface area of the catalyst is 400-800 m2/g。
5. The catalyst for preparing low-carbon olefin from synthesis gas according to claim 1, which is characterized in that: in the pore size distribution of the catalyst, micropores smaller than 2nm are larger than 60%.
6. The catalyst for preparing low-carbon olefin from synthesis gas according to claim 1, which is characterized in that: in the pore size distribution of the catalyst, micropores smaller than 2nm are larger than 80%.
7. The catalyst for preparing low-carbon olefin from synthesis gas according to claim 1, which is characterized in that: the active component, the electronic assistant, the structural assistant and the second structural assistant are embedded into the petroleum coke-based activated carbon amorphous defect and the activated carbon graphite microchip layer, and the size of the active metal crystal grain is 0.5-5 nm.
8. The catalyst for preparing low-carbon olefin from synthesis gas according to claim 1, which is characterized in that: the active component, the electronic assistant, the structural assistant and the second structural assistant are embedded into the petroleum coke-based activated carbon amorphous defect and the activated carbon graphite microchip layer, and the size of the active metal crystal grain is 1-3 nm.
9. The method for preparing a catalyst for preparing light olefins from synthesis gas according to any of claims 1 to 8, wherein: the preparation method comprises the following steps:
(1) mixing petroleum coke, a compound containing active metal, a compound containing a structural assistant, a compound containing a secondary structural assistant and an activating agent, and activating after uniformly mixing;
(2) treating the sample obtained in the step (1) by using an acid solution, then washing until the washing liquid is neutral, and drying the washed solid sample;
(3) and (3) introducing the electronic assistant to the solid sample obtained in the step (2), and then drying and roasting to obtain the catalyst for preparing the low-carbon olefin from the synthesis gas.
10. The preparation method of the catalyst for preparing the light olefins from the synthesis gas according to claim 9, which is characterized by comprising the following steps: the active metal-containing compound in the step (1) is selected from any one of potassium ferrate, sodium ferrate and lithium ferrate.
11. The method for preparing the catalyst for preparing the light olefins from the synthesis gas according to the claim 9 or 10, which is characterized in that: the active metal-containing compound in the step (1) is selected from potassium ferrate.
12. The preparation method of the catalyst for preparing the light olefins from the synthesis gas according to claim 9, which is characterized by comprising the following steps: the compound containing the structural assistant in the step (1) is potassium permanganate or sodium permanganate.
13. The method for preparing the catalyst for preparing the low-carbon olefin from the synthesis gas according to the claim 9 or 12, which is characterized in that: the compound containing the structural assistant in the step (1) is potassium permanganate.
14. The preparation method of the catalyst for preparing the light olefins from the synthesis gas according to claim 9, which is characterized by comprising the following steps: the compound containing the second structural auxiliary agent in the step (1) is one of a sodium salt containing a second auxiliary agent acid radical, a potassium salt containing the second auxiliary agent acid radical or a second auxiliary agent oxide.
15. The method for preparing the catalyst for preparing the low-carbon olefin from the synthesis gas according to claim 9 or 14, which is characterized by comprising the following steps of: the compound containing the second structural auxiliary agent in the step (1) is one of potassium silicate, sodium silicate, potassium titanate, sodium titanate, potassium zirconate, sodium zirconate, silicon dioxide, titanium dioxide and zirconium dioxide.
16. The method for preparing the catalyst for preparing the low-carbon olefin from the synthesis gas according to claim 9 or 14, which is characterized by comprising the following steps of: the compound containing the second structural assistant in the step (1) is one of potassium silicate, silicon dioxide, potassium titanate and titanium dioxide.
17. The preparation method of the catalyst for preparing the light olefins from the synthesis gas according to claim 9, which is characterized by comprising the following steps: the activating agent in the step (1) is one or more of potassium hydroxide, sodium hydroxide, potassium bicarbonate and sodium bicarbonate.
18. The method for preparing the catalyst for preparing the low-carbon olefin from the synthesis gas according to claim 9 or 17, which is characterized by comprising the following steps of: the activating agent in the step (1) is potassium hydroxide.
19. The preparation method of the catalyst for preparing the light olefins from the synthesis gas according to claim 9, which is characterized by comprising the following steps: in the step (1), the mass ratio of petroleum coke, the compound containing active metal, the compound containing structural assistant, the compound containing second structural assistant and the activator is 1: 0.01-0.3: 0.01-0.15: 0.005-0.1: 1 to 5.
20. The method for preparing the catalyst for preparing the low-carbon olefin from the synthesis gas according to the claim 9 or 19, which is characterized in that: in the step (1), the mass ratio of petroleum coke, the compound containing active metal, the compound containing structural assistant, the compound containing second structural assistant and the activator is 1: 0.05-0.15: 0.03-0.06: 0.01-0.05: 2 to 4.
21. The preparation method of the catalyst for preparing the light olefins from the synthesis gas according to claim 9, which is characterized by comprising the following steps: the activation process in the step (1) is as follows: grinding the petroleum coke into powder, then uniformly mixing the powder with an active metal-containing compound, a structural assistant-containing compound, a secondary structural assistant-containing compound and an activating agent, heating to an activating temperature, and cooling to room temperature for subsequent treatment after the activation is completed.
22. The method for preparing the catalyst for preparing the low-carbon olefin from the synthesis gas according to claim 9 or 21, which is characterized by comprising the following steps of: the activation temperature is 600-1000 ℃, and the activation time is 5-240 min.
23. The method for preparing the catalyst for preparing the low-carbon olefin from the synthesis gas according to the claim 9 or 22, which is characterized in that: the activation temperature is 700-900 ℃, and the activation time is 10-120 min.
24. The method for preparing the catalyst for preparing the low-carbon olefin from the synthesis gas according to claim 9 or 21, which is characterized by comprising the following steps of: the activation is carried out under the condition of microwave radiation, and the microwave frequency is 2450MHz or 915 MHz; the microwave power is 1-10 kw per kg of petroleum coke.
25. The method for preparing the catalyst for preparing the light olefins from the synthesis gas according to claim 24, which is characterized by comprising the following steps: the activation is carried out under the condition of microwave radiation, and the microwave frequency is 2450MHz or 915 MHz; the microwave power is 2-4 kw per kg of petroleum coke.
26. The method for preparing the catalyst for preparing the light olefins from the synthesis gas according to claim 24, which is characterized by comprising the following steps: when the activation is carried out under the microwave radiation condition, two-stage activation is carried out, wherein the first stage is activated for 10-60 min at 400-600 ℃ under the vacuum condition, inert gas or nitrogen is introduced to the atmosphere under the constant temperature condition, and the temperature is continuously increased to 700-900 ℃ under the microwave radiation condition for activation for 10-30 min.
27. The preparation method of the catalyst for preparing the light olefins from the synthesis gas according to claim 9, which is characterized by comprising the following steps: the specific process of the step (2) is as follows: and (2) mixing the sample obtained in the step (1) with an acid solution, uniformly mixing, performing solid-liquid separation, and washing the obtained solid with deionized water until the pH value of the filtrate is neutral.
28. The method for preparing the catalyst for preparing the low-carbon olefin from the synthesis gas according to the claim 9 or 27, which is characterized by comprising the following steps: the specific process of the step (2) is as follows: grinding the sample obtained in the step (1) into powder, mixing the powder with an acid solution, uniformly mixing, performing solid-liquid separation, and washing the obtained solid with deionized water until the pH value of the filtrate is neutral.
29. The preparation method of the catalyst for preparing the light olefins from the synthesis gas according to claim 9, which is characterized by comprising the following steps: and (3) the acid solution in the step (2) is a hydrochloric acid solution, a sulfuric acid solution or a nitric acid solution.
30. The method for preparing the catalyst for preparing the low-carbon olefin from the synthesis gas according to the claim 9 or 29, which is characterized by comprising the following steps: and (3) the acid solution in the step (2) is a hydrochloric acid solution.
31. The preparation method of the catalyst for preparing the light olefins from the synthesis gas according to claim 9, which is characterized by comprising the following steps: the concentration of the acid solution is 1-10 wt%, and the mass ratio of the sample obtained in the step (1) to the acid solution is 1: 5-1: 30.
32. the method for preparing the catalyst for preparing the low-carbon olefin from the synthesis gas according to the claim 9 or 31, which is characterized in that: the concentration of the acid solution is 2-5 wt%, and the mass ratio of the sample obtained in the step (1) to the acid solution is 1: 10-1: 20.
33. the preparation method of the catalyst for preparing the light olefins from the synthesis gas according to claim 9, which is characterized by comprising the following steps: and (3) drying at the temperature of 80-200 ℃ for 2-10 h.
34. The method for preparing a catalyst for preparing low-carbon olefins from synthesis gas according to claim 9 or 33, which is characterized by comprising the following steps: and (3) drying at the temperature of 120-180 ℃ for 4-8 h.
35. The preparation method of the catalyst for preparing the light olefins from the synthesis gas according to claim 9, which is characterized by comprising the following steps: the specific process of the step (3) is as follows: and (3) dipping the solid sample obtained in the step (2) by adopting a precursor aqueous solution containing an electronic auxiliary agent, and then drying and roasting to obtain the low-carbon olefin catalyst prepared from the synthesis gas.
36. The method for preparing the catalyst for preparing the light olefins from the synthesis gas according to claim 35, which is characterized by comprising the following steps: the precursor containing the electronic assistant is a soluble potassium-containing compound, and the soluble potassium-containing compound is one or more of potassium nitrate, potassium chloride, potassium sulfate, potassium hydroxide, potassium acetate and potassium citrate.
37. The method for preparing the catalyst for preparing the low-carbon olefin from the synthesis gas according to claim 35 or 36, which is characterized by comprising the following steps of: the precursor containing the electron auxiliary agent is a soluble potassium-containing compound, and the soluble potassium-containing compound is potassium nitrate.
38. The preparation method of the catalyst for preparing the light olefins from the synthesis gas according to claim 9, which is characterized by comprising the following steps: and (3) drying at the temperature of 60-160 ℃ for 2-10 h.
39. The preparation method of the catalyst for preparing the light olefins from the synthesis gas according to claim 9, which is characterized by comprising the following steps: and (3) drying at the temperature of 80-120 ℃ for 4-8 h.
40. The preparation method of the catalyst for preparing the light olefins from the synthesis gas according to claim 9, which is characterized by comprising the following steps: and (3) roasting in an inert atmosphere at the roasting temperature of 300-700 ℃ for 2-10 h.
41. The method for preparing the catalyst for preparing the low-carbon olefin from the synthesis gas according to claim 9 or 40, which is characterized by comprising the following steps of: and (3) roasting in an inert atmosphere at the roasting temperature of 400-600 ℃ for 4-8 h.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1537674A (en) * 2003-04-15 2004-10-20 北京化工大学 Iron/active carbon catalyst used for preparing ethylene, propylene, butylene from synthetic gas
CN104609421A (en) * 2013-11-04 2015-05-13 郭晶晶 Preparation method of active carbon

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1537674A (en) * 2003-04-15 2004-10-20 北京化工大学 Iron/active carbon catalyst used for preparing ethylene, propylene, butylene from synthetic gas
CN104609421A (en) * 2013-11-04 2015-05-13 郭晶晶 Preparation method of active carbon

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