CN111375373B - Adsorbent using active carbon as carrier and preparation method thereof - Google Patents

Adsorbent using active carbon as carrier and preparation method thereof Download PDF

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Publication number
CN111375373B
CN111375373B CN201811643282.1A CN201811643282A CN111375373B CN 111375373 B CN111375373 B CN 111375373B CN 201811643282 A CN201811643282 A CN 201811643282A CN 111375373 B CN111375373 B CN 111375373B
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producing
adsorbent
adsorbent according
copper
drying
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CN111375373A (en
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孙晓丹
宋永一
张舒冬
张庆军
刘继华
方向晨
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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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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0207—Compounds of Sc, Y or Lanthanides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0233—Compounds of Cu, Ag, Au
    • B01J20/0237—Compounds of Cu
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7027—Aromatic hydrocarbons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

The invention discloses an adsorbent taking active carbon as a carrier and a preparation method thereof, wherein the preparation method comprises the following steps: (1) mixing petroleum coke, a copper-containing precursor compound, a soluble salt containing rare earth metal and an activating agent, and activating after uniformly mixing; (2) washing and drying the sample obtained in the step (1); (3) carrying out oxidation treatment on the sample obtained in the step (2); (4) and (4) washing and drying the sample obtained in the step (3) to obtain the adsorbent. The adsorbent comprises an active component and a carrier, wherein the active component is Cu, the auxiliary agent is rare earth metal, and the carrier is petroleum coke-based activated carbon. The preparation method of the invention overcomes the problem that the copper-based adsorbent using the active carbon as the carrier is easy to generate oxide aggregation in the preparation process, and the obtained adsorbent has the advantages of high dispersion of active components, excellent adsorption performance and the like.

Description

Adsorbent using active carbon as carrier and preparation method thereof
Technical Field
The invention belongs to the field of petrochemical industry, relates to an adsorption material and a preparation method thereof, and particularly relates to a copper-based adsorbent loaded by using activated carbon as a carrier and a preparation method thereof.
Background
With the rapid development of C1 chemistry, CO has become an important basic chemical raw material. CO is often associated with H 2 、N 2 、CO 2 And CH 4 The gases are mixed, andthe purification of CO or the purification of CO from a gas mixture containing these gases is a very important problem in the chemical industry. The purification of CO from the mixed gas not only can provide important raw materials for chemical production, but also can improve the effective utilization rate of industrial waste gas and simultaneously can avoid the pollution to the environment. In addition, the existence of trace amount of CO in industrial gas can cause catalyst poisoning of some synthesis reactions, which is very unfavorable for industrial production, for example, the trace amount of CO in raw material gas of ammonia synthesis industry must be purified and removed, so that the purification and removal of trace amount of CO from mixed gas is also very important. Compared with the traditional cryogenic separation method and chemical absorption method, the adsorption separation method has obvious superiority in the recovery process, and the key point for realizing the process is to develop an adsorbent with large adsorption capacity and high adsorption selectivity for CO.
Most of the current developments of CO adsorbents focus on the loading of mono-or divalent copper salts onto a carrier, and the mechanism by which these adsorbents can adsorb CO is mainly the formation of cu (i) -CO complexes. CN101927152A discloses a high-strength adsorbent for gas purification and separation, its preparation and application, the adsorbent effectively introduces CeO 2 To increase the main active component Cu + Or Cu 2+ The dispersibility of ions, the occupancy rate of the metal active center on the surface of the carrier is improved, and Cu is promoted + Effectively complexing with CO in the reaction, effectively improving the separation performance of the adsorbent, but the method has longer operation time. The application of CN103230774A discloses a preparation method of a copper-containing mesoporous adsorbent, which is characterized in that tetraethyl orthosilicate is used for plating a protective layer on a copper-modified mesoporous molecular sieve, so that cuprous oxide can be prevented from being aggregated on a carrier during high-temperature self-reduction, and the adsorption performance of the adsorbent is improved.
In summary, the dispersion state of the cuprous oxide, an active component, on the carrier is an important factor influencing the adsorption effect, and the high dispersion of the oxide on the carrier can greatly improve the adsorption performance of the material, but the adsorption performance of the material is reduced if the oxide is aggregated. Therefore, how to develop a new method for loading the cuprous oxide adsorbent, which realizes the high dispersion of the active component on the carrier and prevents the oxide from aggregation is the key to solve the problems in the prior art.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a copper-based adsorbent loaded by using activated carbon as a carrier and a preparation method thereof. The copper-based adsorbent takes petroleum coke-based activated carbon as a carrier, overcomes the problem that the copper-based adsorbent taking activated carbon as a carrier is easy to generate oxide aggregation in the preparation process, has the advantages of high dispersion of active components, excellent adsorption performance and the like, and is simple to operate, low in production cost and small in environmental pollution.
The first aspect of the invention provides a preparation method of an adsorbent using activated carbon as a carrier, which comprises the following steps:
(1) mixing petroleum coke, a copper-containing precursor compound, a soluble salt containing rare earth metal and an activating agent, and activating after uniformly mixing;
(2) washing and drying the sample obtained in the step (1);
(3) carrying out oxidation treatment on the sample obtained in the step (2);
(4) and (4) washing and drying the sample obtained in the step (3) to obtain the adsorbent.
In the preparation method of the adsorbent, the petroleum coke in the step (1) is preferably pretreated, and the pretreatment comprises the following steps:
(1.1) introducing ammonium phosphate salt into petroleum coke, and then drying;
(1.2) pretreating the sample obtained in the step (1.1) with water vapor-containing gas.
In the method, the ammonium phosphate salt in the step (1.1) is one or more of ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate, and is preferably ammonium phosphate.
In the above method, the method for introducing the ammonium phosphate salt into the petroleum coke in the step (1.1) is performed according to a method known in the art, and comprises one or more of an equal volume impregnation method, a supersaturated impregnation method and a kneading method, and is preferably a supersaturated impregnation method.
In the method, in the step (1.1), the drying temperature is 60-120 ℃, the preferable drying temperature is 80-100 ℃, the drying time is 2-8 hours, and the preferable drying time is 4-6 hours; the drying is further preferably carried out under vacuum conditions.
In the method, the weight ratio of the ammonium phosphate salt to the petroleum coke in the step (1.1) is 0.1-1: 1, preferably 0.3-0.8: 1.
in the method, the water vapor-containing gas in the step (1.2) is water vapor or a mixed gas of water vapor and a carrier gas, and the volume ratio of the water vapor to the carrier gas in the mixed gas is 1: 20-1: 1, preferably 1: 10-1: 2; the carrier gas is nitrogen or inert gas, and the inert gas is one or more of helium, neon, argon, krypton and xenon.
In the method, the pretreatment process in the step (1.2) comprises a first-stage pretreatment, a second-stage pretreatment and a cooling process, wherein the temperature of the first-stage pretreatment is 150-250 ℃, the preferred temperature is 180-220 ℃, and the pretreatment time is 1-6 hours, and the preferred time is 2-4 hours; the second-stage pretreatment temperature is 300-500 ℃, preferably 350-450 ℃, the pretreatment time is 1-6 hours, preferably 2-4 hours, and the second-stage pretreatment is followed by cooling to 20-100 ℃, preferably 40-80 ℃; the cooling process is preferably carried out under nitrogen protection.
In the method, the volume space velocity of the vapor-containing gas in the step (1.2) is 500-2000 h -1 。
In the preparation method of the adsorbent, the copper-containing precursor compound in the step (1) is one or more of copper formate, copper acetate, copper oxalate, copper nitrate, copper hydroxide, basic copper carbonate and copper oxide, and preferably copper hydroxide.
In the preparation method of the adsorbent, the rare earth metal in the step (1) is one or two of La and Ce; the soluble salt containing the rare earth metal can be one or more of nitrate, sulfate and hydrochloride, and is preferably the nitrate of the rare earth metal.
In the preparation method of the adsorbent, the activating agent in the step (1) is one or more of potassium hydroxide, sodium hydroxide, potassium bicarbonate, sodium bicarbonate, potassium carbonate and sodium carbonate, and preferably potassium hydroxide.
In the preparation method of the adsorbent, in the step (1), the mass ratio of the petroleum coke, the copper-containing precursor compound (calculated by the mass of Cu element), the rare earth metal-containing soluble salt (calculated by the mass of rare earth metal element) and the activator is 1: 0.004 to 0.18: 0.004-0.036: 0.5-4, preferably 1: 0.02-0.13: 0.004-0.02: 1 to 3.
In the preparation method of the adsorbent, the activation process in the step (1) is as follows: uniformly mixing petroleum coke, a copper-containing precursor compound, a soluble salt containing rare earth metal and an activating agent, heating to an activation temperature in a nitrogen or inert atmosphere, and cooling to 200-100 ℃ after activation for subsequent treatment, wherein the inert atmosphere is one or more of helium or argon; the activation temperature is 400-1000 ℃, 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 method further preferably comprises two-stage activation, 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 normal pressure 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 adsorbent, the washing in the step (2) is water washing, and the sample obtained in the step (1) is mixed with deionized water, and after uniform mixing, solid-liquid separation is carried out until the pH value of the filtrate is neutral. The mass ratio of the sample obtained in the step (1) to the deionized water is 1: 5-1: 30, preferably 1: 10-1: 20.
in the preparation method of the adsorbent, the drying temperature in the step (2) is 100-200 ℃, 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.
The invention is as describedIn the preparation method of the copper-based adsorbent, the process of carrying out oxidation treatment on the sample obtained in the step (3) comprises the following steps: and (3) mixing the sample obtained in the step (2) with an oxidant aqueous solution, and then carrying out solid-liquid separation. The oxidant is HNO 3 、HClO、H 2 SO 4 、Cl 2 、I 2 、H 2 O 2 、(NH4) 2 S 2 O 8 Preferably H 2 O 2 . The concentration of the oxidant aqueous solution is 1wt% -10 wt%, preferably 1wt% -5 wt%; the mass ratio of the sample obtained in the step (2) to the oxidant aqueous solution is 1: 3-1: 15, preferably 1: 5-1: 10.
in the preparation method of the copper-based adsorbent, the washing in the step (4) is water washing, and the sample obtained in the step (3) is mixed with deionized water, and after uniform mixing, solid-liquid separation is carried out until the pH value of the filtrate is neutral. The mass ratio of the sample obtained in the step (3) to the deionized water is 1: 5-1: 30, preferably 1: 10-1: 20.
in the preparation method of the adsorbent, in the step (4), the drying temperature is 100-200 ℃, 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.
The invention also provides a method for preparing the adsorbent by using the activated carbon as the carrier.
In the adsorbent, the adsorbent comprises an active component and a carrier, wherein the active component is Cu, the auxiliary agent is rare earth metal, the carrier is petroleum coke-based activated carbon, and the mass content of the active component Cu is 1wt% -25 wt%, preferably 5wt% -20 wt% calculated by elements; the mass content of the auxiliary agent rare earth metal calculated by element is 1wt% -5 wt%, preferably 1wt% -3 wt%; the carrier content is 71wt% to 97wt%, preferably 78wt% to 93 wt%. In the adsorbent, the specific surface area of the adsorbent is 1000-3000 m 2 Preferably 1500 to 3000 m/g 2 (ii)/g; the active component is embedded into the amorphous defect of the petroleum coke-based activated carbon and the activated carbon graphite microchip layer, and the size of the active component metal crystal grain is 1-7 nm, preferably 2-5 nm.
In a third aspect, the invention provides a use of the above adsorbent. The adsorbent using the activated carbon as the carrier can be used for separating carbon monoxide, adsorbing and separating ethylene and ethane in refinery dry gas, adsorbing and desulfurizing, adsorbing toluene and the like.
Compared with the prior art, the adsorbent using the active carbon as the carrier and the preparation method thereof have the following advantages:
1. the adsorbent using the activated carbon as the carrier has the advantages of large specific surface area, high pore volume, concentrated pore size distribution, small particle size of active components, high dispersion and the like, and is simple to operate and low in production cost.
2. According to the preparation method of the adsorbent, active metal Cu is introduced in the petroleum coke activation process, the active metal Cu enters a diffusion path generated by the petroleum coke phase through an activating agent, and is tightly combined with amorphous carbon defects or graphite carbon sheet layers under the action of microwave catalysis, so that active metal molecules are better dispersed in a molten state activating agent, and the active metal is further promoted to enter the petroleum coke, and therefore the adsorbent with high dispersion and high temperature stability is obtained, and the problem that the copper-based adsorbent taking the active carbon as a carrier is easy to generate oxide aggregation in the preparation process is solved.
3. The active component of the adsorbent has good stability, does not need to be activated before use, and has high-efficiency separation characteristic.
4. The preparation method of the catalyst comprises the steps of pretreating petroleum coke, introducing ammonium phosphate into the petroleum coke, and treating the petroleum coke by using steam-containing gas, so that the ammonium phosphate is promoted to be decomposed in the petroleum coke to generate ammonia gas and phosphoric acid, the generated ammonia gas provides more primary pores for further activation of the petroleum coke, and meanwhile, the generated phosphoric acid can also be used as an activating agent to carry out primary activation on the petroleum coke, so that a developed pore structure is formed. Solves the problems of serious equipment corrosion and higher production cost caused by that petroleum coke has compact structure, high crystallinity, lacks of primary pores required by activation and needs to adopt strong base with large base-coke ratio to activate pore-forming in inert atmosphere.
5. According to the preparation method of the adsorbent, phosphoric acid generated by decomposing ammonium phosphate salt plays a primary activation role on petroleum coke, and then the subsequent activation of the activating agent is carried out, so that the activation effect is improved, the consumption of the alkali activating agent can be further reduced, the production cost of the adsorbent is greatly reduced, and the environmental pollution is small.
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 samples 2 Measured by an adsorption method.
Example 1
Grinding 100g of petroleum coke into powder, then uniformly mixing with 3.72g of copper hydroxide, 1.51g of lanthanum nitrate and 300g of potassium hydroxide, placing in a tube furnace, and heating to 800 ℃ under the nitrogen atmosphere to activate for 40 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying for 6 hours at 150 ℃ under the vacuum condition. Weighing the dried sample, and mixing the weighed sample with the water according to a mass ratio of 1: 5 with 3% by weight of H 2 O 2 Mixing the water solutions, fully stirring, then carrying out solid-liquid separation, and mixing the obtained solid sample with deionized water until the pH value of the filtrate is neutral. And (3) placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6h under a vacuum condition to obtain the adsorbent which accounts for 5% of Cu and 1% of La by mass of the adsorbent in terms of elements, wherein the adsorbent is marked as C-1.
Example 2
Grinding 100g of petroleum coke into powder, then uniformly mixing with 19.05g of copper hydroxide, 5.81g of lanthanum nitrate and 300g of potassium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, and heating to 900 ℃ under the condition of microwave power of 0.3kw and activating for 20 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 15 is mixed with deionized water, fully stirred,and then carrying out solid-liquid separation until the pH value of the filtrate is neutral, putting the obtained solid sample in a vacuum drying oven, and drying for 6h at 150 ℃ under a vacuum condition. Weighing the dried sample, and mixing the weighed sample with the water according to a mass ratio of 1: 5 with 3% by weight of H 2 O 2 Mixing the water solutions, fully stirring, then carrying out solid-liquid separation, and mixing the obtained solid sample with deionized water until the pH value of the filtrate is neutral. And (3) placing the obtained solid sample in a vacuum drying oven, and drying for 6h at 150 ℃ under a vacuum condition to obtain the adsorbent which accounts for 20% of Cu and 3% of La by mass of the adsorbent in terms of elements, wherein the adsorbent is marked as C-2.
Example 3
Grinding 100g of petroleum coke into powder, uniformly mixing with 13g of copper hydroxide, 3.52g of lanthanum nitrate 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 to activate for 20 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying for 6 hours at 150 ℃ under the vacuum condition. Weighing the dried sample, and mixing the weighed sample with the water according to a mass ratio of 1: 5 with 3% by weight of H 2 O 2 Mixing the water solutions, fully stirring, then carrying out solid-liquid separation, and mixing the obtained solid sample with deionized water until the pH value of the filtrate is neutral. And (3) placing the obtained solid sample in a vacuum drying oven, and drying for 6h at 150 ℃ under a vacuum condition to obtain the adsorbent which accounts for 15% of Cu and 2% of La by mass of the adsorbent in terms of elements, wherein the adsorbent is marked as C-3.
Example 4
Grinding 100g of petroleum coke into powder, uniformly mixing with 3.82g of copper hydroxide, 4.65g of lanthanum nitrate and 300g of sodium hydroxide, placing in a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 600 ℃ under the condition that the microwave power is 0.3kw, 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 0.3kw for activation for 10 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying for 6 hours at 150 ℃ under the vacuum condition. Weighing the dried sample, and mixing the weighed sample with the water according to a mass ratio of 1: 5 with 3% by weight of H 2 O 2 Mixing the water solutions, fully stirring, then carrying out solid-liquid separation, and mixing the obtained solid sample with deionized water until the pH value of the filtrate is neutral. And (3) placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6h under a vacuum condition to obtain the adsorbent which accounts for 5% of Cu and 3% of La by mass of the adsorbent in terms of elements, wherein the adsorbent is marked as C-4.
Example 5
Grinding 100g of petroleum coke into powder, uniformly mixing with 18.45g of copper hydroxide, 1.87g of lanthanum nitrate and 300g of potassium bicarbonate, putting the mixture into a microwave heating furnace with microwave frequency of 2450MHz, vacuumizing, heating to 400 ℃ under the condition that the microwave power is 0.3kw, 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 0.3kw for activation for 30 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying for 6 hours at 150 ℃ under the vacuum condition. Weighing the dried sample, and mixing the weighed sample with the water according to a mass ratio of 1: 5 with 3% by weight of H 2 O 2 Mixing the water solutions, fully stirring, then carrying out solid-liquid separation, and mixing the obtained solid sample with deionized water until the pH value of the filtrate is neutral. And (3) placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6 hours under a vacuum condition to obtain the adsorbent with the mass percent of Cu and La accounting for 20 percent and 1 percent of the mass percent of the adsorbent in terms of elements, wherein the adsorbent is marked as C-5.
Example 6
Grinding 100g of petroleum coke into powder, uniformly mixing with 32.22g of copper nitrate, 3.5g of cerium nitrate 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 to activate for 20 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying for 6 hours at 150 ℃ under the vacuum condition. Weighing the dried sample, and mixing the weighed sample with the water according to a mass ratio of 1: 5 with 3% by weight of H 2 O 2 Mixing the water solutions, fully stirring, then carrying out solid-liquid separation, and mixing the obtained solid sample with deionized water until the pH value of the filtrate is neutral. And (3) placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6h under a vacuum condition to obtain the adsorbent which accounts for 15% of Cu and 2% of Ce in terms of elements by mass and is marked as C-6.
Example 7
Weighing 50g of ammonium phosphate, and dissolving the ammonium phosphate in 200mL of deionized water to obtain a solution A; 100g of petroleum coke was ground to a powder, then added to solution A, left to stand for 1.5h, then filtered, and the resulting solid sample was dried in an oven at 110 ℃ for 5 h. Pretreating the dried solid sample with water vapor at 200 deg.C for 3h (the volume space velocity of water vapor gas is 1200 h) -1 ) And then raising the temperature to 400 ℃, continuing to pretreat for 3h, and then cooling to 60 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
Grinding 100g of the pretreated petroleum coke into powder, uniformly mixing with 13g of copper hydroxide, 3.52g of lanthanum nitrate and 300g of potassium hydroxide, placing the mixture 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 to activate for 20 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven,drying for 6h at 150 ℃ under vacuum. Weighing the dried sample, and mixing the weighed sample with the water according to a mass ratio of 1: 5 with 3% by weight of H 2 O 2 Mixing the water solutions, fully stirring, then carrying out solid-liquid separation, and mixing the obtained solid sample with deionized water until the pH value of the filtrate is neutral. And (3) placing the obtained solid sample in a vacuum drying oven, and drying at 150 ℃ for 6h under a vacuum condition to obtain the adsorbent which accounts for 15% of Cu and 2% of La by mass of the adsorbent in terms of elements, wherein the adsorbent is marked as C-7.
Example 8
Weighing 70g of ammonium hydrogen phosphate, and dissolving in 200mL of deionized water to obtain a solution A; 100g of petroleum coke was ground to a powder, then added to solution A, left to stand for 1.5h, then filtered, and the resulting solid sample was dried in an oven at 110 ℃ for 5 h. Pretreating the dried solid sample with water vapor at 200 deg.C for 3h (volume space velocity of water vapor gas is 800 h) -1 ) And then raising the temperature to 400 ℃, continuing to pretreat for 3h, and then cooling to 60 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
Grinding 100g of the pretreated petroleum coke into powder, uniformly mixing with 13g of copper hydroxide, 3.52g of lanthanum nitrate and 300g of sodium bicarbonate, putting the mixture into 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 to activate for 20 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying for 6 hours at 150 ℃ under the vacuum condition. Weighing the dried sample, and mixing the weighed sample with the water according to a mass ratio of 1: 5 with 3% by weight of H 2 O 2 Mixing the water solutions, fully stirring, then carrying out solid-liquid separation, and mixing the obtained solid sample with deionized water until the pH value of the filtrate is neutral. Placing the obtained solid sample in a vacuum drying oven, drying for 6h at 150 ℃ under the vacuum condition to obtain the adsorbent with the mass percentage of the adsorbent accounting for 15 percent of Cu and 2 percent of La by element, and marking asC-8。
Example 9
Weighing 90g of ammonium dihydrogen phosphate, and dissolving in 200mL of deionized water to obtain a solution A; 100g of petroleum coke was ground to a powder, then added to solution A, left to stand for 1.5h, then filtered, and the resulting solid sample was dried in an oven at 110 ℃ for 5 h. Pre-treating the dried solid sample for 3h at 200 ℃ by using mixed gas with the volume ratio of water vapor to nitrogen being 1:2 (the volume space velocity of the mixed gas is 800 h) -1 ) And then raising the temperature to 400 ℃, continuing to pretreat for 3h, and then cooling to 60 ℃ under the protection of nitrogen to obtain the pretreated petroleum coke.
Grinding 100g of the pretreated petroleum coke into powder, uniformly mixing with 13g of copper hydroxide, 3.52g of lanthanum nitrate and 300g of sodium bicarbonate, putting the mixture into 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 to activate for 20 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying for 6 hours at 150 ℃ under the vacuum condition. Weighing a sample obtained after drying, and mixing the weighed sample with the water according to a mass ratio of 1: 5 with 3% by weight of H 2 O 2 Mixing the water solutions, fully stirring, then carrying out solid-liquid separation, and mixing the obtained solid sample with deionized water until the pH value of the filtrate is neutral. And (3) placing the obtained solid sample in a vacuum drying oven, and drying for 6h at 150 ℃ under a vacuum condition to obtain the adsorbent which accounts for 15% of Cu and 2% of La by mass of the adsorbent in terms of elements, wherein the adsorbent is marked as C-8.
Comparative example 1
Grinding 100g of petroleum coke into powder, then uniformly mixing the powder with 300g of potassium hydroxide, placing the mixture 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, then introducing nitrogen to the normal pressure, and continuously heating to 800 ℃ under the condition that the microwave power is 0.3kw to activate for 20 min.
Grinding the activated sample into powder, weighing, and mixing the powder according to a mass ratio of 1: 15 and deionized water, fully stirring, then carrying out solid-liquid separation until the pH value of the filtrate is neutral, placing the obtained solid sample in a vacuum drying oven, and drying for 6 hours at 150 ℃ under the vacuum condition.
Weighing 32.22g of copper nitrate and 3.52g of lanthanum nitrate, dissolving in 100mL of deionized water, adding into the sample obtained in the step of vacuum drying, uniformly stirring, aging for 2h, then placing in a vacuum drying oven, drying at 150 ℃ for 6h under a vacuum condition, and roasting the dried sample at 700 ℃ for 6h under a nitrogen atmosphere to obtain the adsorbent which accounts for 15% of Cu and 2% of La by mass of the adsorbent in terms of elements and is marked as D-1.
Evaluation conditions were as follows: the adsorbent was packed in a fixed bed adsorber at a loading of 55g, using a feed gas containing 99% hydrogen and 1% CO, and the dynamic adsorption capacity of CO was measured at an adsorption temperature of 25 ℃ and an adsorption pressure of 1bar, and the results are shown in table 1.
TABLE 1 catalyst Properties and reaction Performance
Figure DEST_PATH_IMAGE001

Claims (47)

1. A preparation method of an adsorbent taking activated carbon as a carrier comprises the following steps:
(1) mixing petroleum coke, a copper-containing precursor compound, a soluble salt containing rare earth metal and an activating agent, uniformly mixing and activating, wherein the copper-containing precursor compound is one or more of copper formate, copper acetate, copper oxalate, copper nitrate, copper hydroxide, basic copper carbonate and copper oxide;
(2) washing and drying the sample obtained in the step (1);
(3) carrying out oxidation treatment on the sample obtained in the step (2);
(4) and (4) washing and drying the sample obtained in the step (3) to obtain the adsorbent.
2. The method for producing the adsorbent according to claim 1, wherein: in the step (1), the petroleum coke is pretreated firstly, and the pretreatment comprises the following contents:
(1.1) introducing ammonium phosphate salt into petroleum coke, and then drying;
(1.2) pretreating the sample obtained in the step (1.1) with water vapor-containing gas.
3. The method for producing the adsorbent according to claim 2, wherein: in the step (1.1), the ammonium phosphate salt is one or more of ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate.
4. The method for producing the adsorbent according to claim 2, wherein: in the step (1.1), the ammonium phosphate salt is ammonium phosphate.
5. The method for producing the adsorbent according to claim 2, wherein: in the step (1.1), the drying temperature is 60-120 ℃, and the drying time is 2-8 h.
6. A process for producing the adsorbent according to claim 2 or 5, wherein: in the step (1.1), the drying temperature is 80-100 ℃, and the drying time is 4-6 h.
7. A process for producing the adsorbent according to claim 2 or 5, wherein: the drying in step (1.1) is carried out under vacuum.
8. The method for producing the adsorbent according to claim 2, wherein: in the step (1.1), the weight ratio of the ammonium phosphate to the petroleum coke is 0.1-1: 1.
9. the method for producing the adsorbent according to claim 2 or 8, wherein: in the step (1.1), the weight ratio of the ammonium phosphate to the petroleum coke is 0.3-0.8: 1.
10. the method for producing the adsorbent according to claim 2, wherein: in the step (1.2), the water vapor-containing gas is water vapor or a mixed gas of water vapor and a carrier gas, the volume ratio of the water vapor to the carrier gas in the mixed gas is 1: 20-1: 1, the carrier gas is an inert atmosphere, and the inert atmosphere is one or more of nitrogen, helium, neon, argon, krypton and xenon.
11. The process for producing the adsorbent according to claim 2, wherein: in the step (1.2), the water vapor-containing gas is water vapor or a mixed gas of water vapor and a carrier gas, the volume ratio of the water vapor to the carrier gas in the mixed gas is 1: 10-1: 2, the carrier gas is an inert atmosphere, and the inert atmosphere is one or more of nitrogen, helium, neon, argon, krypton and xenon.
12. The method for producing the adsorbent according to claim 2, wherein: the pretreatment process in the step (1.2) comprises a first-stage pretreatment, a second-stage pretreatment and a cooling process, wherein the temperature of the first-stage pretreatment is 150-250 ℃, and the pretreatment time is 1-6 h; the second-stage pretreatment temperature is 300-500 ℃, and the pretreatment time is 1-6 h; and after the second-stage pretreatment, cooling to 20-100 ℃.
13. The process for producing the adsorbent according to claim 2, wherein: the pretreatment process in the step (1.2) comprises a first-stage pretreatment, a second-stage pretreatment and a cooling process, wherein the temperature of the first-stage pretreatment is 180-220 ℃, and the pretreatment time is 2-4 h; the second-stage pretreatment temperature is 350-450 ℃, and the pretreatment time is 2-4 h; and after the second-stage pretreatment, cooling to 40-80 ℃.
14. A method for producing the adsorbent according to claim 12 or 13, wherein: the cooling process is carried out under the protection of nitrogen.
15The method for producing the adsorbent according to claim 2, wherein: the volume space velocity of the vapor-containing gas in the step (1.2) is 500-2000 h -1 。
16. The method for producing the adsorbent according to claim 1, wherein: in the step (1), the copper-containing precursor compound is copper hydroxide.
17. The method for producing the adsorbent according to claim 1, wherein: in the step (1), the soluble salt containing the rare earth metal is one or more of nitrate, sulfate and hydrochloride.
18. A method for producing the adsorbent according to claim 1 or 17, wherein: in the step (1), the soluble salt containing the rare earth metal is nitrate.
19. The method for producing the adsorbent according to claim 1, wherein: the rare earth metal is one or two of La and Ce.
20. The method for producing the adsorbent according to claim 1, wherein: the activating agent in the step (1) is one or more of potassium hydroxide, sodium hydroxide, potassium bicarbonate, sodium bicarbonate, potassium carbonate and sodium carbonate.
21. A method for producing the adsorbent according to claim 1 or 20, wherein: in the step (1), the activating agent is potassium hydroxide.
22. The method for producing the adsorbent according to claim 1, wherein: in the step (1), the mass ratio of the petroleum coke, the copper-containing precursor compound, the soluble salt containing rare earth metal and the activator in terms of the mass of Cu element is 1: 0.004 to 0.18: 0.004-0.036: 0.5 to 4.
23. A method for producing the adsorbent according to claim 1 or 22, wherein: in the step (1), the mass ratio of the petroleum coke, the copper-containing precursor compound, the soluble salt containing rare earth metal and the activator in terms of the mass of Cu element is 1: 0.02-0.13: 0.004-0.02: 1 to 3.
24. The method for producing the adsorbent according to claim 1, wherein: the activation process in the step (1) is as follows: uniformly mixing petroleum coke, a copper-containing precursor compound, a soluble salt containing rare earth metal and an activating agent, heating to an activation temperature in an inert atmosphere, cooling to 200-100 ℃ after activation is completed, and performing subsequent treatment, wherein the activation temperature is 400-1000 ℃, and the activation time is 5-240 min.
25. A method for producing the adsorbent according to claim 1 or 24, wherein: the activation process in the step (1) is as follows: uniformly mixing petroleum coke, a copper-containing precursor compound, a soluble salt containing rare earth metal and an activating agent, heating to an activation temperature in an inert atmosphere, cooling to 200-100 ℃ after activation is completed, and performing subsequent treatment, wherein the activation temperature is 700-900 ℃, and the activation time is 10-120 min.
26. The method for producing the adsorbent according to claim 1, wherein: the activation process is carried out under the microwave radiation condition, and the microwave frequency is 2450MHz or 915 MHz; the microwave power is 1-10 kW per kg of petroleum coke.
27. The method for producing the adsorbent according to claim 1, wherein: the activation process is carried out under the microwave radiation condition, and the microwave frequency is 2450MHz or 915 MHz; the microwave power is 2-4 kW per kg of petroleum coke.
28. A method for producing the adsorbent according to claim 26 or 27, wherein: 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, an inert atmosphere is introduced to the atmosphere at constant temperature, and the temperature is continuously increased to 700-900 ℃ under the microwave radiation condition for activation for 10-30 min.
29. The method for producing the adsorbent according to claim 1, wherein: and (3) the washing in the step (2) is water washing, firstly, the sample obtained in the step (1) is mixed with deionized water, and after uniform mixing, solid-liquid separation is carried out until the pH value of the filtrate is neutral.
30. The method for producing the adsorbent according to claim 1, wherein: the drying temperature in the step (2) is 100-200 ℃, and the drying time is 2-10 h.
31. A method for producing the adsorbent according to claim 1 or 30, wherein: and (3) drying at the temperature of 120-180 ℃ for 4-8 h.
32. A method for producing the adsorbent according to claim 1 or 30, wherein: and (3) drying in the step (2) under a vacuum condition.
33. The method for producing the adsorbent according to claim 1, wherein: the process of carrying out oxidation treatment on the sample obtained in the step (3) comprises the following steps: and (3) mixing the sample obtained in the step (2) with an oxidant aqueous solution, and then carrying out solid-liquid separation.
34. The method of making the adsorbent of claim 33, wherein: the oxidant is HNO 3 、HClO、H 2 SO 4 、Cl 2 、I 2 、H 2 O 2 、(NH 4 ) 2 S 2 O 8 One or more of them.
35. A method for producing the adsorbent according to claim 33 or 34, wherein: the oxidant is H 2 O 2 。
36. The method of making the adsorbent of claim 33, wherein: the concentration of the oxidant aqueous solution is 1wt% -10 wt%, and the mass ratio of the sample obtained in the step (2) to the oxidant aqueous solution is 1: 3-1: 15.
37. a method for producing the adsorbent according to claim 33 or 36, wherein: the concentration of the oxidant aqueous solution is 1wt% -5 wt%, and the mass ratio of the sample obtained in the step (2) to the oxidant aqueous solution is 1: 5-1: 10.
38. the method for producing the adsorbent according to claim 1, wherein: and (4) washing is water washing, firstly, the sample obtained in the step (3) is mixed with deionized water, and after uniform mixing, solid-liquid separation is carried out until the pH value of the filtrate is neutral.
39. The method for producing the adsorbent according to claim 1, wherein: in the step (4), the drying temperature is 100-200 ℃, and the drying time is 2-10 h.
40. The method for producing the adsorbent according to claim 1, wherein: in the step (4), the drying temperature is 120-180 ℃, and the drying time is 4-8 h.
41. A process for producing the adsorbent according to claim 39 or 40, wherein: drying is carried out under vacuum.
42. An adsorbent using active carbon as a carrier is characterized in that: the adsorbent is prepared by the method of any one of claims 1-41.
43. The sorbent of claim 42, wherein: the adsorbent comprises an active component and a carrier, wherein the active component is Cu, the auxiliary agent is rare earth metal, the carrier is petroleum coke-based activated carbon, the mass content of the active component Cu is 1wt% -25 wt% calculated by elements, the mass content of the auxiliary agent rare earth metal is 1wt% -5 wt% calculated by elements, and the carrier content is 71wt% -97 wt%.
44. The sorbent of claim 43, wherein: the active component Cu accounts for 5-20 wt% of the element; the mass content of the auxiliary agent rare earth metal is 1wt% -3 wt% calculated by element; the content of the carrier is 78wt% -93 wt%.
45. The sorbent of claim 42, wherein: the specific surface area of the adsorbent is 1000-3000 m 2 And the active component is embedded into the amorphous defects of the petroleum coke-based activated carbon and the activated carbon graphite microchip layer, and the size of the metal crystal grains of the active component is 1-7 nm.
46. The sorbent of claim 42, wherein: the specific surface area of the adsorbent is 1500-3000 m 2 (ii)/g; the active component is embedded into the amorphous defect of the petroleum coke-based activated carbon and the activated carbon graphite microchip layer, and the size of the active component metal crystal grain is 2-5 nm.
47. Use of the adsorbent of any one of claims 42 to 46 in carbon monoxide separation, adsorptive separation of ethylene and ethane in refinery dry gas, adsorptive desulfurization, adsorptive toluene.
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CN111375375B (en) * 2018-12-29 2022-06-07 中国石油化工股份有限公司 Desulfurization adsorbent and preparation method thereof
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4713090A (en) * 1985-09-17 1987-12-15 Kansai Netsukagaku Kabushiki Kaisha Adsorbent for separation-recovery of CO, preparing method thereof and process for separation-recovery of high purity CO, using the adsorbent
CN1411903A (en) * 2001-10-19 2003-04-23 石油大学(北京) Micropore carbon adsorbent for storing natural gas and its preparation method
CN101175692A (en) * 2005-03-14 2008-05-07 普莱克斯技术有限公司 Catalytic adsorbents for mercury removal from flue gas and methods of manufacture therefor
DE102007004351A1 (en) * 2007-01-29 2008-07-31 Evonik Degussa Gmbh Solid catalyst for production of acrolein by dehydration of glycerol, contains a tungsten compound and a promoter selected from various metal compounds and-or montmorillonite or acid zeolite
BRPI0802431A2 (en) * 2008-07-28 2010-03-23 Petroleo Brasileiro Sa process of removal of silicon compounds from hydrocarbon streams

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62176540A (en) * 1985-10-18 1987-08-03 Nippon Steel Corp Method for activating adsorbent for separating carbon monoxide
FR2668465B1 (en) * 1990-10-30 1993-04-16 Inst Francais Du Petrole PROCESS FOR REMOVAL OF MERCURY OR ARSENIC IN A FLUID IN THE PRESENCE OF A MASS OF MERCURY AND / OR ARSENIC CAPTATION.
CN1151878C (en) * 2000-09-29 2004-06-02 北京大学 Copper aluminium-cerium aluminium compound oxide combustion catalyst, its preparation and use
CN1693189A (en) * 2005-04-28 2005-11-09 华东理工大学 Method for preparing high ratio surface area active carbon of middle pore-riched
CN101480603B (en) * 2008-12-30 2011-05-04 上海纳米技术及应用国家工程研究中心有限公司 Nitrous oxides gas adsorbing substance and preparation method thereof
US8356992B2 (en) * 2009-11-30 2013-01-22 Chevron U.S.A. Inc. Method and system for capturing carbon dioxide in an oxyfiring process where oxygen is supplied by regenerable metal oxide sorbents
CN101927152B (en) * 2010-03-12 2012-10-03 大连海鑫化工有限公司 High-strength gas purifying and separating adsorbent as well as preparation and application thereof
CN102000547B (en) * 2010-11-17 2012-12-19 上海纳米技术及应用国家工程研究中心有限公司 Cuprous chloride-modified honeycomb activated carbon adsorbing material and preparation method thereof
CN103894202B (en) * 2014-04-11 2015-10-28 中国石油天然气集团公司 A kind of oil-polluted water ozone catalytic oxidation catalyst and manufacture method thereof
CN104492375B (en) * 2014-12-15 2017-03-15 西南化工研究设计院有限公司 A kind of adsorbent for reclaiming CO from industrial tail gas and its preparation method and application
CN105749858A (en) * 2016-01-11 2016-07-13 昆明理工大学 Preparation method of carbon monoxide absorbent
CN105819443B (en) * 2016-03-04 2019-03-26 四川大学 It is a kind of to prepare active carbon and method using discarded plant based biomass
CN106517195A (en) * 2016-11-14 2017-03-22 天津工业大学 Method for preparing porous carbon from phosphate activated biomass and applying porous carbon to supercapacitors

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4713090A (en) * 1985-09-17 1987-12-15 Kansai Netsukagaku Kabushiki Kaisha Adsorbent for separation-recovery of CO, preparing method thereof and process for separation-recovery of high purity CO, using the adsorbent
CN1411903A (en) * 2001-10-19 2003-04-23 石油大学(北京) Micropore carbon adsorbent for storing natural gas and its preparation method
CN101175692A (en) * 2005-03-14 2008-05-07 普莱克斯技术有限公司 Catalytic adsorbents for mercury removal from flue gas and methods of manufacture therefor
DE102007004351A1 (en) * 2007-01-29 2008-07-31 Evonik Degussa Gmbh Solid catalyst for production of acrolein by dehydration of glycerol, contains a tungsten compound and a promoter selected from various metal compounds and-or montmorillonite or acid zeolite
BRPI0802431A2 (en) * 2008-07-28 2010-03-23 Petroleo Brasileiro Sa process of removal of silicon compounds from hydrocarbon streams

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Copper loaded on activated carbon as an efficient adsorbent for removal of methylene blue;Shu Jianhua等;《RSC ADVANCES》;20170315;第7卷(第24期);全文 *
Surface functionalized carbon microspheres for the recovery of copper ion from refinery wastewater;Mondal Subrata等;《KOREAN JOURNAL OF CHEMICAL ENGINEERING》;20180117;第35卷(第1期);全文 *

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