CN114653338B - Simultaneously removing CS in natural gas 2 Nitrogen-doped metal ion loaded adsorbent with Hg and preparation method thereof - Google Patents
Simultaneously removing CS in natural gas 2 Nitrogen-doped metal ion loaded adsorbent with Hg and preparation method thereof Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000003463 adsorbent Substances 0.000 title claims abstract description 54
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 40
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 73
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 25
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- 238000001179 sorption measurement Methods 0.000 claims abstract description 23
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 22
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- 239000010949 copper Substances 0.000 description 38
- 239000000243 solution Substances 0.000 description 37
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- 229910052746 lanthanum Inorganic materials 0.000 description 5
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- 238000004364 calculation method Methods 0.000 description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 2
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 125000001741 organic sulfur group Chemical group 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 201000001320 Atherosclerosis Diseases 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005267 amalgamation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
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- 238000006460 hydrolysis reaction Methods 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
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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
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- 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
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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
- B01J20/0203—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
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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
- B01J20/0203—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
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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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/103—Sulfur containing contaminants
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Abstract
The invention discloses a method for simultaneously removing CS in natural gas 2 And Hg-doped metal ion loaded adsorbent and a preparation method thereof, and relates to the technical field of desulfurization and demercuration adsorbents. Firstly, cross-linking sodium alginate with ethylene glycol methacrylate and acrylic acid, and then freeze-drying to obtain a multipolar pore material of a sodium alginate film; thereafter at N 2 And NH 3 Carbonizing under the condition to obtain an adsorption material doped with nitrogen; finally, the obtained activated carbon and Cu are immersed by adopting an ultrasonic/microwave auxiliary impregnation method 2+ 、La 3+ 、Fe 3+ And (3) mixing the salt solution of the metal ions to load the metal ions into the nitrogen-doped adsorption material, so as to prepare the nitrogen-doped metal oxide load type adsorbent with the multistage holes. The nitrogen-doped metal ion loaded adsorbent can simultaneously remove CS at room temperature 2 And Hg, and the removal efficiency is more than 95 percent.
Description
Technical Field
The invention relates to the technical field of desulfurization and demercuration adsorbents, in particular to a method for simultaneously removing CS in natural gas 2 And Hg nitrogen-doped metal ion loaded adsorbent and a preparation method thereof.
Background
Natural gas is used as a high-quality and high-efficiency clean energy source, and development and utilization of the natural gas are widely paid attention to. The main component of the raw material natural gas is mainly methane, and in addition, the raw material natural gas also contains water and CO 2 、H 2 S, organic Sulfur (COS, CS) 2 、CH 3 SH, etc.), heavy hydrocarbons, N 2 Impurities such as mercury and arsenic. Wherein carbon disulphide (CS) 2 ) Listed as a harmful gaseous contaminant, is considered one of the most toxic solvents, and contacts CS in poorly ventilated plants 2 Can accelerate the development of atherosclerosis and coronary artery disease. Elemental mercury has high toxicity and biological enrichment, and can cause great harm to human life and environment when entering the atmosphere in the natural gas processing or combustion process. In addition, during the low temperature treatment of natural gas, mercury accumulation easily corrodes the aluminum heat exchanger through amalgamation and liquid metal embrittlement mechanisms, resulting in safety accidents.
The natural gas purification process in the prior art is provided with independent desulfurization and mercury removal units, and gaseous sulfur and elemental mercury are independently removed in different devices, so that the following problems exist:
(1) The removal accuracy is low. The existing desulfurizing agent has poor removal performance on organic sulfur, and meanwhile, impurities such as acid gas, water vapor, liquid entrainment and the like contained in natural gas can obviously reduce the desulfurization and mercury removal efficiency. (2) secondary pollution is serious. The desulfurization waste liquid, desulfurization solid waste and waste mercury removal agent generated by natural gas purification in China are respectively up to 400 ten thousand tons, 60 ten thousand tons and more than 10 ten thousand tons. The desulfurization waste liquid and the desulfurization solid waste are rich in supersaturated sulfite, sulfate, sulfide and heavy metal, have higher biotoxicity, and cause serious secondary pollution to underground water resources and soil by direct discharge or accumulation; the waste mercury removing agent is a typical solid dangerous waste, and mercury in the surface adsorption state of the waste mercury removing agent is easy to escape again along with the change of environmental conditions, so that serious harm is caused to the atmosphere and water resources. (3) disposal of the spent adsorbent. At present, a great deal of research is carried out on desulfurization and mercury removal waste disposal by Chinese scholars, and favorable results are obtained. For example, a desulfurization waste liquid salt extraction recycling technology, a desulfurization solid waste neutralization method treatment technology, a mercury-containing hazardous waste solidification stabilization technology and the like. The technology effectively realizes the reduction and reclamation of wastes, has good economic and environmental benefits, but can not meet the near zero emission requirement of the natural gas desulfurization and demercuration wastes due to the limited treatment scale. And (4) the operation energy consumption is high. The desulfurization and demercuration units are respectively and independently arranged to cause that the devices and equipment in the purification process are more, the process is complex and the pressure drop is too high, thereby improving the operation energy consumption and the operation cost.
However, at present, CS removal is concerned with natural gas 2 And Hg are mainly carried out by removing single substances through different catalysts, and the respective catalysts have corresponding defects. For example, application No. 201410424352.X discloses a mercury scavenger made from the following components: the invention provides a treatment method for treating mercury-containing coal-fired flue gas by using an amine, carbon disulfide and potassium hydroxide. But the mercury scavenger is not suitable for removing carbon disulfide and mercury in natural gas. Application number 201710816125.5 discloses a natural gas mercury removal adsorbent and a preparation method thereof, wherein the natural gas mercury removal adsorbent comprises the following components: al (Al) 2 O 3 The mass fraction is 82% -95%, the mass fraction of sulfur is 4% -12%, and the mass fraction of copper sulfide is 1% -6%. The application number 202110301992.1 discloses a carbon aerogel microsphere for adsorbing carbonyl sulfide and mercury and a preparation method thereof, wherein metal is loaded on sodium alginate and is calcined at high temperature to obtain an adsorbent, the adopted metal is Sn and Fe, the combined removal of sulfur and mercury in natural gas is developed at present to control the development trend of pollutants,has high research value.
Disclosure of Invention
One of the purposes of the invention is to provide a method for simultaneously removing CS in natural gas 2 And Hg-doped metal ion loaded adsorbent, and the adsorbent prepared by the method can simultaneously remove CS in natural gas at room temperature 2 And Hg, and has excellent desulfurization and demercuration effects.
In order to achieve the above object, the present invention brings the following advantageous technical effects:
CS in natural gas is got rid of simultaneously 2 And the preparation method of the Hg nitrogen-doped metal ion loaded adsorbent sequentially comprises the following steps:
s1, respectively mixing ethylene glycol methacrylate and acrylic acid serving as cross-linking agents with sodium alginate solutions with different concentrations and different pH values, stirring at 20-40 ℃ for reaction for 5-7 h, and freeze-drying to obtain a sodium alginate film;
s2, putting the sodium alginate film in N 2 And NH 3 Carbonizing at 500-550 ℃ in the atmosphere to obtain the nitrogen-doped adsorption material;
s3, cu (NO) 3 ) 2 Solution, la (NO) 3 ) 3 Solution and Fe (NO) 3 ) 3 Mixing the solutions together, and using ultrasonic immersion method to make metal ion Cu 2+ 、La 3+ 、Fe 3+ Loading the mixture on a nitrogen-doped adsorption material to obtain the nitrogen-doped metal ion loaded adsorbent.
As a preferable scheme of the invention, in the step S1, the mass ratio of the sodium alginate to the cross-linking agent is 1:0.1-1.1, the concentration of the sodium alginate solution is 0.5-5 w%, and the pH of the sodium alginate solution is 5-7.
As another preferable mode of the invention, in the step S2, the heating rate in carbonization is set to be 5 ℃/min, and the carbonization time is 1-4 h.
Further preferably, in step S3, in the nitrogen-doped metal ion-loaded adsorbent, the loading amount of the active metal ions is not less than 50% of the total mass of the adsorbent, wherein three metal ions Cu 2+ 、La 3+ 、Fe 3+ The mass ratio of (2) is 1-2:1-2.
Further preferably, in step S3, the ultrasonic impregnation time is 15-30 min, the temperature is 35-40 ℃, and the ultrasonic frequency is 4-10 kHz.
Another object of the present invention is to provide a method for simultaneously removing CS from natural gas 2 The nitrogen-doped metal ion loaded adsorbent prepared by the preparation method of the nitrogen-doped metal oxide loaded adsorbent of Hg is a porous carbon shell structure with adjustable pore diameter, and porous carbon shell structures with different pore diameters can be obtained by adjusting the mass ratio of sodium alginate to a cross-linking agent.
The application of the nitrogen-doped metal oxide supported adsorbent comprises the following steps: the nitrogen-doped metal ion supported adsorbent is placed in a fixed bed reactor, and the test conditions set the airspeed to 30000h -1 The temperature is 30 ℃; the simulated gas composition is as follows in percentage by mass: 30% CH 4 、20％CO、40％H 2 ，400ppm CS 2 Nitrogen was equilibrated.
Further, three metal ions Cu 2+ 、La 3+ 、Fe 3+ When the mass ratio of the metal ions is 1:2:2, the obtained adsorbent has the best mercury removal and desulfurization effects at the same time.
Further, the mass ratio of the sodium alginate to the cross-linking agents ethylene glycol methacrylate and acrylic acid is 1:0.5.
The following main reaction principle of the nitrogen-doped metal oxide supported adsorbent of the invention and the simultaneous removal of CS in natural gas 2 And the Hg removal principle are described below.
Firstly, ethylene glycol methacrylate and acrylic acid are used as cross-linking agents to be cross-linked with sodium alginate, and oxygen, carboxyl and other groups can be provided to the sodium alginate through the cross-linking agents, so that the adsorbent with multipolar holes is obtained;
secondly, placing the sodium alginate film obtained after crosslinking in a tube furnace, and adding the sodium alginate film into N 2 +NH 3 Carbonizing under atmosphere to prepare nitrogen-doped adsorption material;
finally, absorbing nitrogen by using ultrasonic auxiliary dipping methodMaterial and Cu 2+ 、La 3+ 、Fe 3+ Mixing the salt solutions of the metal ions to load the metal ions into the nitrogen-doped active carbon, and preparing the nitrogen-doped metal oxide load type adsorption material with different pore sizes. The invention enables CS to be carried by loading metal as an active site 2 After conversion to COS hydrolysis to H 2 S is converted into metal sulfide, and the metal sulfide can be continuously used as an active site to react with Hg to generate HgS, so that CS is removed simultaneously 2 And Hg.
Selecting ethylene glycol methacrylate and acrylic acid as cross-linking agents to cross-link with sodium alginate, and adding oxygen, carboxyl and the like into the sodium alginate to obtain the adsorbent with multipolar holes; the rare earth element lanthanum is easy to combine with sulfur element, and the invention ensures the mode of carbonizing before loading metal ions, and Cu is loaded after carbonization 2+ 、Fe 3+ 、La 3+ To increase the adsorption of CS by the adsorbent 2 And Hg, and ferric oxide may decompose under high temperature conditions to form ferric oxide, and carbonization followed by loading may avoid this.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) In terms of raw material selection, the invention selects the sodium alginate with low cost and easy availability principle, has wide sources and high carbon content, and is a raw material with sustainable development characteristic.
(2) Examples study of the different loading ratios of actives to CS 2 And the influence of Hg removal efficiency, researches show that the sodium alginate film obtained after crosslinking is carbonized first, and then active metal is loaded on the sodium alginate film in an ultrasonic-assisted dipping mode, so that the desulfurization and demercuration efficiency of the prepared adsorption material is best.
(3) Experiments further prove that Cu 2+ 、La 3+ 、Fe 3+ When the adsorbent is loaded into the nitrogen-doped sodium alginate according to the mass ratio of 1:2:2, the desulfurization and mercury removal effects of the adsorbent are best.
In summary, the invention selects sodium alginate as raw material, firstly, the sodium alginate is crosslinked with ethylene glycol methacrylate and acrylic acid, and then the cold treatment is carried outFreeze-drying to obtain multipolar pore material; thereafter at N 2 And NH 3 Carbonizing under the condition to obtain an adsorption material doped with nitrogen; finally, the obtained activated carbon and Cu are immersed by adopting an ultrasonic/microwave auxiliary impregnation method 2+ 、La 3 + 、 Fe 3+ And (3) mixing the salt solution of the metal ions to load the metal ions into the nitrogen-doped adsorption material, so as to prepare the nitrogen-doped metal ion load type adsorbent with the multistage holes. The adsorbent has good CS at room temperature 2 And Hg simultaneous removal efficiency.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 shows that the total active metal loading is 50%, cu: la: sorbent CS when fe=1:1:1, 1:1:2, 1:2:1, 1:2:2, 2:1:1, 2:1:2, 2:2:1 2 The removal efficiency (carbonization temperature 500 ℃ C., carbonization time 3 h);
FIG. 2 shows CS of the adsorbent at carbonization times of 1, 2, 3, and 4 hours, respectively 2 And Hg removal efficiency (total loading of 50wt%, cu: la: fe=1:2:2);
FIG. 3 is a schematic diagram of the cross-linking of sodium alginate with ethylene glycol methacrylate and acrylic acid according to the present invention.
Detailed Description
The invention provides a method for simultaneously removing CS in natural gas 2 And Hg-doped metal ion loaded adsorbent and a preparation method thereof, in order to make the advantages and technical scheme of the invention clearer and more definite, the invention is further described below with reference to specific examples.
The raw materials required by the invention can be purchased through commercial sources.
The evaluation method of the catalyst activity comprises the following steps:
the detection method comprises the following steps: the outlet CS was detected using a fixed bed reactor, using a gas chromatograph (GC-9720 Plus) and a mercury meter (Lumex RA-915) 2 And Hg concentration.
Experimental conditions: space velocity 30000h -1 The temperature was 30 ℃. The simulated gas composition is: 30% CH 4 ，20％CO，40％H 2 ，400ppm CS 2 Nitrogen was equilibrated. The water was supplied using a saturator system and the Relative Humidity (RH) was used to represent the water content. Heating the Hg permeate tube in a water bath provides Hg in the simulated gas. A mass flow controller was used to control the total flow to 1L/min.
The evaluation method comprises the following steps: can pass CS in front and back smoke 2 The concentration is varied to obtain desulfurization efficiency. The calculation method is as shown in formula (1):
the capacity represents the mass of the adsorbent for adsorbing Hg and COS per unit mass, and the calculation method is shown as the formula (2)
Example 1:
firstly, preprocessing sodium alginate: 4g sodium alginate was weighed and completely dissolved in 396mL deionized water to prepare a 1wt% sodium alginate solution. The mass ratio of the sodium alginate to the cross-linking agent ethylene glycol methacrylate to the acrylic acid is 1:0.5, and the cross-linking is carried out for 6 hours at 30 ℃; pouring the crosslinked solution into a mould, and freeze-drying at-70 to-30 ℃ for 24-72 hours to obtain a sodium alginate film; the crosslinking mechanism of the sodium alginate and the crosslinking agent is shown in figure 3;
secondly, placing the sodium alginate film in a tube furnace to form a sodium alginate film in N 2 +NH 3 Carbonizing at 500 ℃ under atmosphere (the heating rate is set to 5 ℃/min) for 3 hours to prepare the nitrogen-doped adsorption material;
step three, 1.2g of Cu (NO) is weighed 3 ) 2 ·3H 2 O, adding into 24mL deionized water to prepare Cu (NO) 3 ) 2 A solution; weigh 1.5gLa (NO) 3 ) 3 ·6H 2 O, adding into 11mL deionized water to prepare La (NO) 3 ) 3 The solution was weighed out simultaneously 5.8g of Fe (NO 3 ) 3 ·9H 2 O, adding into 66mL deionized water to prepare Fe (NO) 3 ) 3 Solution, so that mass ratio of Cu to La:Fe＝1:2:2。
Fourth, adding 25mL of 0.2mol/L Cu (NO) into the carbonized nitrogen-doped adsorption material 3 ) 2 Solution, 12mL of 0.2mol/L La (NO) 3 ) 3 Solution and 72ml of 0.2mol/L Fe (NO) 3 ) 3 A solution. The obtained activated carbon is impregnated with Cu by using an ultrasonic auxiliary impregnation method 2+ 、La 3+ 、Fe 3+ Mixing the salt solution of the metal ions to load the metal ions into the nitrogen-doped active carbon to prepare the nitrogen-doped metal oxide ion-loaded adsorption material with multipolar holes.
Experiments were carried out on the nitrogen-doped metal ion-loaded adsorption material prepared in this example at room temperature,
space velocity 30000h -1 The temperature was 30 ℃. The simulated natural gas 30% CH is selected 4 ，20％CO，40％H 2 ，400ppm CS 2 And balancing nitrogen, heating the Hg permeation tube in a water bath to make Hg concentration 300 mug/m 3 for experiments.
The experimental result shows that the carbon disulfide removal rate is always 100% within 120min, the mercury removal efficiency is kept 100% within 150min, and the desulfurization rate reaches 96% and the mercury removal rate reaches 97% when the mass ratio of the sodium alginate to the cross-linking agent ethylene glycol methacrylate to the acrylic acid is 1:0.5.
Example 2:
the difference from example 1 is that in the third step Cu: la: fe=1:1:1.
Space velocity 30000h -1 The temperature was 30 ℃. The simulated natural gas 30% CH is selected 4 ，20％CO，40％H 2 ，400ppm CS 2 The Hg permeation tube was heated in a water bath to a Hg concentration of 300. Mu.g/m by equilibrating the nitrogen gas 3 Experiments were performed. The desulfurization efficiency is kept at 100% in 60min when Cu is La and Fe is=1:1:1; the mercury removal efficiency was 100% in 60min, and then began to drop.
Example 3:
the difference from example 1 is that in the third step Cu: la: fe=1:1:2.
Space velocity 30000h -1 The temperature was 30 ℃. The simulated natural gas 30% CH is selected 4 ，20％CO，40％H 2 ，400ppm CS 2 The Hg permeation tube was heated in a water bath to a Hg concentration of 300. Mu.g/m by equilibrating the nitrogen gas 3 Experiments were performed. The experimental result is kept at 100% in 90min of desulfurization efficiency when Cu is La and Fe is=1:1:2; the mercury removal efficiency is kept at 100% within 100 min.
Example 4:
the difference from example 1 is that in the third step Cu: la: fe=1:2:1.
Space velocity 30000h -1 The temperature was 30 ℃. The simulated natural gas 30% CH is selected 4 ，20％CO，40％H 2 ，400ppm CS 2 The Hg permeation tube was heated in a water bath to a Hg concentration of 300. Mu.g/m by equilibrating the nitrogen gas 3 Experiments were performed. The experimental result is kept at 100% in 60min of desulfurization efficiency when Cu is La and Fe is=1:2:1; the mercury removal efficiency is maintained at 100% within 90 min.
Example 5:
the difference from example 1 is that in the third step Cu: la: fe=2:1:1.
Space velocity 30000h -1 The temperature was 30 ℃. The simulated natural gas 30% CH is selected 4 ，20％CO，40％H 2 ，400ppm CS 2 The Hg permeation tube was heated in a water bath to a Hg concentration of 300. Mu.g/m by equilibrating the nitrogen gas 3 Experiments were performed. The experimental result shows that the desulfurization efficiency is kept at 100% in 60min and the mercury removal efficiency is kept at 100% in 80min when the Cu is La and the Fe is=2:1:1.
Example 6:
the difference from example 1 is that in the third step Cu: la: fe=2:1:2.
Space velocity 30000h -1 The temperature was 30 ℃. The simulated natural gas 30% CH is selected 4 ，20％CO，40％H 2 ，400ppm CS 2 The Hg permeation tube was heated in a water bath to a Hg concentration of 300. Mu.g/m by equilibrating the nitrogen gas 3 Experiments were performed. The experimental result is kept at 100% in 90min and is reduced to 95% in 120min and 89% in 150min when the desulfurization efficiency is 90min when the desulfurization efficiency is Cu and La are Fe=2:1:2; the mercury removal efficiency remained at 100% for 100min and then decreased to 92%.
Example 7:
the difference from example 1 is that in the third step Cu: la: fe=2:2:1.
Space velocity 30000h -1 The temperature was 30 ℃. The simulated natural gas 30% CH is selected 4 ，20％CO，40％H 2 ，400ppm CS 2 The Hg permeation tube was heated in a water bath to a Hg concentration of 300. Mu.g/m by equilibrating the nitrogen gas 3 Experiments were performed. The experimental result was kept at 100% for 90min at Cu: la: fe=2:2:1, and then dropped to 98.6% at 120 min; the mercury removal efficiency remained 100% at 120min, then decreased to 95%.
From the above examples 1 to 7, it is understood that the adsorbent of the present invention has a certain influence on desulfurization and demercuration depending on the ratio of the supported metal.
Example 8:
the difference from example 1 is that in the first step the mass ratio of sodium alginate to the cross-linking agents ethylene glycol methacrylate and acrylic acid is 1:0.1.
Space velocity 30000h -1 The temperature was 30 ℃. The simulated natural gas 30% CH is selected 4 ，20％CO，40％H 2 ，400ppm CS 2 The Hg permeation tube was heated in a water bath to a Hg concentration of 300. Mu.g/m by equilibrating the nitrogen gas 3 Experiments were performed. The experimental result shows that the desulfurization efficiency is 85% and the mercury removal efficiency is 85% at the carbonization temperature of 500 ℃.
Example 9:
the difference from example 1 is that in the first step the mass ratio of sodium alginate to the cross-linking agents ethylene glycol methacrylate and acrylic acid is 1:0.3.
Space velocity 30000h -1 The temperature was 30 ℃. The simulated natural gas 30% CH is selected 4 ，20％CO，40％H 2 ，400ppm CS 2 The Hg permeation tube was heated in a water bath to a Hg concentration of 300. Mu.g/m by equilibrating the nitrogen gas 3 Experiments were performed. The experimental result shows that the desulfurization efficiency is 89% and the mercury removal efficiency is 86% at the carbonization temperature of 500 ℃.
Example 10:
the difference from example 1 is that in the first step the mass ratio of sodium alginate to the cross-linking agents ethylene glycol methacrylate and acrylic acid is 1:0.7.
Space velocity 30000h -1 The temperature was 30 ℃. The simulated natural gas 30% CH is selected 4 ，20％CO，40％H 2 ，400ppm CS 2 The Hg permeation tube was heated in a water bath to a Hg concentration of 300. Mu.g/m by equilibrating the nitrogen gas 3 Experiments were performed. The experimental result shows that the desulfurization efficiency is 95.3% and the mercury removal efficiency is 96% at the carbonization temperature of 500 ℃.
Example 11:
the difference from example 1 is that in the first step the mass ratio of sodium alginate to the cross-linking agents ethylene glycol methacrylate and acrylic acid is 1:0.9.
Space velocity 30000h -1 The temperature was 30 ℃. The simulated natural gas 30% CH is selected 4 ，20％CO，40％H 2 ，400ppm CS 2 The Hg permeation tube was heated in a water bath to a Hg concentration of 300. Mu.g/m by equilibrating the nitrogen gas 3 Experiments were performed. The experimental result shows that the desulfurization efficiency is 89% and the mercury removal efficiency is 88% at the carbonization temperature of 500 ℃.
Example 12:
the difference from example 1 is that in the first step the mass ratio of sodium alginate to the cross-linking agents ethylene glycol methacrylate and acrylic acid is 1:1.1.
Space velocity 30000h -1 The temperature was 30 ℃. The simulated natural gas 30% CH is selected 4 ，20％CO，40％H 2 ，400ppm CS 2 The Hg permeation tube was heated in a water bath to a Hg concentration of 300. Mu.g/m by equilibrating the nitrogen gas 3 Experiments were performed. The experimental result shows that the desulfurization efficiency is 87% and the mercury removal efficiency is 88% at the carbonization temperature of 500 ℃.
Fig. 1 shows that the total active metal loading is 50%, cu: la: sorbent CS when fe=1:1:1, 1:1:2, 1:2:1, 1:2:2, 2:1:1, 2:1:2, 2:2:1 2 And Hg removal efficiency map (carbonization temperature 500 ℃ C., carbonization time 3 h);
FIG. 2 shows CS of the adsorbent for carbonization times of 1, 2, 3, and 4 hours, respectively 2 And Hg removal efficiency (total loading of 50wt%, cu: la: fe=1:2:2);
from fig. 1, it can be derived that: the removal rate of the adsorbents with 7 proportions reaches 100% in 60min, but with the increase of time, cu: la: the adsorbent with Fe=1:2:2 maintains 100% removal rate within 150min, and other proportions of adsorbents are greatly reduced; from fig. 2, it can be derived that: although the CS2 removal rate is the same when the mass ratio of sodium alginate to the cross-linking agent ethylene glycol methacrylate and acrylic acid is 1:0.5 to 1:0.7, the Hg removal rate is higher than when the mass ratio of sodium alginate to the cross-linking agent ethylene glycol methacrylate and acrylic acid is 1:0.5 to be higher than 1:0.7, so that 1:0.5 is the optimal cross-linking ratio.
Comparative example 1:
firstly, preprocessing sodium alginate: 4g sodium alginate was weighed and completely dissolved in 396mL deionized water to prepare a 1wt% sodium alginate solution. The mass ratio of the sodium alginate to the cross-linking agent ethylene glycol methacrylate to the acrylic acid is 1:0.5. Crosslinking for 6h at 30 ℃, pouring the crosslinked solution into a mould, and freeze-drying at-70 to-30 ℃ for 24-72h to obtain the sodium alginate film;
secondly, pouring the crosslinked solution into a mould, and preprocessing the active component material: 1.2g of Cu (NO) was weighed out 3 ) 2 ·3H 2 O, adding into 24mL deionized water to prepare Cu (NO) 3 ) 2 A solution; weigh 1.5gLa (NO) 3 ) 3 ·6H 2 O, adding into 11mL deionized water to prepare La (NO) 3 ) 3 The solution was weighed out simultaneously 5.8g of Fe (NO 3 ) 3 ·9H 2 O, adding into 66mL deionized water to prepare Fe (NO) 3 ) 3 The solution was such that Cu: la: fe=1:2:2.
Thirdly, adding 25mL of 0.2mol/L Cu (NO) into the sodium alginate film 3 ) 2 Solution, 12mL of 0.2mol/L La (NO) 3 ) 3 Solution and 72ml of 0.2mol/L Fe (NO) 3 ) 3 A solution. And loading metal ions into sodium alginate by using an ultrasonic-assisted impregnation method to prepare the sodium alginate aerogel.
Fifthly, placing the sodium alginate aerogel in a tube furnace to obtain N-type sodium alginate aerogel 2 +NH 3 Carbonizing at 500 deg.c (temperature raising rate set to 5 deg.c/min) for 3 hr to obtain metal oxide loadA type adsorbent.
The measurement is as follows: the adsorbent obtained in comparative example 1 had a Hg removal rate of 96% and a CS 2 The removal rate was 89%.
Comparative example 2:
firstly, preprocessing sodium alginate: 4g sodium alginate was weighed and completely dissolved in 396mL deionized water to prepare a 1wt% sodium alginate solution. The mass ratio of the sodium alginate to the cross-linking agent ethylene glycol methacrylate to the acrylic acid is 1:0.5, and the cross-linking is carried out for 6 hours at 30 ℃; pouring the crosslinked solution into a mould, and freeze-drying at-70 to-30 ℃ for 24-72 hours to obtain a sodium alginate film;
secondly, placing the sodium alginate film in a tube furnace to form a sodium alginate film in N 2 +NH 3 Carbonizing at 500 ℃ under atmosphere (the heating rate is set to 5 ℃/min) for 3 hours to prepare the nitrogen-doped adsorption material;
thirdly, preprocessing the active component material: weigh 4.0g Cu (NO) 3 ) 2 ·3H 2 O, adding into 80mL deionized water to prepare Cu (NO) 3 ) 2 The solution was weighed out simultaneously with 4.8g of Fe (NO 3 ) 3 ·9H 2 O, adding into 55mL deionized water to prepare Fe (NO) 3 ) 3 A solution. Adding 85mL of 0.2mol/L Cu (NO) to the carbonized nitrogen-doped adsorption material 3 ) 2 60mL of solution, 0.2mol/L Fe (NO) 3 ) 3 Solution such that Cu: fe=1:2. The obtained activated carbon is impregnated with Cu by using an ultrasonic auxiliary impregnation method 2+ And Fe (Fe) 3+ Mixing the salt solution of the metal ion and loading the metal ion into the nitrogen-doped active carbon to prepare the nitrogen-doped metal oxide loaded adsorption material with multipolar holes.
The measurement is as follows: comparative example 2 adsorbent CS 2 The removal efficiency is 89% and the removal efficiency of Hg is 87%.
Comparative example 3:
firstly, preprocessing sodium alginate: 4g sodium alginate was weighed and completely dissolved in 396mL deionized water to prepare a 1wt% sodium alginate solution. The mass ratio of the sodium alginate to the cross-linking agent ethylene glycol methacrylate to the acrylic acid is 1:0.5, and the cross-linking is carried out for 6 hours at 30 ℃; pouring the crosslinked solution into a mould, and freeze-drying at-70 to-30 ℃ for 24-72 hours to obtain a sodium alginate film; the crosslinking mechanism of the sodium alginate and the crosslinking agent is shown in figure 3;
secondly, placing the sodium alginate film in a tube furnace to form a sodium alginate film in N 2 +NH 3 Carbonizing at 500 ℃ under atmosphere (the heating rate is set to 5 ℃/min) for 3 hours to prepare the nitrogen-doped adsorption material;
step three, 1.2g of Cu (NO) is weighed 3 ) 2 ·3H 2 O, adding into 24mL deionized water to prepare Cu (NO) 3 ) 2 A solution; weigh 2.0gCe (NO) 3 ) 3 ·6H 2 O, adding into 21mL deionized water to prepare Ce (NO) 3 ) 3 The solution was weighed out simultaneously 5.8g of Fe (NO 3 ) 3 ·9H 2 O, adding into 66mL deionized water to prepare Fe (NO) 3 ) 3 The solution was such that the mass ratio Cu: ce: fe=1:2:2.
Fourth, adding 25mL of 0.2mol/L Cu (NO) into the carbonized nitrogen-doped adsorption material 3 ) 2 Solution, 23mL 0.2mol/L Ce (NO) 3 ) 3 Solution and 72ml of 0.2mol/L Fe (NO) 3 ) 3 A solution. The obtained activated carbon is impregnated with Cu by using an ultrasonic auxiliary impregnation method 2+ 、Ce 3+ 、Fe 3+ Mixing the salt solution of the metal ion and loading the metal ion into the nitrogen-doped active carbon to prepare the nitrogen-doped metal oxide loaded adsorption material with multipolar holes.
The measurement is as follows: comparative example 2 adsorbent CS 2 The removal efficiency is 93% and the removal efficiency of Hg is 89%.
From the above examples 1 to 12, it is known that the adsorbent of the present invention has a certain influence on desulfurization and demercuration due to the different proportions of sodium alginate and cross-linking agent ethylene glycol methacrylate and acrylic acid, and has different pore structures of the carrier and different efficiencies, and the desulfurization and demercuration rate is optimal when the proportion of sodium alginate and cross-linking agent ethylene glycol methacrylate and acrylic acid is 1:0.5.
The parts not described in the invention can be realized by referring to the prior art.
It is noted that any equivalent or obvious modification made by those skilled in the art under the teachings of this specification shall fall within the scope of this invention.
Claims (3)
1. Nitrogen-doped metal oxide supported adsorbent as catalyst for simultaneous removal of CS in natural gas 2 And the application in Hg, characterized in that the preparation method of the nitrogen-doped metal oxide loaded adsorbent sequentially comprises the following steps:
s1, respectively mixing ethylene glycol methacrylate and acrylic acid serving as cross-linking agents with sodium alginate solutions with different concentrations and different pH values, stirring at 20-40 ℃ for reaction for 5-7 h, and freeze-drying to obtain a sodium alginate film;
s2, putting the sodium alginate film in N 2 And NH 3 Carbonizing at 500-550 ℃ in the atmosphere to obtain the nitrogen-doped adsorption material;
s3, cu (NO) 3 ) 2 Solution, la (NO) 3 ) 3 Solution and Fe (NO) 3 ) 3 Mixing the solutions together, and using ultrasonic immersion method to make metal ion Cu 2+ 、La 3+ 、Fe 3+ Loading the nitrogen-doped metal ion loaded adsorbent on a nitrogen-doped adsorption material to obtain the nitrogen-doped metal ion loaded adsorbent;
in the step S1, the mass ratio of the sodium alginate to the cross-linking agent is 1:0.5 or 1:0.7, the concentration of the sodium alginate solution is 0.5-5 wt%, and the pH of the sodium alginate solution is 5-7;
in the step S3, the ultrasonic dipping time is 15-30 min, the temperature is 35-40 ℃, and the ultrasonic frequency is 4-10 kHz;
in the step S3, in the nitrogen-doped metal ion loaded adsorbent, the loading amount of active metal ions is not less than 50% of the total mass of the adsorbent, and three metal ions Cu 2+ 、La 3+ 、Fe 3+ The mass ratio of (2) is 1:2:2;
the application is that the nitrogen-doped metal ion loaded adsorbent is placed in a fixed bed reactor, and the test condition sets the airspeed to 30000h -1 The temperature is 30 ℃; the simulated gas composition is as follows in percentage by mass: 30% CH 4 、20％CO、40％H 2 ，400ppm CS 2 And balancing nitrogen, and heating the Hg permeation tube in a water bath to ensure that the Hg concentration is 300 mug/m.
2. The nitrogen-doped metal oxide-loaded adsorbent as claimed in claim 1 for simultaneous removal of CS from natural gas as a catalyst 2 And Hg, characterized by: in the step S2, the heating rate during carbonization is set to be 5 ℃/min, and the carbonization time is 1-4 h.
3. The nitrogen-doped metal oxide-loaded adsorbent as claimed in claim 1 for simultaneous removal of CS from natural gas as a catalyst 2 And Hg, characterized by: the nitrogen-doped metal oxide supported adsorbent is a porous carbon shell structure with adjustable pore diameter.
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