CN111804293B - Preparation method of porous alumina loaded transition metal and application of porous alumina loaded transition metal in removal of COS - Google Patents

Preparation method of porous alumina loaded transition metal and application of porous alumina loaded transition metal in removal of COS Download PDF

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CN111804293B
CN111804293B CN202010458183.7A CN202010458183A CN111804293B CN 111804293 B CN111804293 B CN 111804293B CN 202010458183 A CN202010458183 A CN 202010458183A CN 111804293 B CN111804293 B CN 111804293B
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transition metal
aluminum
porous alumina
acid
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江莉龙
刘时球
刘福建
梁诗景
肖益鸿
曹彦宁
郑勇
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China Ryukyu Technology Co ltd
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Abstract

The invention provides a preparation method of porous alumina supported transition metal and application thereof in COS removal, wherein the preparation method of the porous alumina supported transition metal comprises the following steps: grinding the precursor compound of aluminum, transition metal salt and soft template, then dripping acid, solidifying, washing, drying and roasting. The preparation method adopts a grinding mode, does not need to add an organic solvent, and does not cause harm to the environment; the washing step after solidification can improve the pore structure and specific surface area of the catalyst; a drying step before calcination, which can prevent pore blocking and increase the specific surface area of the catalyst; the soft template can be converted into carbon dioxide and water to be removed through a roasting step, and the precursor compound of aluminum is converted into aluminum oxide and carries transition metal, so that the catalytic performance of the aluminum oxide is improved; and the preparation method is simple, and the prepared porous alumina loaded transition metal has good stability and high COS conversion rate.

Description

Preparation method of porous alumina loaded transition metal and application of porous alumina loaded transition metal in removal of COS
Technical Field
The invention relates to the technical field of catalysts, in particular to a preparation method of porous alumina supported transition metal and application thereof in COS removal.
Background
Carbonyl sulfide (COS) widely exists in chemical raw material gas produced by using coal, coke, residual oil, natural gas and the like as raw materials, and sulfide not only corrodes pipeline equipment, but also causes sulfur poisoning to catalysts in downstream process flows to deactivate the catalysts. The removal of carbonyl sulfide has important significance.
The COS removing method mainly comprises a dry method and a wet method, wherein the wet method comprises an organic amine absorbing method, a potassium hydroxide absorbing method and the like, and has the advantages of large treated air flow and low organic sulfur removing rate and poor gas selectivity; compared with the wet method, the dry method has the advantages of high desulfurization precision, simple operation and the like, and mainly comprises a hydrolysis conversion method, an oxidation conversion method and a hydrogenation conversion method. Most of the water vapor required in the hydrolysis process of the hydrolysis conversion method is already in the raw material gas, and no additional addition is needed; and the reaction does not need a hydrogen source; compared with the oxidation conversion method and the hydro-conversion method, the method has the advantages of energy consumption saving, low temperature, no consumption of raw materials, less side reaction and the like. Therefore, the hydrolytic conversion method is most widely used.
The most commonly used hydrolysis catalysts are those prepared from Al 2 O 3 As a carrier, other active components or auxiliary agents are loaded, so that the catalytic activity is improved, and the COS hydrolysis conversion rate is improved. At Al 2 O 3 The active components loaded on the catalyst are alkali metal, alkaline earth metal and transition metal oxides. For example, chinese patent document CN106861665A discloses an alumina carbonylThe preparation method of the sulfur catalyst comprises the following steps of (1) providing soluble aluminum salt, polystyrene microspheres, mesoporous template agent P123, potassium oxalate, oxalic acid, glycol, methanol, absolute ethyl alcohol, fatty alcohol polyoxyethylene ether and distilled water; (2) Preparing a solution of an alumina precursor, preparing a solution of a mesoporous template agent, preparing a macroporous template of polystyrene microspheres and preparing an active component precursor potassium oxalate coordination solution; (3) Mixing the solution of the alumina precursor and the solution of the mesoporous template agent to obtain a mixed solution; (4) Immersing the polystyrene microsphere macroporous template in the mixed solution and filling the mixed solution into the polystyrene microsphere macroporous template to obtain a primary complex; (5) Spraying and adding the active component precursor potassium oxalate coordination solution into the primary complex and allowing the active component precursor potassium oxalate coordination solution to permeate into the primary complex so as to obtain a secondary complex; (6) Roasting the secondary complex by a two-stage temperature programming roasting method to obtain the alumina carbonyl sulfide hydrolysis catalyst with the step holes.
Although the alumina carbonyl sulfide catalyst prepared by the method has good desulfurization effect, the preparation method is complex in preparation process, and a large amount of organic solvents are used to pollute the environment.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that the preparation method of the alumina carbonyl sulfide catalyst in the prior art is complicated and a large amount of organic solvent is used in the preparation process, thereby providing a preparation method of porous alumina supported transition metal and application thereof in removing COS.
Therefore, the invention provides the following technical scheme:
a preparation method of porous alumina supported transition metal comprises the following steps:
grinding the precursor compound of aluminum, transition metal salt and soft template, then dripping acid, solidifying, washing, drying and roasting.
Further, the grinding time is 3-10min.
Further, the molar ratio of the precursor compound of aluminum to the transition metal salt is (8-12): 0.02-0.04;
the mass ratio of the precursor compound of aluminum to the soft template is (1.8-2.2) (0.125-1);
the mass volume ratio of the precursor compound of aluminum to the acid is (1.8-2.2) g: (0.01-0.1) ml.
Further, the curing temperature is 60-180 ℃ and the curing time is 1-24 hours.
Further, the solvent used for washing is ethanol;
the drying temperature is 60-80 ℃ and the drying time is 6-10h.
Further, the roasting temperature is 400-550 ℃, the time is 1-24h, and the heating rate is 2-5 ℃/min.
Further, the precursor compound of Al is at least one of aluminum isopropoxide, aluminum isobutanol, aluminum sec-butoxide and aluminum ethoxide;
the transition metal salt is acetate and/or citrate of transition metal;
the soft template is Cetyl Trimethyl Ammonium Bromide (CTAB) and/or Polyethylenimine (PEI);
the acid is at least one of acetic acid, phosphoric acid, sulfuric acid, formic acid, hydrochloric acid, oxalic acid and citric acid.
Further, the acetate is at least one of iron acetate, cobalt acetate, nickel acetate, copper acetate and zinc acetate;
the citrate is at least one of ferric citrate, cobalt citrate, nickel citrate, cupric citrate and zinc citrate.
The invention also provides the porous alumina supported transition metal prepared by the preparation method of the porous alumina supported transition metal.
The invention also provides application of the porous alumina supported transition metal prepared by the preparation method of the porous alumina supported transition metal in removing COS.
The technical scheme of the invention has the following advantages:
1. the preparation method of the porous alumina supported transition metal provided by the invention comprises the following steps: grinding the precursor compound of aluminum, transition metal salt and soft template, then dripping acid, solidifying, washing, drying and roasting. According to the preparation method, an organic solvent is not required to be added in a grinding mode, so that the harm to the environment is avoided, the pressure is not generated in the reaction process, and the large-scale production is facilitated; the precursor compound of unreacted aluminum and the soft template can be washed away in the washing step after solidification, so that the pore structure and the specific surface area of the catalyst are improved; a drying step before calcination, which can prevent pore blocking and increase the specific surface area of the catalyst; the soft template can be converted into carbon dioxide and water to be removed through a roasting step, and the precursor compound of aluminum is converted into aluminum oxide and carries transition metal, so that the catalytic performance of the aluminum oxide is improved; and the preparation method is simple, and the prepared porous alumina loaded transition metal has high conversion rate and good stability on carbonyl sulfide (COS).
2. According to the preparation method of the porous alumina supported transition metal, provided by the invention, the time for grinding is limited, so that the catalytic performance and stability of the prepared porous alumina supported transition metal can be further improved; preventing poor distribution of pore structures due to too short grinding time; the milling time is too long, resulting in a slight clogging of the pore size.
3. According to the preparation method of the porous alumina supported transition metal, the pore structure, the formability, the specific surface area and the catalytic performance of the prepared porous alumina supported transition metal can be further improved by limiting the use amounts of the precursor compound of aluminum, the transition metal salt, the soft template and the acid.
4. According to the preparation method of the porous alumina supported transition metal, provided by the invention, the pore size distribution, the specific surface area and the catalytic performance of the prepared porous alumina supported transition metal can be further improved by limiting the curing temperature and the curing time.
5. According to the preparation method of the porous alumina supported transition metal, provided by the invention, the pore size distribution and pore structure of the prepared porous alumina supported transition metal can be further improved by limiting ethanol as a washing solvent, and the washed waste liquid can be recycled without causing pollution.
6. According to the preparation method of the porous alumina supported transition metal, provided by the invention, the specific surface area, the catalytic performance and the stability of the prepared porous alumina supported transition metal can be further improved by limiting the roasting temperature, the roasting time and the heating rate.
7. According to the preparation method of the porous alumina supported transition metal, provided by the invention, the pore size distribution, pore structure, specific surface area and catalytic performance of the prepared porous alumina supported transition metal can be further improved by limiting the precursor compound, the transition metal salt, the soft template and the acid.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern of a porous alumina-supported transition metal prepared in examples 1-3 of the present invention;
FIG. 2 is a porous alumina-supported transition metal N prepared in examples 1-3 of the present invention 2 An adsorption and desorption curve;
FIG. 3 is a graph showing the specific surface area-pore size distribution of the porous alumina-supported transition metal prepared in examples 1 to 3 of the present invention;
FIG. 4 is a graph showing the selective adsorption curves of carbonyl sulfide (COS), nitrogen, and hydrogen of a porous alumina-supported transition metal prepared in example 1 of the present invention.
Reference numerals:
the numerical references in the various drawings represent corresponding embodiments, respectively.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a porous alumina zinc-supported catalyst, which is prepared by the following steps:
mixing and grinding aluminum isopropoxide, zinc acetate and CTAB for 5min, transferring to a polytetrafluoroethylene lining reaction kettle, dropwise adding acetic acid, stirring uniformly, transferring to a 100 ℃ drying box for curing for 24h, washing out unreacted aluminum isopropoxide and CTAB by ethanol after curing, drying at 70 ℃ for 6h, heating to 550 ℃ at a speed of 2 ℃/min in an air atmosphere, and roasting for 20h to obtain the zinc-loaded alumina catalyst.
Wherein, the mol ratio of the aluminum isopropoxide to the zinc acetate is 10:0.03;
the mass ratio of the aluminum isopropoxide to the CTAB is 2.0:0.5;
the mass volume ratio of the aluminum isopropoxide to the acetic acid is 2.0g:0.1ml.
Example 2
The embodiment provides a porous alumina-supported iron catalyst, which is prepared by the following steps:
mixing and grinding aluminum isopropoxide, ferric acetate and CTAB for 3min, transferring to a polytetrafluoroethylene lining reaction kettle, dropwise adding formic acid, stirring uniformly, transferring to a 60 ℃ drying box for curing for 18h, washing out unreacted aluminum isopropoxide and CTAB by using ethanol after curing, drying at 80 ℃ for 10h, heating to 500 ℃ at a speed of 5 ℃/min in an air atmosphere, and roasting for 24h to obtain the aluminum oxide-loaded iron catalyst.
Wherein, the mol ratio of the aluminum isopropoxide to the ferric acetate is 8:0.02;
the mass ratio of the aluminum isopropoxide to the CTAB is 1.8:1;
the mass volume ratio of the aluminum isopropoxide to the acetic acid is 1.8g:0.01ml.
Example 3
The embodiment provides a porous alumina supported copper catalyst, and the preparation method thereof is as follows:
mixing and grinding aluminum isobutanol, copper acetate and CTAB for 10min, transferring to a polytetrafluoroethylene lining reaction kettle, dropwise adding hydrochloric acid, stirring uniformly, transferring to a 180 ℃ drying box for curing for 3h, washing out unreacted aluminum isopropoxide and CTAB by ethanol after curing, drying at 60 ℃ for 7h, and heating to 450 ℃ at a speed of 3 ℃/min in an air atmosphere for 1h to obtain the aluminum oxide copper-loaded catalyst.
Wherein, the mol ratio of the aluminum isobutanol to the copper acetate is 8:0.04;
the mass ratio of the aluminum isobutanol to the CTAB is 1.8:0.125;
the mass volume ratio of the aluminum isobutanol to the acetic acid is 1.8g:0.1ml.
Example 4
The embodiment provides a porous alumina supported cobalt and copper catalyst, the preparation method of which is as follows:
mixing and grinding aluminum sec-butoxide, cobalt citrate, copper citrate and CTAB for 4min, transferring to a polytetrafluoroethylene-lined reaction kettle, dropwise adding citric acid, stirring uniformly, transferring to a drying box at 80 ℃ for curing for 20h, washing out unreacted aluminum isopropoxide and CTAB by using ethanol after curing, drying at 70 ℃ for 8h, heating to 400 ℃ at a speed of 4 ℃/min in an air atmosphere, and roasting for 15h to obtain the catalyst of aluminum oxide loaded with cobalt and copper.
Wherein, the mol ratio of the aluminum sec-butoxide, the cobalt citrate and the cupric citrate is 12:0.01:0.01;
the mass ratio of the aluminum sec-butoxide to the CTAB is 2.2:0.125;
the mass volume ratio of the aluminum sec-butoxide to the citric acid is 2.2g:0.01ml.
Example 5
The embodiment provides a porous alumina supported nickel catalyst, which is prepared by the following steps:
mixing and grinding aluminum ethoxide, nickel acetate, CTAB and PEI for 8min, transferring to a polytetrafluoroethylene lining reaction kettle, dropwise adding acetic acid and citric acid, stirring uniformly, transferring to a 120 ℃ drying box for curing for 6h, washing out unreacted aluminum isopropoxide, CTAB and PEI by using ethanol after curing, drying for 9h at 70 ℃, heating to 530 ℃ at a speed of 5 ℃/min in an air atmosphere, and roasting for 5h to obtain the aluminum oxide supported nickel catalyst.
Wherein, the mol ratio of the aluminum ethoxide to the nickel acetate is 12:0.04;
the mass ratio of aluminum ethoxide to PEI to CTAB is 2.2:0.5:0.5;
the mass volume ratio of aluminum ethoxide to acetic acid to citric acid is 2.2g:0.05ml:0.05ml.
Example 6
The embodiment provides a porous alumina supported copper and iron catalyst, the preparation method of which is as follows:
mixing and grinding aluminum isopropoxide, aluminum ethoxide, cupric citrate, ferric acetate and PEI for 6min, transferring to a polytetrafluoroethylene-lined reaction kettle, dropwise adding citric acid, uniformly stirring, transferring to a drying oven at 150 ℃ for curing for 1h, washing out unreacted aluminum isopropoxide, aluminum ethoxide and PEI by using ethanol after curing, drying at 70 ℃ for 6h, heating to 420 ℃ at a speed of 2 ℃/min in an air atmosphere, and roasting for 12h to obtain the aluminum oxide-loaded copper and iron catalyst.
Wherein, the mol ratio of the aluminum isopropoxide to the aluminum ethoxide to the copper citrate to the ferric acetate is 5:5:0.01:0.01;
the mass ratio of the mixture of aluminum isopropoxide and aluminum ethoxide to PEI is 2.0:0.8;
the mass volume ratio of the mixture of aluminum isopropoxide and aluminum ethoxide to citric acid is 2.0g:0.05ml.
Comparative example 1
The comparative example provides a porous alumina zinc supported catalyst, which is prepared as follows:
dissolving aluminum isopropoxide, zinc acetate and CTAB in ethanol, uniformly mixing, dropwise adding acetic acid, uniformly stirring, transferring to a drying oven at 100 ℃ for curing for 24 hours, washing out unreacted aluminum isopropoxide and CTAB by using ethanol after curing, drying at 70 ℃ for 6 hours, and heating to 550 ℃ at a speed of 2 ℃/min in an air atmosphere for 20 hours to obtain the zinc-loaded catalyst of aluminum oxide.
Wherein, the mol ratio of the aluminum isopropoxide to the zinc acetate is 10:0.03;
the mass ratio of the aluminum isopropoxide to the CTAB is 2.0:0.5;
the mass volume ratio of the aluminum isopropoxide to the acetic acid is 2.0g:0.1ml.
Experimental example 1
XRD, pore size distribution and adsorption performance tests were respectively carried out on each of the porous alumina-supported transition metal catalysts prepared in examples 1 to 3, wherein XRD was carried out by using an X-ray diffractometer manufactured by PANalytical, netherlands and having a model of X' PertPRO, and the specific test method is as follows:
the X-ray source is a Cu target, the incident wavelength of K alpha is 0.15418nm, the working voltage of the graphite monochromator is 40kV, the working current is 40mA, the scanning speed is 0.20s/step, the step length is 0.013 degrees/step, and the scanning range is 20-80 degrees.
The analysis of physical structure parameters such as specific surface area and pore size was performed by using ASAP 2020M physical adsorption instrument from micromeric company. The specific test method comprises the following steps: weighing 0.1g of the sieved catalyst sample with 40-60 meshes, respectively, and degassing at 160deg.C under high vacuum for 12 hr to obtain high-purity N 2 As adsorbate, low temperature N was obtained by testing at liquid nitrogen temperature (-196 ℃ C.) 2 Adsorption and desorption isotherms, and the specific surface area and pore size distribution of the catalyst are obtained.
COS, N using a TriStarII physical adsorption apparatus model produced by micromeritic Co., ltd 2 And H 2 Is used for the selective adsorption performance test of (1). The specific test method comprises the following steps: weighing 100mg of the sieved catalyst sample with 40-60 meshes, degassing at 160 ℃ under high vacuum for 12 hours, and respectively preparing high-purity COS and N 2 、H 2 The test temperature was 0 ℃ for the adsorbate gas.
As can be seen from FIG. 1, the catalysts prepared in examples 1-3 all showed two relatively weak diffraction peaks at 40-50 degrees and 60-70 degrees, which indicates that the catalyst structure with alumina as the carrier was synthesized, and no diffraction peak of transition metal was observed, which indicates that the transition metal was uniformly dispersed on the alumina carrier.
As can be seen from FIGS. 2 and 3, the catalysts prepared in examples 1-3 all exhibited typical type IV isotherms, N 2 Adsorption capacity is 0.6<P/P 0 <The mesoporous material has larger specific surface area, relatively large pore diameter and regular pore canal structure, and can well adsorb sulfide.
As can be seen from FIG. 4, in COS, N 2 And H 2 The catalyst prepared in example 1 has excellent selective adsorption performance to COS in ternary gas.
Experimental example 2
The catalysts prepared in each example and comparative example were subjected to catalytic performance tests, and the test results are shown in table 1, and the specific test methods are as follows: the catalyst loading is 0.2g, the reaction temperature is 30-170 ℃, and the COS concentration in the raw material gas is 110mg/m 3 ，N 2 For balancing the gas, the inner diameter of the reaction tube is 5mm, the flow rate of the raw material gas is 20ml/min, and the temperature of water vapor in the reactant is 40 ℃.
The stability test is carried out in the same device, and the test conditions are as follows: the catalyst loading was 0.2g, the reaction temperature was 110℃and the COS concentration in the feed gas was 110mg/m 3 ，N 2 For balancing gas, the inner diameter of the reaction tube is 5mm, the flow rate of the raw material gas is 20ml/min, the temperature of water vapor in the reactant is 40 ℃, and the long-acting stability test time is 40h.
The activity and stability results of the catalysts prepared in each example and comparative example are expressed in terms of COS conversion, and the concentration of COS in the feed gas and the discharge gas are tracked by using a FL-GC9720 gas chromatograph.
The calculation formula of COS conversion rate is:
COS conversion (%) = (mass of COS in feed gas-mass of COS in feed gas)/mass of COS in feed gas x 100%.
Table 1 test results
Figure BDA0002509824570000101
Figure BDA0002509824570000111
As can be seen from the data in the table, the porous alumina supported transition metal catalyst provided by the invention has good carbonyl sulfide (COS) conversion efficiency and good stability; the preparation method is simple, and no organic solvent is needed in the preparation process.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.

Claims (4)

1. The preparation method of the porous alumina supported transition metal is characterized by comprising the following steps of: grinding an aluminum precursor compound, transition metal salt and a soft template, then dropwise adding acid, solidifying, washing, drying and roasting to obtain the aluminum precursor;
grinding for 3-10min;
the molar ratio of the precursor compound of aluminum to the transition metal salt is (8-12): 0.02-0.04;
the soft template is cetyl trimethyl ammonium bromide and/or polyethylenimine;
the precursor compound of the aluminum is at least one of aluminum isopropoxide, aluminum isobutanol, aluminum sec-butoxide and aluminum ethoxide; the transition metal salt is acetate and/or citrate of transition metal; the acid is at least one of acetic acid, phosphoric acid, sulfuric acid, formic acid, hydrochloric acid, oxalic acid and citric acid;
the solvent used for washing is ethanol;
drying at 60-80deg.C for 6-10 hr;
the mass ratio of the precursor compound of aluminum to the soft template is (1.8-2.2) (0.125-1);
the mass volume ratio of the precursor compound of aluminum to the acid is (1.8-2.2): (0.01-0.1);
the curing temperature is 60-180 ℃ and the curing time is 1-24 hours;
the roasting temperature is 400-550 ℃, the time is 1-24h, and the heating rate is 2-5 ℃/min.
2. The method for preparing a porous alumina supported transition metal according to claim 1, wherein the acetate is at least one of iron acetate, cobalt acetate, nickel acetate, copper acetate or zinc acetate;
the citrate is at least one of ferric citrate, cobalt citrate, nickel citrate, cupric citrate and zinc citrate.
3. The porous alumina-supported transition metal produced by the process for producing a porous alumina-supported transition metal according to claim 1 or 2.
4. Use of the porous alumina-supported transition metal produced by the process for producing a porous alumina-supported transition metal according to claim 1 or 2 for removing COS.
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