CN115707515B - Catalyst with deoxidizing function and preparation method and application thereof - Google Patents
Catalyst with deoxidizing function and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title abstract description 65
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 17
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims description 95
- 239000007789 gas Substances 0.000 claims description 74
- 238000000034 method Methods 0.000 claims description 51
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 49
- 239000001301 oxygen Substances 0.000 claims description 49
- 229910052760 oxygen Inorganic materials 0.000 claims description 49
- 239000003795 chemical substances by application Substances 0.000 claims description 37
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 24
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 24
- 229910052783 alkali metal Inorganic materials 0.000 claims description 23
- 150000001340 alkali metals Chemical class 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 18
- 238000010304 firing Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000003607 modifier Substances 0.000 claims description 11
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- 239000013543 active substance Substances 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- 239000012018 catalyst precursor Substances 0.000 claims description 8
- 238000006392 deoxygenation reaction Methods 0.000 claims description 8
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- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
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- 229910052708 sodium Inorganic materials 0.000 claims description 4
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
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- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 12
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000007084 catalytic combustion reaction Methods 0.000 description 3
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- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
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- 239000002994 raw material Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 2
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- 238000002485 combustion reaction Methods 0.000 description 2
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
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- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
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- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
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- 238000004438 BET method Methods 0.000 description 1
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to the technical field of deoxidization catalysts, and discloses a catalyst with a deoxidization function, a preparation method and application thereof. The deoxidizing catalyst has low hydrocarbon gas consumption, high active temperature deoxidizing efficiency, excellent carbon deposit resistance and service life over 800 hr.
Description
Technical Field
The invention relates to the technical field of deoxidization catalysts, in particular to a catalyst with a deoxidization function, a preparation method and application thereof.
Background
Oxygen-containing organic hydrocarbon gases or oxygen-containing tail gases are common gases in the current chemical production and storage and transportation processes, but the gases generally bring explosion risks due to high oxygen content. SH 3009-2013 (design Specification for combustible gas emission systems for petrochemical industry) 5.3.1 states that the combustible gas with the oxygen content of more than 2 volume percent should not be discharged into the combustible gas emission systems of the whole factory, such as a torch, an incinerator and the like.
Currently, in order to solve the above problems, the industry mainly adopts a method of discharging a flare or diluting nitrogen, however, the method of discharging the flare causes a great deal of waste of hydrocarbon gas and possibly has danger, and the method of diluting nitrogen causes great nitrogen consumption and increased energy consumption, so that both methods affect economic benefits.
The safety treatment technology containing the organic gas has more application scenes. For example, the oxygen content in the propylene tail gas generated by the propylene oxide plant generally fluctuates in the range of 0.2-8% by volume, and the propylene tail gas cannot be discharged into a combustible gas discharge system according to the specification, and the oxygen content needs to be reduced to below 0.5% by volume and then discharged or reduced to below 0.1% by volume for recycling. Industrial exhaust gases with the risk of explosion like other hydrocarbon gases and oxygen face the problem of difficult exhaust gas treatment. Therefore, in order to reduce the risk of explosion, recycle hydrocarbon gas, or ensure that the hydrocarbon gas or tail gas containing oxygen meets the emission requirements, it is necessary to deoxidize the hydrocarbon gas or tail gas containing oxygen.
The prior deoxidization technology mainly comprises physical adsorption deoxidization, chemical absorption deoxidization, active carbon combustion deoxidization and catalytic combustion deoxidization. Wherein catalytic combustion deoxidization is a deoxidization method with a wider application range.
Liu Yingjie et al have provided a novel deoxidizing catalyst (development of liquid propylene deoxidizing catalyst [ J)]Industrial catalysis, 2016,24 (01): 61-64). The catalyst for deoxidizing liquid propylene is prepared through loading Pd metal salt and transition metal salt onto gamma-alumina via stepped soaking process and high temperature roasting. The catalyst does not need to be activated before being used and has a space velocity of 2500h -1 And the outlet O can be obtained under the condition of the reaction temperature of 40 DEG C 2 The content is removed to be less than 1.0x10 -6 . Catalyst stabilizationThe sexual experiments show that the catalyst activity is unchanged and the side reaction of propylene hydrogenation is not increased when the reaction is carried out for 100 hours at 40 ℃. Aiming at liquid propylene deoxidation, the prepared catalyst can meet the requirement of an outlet O 2 Low content and low propane increment. But the deoxidizing efficiency, selectivity and service life of the deoxidizing catalyst are still to be improved.
Disclosure of Invention
The invention aims to overcome the defects of short service life of the deoxidizing catalyst and suitability of the deoxidizing catalyst for O 2 Low content of hydrocarbon gas or tail gas, and the like. The invention provides a catalyst with a deoxidization function, a preparation method and application thereof, and the catalyst with the deoxidization function can be suitable for hydrocarbon gas or tail gas with oxygen content below 10 volume percent and has the characteristics of high selectivity and long service life.
In order to achieve the above object, the first aspect of the present invention provides a catalyst having a deoxidizing function, the catalyst comprising a support, and an active ingredient and a co-agent supported on the support, the co-agent comprising a first co-agent comprising an alkali metal and an alkaline earth metal and optionally a second co-agent selected from the fourth period transition metals, the active ingredient being selected from the group consisting of noble metals.
In a second aspect, the present invention provides a method for preparing a catalyst having a deoxidizing function, the method comprising:
(1) First calcining the carrier precursor with the modifier and optionally the second co-agent precursor at 450-1000 ℃;
(2) Then loading an active component precursor and a first active agent precursor on the first roasting product to obtain a catalyst precursor;
(3) Then, carrying out second roasting on the catalyst precursor;
wherein the modifier is ammonium chloride and/or urea; the first coagent precursor comprises an alkali metal precursor and an alkaline earth metal precursor; the second coagent precursor is selected from a fourth cycle transition metal precursor; the active component precursor is selected from noble metal precursors.
In a third aspect the invention provides a method of deoxygenating an oxygen containing gas, the method comprising: under deoxidization reaction conditions, the oxygen-containing gas is contacted with a deoxidizing catalyst, which is the catalyst described above.
The catalyst has the advantages of specific pore diameter structure, specific active components and active auxiliary agent, high deoxidization performance and strong stability. Compared with the existing deoxidizing catalyst, the deoxidizing catalyst has the advantages of low hydrocarbon gas consumption, high deoxidizing efficiency and selectivity, excellent anti-carbon performance and service life of more than 800 hours.
When the method is used for deoxidizing the oxygen-containing gas, the gas-phase explosion problem caused by oxygen accumulation in the recycling process of the raw material gas can be avoided, the safety of the production process is improved, the consumption of hydrocarbon components is reduced, and the economic benefit is improved.
By adopting the preferred embodiment of the invention, the catalyst containing the fourth period transition metal has better sulfur resistance, and the service life of the catalyst can be further prolonged when oxygen-containing gas and sulfur-containing (such as hydrogen sulfide and sulfur dioxide) gas are deoxidized.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In a first aspect, the present invention provides a catalyst having a deoxygenation function, the catalyst comprising a support and an active component and a co-agent supported on the support, the co-agent comprising a first co-agent comprising an alkali metal and an alkaline earth metal and optionally a second co-agent selected from the fourth period transition metals, the active component being selected from the group consisting of noble metals.
According to the present invention, preferably, the weight ratio of the first co-agent, the second co-agent and the active component is 6 to 100 in terms of metal element: 0-100:1, preferably 10-75:3-50:1.
according to the invention, preferably, the weight ratio of the carrier to the active component in terms of metallic element is 50-1000:1, preferably 80-950:1.
in the present invention, unless otherwise specified, the total amount of catalyst=the amount of active component in terms of metal element+the amount of first active auxiliary in terms of metal element+the amount of carrier.
According to the present invention, preferably, the weight ratio of the alkali metal to the alkaline earth metal is 5 to 10:1, more preferably, the weight ratio of alkali metal to alkaline earth metal is 6-9:1. the deoxidization performance of the catalyst can be further improved by compounding an alkali metal with an alkaline earth metal.
According to the present invention, the active component is selected from noble metals common in the art, preferably, the active component is selected from at least one of Pt, pd, ru, rh, ag and Ir; more preferably, the active component is selected from at least one of Pt, pd and Ru.
According to the present invention, preferably, the alkali metal is selected from at least one of Na, K, and Cs; the alkaline earth metal is selected from at least one of Mg, ca and Ba; most preferred is a combination of Na and Mg, or a combination of K and Ca.
According to the present invention, preferably, the fourth-period transition metal is selected from at least one of Fe, co, ni, zn and Cr.
According to the present invention, preferably, the support is selected from at least one of alumina (gamma-alumina), silica, titania and carbon nanotubes.
According to the present invention, preferably, the specific surface area of the catalyst is 120 to 260m 2 And/g. Preferably, the catalyst has a pore volume of 0.4-0.8cm 3 And/g. Preferably, the average pore diameter of the catalyst is from 6 to 25nm.
In a second aspect, the present invention provides a method for preparing a catalyst having a deoxidizing function, the method comprising:
(1) First calcining the carrier precursor with the modifier and optionally the second co-agent precursor at 450-1000 ℃;
(2) Then loading an active component precursor and a first active agent precursor on the first roasting product to obtain a catalyst precursor;
(3) Then, carrying out second roasting on the catalyst precursor;
wherein the modifier is ammonium chloride and/or urea; the first coagent precursor comprises an alkali metal precursor and an alkaline earth metal precursor; the second coagent precursor is selected from a fourth cycle transition metal precursor; the active component precursor is selected from noble metal precursors.
According to the invention, preferably, the weight ratio of the carrier precursor to the modifier is 5-10:1.
according to the present invention, preferably, the time of the first firing is 1 to 10 hours.
According to the present invention, preferably, the first firing is performed in air.
According to the present invention, preferably, the first firing is performed by: heating the carrier precursor and the modifier to a temperature of 450-1000 ℃ (e.g., 450 ℃, 490 ℃, 510 ℃, 550 ℃, 590 ℃, 610 ℃, 640 ℃, 660 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃ or any value between the above values) at a heating rate of 200-600 ℃/h (e.g., 200 ℃/h, 210 ℃/h, 250 ℃/h, 290 ℃/h, 310 ℃/h, 350 ℃/h, 390 ℃/h, 410 ℃/h, 500 ℃/h, 600 ℃/h or any value between the above values), and calcining at the temperature for 1-10 hours (e.g., 1h, 2h, 3h, 4h, 5h, 6h, 8h, 10h or any value between the above values).
According to the present invention, it is preferable that the temperature of the second firing is lower than the temperature of the first firing by 0 to 50 ℃. Preferably, the rate of temperature rise of the second firing is 140-240 ℃ lower than the rate of temperature rise of the first firing. More preferably, the second firing process includes: performing second roasting at 300-800 ℃ for 1-5h; or heating to 300-800 ℃ at 60-160 ℃/h, and then keeping the temperature for 1-5h.
According to the present invention, preferably, the second firing is performed in air.
In the present invention, in order to obtain the catalyst as described above for the active component and the co-agent, one skilled in the art can select the active component precursor and the co-agent precursor according to the kinds of the active component and the co-agent, and detailed description thereof will be omitted.
According to the present invention, preferably, the carrier precursor is selected from at least one of pseudo-boehmite, silica sol, water glass, alumina sol, tetrabutyl titanate, and activated carbon. When the adopted carrier precursor contains water or exists in a liquid form, the carrier precursor needs to be pretreated, for example, when at least one of water glass, silica sol and alumina sol is adopted as the carrier precursor, the water content of the carrier precursor needs to be reduced by pretreatment of the carrier precursor so as to meet the use requirement of the carrier precursor; when tetrabutyl titanate is used as a carrier precursor, the carrier precursor is required to be hydrolyzed, and then the moisture and alcohol are volatilized to reduce the moisture content of the carrier precursor so as to meet the use requirement of the carrier precursor.
According to the present invention, preferably, the active component precursor is selected from at least one of nitrate, chloride, acetate and metal acetylacetonate of a noble metal, more preferably, the active component precursor is selected from palladium chloride and/or chloroplatinic acid.
According to the present invention, preferably, the alkali metal precursor is selected from at least one of nitrate, chloride and acetate of alkali metal. Preferably, the alkaline earth metal precursor is selected from at least one of nitrate, chloride and acetate of alkaline earth metal.
According to the present invention, preferably, the second coagent precursor is selected from at least one of nitrate, chloride and acetate of the fourth period transition metal.
According to the present invention, preferably, the active ingredient precursor, the first active ingredient precursor and the second active ingredient precursor are used in such an amount that the weight ratio of the first active ingredient to the active ingredient, calculated as metal element, in the prepared catalyst is 6 to 100:0-100:1, preferably 10-75:3-50:1.
according to the present invention, preferably, the active component precursor and the carrier precursor are used in such an amount that the weight ratio of the carrier to the active component in terms of metal element in the catalyst to be produced is 50 to 1000:1, preferably 80-950:1.
according to the present invention, preferably, the alkali metal precursor and the alkaline earth metal precursor are used in such an amount that the weight ratio of the alkali metal to the alkaline earth metal in the catalyst obtained is 5 to 10:1, a step of; more preferably, the weight ratio of alkali metal to alkaline earth metal is 6-9:1.
according to the present invention, preferably, step (1) further comprises: before the first calcination, the support precursor is impregnated with an impregnating solution containing a modifier and a fourth-period transition metal precursor, and then dried.
According to the present invention, the amount of the impregnating solution may be preferably the saturated water absorption amount of the carrier precursor or may exceed the saturated water absorption amount of the carrier precursor, as long as the second co-agent can be supported on the carrier precursor.
According to the present invention, preferably, in the step (2), the method of loading the active component precursor and the first co-agent precursor onto the first baked product is an impregnation method; more preferably, the loading of the reactive component precursor and the first co-agent precursor onto the first calcined product comprises:
A. preparing an impregnating solution containing an active component precursor and a first active auxiliary agent precursor, wherein the pH value of the impregnating solution is 0.5-4 or 9-13;
B. and (3) immersing the first roasting product in the impregnating solution, and optionally drying after the impregnation is finished.
According to the present invention, it is preferable that the impregnation method be either an excess impregnation method or an isovolumetric impregnation method, as long as the active ingredient and the first co-agent can be supported on the first calcined product.
Preferably, according to the present invention, the process of preparing the impregnating solution containing the active component precursor and the first co-agent precursor includes: the active component precursor is dissolved in acid solution or alkali solution, then mixed with the first active auxiliary agent precursor, and then water is introduced to adjust the pH value of the system to be 0.5-4 or 9-13.
According to the present invention, preferably, the acid solution is selected from at least one of hydrochloric acid, nitric acid and acetic acid. Preferably, the alkali solution is selected from at least one of ammonia water, sodium hydroxide and sodium carbonate.
According to the invention, preferably, in step B, the time of the impregnation is between 0.5 and 10 hours.
In a third aspect the invention provides a method of deoxygenating an oxygen containing gas, the method comprising: under deoxidization reaction conditions, the oxygen-containing gas is contacted with a deoxidizing catalyst, which is the catalyst described above.
According to a preferred embodiment of the invention, the process is carried out in the presence of a stabilizator gas, which is a gaseous alkane. The ratio of the volume of the stabilizing gas to the volume of the oxygen is not less than 4, preferably more than 5. The stabilizing gas is selected from C1-C4 alkanes, preferably at least one of methane, ethane and propane. According to the invention, the stabilizing gas can be introduced from the outside. However, when the oxygen-containing gas carries gaseous alkane, it may not be necessary to introduce gaseous alkane from the outside as the stabilizing gas, or the amount of the stabilizing gas introduced from the outside may be reduced accordingly, that is, "stabilizing gas" in the present invention may refer to only gaseous alkane carried in the oxygen-containing gas, may refer to only gaseous alkane introduced from the outside, and may refer to a mixture of gaseous alkane carried in the oxygen-containing gas and gaseous alkane introduced from the outside. In the present invention, the stabilizing gas is only a gaseous alkane, and thus, the content of other inactive gases (i.e., gases that do not react with any of hydrogen, oxygen, other flammable gases in the system, such as helium, nitrogen, argon, carbon dioxide, steam, etc.) in the oxidation reaction system is maintained at a low level, for example, less than 10 vol%, less than 5 vol%, less than 3 vol%, less than 2 vol%, less than 1 vol%, less than 0.5 vol%, less than 0.05 vol%, or less.
According to the invention, the temperature of the deoxygenation reaction is lower than that of the stabilizator (gaseous alkane) catalytic combustionThe ignition temperature of the combustion is so as to avoid the catalytic combustion reaction of stable gas and oxygen. Preferably, the deoxygenation reaction conditions include: the reaction temperature is 0-550 ℃, the pressure is 0.01-10MPa, and the gas volume space velocity is 500-25000h -1 。
According to the present invention, the oxygen concentration in the oxygen-containing gas is preferably 10 vol% or less, and may be more than 2 vol%, preferably 3 to 99.5 vol% (e.g., 2.5 vol%, 2.8 vol%, 3 vol%, 4 vol%, 5 vol%, 6 vol%, 10 vol%, 20 vol%, 30 vol%, 40 vol%, 50 vol%, 55 vol%, 60 vol%, 70 vol%, 80 vol%, 90 vol%, 93 vol%, 96 vol%, 99 vol%, or any value between the above values).
According to the present invention, preferably, the oxygen-containing gas contains oxygen and other hydrocarbon gases.
According to the present invention, preferably, the hydrocarbon gas is at least one of C1-C4 alkane, C2-C4 alkene, and C2-C4 alkyne, more preferably at least one selected from ethylene, ethylene oxide, propylene oxide, 1-butene, 2-butene, isobutylene, 1, 3-butadiene, acetylene, propyne, 1-butyne, 2-butyne, vinyl chloride, 3-chloropropene, 1-chloropropane, 2-chloropropane, and epichlorohydrin.
The present invention will be described in detail by way of preparation examples. In the following preparation examples, the procedure was as follows,
the raw materials adopted are all commercial raw materials.
Preparation example 1
(1) Mixing pseudo-boehmite powder and ammonium chloride solid according to the weight ratio of 5:1, and then carrying out first roasting to obtain a first roasting product, wherein the first roasting conditions comprise: raising the temperature to 500 ℃ at a heating rate of 300 ℃/h, and roasting for 5h at the temperature.
(2) According to the stoichiometric ratio of each component in the catalyst, palladium chloride is dissolved in 0.1mol/L dilute hydrochloric acid, sodium nitrate and magnesium nitrate are added after complete dissolution, the mixture is stirred uniformly, and then water is introduced to adjust the pH value to 3, so as to obtain the impregnating solution. And (3) placing the first roasting product into impregnating solution, impregnating for 5 hours, stirring and evaporating at 120 ℃ to dryness after the impregnation is completed, and drying in an oven at 80 ℃ for 12 hours to obtain the catalyst precursor.
(3) The catalyst precursor is then subjected to a second calcination in air, the second calcination conditions comprising: heating to 500 ℃ at 100 ℃ per hour, and keeping the temperature for 3 hours.
PREPARATION EXAMPLES 2-3
The catalyst preparation was carried out in the same manner as in preparation example 1 except that the stoichiometric ratio of each component in the catalyst was different from that in preparation example 1, and the catalyst preparation conditions were different, as shown in Table 1.
TABLE 1
Preparation example 4
The catalyst preparation was carried out as in preparation example 1, except that the stoichiometric ratio of the components in the catalyst was different from that in preparation example 1, and the procedure for preparing the carrier was different: fe (NO) 3 ) 3 And dissolving urea in deionized water to prepare an impregnating solution, then placing pseudo-boehmite powder in the impregnating solution for impregnating for 3 hours, stirring and evaporating to dryness at 80 ℃, heating to 500 ℃ at a heating rate of 300 ℃/h, and roasting at 500 ℃ for 7 hours to obtain a first roasting product.
Preparation example 5
The catalyst preparation was carried out as in preparation example 1, except that the amount of the coagent to be charged was such that the weight ratio of sodium nitrate to magnesium nitrate, calculated as metal element, was 1:1.
preparation example 6
The catalyst preparation was carried out as in preparation example 1, except that magnesium nitrate was replaced with sodium nitrate.
Preparation example 7
The catalyst preparation was carried out as in preparation example 1, except that sodium nitrate was replaced with magnesium nitrate.
Preparation example 8
The catalyst preparation was carried out as in preparation example 1, except that the amount of the coagent to be charged was such that the weight ratio of sodium nitrate to magnesium nitrate, calculated as metal element, was 1:5.
preparation example 9
The catalyst preparation was carried out as in preparation example 1, except that the stoichiometric ratio of the components in the catalyst was different from that in preparation example 1, and the procedure for preparing the carrier was different: co (NO) 3 ) 2 And dissolving urea in deionized water to prepare an impregnating solution, then placing pseudo-boehmite powder in the impregnating solution for impregnating for 3 hours, stirring and evaporating to dryness at 120 ℃, heating to 650 ℃ at a heating rate of 200 ℃/h, and roasting for 5 hours at 650 ℃ to obtain a first roasting product.
Preparation example 10
The catalyst preparation was carried out as in preparation example 1, except that the stoichiometric ratio of the components in the catalyst was different from that in preparation example 1, and the procedure for preparing the carrier was different: zn (NO) 3 ) 2 And dissolving urea in deionized water to prepare an impregnating solution, then placing pseudo-boehmite powder in the impregnating solution for impregnating for 3 hours, stirring and evaporating to dryness at 120 ℃, heating to 600 ℃ at a heating rate of 400 ℃/h, and roasting at 600 ℃ for 2 hours to obtain a first roasting product.
PREPARATION EXAMPLE 11
The catalyst preparation was carried out in the same manner as in preparation example 4, except that the stoichiometric ratio of each component in the catalyst was different from that in preparation example 4.
Comparative preparation example 1
The catalyst preparation was carried out in the same manner as in preparation example 1 except that pseudo-boehmite was directly calcined at 1200℃for 5 hours to obtain a support.
Comparative preparation example 2
The catalyst preparation was carried out as in preparation example 1, except that the ammonium chloride solid was replaced with N, N-dimethylformamide.
Comparative preparation example 3
The catalyst preparation was carried out in the same manner as in preparation example 1, except that magnesium nitrate and sodium nitrate were replaced with ferric nitrate.
Test example 1
The structural parameters of the catalysts prepared in the above preparation examples and comparative preparation examples were characterized, and the results are shown in table 2. The elemental compositions of the catalysts prepared in the preparation examples and the comparative preparation examples are characterized, the content of the metal element of the active component and the content of the metal element of the first active auxiliary agent are shown in table 2, and the balance is the carrier.
Specific surface area and pore size distribution test: using US microphonesThe physical adsorption instrument of II 3020, a specific surface area analysis and a pore structure were performed. Specific test conditions include the use of N at-196℃C (liquid nitrogen temperature) 2 Measuring surface area and pore structure by adsorption method, and vacuum-pumping sample at 300deg.C until pressure is less than 10 -3 Pa, the measurement method is a static method. The specific surface area and pore structure were calculated by BET method based on adsorption isotherms.
The content of each component in the catalyst was tested by ICP-AES method.
TABLE 2
Note that: r represents the weight ratio of alkali metal to alkaline earth metal; the active component content and the first co-agent content are calculated as elemental metals.
Further analysis gave that the ratios of the content of the second coagent to the content of the active ingredient in terms of metal element in preparation example 4, preparation example 9, preparation example 10, preparation example 11 and comparative preparation example 3 were 3, 5, 10 and 50 in this order.
Test example 2
(1) The catalysts prepared in the above preparation examples and comparative preparation examples were used for oxygen-containing gasThe deoxidizing treatment of the body, the conditions of the deoxidizing treatment include: the reaction temperature is 60 ℃, the pressure is 0.3MPa, and the gas volume space velocity is 5000h -1 The oxygen-containing gas contains oxygen and hydrocarbon gas, methane (stabilizing gas) and hydrogen (reducing gas) are mixed with the oxygen-containing gas, and the molar ratio of the hydrogen to the oxygen in the mixed gas is 2.2:1, the volume ratio of methane to oxygen is 15. The oxygen concentration in the oxygen-containing gas and the oxygen concentration after the reaction are shown in table 3.
(2) The catalysts prepared in the above preparation examples and comparative preparation examples were subjected to life test measurement, and tested according to the conditions of the deoxidation treatment in the step (1), and the life of the catalyst was characterized by the time of catalyst deactivation, which means that: when the oxygen conversion of the catalyst is less than 80% of the initial conversion, the catalyst is considered to be deactivated, and when the total duration of the deoxygenation treatment operation is the life of the catalyst, a duration greater than a certain duration means that the catalyst has not been deactivated for the duration, but the experiment is not continued. The results are shown in Table 3.
TABLE 3 Table 3
Note that: the gas content values or selectivities shown refer to the average value of the detection of the system running to catalyst deactivation.
As can be seen from the results of Table 3, the catalyst of the present invention can be used to improve the deoxidizing performance and the service life of the catalyst as compared with comparative examples 1 to 3. By adopting the catalyst of the preferred embodiment of the invention, the deoxidization performance is further improved, and the service life of the catalyst is further prolonged.
Test example 3
(1) The catalysts prepared in preparation examples 1 to 4 and preparation examples 9 to 10 described above were subjected to sulfur resistance test under the conditions of the deoxidation treatment of step (1) in test example 2, except that the oxygen-containing gas contained oxygen, hydrogen sulfide and hydrocarbon gas. Oxygen concentration in the oxygen-containing gas and hydrogen sulfide concentration, and oxygen concentration after the reaction. As shown in table 4.
(2) Life test measurement was performed in accordance with the method of step (1) in test example 2. The results are shown in Table 4.
TABLE 4 Table 4
From the results of Table 4, it is understood that the catalyst containing the fourth-period transition metal of the present invention has a longer service life when the hydrogen sulfide-containing gas is contained in the oxygen-containing gas.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (20)
1. A catalyst having a deoxidizing function, the catalyst comprising a support and an active component and a co-agent supported on the support, characterized in that the co-agent comprises a first co-agent comprising an alkali metal selected from at least one of Na, K and Cs and an alkaline earth metal, and optionally a second co-agent; the alkaline earth metal is selected from at least one of Mg, ca and Ba; the second active auxiliary agent is selected from at least one of Fe, co, ni, zn and Cr; the active component is at least one selected from Pt, pd, ru, rh, ag and Ir;
the weight ratio of the first active agent to the second active agent to the active components is 6-100 based on metal elements: 0-100:1, a step of; the weight ratio of the carrier to the active component calculated by metal element is 50-1000:1, a step of; the weight ratio of the alkali metal to the alkaline earth metal is 5-10:1, a step of; the carrier is at least one of gamma-alumina, silicon dioxide, titanium dioxide and carbon nano tubes; the average pore diameter of the catalyst is 6-25nm.
2. The catalyst of claim 1, wherein the weight ratio of the first co-agent, the second co-agent, and the active component, expressed as metal elements, is 10-75:3-50:1.
3. the catalyst according to claim 1, wherein the weight ratio of the carrier to the active component in terms of metal element is 80-950:1.
4. a catalyst according to any one of claims 1 to 3, wherein the specific surface area of the catalyst is 120 to 260m 2 Per g, pore volume of 0.4-0.8cm 3 /g。
5. A method for preparing a catalyst having a deoxidizing function, the method comprising:
(1) First calcining the carrier precursor with the modifier and optionally the second co-agent precursor at 450-1000 ℃;
(2) Then loading an active component precursor and a first active agent precursor on the first roasting product to obtain a catalyst precursor;
(3) Then, carrying out second roasting on the catalyst precursor;
wherein the modifier is ammonium chloride and/or urea; the first coagent precursor comprises an alkali metal precursor and an alkaline earth metal precursor; the alkali metal in the alkali metal precursor is at least one of Na, K and Cs; the alkaline earth metal in the alkaline earth metal precursor is at least one selected from Mg, ca and Ba; the second co-agent in the second co-agent precursor is selected from at least one of Fe, co, ni, zn and Cr; the active component in the active component precursor is at least one of Pt, pd, ru, rh, ag and Ir;
the usage amount of the active component precursor, the first active agent precursor and the second active agent precursor is such that the weight ratio of the first active agent, the second active agent and the active component in the prepared catalyst is 6-100 based on metal elements: 0-100:1, a step of; the active component precursors and the carrier precursors are used in an amount such that the weight ratio of the carrier to the active component calculated as metal element in the prepared catalyst is 50-1000:1, a step of; the alkali metal precursor and the alkaline earth metal precursor are used in an amount such that the weight ratio of the alkali metal to the alkaline earth metal in the prepared catalyst is 5-10:1, a step of;
the carrier precursor is at least one selected from pseudo-boehmite, silica sol, water glass, alumina sol, tetrabutyl titanate and active carbon;
the weight ratio of the carrier precursor to the modifier is 5-10:1.
6. the method of claim 5, wherein the first firing is performed by: the carrier precursor, the modifier and optionally the second co-agent precursor are heated to 450-1000 ℃ at a heating rate of 200-600 ℃/h and calcined at that temperature for 1-10 hours.
7. The method of claim 5, wherein the second firing is at a temperature 0-50 ℃ lower than the first firing.
8. The method of claim 5, wherein the rate of temperature rise of the second firing is 140-240 ℃ lower than the rate of temperature rise of the first firing.
9. The method of claim 5, wherein the second firing comprises: and (3) performing second roasting at 300-800 ℃ for 1-5 hours, or heating to 300-800 ℃ at 60-160 ℃/h and then performing constant temperature for 1-5 hours.
10. The method of claim 5, wherein the active component precursor is selected from at least one of a nitrate, chloride, acetate, and metal acetylacetonate of the active component.
11. The method of claim 5, wherein the alkali metal precursor is selected from at least one of a nitrate, chloride, and acetate of an alkali metal.
12. The method of claim 5, wherein the alkaline earth metal precursor is selected from at least one of a nitrate, chloride, and acetate of an alkaline earth metal.
13. The method of claim 5, wherein the second co-agent precursor is selected from at least one of a nitrate, chloride, and acetate of a second co-agent.
14. The method of claim 5, wherein the amounts of the active component precursor, the first co-agent precursor, and the second co-agent precursor are such that the catalyst is prepared such that the weight ratio of the first co-agent, the second co-agent, and the active component, expressed as metal elements, is from 10 to 75:3-50:1.
15. the method according to claim 5, wherein the active component precursor and the carrier precursor are used in such an amount that the weight ratio of the carrier to the active component in terms of metal element in the catalyst obtained is 80 to 950:1.
16. a method of deoxygenating an oxygen-containing gas, the method comprising: contacting an oxygen-containing gas with a deoxygenation catalyst under deoxygenation reaction conditions, the deoxygenation catalyst being a catalyst according to any one of claims 1-15.
17. The method of claim 16, wherein the deoxygenation reaction conditions comprise: the reaction temperature is 0-550 ℃, the pressure is 0.01-10MPa, and the gas volume space velocity is 500-25000h -1 。
18. The method of claim 17, wherein the oxygen-containing gas has an oxygen concentration of 10% by volume or less.
19. The method of claim 17, wherein the oxygen-containing gas comprises oxygen and a hydrocarbon gas.
20. The method of claim 19, wherein the hydrocarbon gas is at least one of a C1-C4 alkane, a C2-C4 alkene, and a C2-C4 alkyne.
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