CN102631943A - Iron-phosphorus-base catalyst for preparing bromomethane by methane oxybromination, and preparation method and application thereof - Google Patents
Iron-phosphorus-base catalyst for preparing bromomethane by methane oxybromination, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an Fe-P-O/SBA-15 catalyst for preparing bromomethane and CO by methane oxybromination, which is composed of an active component and a support, wherein the active component comprises one or more of FePO4, Fe2P2O7 and alpha-Fe3(P2O7)2; the active component accounts for 1.0-60.0% of the catalyst by weight; the Fe/Si mol ratio in the catalyst is 0.001-1.0; the P/Si mol ratio in the catalyst is 1.0-5.0; the support is an SBA-15 full-silicon molecular sieve; and the specific area of the catalyst is 100-1500m<2>/g, and the pore volume is 0.65-1.20m<3>/g. The preparation method of the catalyst comprises the following steps: by using ferric salt, phosphoric acid [H3PO4] and ethyl orthosilicate [(C2H5O)4Si] as precursors and a triblock polymer [(EO)20(PO)70(EO)20] (P123 for short) as a template, introducing the active component into the support by a hydrothermal method, washing, filtering, drying, roasting and forming to obtain the Fe-P-O/SBA-15 catalyst.
Description
Technical field
The present invention relates to a kind of bromine oxidation of methane that is used for prepares Fe-P-O/ total silicon molecular sieve SBA-15 catalyst, its preparation method of bromomethane and CO and is used for methane, oxygen and the HBr aqueous solution and prepare Celfume and CO.
Background technology
Natural gas is considered to the cleanest fossil energy, along with the raising day by day of human survival energy consumption, is to reduce human key issues to the petroleum resources dependence with conversion of natural gas for other chemical raw materials how.The main path of gas industry utilization at present is at first through the steam reforming synthesis gas, then through the indirect reformer of follow-up Fischer-Tropsch synthesis realization natural gas to chemicals.Because this process energy consumption is high, flow process is complicated, only the application in the large-scale natural gas gas field can produce economic benefit.The characteristics that the natural gas field exists resource to disperse, and distribution is main with middle-size and small-size gas field mainly.This just requires to develop a kind of efficient, flexible operation, the simple conversion of natural gas new technology of flow process.The exploitation of methane activation catalyst system and catalyzing efficiently is a key link wherein.
Early disclosing a kind of among the CN 1640864 is CH with methane conversion at first through the bromine oxidation of methane reaction
3Br and CO, the latter obtain the method for methyl alcohol or dimethyl ether through hydrolysis.Subsequently, disclose among the CN 1724503A a kind of with CH
3Br/CO reacts acetic acid synthesized method through liquid-phase carbonylation on the Rh-KI-PPh3 catalyst.The disclosed bromine oxidation of above patent route can be avoided the synthesis gas route of high energy consumption, realizes the unconventional activation of methane.The intermediate product CH that this technology obtains
3Br and CO are the synthetic multiple choices that provide of downstream chemical article, like acetic acid synthesized, dimethyl ether and alkene etc.Therefore, this is that a flow process is short, the methane activation new technology of flexible operation.
Bibliographical information methane and halogen simple substance (Cl
2Or Br
2) at solid super-strong acid (20%NbOF
3/ Al
2O
3) or solid supported noble metal (0.5%Pt/Al
2O
3) under the catalyst action can highly selective below 250 ℃ be converted into a halide (G.A.Olah, Acc.Chem.Res., 1987,20,422-428).Report methane such as Degirmenci and Br
2At solid super-strong acid (ZrO
2-SO
4 2-/ SBA-15) under the catalyst action, can 340 ℃ of reaction temperatures be issued to 69% methane conversion and 99% the monobromo methane selectively (V.Degirmenci, A.Yilmaz, D.Uner, Catal.Today, 2009,142,30-33).Li etc. have reported a kind of at 250 ℃ of MoO that can methane be passed through the bromination reaction activation below the reaction temperature
2(H
2O)
2/ Zn-MCM-48 catalyst, its product mainly are methyl alcohol and dimethyl ether, also generate bromomethane and a spot of CO simultaneously
2(F.B3.Li, G.Q.Yuan, Angew.Chem.Int.Ed., 2006,45,6541-6544) a kind of Ru/SiO that is applied to the bromine oxidation of methane reaction is disclosed among the .CN 1640864
2Catalyst reports that this catalyst system and catalyzing methane conversion when reaction temperature is 530 ℃ can reach 19.1%, CH
3The selectivity of Br is up to 90%.A kind of RuNiBaLaO/SiO is disclosed among CN 1724503 and the CN 101041609
2Catalyst.Under this catalyst action, methane conversion reached 70% when reaction temperature was 660 ℃, primary product CH
3The global selectivity of Br and CO is 89%, and the two mol ratio is approaching.But patent does not provide the result of the stability experiment on this catalyst.A kind of FePO is disclosed among the CN 101992111
4/ SiO
2Catalyst.Under this catalyst action, methane conversion reached 50% when reaction temperature was 570 ℃, primary product CH
3The global selectivity of Br and CO is 95%, and mol ratio is approaching.Bibliographical information FePO
4/ SiO
2Carbon distribution takes place in reaction after a period of time in catalyst, and cause active the reduction (R.H.Lin, Y.J.Ding, L.F.Gong, W.D.Dong, W.M.Chen, Y.Lu, Cat.Today, 2011,164,34-39).Bibliographical information Rh/SiO is also arranged
2Catalyst applications in bromine oxidation of methane reaction (Z.Liu, L.Huang, W.S.Li, F.Yang, C.T.Au and X.P.Zhou, J.Mol.Catal.A:Chem., 2007,273,14-20).This catalyst Rh loading is higher, reaction temperature also higher (660 ℃).Liu etc. adopt the synthetic Rh/SiO of sol-gal process
2Catalyst has also been investigated its catalytic methane bromine oxidation reaction performance, even this catalyst can obtain near 40% methane conversion and 90%CH under 660 ℃ of reaction temperatures
3The Br selectivity, but noble metal Rh significantly loss of existence after reaction was near 700 hours (Z.Liu, W.S.Li, X.P.Zhou, J.Nat.Gas.Chem., 2010,19,522-529).
Summary of the invention
It is catalyst based to the object of the present invention is to provide a kind of bromine oxidation of methane to prepare the iron phosphorus of Celfume and CO.
Another purpose of the present invention is to provide that a kind of to prepare the method for above-mentioned catalyst and utilize this catalyst be raw material with methane, oxygen and the HBr aqueous solution, and high activity, highly selective prepare the method for Celfume and CO.
In order to realize the object of the invention, the present invention provides the characteristic of catalyst to be:
Active component is FePO
4, Fe
2P
2O
7Or α-Fe
3(P
2O
7)
2In one or more; The weight of active component is 1.0～60.0% of catalyst weight;
Fe/Si element mol ratio is 0.001～1.0 in the catalyst;
P/Si element mol ratio is 1.0～5.0 in the catalyst;
The weight of active component is 1.0～40.0% of catalyst weight in the catalyst;
The carrier of catalyst is mesoporous SBA-15 total silicon molecular sieve;
The specific area of catalyst carrier is 300～1200m
2/ g, pore volume are 0.65～1.20m
3/ g.
In the catalyst of the invention described above, the weight of preferable active component is 1.0～40.0% of catalyst weight; Fe/Si element mol ratio is 0.004～0.6 in the preferable catalyst; P/Si element mol ratio is 1.5～4.5 in the preferable catalyst; The specific area of preferable catalyst is 300～1200m
2/ g, pore volume are 0.70～1.10m
3/ g.
Preparation of catalysts of the present invention is a presoma with molysite, phosphoric acid and ethyl orthosilicate, with triblock polymer P123 [(EO)
20(PO)
70(EO)
20] be template, adopt the mode of hydro-thermal method, with active component (FePO with " treating different things alike "
4, Fe
2P
2O
7Or α-Fe
3(P
2O
7)
2) original position introducing carrier, form through washing, filtration, drying, roasting, moulding again.
The concrete preparation method of catalyst is following:
(1) will measure the triblock polymer P123 (EO) of ratio
20(PO)
70(EO)
20, H
3PO
4Mix with deionized water, and obtained solution A in 1-10 hour in 30-90 ℃ of stirring.Molysite, ethyl orthosilicate and the deionized water of metering ratio are at room temperature stirred and obtained solution B in 0.5-5 hour.Under vigorous stirring, solution B is added solution A, and the continuation stirring obtained emulsion C in 12-48 hour.With emulsion C transfer in the hydro-thermal synthesis reactor with 60-120 ℃ of temperature under crystallization 12-48 hour.Again with after the washing of the slurry filtration that contains deposition that makes in the water heating kettle, deionized water, filter cake is in 60 ℃ of oven dry, at last in Muffle furnace in 400-800 ℃ of roasting 2-12 hour.Roasting gained pressed powder obtains described catalyst granules behind compressing tablet.
Phosphate aqueous solution (H in the above-mentioned solution A
3PO
4Quality proportion is 85%) and triblock polymer P123 (EO)
20(PO)
70(EO)
20Weight ratio be 1.0～10.0; Fe/Si element mol ratio is 0.001～1.0 in the solution B.
Above-mentioned institute adds deionized water and ethyl orthosilicate [(C
2H
5O)
4Si] mol ratio be 50: 1～250: 1.
(2) will measure molysite, the triblock polymer P123 (EO) of ratio
20(PO)
70(EO)
20, H
3PO
4Mix with deionized water, and obtained solution D in 30-90 ℃ of stirred in water bath 10-48 hour.Obtained solution E in 0.5-24 hour with under room temperature, stirring in a certain amount of ethyl orthosilicate adding deionized water.Under vigorous stirring, solution D is added solution E, and the continuation stirring obtained emulsion F in 12-48 hour.With emulsion F transfer in the hydro-thermal synthesis reactor with 90-120 ℃ of temperature under crystallization 12-48 hour.Again with after the washing of the slurry filtration that contains deposition that makes in the water heating kettle, deionized water, filter cake is in 60 ℃ of oven dry, at last in Muffle furnace in 400-800 ℃ of roasting 2-12 hour.Roasting gained pressed powder obtains described catalyst behind compressing tablet.
Phosphate aqueous solution (H in the above-mentioned solution D
3PO
4Quality proportion is 85%) and triblock polymer P123 (EO)
20(PO)
70(EO)
20Weight ratio be 1.0～10.0, P/Fe element mol ratio is 2.0～1300.0; Ethyl orthosilicate [(C in molysite and the solution E in the solution D
2H
5O)
4Si] ratio be 0.001～1.0 proportioning according to Fe/Si element mol ratio.
Above-mentioned institute adds deionized water and ethyl orthosilicate [(C
2H
5O)
4Si] mol ratio be 50: 1～250: 1.
Catalyst applications of the present invention prepares in the reaction of Celfume and CO at bromine oxidation of methane, and its reaction temperature interval is 400～800 ℃, CH
4/ HBr mol ratio is 0.5～2.0, CH
4/ O
2Mol ratio 0.5～10, HBr aqueous solution inlet amount 1.0～10.0mL/h.
The characteristics of catalyst of the present invention are:
1) structural stability of excellence under the high-temperature water heat condition;
2) active component (FePO
4, Fe
2P
2O
7Or α-Fe
3(P
2O
7)
2) strong with carrier S BA-15 molecular sieve adhesion, active component runs off few in the bromine oxidation of methane course of reaction;
3) good stable property and excellent anti-carbon performance in the bromine oxidation of methane reaction.
The specific embodiment
The technical characterstic that the invention is further illustrated by the following examples, but these embodiment can not limit the present invention.
Embodiment 1:
With 16.0g triblock polymer P123 (EO)
20(PO)
70(EO)
20, 28.06g phosphate aqueous solution (phosphoric acid quality proportion is 85%) and 562g deionized water mix, and 35 ℃ of mechanical agitation obtained solution A in 2 hours in water-bath.With 2.89g nine nitric hydrate iron [Fe (NO
3)
3.9H
2O], 32.8mL ethyl orthosilicate and 40mL deionized water at room temperature magnetic agitation obtained solution B in 0.5 hour.Under 35 ℃ of violent mechanical agitation, solution B is added solution A, and the continuation stirring obtained emulsion C in 20 hours.Emulsion C was transferred in the hydro-thermal synthesis reactor under 90 ℃ of temperature crystallization 24 hours.Again with after the slurry filtration that contains deposition that makes in the water heating kettle, the deionized water washing; Filter cake is in 60 ℃ of oven dry; At last in Muffle furnace in 600 ℃ of roastings 4 hours; (during inductively coupled plasma (ICP) specimen formed, the P/Si mol ratio was 1.65, and the Fe/Si mol ratio is 0.048, nitrogen physisorption specimen specific area is 764m to obtain solid sample
2/ g, pore volume are 0.99m
3/ g).Prepared sample compressing tablet and sieve are got 20-40 order particle packs into and estimates in the fixed-bed quartz reactor.Product adopts gas chromatographic analysis.Reaction condition is: catalyst filling amount 2.0g, methane feed 10mL/min, O
2Charging 5mL/min, HBr/H
2O (HBr quality proportion 40%) charging 3mL/h, 590 ℃ of reaction temperatures, normal pressure.Reaction result is: methane conversion is 47%, and the monobromo methane selectively is 40.9%, and the methylene bromide selectivity is 8.2%, and the CO selectivity is 49.7%, CO
2Selectivity is 1.2%.
Methane conversion and selectivity of product are calculated as follows:
Methane conversion=(the methane molal quantity of conversion) ÷ (getting into the methane molal quantity of reactor) * 100%
Monobromo methane selectively=(generating the molal quantity of a Celfume) ÷ (the methane molal quantity of conversion) * 100%
Methylene bromide selectivity=(generating the molal quantity of methylene bromide) ÷ (the methane molal quantity of conversion) * 100%
CO
xSelectivity=(generate CO
xMolal quantity) ÷ (the methane molal quantity of conversion) * 100%
Embodiment 2:
16.0g triblock polymer P123,28.06g phosphate aqueous solution (phosphoric acid quality proportion is 85%) and 556g deionized water are mixed, and 35 ℃ of mechanical agitation obtained solution A in 2 hours in water-bath.With 6.51g iron chloride [FeCl
3.6H
2O], 32.8mL ethyl orthosilicate and 40mL deionized water at room temperature magnetic agitation obtained solution B in 0.5 hour.Under 35 ℃ of violent mechanical agitation, solution B is added solution A, and the continuation stirring obtained emulsion C in 20 hours.Emulsion C was transferred in the hydro-thermal synthesis reactor under 100 ℃ of temperature crystallization 24 hours.Again with after the slurry filtration that contains deposition that makes in the water heating kettle, the deionized water washing; Filter cake is in 80 ℃ of oven dry; At last in Muffle furnace in 600 ℃ of roastings 4 hours, (during inductively coupled plasma (ICP) specimen formed, the P/Si mol ratio was 1.63 to obtain solid sample; The Fe/Si mol ratio is 0.16, and nitrogen physisorption specimen specific area is 660m
2/ g, pore volume are 0.83m
3/ g).Prepared sample compressing tablet and sieve are got 20-40 order particle packs into and estimates in the fixed-bed quartz reactor.Product adopts gas chromatographic analysis.Reaction condition is: catalyst filling amount 1.0g, methane feed 10mL/min, O
2Charging 5mL/min, HBr/H
2O (HBr quality proportion 40%) charging 3mL/h, 570 ℃ of reaction temperatures, normal pressure.Reaction result is: methane conversion is 44.6%, and the monobromo methane selectively is 33.3%, and the methylene bromide selectivity is 15.8%, and the CO selectivity is 50.2%, CO
2Selectivity is 0.7%.
Embodiment 3:
16.0g triblock polymer P123,41.16g phosphate aqueous solution (phosphoric acid quality proportion is 85%) and 562g deionized water are mixed, and 35 ℃ of mechanical agitation obtained solution A in 2 hours in water-bath.With 3.82g ferrous sulfate [FeSO
4.7H
2O], 32.8mL ethyl orthosilicate and 40mL deionized water at room temperature magnetic agitation obtained solution B in 0.5 hour.Under 35 ℃ of violent mechanical agitation, solution B is added solution A, and the continuation stirring obtained emulsion C in 20 hours.Emulsion C was transferred in the hydro-thermal synthesis reactor under 110 ℃ of temperature crystallization 24 hours.Again with after the slurry filtration that contains deposition that makes in the water heating kettle, the deionized water washing; Filter cake is in 60 ℃ of oven dry; At last in Muffle furnace in 600 ℃ of roastings 4 hours, (during inductively coupled plasma (ICP) specimen formed, the P/Si mol ratio was 2.42 to obtain solid sample; The Fe/Si mol ratio is 0.093, and nitrogen physisorption specimen specific area is 769m
2/ g, pore volume are 1.014m
3/ g).Prepared sample compressing tablet and sieve are got 20-40 order particle packs into and estimates in the fixed-bed quartz reactor.Product adopts gas chromatographic analysis.Reaction condition is: catalyst filling amount 1.0g, methane feed 25mL/min, O
2Charging 5mL/min, HBr/H
2O (HBr quality proportion 40%) charging 8mL/h, 610 ℃ of reaction temperatures, normal pressure.Reaction result is: methane conversion is 22.8%, and the monobromo methane selectively is 69.8%, and the methylene bromide selectivity is 11.3%, and the CO selectivity is 16.9%, CO
2Selectivity is 2.0%.
Embodiment 4:
16.0g triblock polymer P123,84.19g phosphate aqueous solution (phosphoric acid quality proportion is 85%) and 562g deionized water are mixed, and 35 ℃ of mechanical agitation obtained solution A in 2 hours in water-bath.With 0.289g nine nitric hydrate iron [Fe (NO
3)
3.9H
2O], 32.8mL ethyl orthosilicate and 40mL deionized water at room temperature magnetic agitation obtained solution B in 0.5 hour.Under 35 ℃ of violent mechanical agitation, solution B is added solution A, and the continuation stirring obtained emulsion C in 20 hours.Emulsion C was transferred in the hydro-thermal synthesis reactor under 120 ℃ of temperature crystallization 24 hours.Again with after the slurry filtration that contains deposition that makes in the water heating kettle, the deionized water washing; Filter cake is in 60 ℃ of oven dry; At last in Muffle furnace in 600 ℃ of roastings 4 hours, (during inductively coupled plasma (ICP) specimen formed, the P/Si mol ratio was 4.95 to obtain solid sample; The Fe/Si mol ratio is 0.0047, and nitrogen physisorption specimen specific area is 546m
2/ g, pore volume are 0.67m
3/ g).Prepared sample compressing tablet and sieve are got 20-40 order particle packs into and estimates in the fixed-bed quartz reactor.Product adopts gas chromatographic analysis.Reaction condition is: catalyst filling amount 1.0g, methane feed 10mL/min, O
2Charging 5mL/min, HBr/H
2O (HBr quality proportion 40%) charging 10mL/h, 650 ℃ of reaction temperatures, normal pressure.Reaction result is: methane conversion is 43.2%, and the monobromo methane selectively is 61.4%, and the methylene bromide selectivity is 5.2%, and the CO selectivity is 31.9%, CO
2Selectivity is 1.5%.
Embodiment 5:
4.24g ferrous acetate [Fe (CH with the metering ratio
3COO)
2], 16.0g triblock polymer P123,28.06g phosphate aqueous solution (phosphoric acid quality proportion is 85%) and 562g deionized water mix, and obtained solution D in 16 hours in 60 ℃ of stirred in water bath.With obtaining solution E in 2 hours in the stirring of room temperature lower magnetic force in the 32.8g ethyl orthosilicate adding 40mL deionized water.Under violent mechanical agitation, solution D is added solution E, and the continuation stirring obtained emulsion F in 24 hours.Emulsion F was transferred in the hydro-thermal synthesis reactor under 90 ℃ of temperature crystallization 24 hours.Again with after the washing of the slurry filtration that contains deposition that makes in the water heating kettle, deionized water, filter cake is in 60 ℃ of oven dry, at last in Muffle furnace in 600 ℃ of roastings 4 hours.Roasting gained pressed powder obtains described catalyst behind compressing tablet (in inductively coupled plasma (ICP) the specimen composition, the P/Si mol ratio is 1.65, and the Fe/Si mol ratio is 0.17, and nitrogen physisorption specimen specific area is 700m
2/ g, pore volume are 0.89m
3/ g).Reaction condition is: catalyst filling amount 2.0g, methane feed 10mL/min, O
2Charging 5mL/min, HBr/H
2O (HBr quality proportion 40%) charging 4mL/h, 580 ℃ of reaction temperatures, normal pressure.Reaction result is: methane conversion is 43.8%, and the monobromo methane selectively is 49.8%, and the methylene bromide selectivity is 11.0%, and the CO selectivity is 36.9%, CO
2Selectivity is 2.3%.
Embodiment 6:
52.08g ferric nitrate [Fe (NO with the metering ratio
3)
3.9H
2O], 16.0g triblock polymer P123,41.16g phosphate aqueous solution (phosphoric acid quality proportion is 85%) and 560g deionized water mix, and obtained solution D in 16 hours in 80 ℃ of stirred in water bath.With obtaining solution E in 12 hours in the stirring of room temperature lower magnetic force in the 32.8g ethyl orthosilicate adding 40mL deionized water.Under violent mechanical agitation, solution D is added solution E, and the continuation stirring obtained emulsion F in 24 hours.Emulsion F was transferred in the hydro-thermal synthesis reactor under 100 ℃ of temperature crystallization 24 hours.Again with after the washing of the slurry filtration that contains deposition that makes in the water heating kettle, deionized water, filter cake is in 60 ℃ of oven dry, at last in Muffle furnace in 600 ℃ of roastings 4 hours.Roasting gained pressed powder obtains described catalyst behind compressing tablet (in inductively coupled plasma (ICP) the specimen composition, the P/Si mol ratio is 2.40, and the Fe/Si mol ratio is 0.95, and nitrogen physisorption specimen specific area is 802m
2/ g, pore volume are 0.92m
3/ g).Reaction condition is: catalyst filling amount 1.0g, methane feed 15mL/min, O
2Charging 5mL/min, HBr/H
2O (HBr quality proportion 40%) charging 3mL/h, 600 ℃ of reaction temperatures, normal pressure.Reaction result is: methane conversion is 36.5%, and the monobromo methane selectively is 50.8%, and the methylene bromide selectivity is 10.3%, and the CO selectivity is 37.9%, CO
2Selectivity is 1.0%.
Embodiment 7:
6.51g ferric nitrate [Fe (NO with the metering ratio
3)
3.9H
2O], 16.0g triblock polymer P123,41.16g phosphate aqueous solution (phosphoric acid quality proportion is 85%) and 560g deionized water mix, and obtained solution D in 16 hours in 80 ℃ of stirred in water bath.With obtaining solution E in 12 hours in the stirring of room temperature lower magnetic force in the 32.8g ethyl orthosilicate adding 40mL deionized water.Under violent mechanical agitation, solution D is added solution E, and the continuation stirring obtained emulsion F in 24 hours.Emulsion F was transferred in the hydro-thermal synthesis reactor under 100 ℃ of temperature crystallization 24 hours.Again with after the washing of the slurry filtration that contains deposition that makes in the water heating kettle, deionized water, filter cake is in 60 ℃ of oven dry, at last in Muffle furnace in 400 ℃ of roastings 12 hours.Roasting gained pressed powder obtains described catalyst behind compressing tablet (in inductively coupled plasma (ICP) the specimen composition, the P/Si mol ratio is 2.37, and the Fe/Si mol ratio is 0.095, and nitrogen physisorption specimen specific area is 855m
2/ g, pore volume are 0.82m
3/ g).Reaction condition is: catalyst filling amount 1.0g, methane feed 15mL/min, O
2Charging 5mL/min, HBr/H
2O (HBr quality proportion 40%) charging 3mL/h, 600 ℃ of reaction temperatures, normal pressure.Reaction result is: methane conversion is 37.8%, and the monobromo methane selectively is 48.8%, and the methylene bromide selectivity is 9.0%, and the CO selectivity is 40.9%, CO
2Selectivity is 1.3%.
Embodiment 8:
16.0g triblock polymer P123,41.16g phosphate aqueous solution (phosphoric acid quality proportion is 85%) and 562g deionized water are mixed, and 35 ℃ of mechanical agitation obtained solution A in 2 hours in water-bath.With 3.82g ferrous sulfate [FeSO
4.7H
2O], 32.8mL ethyl orthosilicate and 40mL deionized water at room temperature magnetic agitation obtained solution B in 0.5 hour.Under 35 ℃ of violent mechanical agitation, solution B is added solution A, and the continuation stirring obtained emulsion C in 20 hours.Emulsion C was transferred in the hydro-thermal synthesis reactor under 110 ℃ of temperature crystallization 24 hours.Again with after the slurry filtration that contains deposition that makes in the water heating kettle, the deionized water washing; Filter cake is in 60 ℃ of oven dry; At last in Muffle furnace in 500 ℃ of roastings 10 hours, (during inductively coupled plasma (ICP) specimen formed, the P/Si mol ratio was 2.45 to obtain solid sample; The Fe/Si mol ratio is 0.091, and nitrogen physisorption specimen specific area is 705m
2/ g, pore volume are 1.0m
3/ g).Prepared sample compressing tablet and sieve are got 20-40 order particle packs into and estimates in the fixed-bed quartz reactor.Product adopts gas chromatographic analysis.Reaction condition is: catalyst filling amount 1.0g, methane feed 25mL/min, O
2Charging 5mL/min, HBr/H
2O (HBr quality proportion 40%) charging 6mL/h, 630 ℃ of reaction temperatures, normal pressure.Reaction result is: methane conversion is 21.3%, and the monobromo methane selectively is 49.8%, and the methylene bromide selectivity is 6.3%, and the CO selectivity is 40.4%, CO
2Selectivity is 3.5%.
Embodiment 9:
16.0g triblock polymer P123,28.06g phosphate aqueous solution (phosphoric acid quality proportion is 85%) and 556g deionized water are mixed, and 35 ℃ of mechanical agitation obtained solution A in 2 hours in water-bath.With 6.51g iron chloride [FeCl
3.6H
2O], 32.8mL ethyl orthosilicate and 40mL deionized water at room temperature magnetic agitation obtained solution B in 0.5 hour.Under 35 ℃ of violent mechanical agitation, solution B is added solution A, and the continuation stirring obtained emulsion C in 20 hours.Emulsion C was transferred in the hydro-thermal synthesis reactor under 100 ℃ of temperature crystallization 24 hours.Again with after the slurry filtration that contains deposition that makes in the water heating kettle, the deionized water washing; Filter cake is in 80 ℃ of oven dry; At last in Muffle furnace in 800 ℃ of roastings 2 hours, (during inductively coupled plasma (ICP) specimen formed, the P/Si mol ratio was 1.62 to obtain solid sample; The Fe/Si mol ratio is 0.15, and nitrogen physisorption specimen specific area is 529m
2/ g, pore volume are 0.78m
3/ g).Prepared sample compressing tablet and sieve are got 20-40 order particle packs into and estimates in the fixed-bed quartz reactor.Product adopts gas chromatographic analysis.Reaction condition is: catalyst filling amount 1.0g, methane feed 10mL/min, O
2Charging 5mL/min, HBr/H
2O (HBr quality proportion 40%) charging 5mL/h, 600 ℃ of reaction temperatures, normal pressure.Reaction result is: methane conversion is 47.6%, and the monobromo methane selectively is 43.0%, and the methylene bromide selectivity is 10.6%, and the CO selectivity is 45.4%, CO
2Selectivity is 1.0%.
Claims (9)
1. one kind is used for the Fe-P-O catalyst that bromine oxidation of methane prepares Celfume and CO, and this catalyst is made up of active component and carrier, wherein:
Active component is FePO
4, Fe
2P
2O
7Or α-Fe
3(P
2O
7)
2In one or more; The weight of active component is 1.0～60.0% of catalyst weight;
Fe/Si element mol ratio is 0.001～1.0 in the catalyst;
P/Si element mol ratio is 1.0～5.0 in the catalyst;
Carrier is the total silicon molecular sieve SBA-15;
The specific area of catalyst is 100～1500m
2/ g, pore volume are 0.65～1.20m
3/ g.
2. catalyst according to claim 1, wherein, the weight of said active component is 1.0～40.0% of catalyst weight.
3. catalyst according to claim 1, wherein, Fe/Si element mol ratio is 0.004～0.6 in the said catalyst.
4. catalyst according to claim 1, wherein, P/Si element mol ratio is 1.5～4.5 in the said catalyst.
5. catalyst according to claim 1, wherein, the specific area of said catalyst is 300～1200m
2/ g, pore volume are 0.70～1.10m
3/ g.
6. method for preparing the said catalyst of claim 1, its key step is:
Catalyst is a presoma with molysite, phosphate aqueous solution and ethyl orthosilicate, with triblock polymer [(EO)
20(PO)
70(EO)
20] be template, adopt hydro-thermal method, with active component (FePO
4, Fe
2P
2O
7Or α-Fe
3(P
2O
7)
2) original position introducing carrier, form through washing, filtration, drying, roasting, moulding again; Wherein the synthetic crystallization temperature of hydro-thermal is 90-120 ℃, and crystallization time is 12-48 hour; Sintering temperature is 400-800 ℃, and roasting time is 2-12 hour.
7. preparation method according to claim 6, said molysite is one or more in ferric nitrate, iron chloride, frerrous chloride, ferric sulfate, ferrous sulfate, ferric acetate, ferrous acetate, ferric oxalate and the ferrous oxalate.
8. preparation method according to claim 6, said H
3PO
4Quality proportion is 85% phosphate aqueous solution and triblock polymer (EO)
20(PO)
70(EO)
20Weight ratio be 1.0～10.0.
9. the said catalyst of claim 1 prepares the application among Celfume and the CO at bromine oxidation of methane, and its reaction temperature interval is 400～800 ℃, CH
4/ O
2Mol ratio is 0.5～10, and HBr aqueous solution inlet amount is 1.0～10.0ml/h.
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| CN114011454A (en) * | 2021-11-29 | 2022-02-08 | 上海氯碱化工股份有限公司 | Catalyst for preparing chlorine by oxidizing hydrogen chloride and preparation method thereof |
| CN114011454B (en) * | 2021-11-29 | 2023-12-05 | 上海氯碱化工股份有限公司 | Catalyst for preparing chlorine by hydrogen chloride oxidation and preparation method thereof |
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