CN1072615A - The methane oxidation coupling catalyst for making ethylene - Google Patents
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Abstract
The methane oxidation coupling catalyst for making ethylene relates to alkaline earth metal oxide, and the main assembly of catalyzer is M
1O-M
2CO
3, M in the formula
1Be selected from Mg, Ca, Sr, Ba, M
2Be selected from Ca, Sr, Ba.Adopt catalyzer of the present invention at 700-800 ℃ of temperature of reaction, methane air speed 5000-50000h
-1, methane/oxygen=10: 1-2: under 1 the reaction conditions, can obtain methane conversion 10-35%, C
2Yield 5-23%, C
2The reaction result of selectivity 40-80%.
Description
Background of invention
The present invention relates to methane oxidation coupling catalyst for ethylene reaction produced and process, belong to switching through of natural gas straight and utilize technology.
The main source of methane is a Sweet natural gas, at associated gas, also contains a certain amount of methane in the tail gas of coalfield associated gas and petroleum refining process.The composition of Sweet natural gas is different because of the place of production, and wherein methane content is generally more than 80%-98%.Except that methane, also contain a small amount of ethane, propane, butane, pentane, hydrogen sulfide, carbonic acid gas, nitrogen and helium in the Sweet natural gas.
Hydrogen/the carbon atomic ratio of methane is 4, and it is not only a kind of energy of cleaning, also is the desirable feedstock of producing organic chemical industry's product.But because the methane molecule quite stable directly carries out relatively difficulty of chemical process.Sweet natural gas is except that directly doing the fuel, and the utilization on chemical industry mainly is the gas making raw material as synthetic ammonia, or is converted into resynthesis liquid fuel behind the synthetic gas (the MTG method of the synthetic and Mobil of Fischer-Tropsch) and Chemicals.In recent years, because the petroleum resources worsening shortages, the reserves that Sweet natural gas is verified are very abundant again, thereby the processing and utilization of Sweet natural gas caused the generally attention of countries in the world.Wherein the most attractive approach is by directly oxidizing methane coupling system ethene, because ethene is the basic chemical raw materials of tonnage maximum.Can utilize existing petrochemical process to produce various chemical or liquid fuel by ethene.Opened up new approach for rationally utilizing abundant natural gas source.Methane oxidation coupling is hydrogen and carbon monoxide by steam reformation with methane conversion with elder generation, and indirect methods such as resynthesis hydro carbons or alcohols are compared, and not only process is simple, and considers it also is rational from viewpoint of energy.Methane oxidation coupling system ethene also can avoid light oil cracking route propylene simultaneously to cause the problem of propylene surplus.Since the Kcller of U.S.'s union carbide corporation and Bhasin in nineteen eighty-two delivered utilize the reducible metal oxide catalyzer to carry out the initiative work of methane oxidation coupling system ethene since, methane oxidation coupling has become one of research topic the most popular in the catalytic field.Attracted the scientific and technical personnel of countries in the world to be engaged in this important function for of research.Up to the present, people filter out, and hundreds of catalyzer preferably are broadly divided into four big classes: 1. the oxide compound of basic metal and alkaline-earth metal and halogenide, 2. variable valency metal oxide compound, 3. rare-earth oxide, the composite oxides that 4. have definite structure.
1. the oxide compound of basic metal and alkaline-earth metal and halogenide
It is effective methane oxidation coupling catalyst for making ethylene that people such as Lunsford have at first reported the Li/MgO oxide compound, and temperature of reaction is 720 ℃, CH
4/ O
2=2: 1 o'clock, C
2The hydrocarbon yield is 19.4%, and similarly catalyst system also has Na/CaO, Li/ZnO etc.This field development is very fast, and Baerns has at length investigated the oxidative coupling of methane performance of the salt of alkaline earth metal oxide and correspondence thereof.The result shows that CaO and MgO are best carriers, C
2Selectivity is up to 80%, and the roasting condition of catalyzer has considerable influence to reaction result; Mix the composite oxides that form between alkaline earth metal oxide and not only have higher C
2Selectivity, and life-time service catalyst performance stabilised.Though alkali-metal halogenide has very high activity and C
2Selectivity, but, make the permanent stability of catalyzer be difficult to solve because under reaction conditions, halogen participates in reaction and runs off.On CaO, the SrO of the patent that Akishika.Keniich delivers [JP87267243] report, the BaO System Catalyst at 750 ℃ of temperature of reaction, GHSV=6000h
-1The time can get 26% methane conversion and 49% C2 selectivity.
2. variable valency metal oxide compound
People such as Keller and Bhasin adopts CH between 500-1000 ℃
4-N
2/ air/N
2The method of recycle feed reduces to have investigated under the condition of gas phase catalytic reaction supporting in r-Al
2O
3On a series of oxide compounds.Found that low melting point metal oxide compounds such as Sn, Pb, Sb, Bi, Ti, Cd and Mn have relative higher catalytic activity, these metallic cations all have two kinds and two or more stable valence states, lattice oxygen is participated in the methane activation process directly, meets oxidation-reduction (Redox) mechanism.Hinsen and Bearns found PbO/Al under the condition of methane and the common charging of oxygen afterwards
2O
3Catalyzer has high activity and C
2Hydrocarbon-selective.But because the distillation of Pb.The easy inactivation of catalyzer.
3. rare earth metal oxide catalyst
People such as Otsuka have tested the katalysis of rare-earth oxides all in the periodictable to methane oxidation coupling, found that Sm
2O
3Reactivity worth best, when air speed is 2x10
5h
-1The time.C
2Hydrocarbon-selective can reach 94%.Human MISER technology such as Lin are to pure La
2O
3Result of study show that methane produces the fastest of methyl free radicals from the teeth outwards, and in rare-earth oxide La
2O
3Price minimum.Therefore at present to La
2O
3Caused extensive studies interest as methane oxidative coupling catalyst.
4. the composite oxides that have ad hoc structure
This compounds is of a tightly knit structure, is subjected to research worker's attention in recent years gradually.For example Hidetoshi finds to have the SrZrO of perovskite structure
3, can get 11.7% C
2Yield, the LaAlO of human spray shaping methods such as Tagawa preparation
3(non-uhligite) catalyzer.Can get 17% C
2The hydrocarbon yield.Kurtungar has prepared a series of rock salt (ABO that have
2) compound of structure.LiYO wherein
2Catalytic performance is best, C
2The hydrocarbon yield is near 16%.The catalyzer of the bannisterite type of Thomas preparation then can obtain 19.5% C
2The hydrocarbon yield.
Catalyzer is except that active and selectivity, and its stability also is that can be related to industrialized key.There is alkali-metal losing issue in the alkaline-earth oxide catalyzer of existing alkali metals modified.As Ito observe Li/MgO at 793K through reaction in 16 hours, methane conversion just drops to 20.3% from 27%, catalyst surface area is from 8.9m
2/ g reduces to 2.0m
2/ g.Li lost after Kimble reported this catalyzer life-time service, and other alkali metal is volatilization easily also, 1073K reaction 3.5 hours, had lost 40+10% as the Na ion, and the Rb ion can lose about 90%.There is alkali-metal losing issue equally in rare earth oxide catalyst with alkali metals modified.Be impregnated with the Sm of Na according to the Korf report
2O
3Catalyzer, its deactivation cause are because the loss of sodium on the one hand, the Na in 60 hours catalysts
2CO
3Content can drop to 20mol% from initial 55mol%; If Sm with the Ca dipping
2O
3, activity and selectivity are just very stable, do not change through 925 hours behaviour in service, and the Ca ion does not run off yet.
Of transition metal oxide itself is also volatile.As reporting PbO/Al according to Hinsen
2O
3Catalyst reaction is obvious inactivation after a couple of days, and the loss of Pb or PbO is arranged.Except that loss of active component, also has the sintering problem.As Pb/SiO
2Through reaction in 14 hours, surface-area was from 20m at 1013K
2/ g becomes 1.5m
2/ g.
The objective of the invention is to be to overcome the deficiency of prior art and propose to develop a kind of catalyzer that oxidative coupling of methane is had high-activity high-selectivity and good stability.We find, adopt different preparation methods, with the second main group alkaline earth metal oxide and corresponding oxysalt thereof, can satisfy this requirement with different components and the catalyzer of forming preparation.
Detailed description of the present invention
The present invention is high reactivity, highly selective, high stability, low cost, hypotoxicity, resourceful methane oxidation coupling catalyst for making ethylene.Adopt alkaline earth metal compound compound system catalyzer.Main component is oxide compound and the oxysalt based on the second main group metal Mg, Ca, Sr, Ba.And adopt different preparation methods to prepare.
Total body catalyst consists of: M
1O-M
2CO
3, M wherein
2Be selected from one or more classes M2 among Mg, Ca, Sr, the Ba and be selected among Ca, Sr, the Ba one or more, its content can change between 0-100mol%.
Prepare this catalyzer except that adopting coprecipitation method commonly used, also can adopt Slurry mixing, mechanical mixing, ultrasonic dispersing method etc.Precipitation is generally (NH with precipitation agent
4)
2CO
3And NH
3-H
2O is with (NH
4)
2CO
3Be main.Coprecipitation mode is to drip alkaline precipitating agent to make the ascending just precipitation of stock liquid pH value.
1. coprecipitation method
The raw material salt strength of solution is in metal ion content 10-70%, and precipitation agent concentration is about 1.When just precipitating, precipitation agent adds speed control and reached son decide the terminal point pH value in 10-30 minute, and sedimentary terminal point pH value is looked composition and is different between the 7-10 and changes.
Post precipitation is with filter cake washing 2-6 time, and each water consumption is 1/10 to 1/2 of a raw material salt solution with water amount.Wash temperature is a room temperature, and raw material salt solution preparation water and washing of precipitate water are distilled water.
Through washing, the filter cake that filter is done is dry under 80-120 ℃, time 4-6 hour.
Dried filter cake is heated to 700-850 ℃ in air atmosphere, activate 4-6 hour, reduces to the room temperature discharging then.
2. Slurry mixing
With the abundant porphyrize of raw material.Raw material is metal oxide on the alkali, carbonate or subcarbonate.
Raw material behind the porphyrize is mixed by a certain percentage.
Add distilled water in mixture, the water yield is raw material weight 1/2-2 times.
Said mixture is fully stirred, churning time 20-30 minute, pulp.
With the oven dry of above-mentioned paste mixture, temperature 80-120 ℃ time 2-8 hour.
Oven dry back material is heated to 700-800 ℃ of roasting, time 4-8 hour in air atmosphere.Reduce to the room temperature discharging then.
3. ultrasonic dispersing method:
Take by weighing preparation catalyzer oxide compound or the salt used in proportion, mix behind the porphyrize respectively, add again behind a certain amount of Skellysolve A, put into stink cupboard and evaporate, move into 120 ℃ of oven for drying then with ultra-sonic oscillation 2 hours.Put into muffle furnace again in 780 ℃ of following roastings 6 hours, take out after being cooled to room temperature.Pulverize, sieve into 24-50 order particle.
When catalyzer consists of MgO-CaO-SrCO
3-BaCO
3The time, each component content is between 0-100%.
When catalyzer consists of MgO-BaCO
3The time, wherein MgO accounts for 0-100%(mol), BaCO
3Account for 0-100%(mol).
When catalyzer consists of MgO-SrCO
3-BaCO
3The time, wherein MgO accounts for 20-65%(mol), SrCO
3Account for 10-35%(mol), BaCO
3Account for 20-65%(mol).
When catalyzer consists of CaO-SrCO
3-BaCO
3The time, wherein CaO accounts for 20-65%(mol), SrCO
3Account for 10-35%(mol), BaCO
3Account for 20-65%9mol).
When catalyzer consists of CaO-CaCO
3-BaCO
3The time, BaCO wherein
3Account for 10-95%(mol).
When catalyzer consists of SrCO
3-BaCO
3The time, SrCO wherein
3Account for 10-55%.
When catalyzer consists of MgO-BaCO
3The time, MgO accounts for 45-75%(mol).
When catalyzer consists of: MgO-CaO-SrCO
3The time, each component content is between 0-100%.
The preparation method of methane oxidation coupling catalyst for making ethylene adopts coprecipitation method, Slurry mixing or the preparation of ultrasonic dispersing method.Its activation temperature is: 700 ℃-850 ℃, and time 4-8 hour.
When adopting the ultrasonic dispersing method, used ultrasonic dispersing agent is a Skellysolve A.
Catalyzer behind the high-temperature activation has clear and definite crystal phase structure.As MgO/BaCO
3Be MgO phase and BaCO
3Phase, no cenotype generates.
Adopt catalyzer of the present invention, under proper reaction conditions, methane can generate ethene and ethane with higher transformation efficiency and selectivity.
In the oxidative coupling process, the oxygen donator of methane and certain mol proportion (as air) passes through beds.
In the present invention, alcoxyl is than adopting 10: 1-2: 1, and optimum range is 5: 1-5: 2.
In the present invention, adopt fixed-bed reactor or fluidized-bed reactor, based on fixed-bed reactor.
In the present invention, temperature of reaction is 760-820 ℃, and optimum range is 770-790 ℃.
The methane air speed is 5000-50000h
-1Reactor is operated under normal pressure.
Compared with the prior art prescription of the present invention and technology have outstanding substantive distinguishing features and obvious improvement, show: catalyst structure is stable, is easy to preparation; The catalyst activity height, good stability; The space-time yield height has the industrial applications prospect.
Example 1.
Get the Mg(OH of 10g)
2-4MgCO
3-6H
2O fully adds 10ml distilled water behind the porphyrize, constantly stirs into pulpous state, puts into baking oven then and dries by the fire 4 hours down to doing at 120 ℃, takes out then and moves into muffle furnace, is warming up to 780 ℃, roasting 6 hours; Calcination atmosphere is an air.The cooling back is taken out broken, sieves into 24-50 order particle for activity rating.In the catalyzer loading amount is on the silica glass fixed bed of 0.25g.Under reaction gas (methane and air) air-flow, be warming up to 780 ℃, stablize 30min afterreaction gained and the results are shown in table 1.
The reaction result of table 1. methane/air (1: 1) on MgO
Reaction numbering reaction temperature methane air speed reaction result
℃ (x10
4h
-1) methane conversion C
2Yield selectivity %
% % C
2CO
2C
2H
4C
2H
6
1 780 0.20 21.8 13.3 61.3 38.7 37.7 23.6
2 780 0.30 22.4 14.1 63.8 36.2 38.5 25.3
3 780 0.40 23.7 15.9 66.9 33.1 40.0 26.9
4 780 0.45 23.7 15.9 67.2 37.8 39.8 27.4
Example 2
5.13 gram Mg(NO
3)
2-6H
2O, 5.23 gram Ba(NO
3)
2Be dissolved in 40 ml waters, under constantly stirring, add (the NH of 1M with fast speeds
4)
2CO
3Solution made the pH value of precipitated solution reach 9 in 10 minutes, stirred 10 minutes after-filtration, and filter cake is given a baby a bath on the third day after its birth inferior with distilled water, each water consumption 50ml.Filter is done the back filter cake and is put into 120 ℃ of homothermic baking oven oven dry 6 hours, moves to then in the muffle furnace, 750 ℃ of following roastings 4 hours.The cooling back is taken out broken, sieves into 24-50 order particle for activity rating.In the catalyzer loading amount is 0.250 gram, on the silica glass fixed-bed reactor, is heated to temperature of reaction in the reaction gas flow of methane/air=1, stablizes sampling analysis behind the 30min.The gained reaction result sees Table two.
Table 2.
Reaction numbering temperature of reaction methane air speed reaction result
℃ (x10
4h
-1) methane conversion C
2Yield selectivity %
% % C
2CO
2C
2H
4C
2H
6
1 755 1.28 22.6 15.4 67.9 32.1 37.8 30.2
2 780 1.28 22.4 15.1 67.1 32.9 39.5 27.6
3 780 1.44 21.2 14.4 68.1 31.9 40.0 28.1
Example 3.
Take by weighing Mg(OH by a certain percentage)
2-4MgCO
3-6H
2O and BaCO
3, mix after fully grinding about 10 clocks, add the distilled water of equivalent, fully stir and put into 120 ℃ of homothermic baking ovens oven dry (4 hours) after 20 minutes, move into then in the muffle furnace, be warming up to 780 ℃, roasting 4 hours.Take out the cooling back, and fragmentation is sieved into 24-50 order particle and used for activity rating.Activity rating carries out on the thermostatic type fixed bed, and catalyzer loading amount 0.25 gram is reflected under the normal pressure and carries out, and actual conditions and reaction result see Table 3-1,3-2,3-3,3-4.
Reaction result (780 ℃ of the temperature of reaction of table 3-1. different Mg O content catalyzer; Air speed 1.28x10
4h
-1;
Methane/air=1; Catalyst-assembly 0.25 gram)
Catalyzer Mg content reaction result
Numbering mol% methane conversion C
2Yield selectivity %
% % C
2CO
2C
2H
4C
2H
6
1 0 6.9 4.8 69.5 30.5 21.3 48.2
2 17.9 6.3 4.3 69.1 30.9 35.2 33.9
3 32.9 10.1 8.1 75.9 24.1 27.1 48.8
4 45.6 22.5 16.4 73.2 26.8 36.9 36.2
5 56.6 22.9 16.4 71.9 28.1 36.1 35.9
6 61.6 23.9 17.3 72.4 27.6 36.8 35.6
7 66.2 23.3 16.7 72.6 27.4 37.0 35.0
8 74.6 22.2 15.5 69.8 30.2 38.3 31.6
9 80.1 21.8 14.5 66.7 33.3 35.0 31.7
10 88.7 21.1 14.1 66.8 33.2 38.6 28.1
11 99.0 23.3 14.9 64.1 35.9 36.7 27.5
12 100 23.4 15.4 66.0 34.0 39.7 26
Reaction result (780 ℃ of temperature of reaction under the table 3-2. different in flow rate; Methane/air=1; Catalyst n o.6)
Experiment numbers methane air speed reaction result
(x10
4h
-1) methane conversion C
2Yield selectivity %
% % C
2CO
2C
2H
4C
2H
6
1 0.12 21.5 14.2 66.2 33.8 37.6 28.6
2 0.40 23.4 16.7 71.4 28.6 38.7 32.7
3 0.96 23.0 16.2 70.2 29.8 35.2 35.0
4 1.32 23.3 16.6 71.1 28.9 36.1 35.0
5 1.92 23.1 16.4 70.9 29.1 36.0 35.0
6 2.60 23.0 16.3 70.7 29.3 35.2 35.4
Reaction result (780 ℃ of temperature of reaction, air speed 2.56 * 10 that table 3-3 different feeds is formed
4h
-1Catalyst n o.6, loading amount 0.25 gram)
Reaction numbering air/methane reaction result
Methane conversion C
2Yield selectivity %
% % C
2CO
2C
2H
4C
2H
6
1 1.0:1 23.2 16.0 69.1 30.9 35.0 34.0
2 1.2:1 25.5 16.4 64.1 35.9 33.3 30.9
3 1.4:1 27.3 16.
60.0 40.0 32.6 27.4
4 1.5:1 29.1 18.5 63.6 36.4 35.5 28.1
5 1.8:1 30.1 18.0 59.9 40.1 33.2 26.7
Table 3-4 short-term stability is investigated (780 ℃ of temperature of reaction, air speed 1.28 * 10
4h
-1,
Catalyst n o.6, loading amount 0.25 gram, methane/air=1)
Reaction times (hour) 148 12 16 20
Methane conversion % 23.6 23.7 24.1 23.8 23.6 23.9
C
2Yield % 16.4 16.8 17.1 16.9 16.9 17.3
C
2Selectivity % 69.3 70.9 71.3 71.0 71.6 72.4
The MgO/BaCO of one of table 3-1 presentation of results series catalyst of the present invention
3In as Mg/(Mg+Ba)=good result is arranged, wherein with MgO%(mol during 45%-75%)=61.6 catalyzer has optimum.Table 3-2 is the result under o'clock different air speeds of methane/air=1, and this catalyzer can obtain a good result under high-speed, thereby has high space-time yield.Table 3-3 is MgO%(mol among the present invention)=61.6 catalyzer on the reaction result formed of different material.From one of the visible the present invention of table 3-4 MgO/BaCO
3Catalyzer has good stability.
Example 4
Magnesium salts barium salt ratio is with No.6 in the example 3.Mix behind the porphyrize respectively, add the 100ml Skellysolve A, disperseed in 2 hours with ultra-sonic oscillation, taking-up is then put into stink cupboard and is treated to put into after Skellysolve A evaporates fully 120 ℃ of homothermic baking ovens and dry, and moves into then and is warming up to 780 ℃ of roastings 6 hours in the muffle furnace.Take out after being cooled to room temperature, pulverize, sieve into the 24-50 order and use for activity rating.Evaluation method is with example 1.When methane/air=1,780 ℃ of temperature of reaction, GHSV=1.3x10
4h
-1The time can obtain 22.4% methane conversion, 72.6% C
2Hydrocarbon yield and 16.3% C
2Yield.
Example 5
Claim 2.56 gram Mg(NO
3)
2-6H
2O, 2.12 gram Sr(NO
3)
2Reach 2.61 gram Ba(NO
3)
2Add in the 50ml water, constantly stir and be heated to 50-70 ℃, when constantly stirring, add (the NH of 1M then with fast speeds to dissolving
4)
2CO
3Solution stirs 10 minutes after-filtration during to PH=9.Filter cake washing, oven dry, roasting, screening is with example 2.The catalyst activity evaluation is also with example 2.The result shows, the present invention's MgO/SrCO
3/ BaCO
3Catalyzer is at 765 ℃, GHSV=1.12x10
4h
-1, methane/air=1.Can obtain 21.8% methane conversion, 76.1% C under the condition
2Hydrocarbon-selective and 16.6% C
2The hydrocarbon yield.
Example 6
2.36 gram Ca(NO
3)
2-4H
2O, 2.12 gram Sr(NO
3)
2Reach 2.61 gram Ba(NO
3)
2, the catalyzer that use-case 2 prepares with quadrat method, at 760 ℃, GHSV=2.4x10
4h
-1, methane/air=1 o'clock can obtain 23.1% methane conversion, 68.6% C
2Hydrocarbon-selective and 15.8% C
2The hydrocarbon yield.
Example 7
Claim 4.72 gram Ca(NO
3)
2-4H
2O, 5.23 gram Ba(NO
3)
2, use-case 2 prepares catalyzer with quadrat method, and the result shows, the present invention's CaO-CaCO
3/ BaCO
3Catalyzer is at 760 ℃, GHSV=4.5x10
4h
-1, can obtain 23.5% methane conversion, 70.7% C under the condition of methane/air=1
2Hydrocarbon-selective and 16.6 C
2The hydrocarbon yield
Example 8
Claim 4.23 gram Sr(NO
3)
2, 5.23 gram Ba(NO
3)
2, use-case 2 prepares catalyzer with quadrat method, and the result shows, the present invention's SrCO
3/ BaCO
3Catalyzer is at 745 ℃, GHSV=1.44x10
4h
-1, air: CH
4Can obtain the C of 22.0% methane conversion 67.2% under=1.0: 1 condition
2Hydrocarbon-selective and 14.8% C
2The hydrocarbon yield.
Example 9
Claim 2.56 gram Mg(NO
3)
2-6H
2O, 2.36 gram Ca(NO
3)
2-4H
2O, 2.12 gram Sr(NO
3)
2, use-case 2 same methods prepare catalyzer, and the result shows, the present invention's MgO/CaCO
3/ SrCO
3Catalyzer is at 730 ℃, GHSV=1.3x10
4h
-1, methane/air=1 condition can obtain 22.2% methane conversion, 66.2% C
2Hydrocarbon-selective and 14.7% C
2The hydrocarbon yield.
Example 10
Claim 2.56 gram Mg(NO
3)
2-6H
2O, 2.36 gram Ca(NO
3)
2-4H
2O, 2.12 gram Sr(NO
3)
2, 2.61 gram Ba(NO
3)
2, use-case 2 is with the catalyzer of quadrat method preparation, and the result shows, the present invention's MgO/CaCO
3/ SrCO
3/ BaCO
3Catalyzer is at 760 ℃, GHSV=0.55x10
4h
-1, can obtain 21.3% methane conversion under the condition of methane/air=1,63.7% C
2Hydrocarbon-selective and 13.5% C
2The hydrocarbon yield.
Claims (11)
1, methane oxidation coupling catalyst for making ethylene relates to the oxide compound of alkaline-earth metal, and it is characterized in that: main assembly is: M
1O-M
2CO
3, wherein M1 is selected from one or more among Mg, Ca, Sr, the Ba, and M2 is selected from one or more among Ca, Sr, the Ba, and its content can change between 0-100mol%.
2, catalyzer as claimed in claim 1 is characterized in that: consist of MgO-CaO-SrCO
3-BaCO
3
3, catalyzer as claimed in claim 1 is characterized in that: consist of MgO-BaCO
3
4, catalyzer as claimed in claim 1 is characterized in that: consist of MgO-SrCO
3-BaCO
3, wherein MgO accounts for 20-65%(mol), SrCO
3Account for 10-35%(mol), BaCO
3Account for 20-65%(mol).
5, catalyzer as claimed in claim 1 is characterized in that: consist of CaO-SrCO
3-BaCO
3, wherein CaO accounts for 20-65%(mol), SrCO
3Account for 10-35%(mol), BaCO
3Account for 20-65%9mol).
6, catalyzer as claimed in claim 1 is characterized in that: consist of CaO-CaCO
3-BaCO
3, BaCO wherein
3Account for 10-95%(mol).
7, catalyzer as claimed in claim 1 is characterized in that: consist of SrCO
3-BaCO
3SrCO wherein
3Account for 10-55%(mol).
8, catalyzer as claimed in claim 1 or 2 is characterized in that: consist of: MgO-CaO-SrCO
3
9, as claim 1 or 3 described catalyzer, it is characterized in that: MgO accounts for 45-75%(mol).
10, the preparation method of methane oxidation coupling catalyst for making ethylene adopts coprecipitation method, Slurry mixing or the preparation of ultrasonic dispersing method.It is characterized in that: 700 ℃-850 ℃, time 4-8 hour.
11, method for preparing catalyst as claimed in claim 10, when adopting the ultrasonic dispersing method, it is characterized in that: used ultrasonic dispersing agent is a Skellysolve A.
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|---|---|---|---|
| CN 91111291 CN1072615A (en) | 1991-11-28 | 1991-11-28 | The methane oxidation coupling catalyst for making ethylene |
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|---|---|---|---|
| CN 91111291 CN1072615A (en) | 1991-11-28 | 1991-11-28 | The methane oxidation coupling catalyst for making ethylene |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102471181A (en) * | 2009-06-29 | 2012-05-23 | 弗纳技术股份有限公司 | Process for the oxidative coupling of methane |
| CN107175127A (en) * | 2017-05-26 | 2017-09-19 | 南京工业大学 | Supported composite metal molecular sieve catalyst for catalyzing chloromethane coupling to prepare low-carbon olefin |
-
1991
- 1991-11-28 CN CN 91111291 patent/CN1072615A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102471181A (en) * | 2009-06-29 | 2012-05-23 | 弗纳技术股份有限公司 | Process for the oxidative coupling of methane |
| CN107175127A (en) * | 2017-05-26 | 2017-09-19 | 南京工业大学 | Supported composite metal molecular sieve catalyst for catalyzing chloromethane coupling to prepare low-carbon olefin |
| CN107175127B (en) * | 2017-05-26 | 2019-12-17 | 南京工业大学 | Supported composite metal molecular sieve catalyst for catalyzing chloromethane coupling to prepare low-carbon olefin |
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