CN100588461C - Process for preparation of catalysts for making synthesis gas through tri-reforming of methane - Google Patents
Process for preparation of catalysts for making synthesis gas through tri-reforming of methane Download PDFInfo
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- CN100588461C CN100588461C CN200610089007A CN200610089007A CN100588461C CN 100588461 C CN100588461 C CN 100588461C CN 200610089007 A CN200610089007 A CN 200610089007A CN 200610089007 A CN200610089007 A CN 200610089007A CN 100588461 C CN100588461 C CN 100588461C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a preparation method of a catalyst for methane tri-reforming to synthesis gas. The catalyst carrier is dipped in the first solution at first, and the first precursor is prepared by drying and roasting; the dosage of the solvent in the first solution and the soluble nickel salt is determined by the mass of the catalyst carrier; the first precursor is then dipped in the second solution and the invention is prepared by re-drying, roasting and deoxidization; the dosage of the promoter soluble salt and the solvent is determined by the mass of the catalyst carrier; the carrier is prepared by the co-deposition method and surface induced coating method; the prepared catalyst has high activity and stability; on the condition of the oxygen, the rate of conversion of the catalytic carbon dioxide is extremely close to the balance conversion. On the conditions of 850 DEG C, 1 atm, CH4:CO2:H2O:O2 is equal to 1:0.48:0.54:0.1 and GHSV is equal to 10080h-1, the rate of conversion of methane reaches 92.27 percent, the rate o conversion of the carbon dioxide reaches 78.91 percent. On the condition, the activity is not reduced after continuous operation for 50 hours.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method that is used for making synthesis gas through tri-reforming of methane, with and application in making synthesis gas through tri-reforming of methane.
Background technology
By the methane preparing synthetic gas that sets out three approach are arranged, i.e. reforming methane with carbon dioxide " formula (1) ", steam reformation methane " formula (2) " and methane portion oxidation " formula (3) ":
CH
4+CO
2＝2CO+2H
2 ΔH＝247.3kJ/mol (1)
CH
4+H
2O＝CO+3H
2 ΔH＝206.3kJ/mol (2)
CH
4+1/2O
2＝CO+2H
2 ΔH＝-35.6kJ/mol (3)
These three reactions respectively have pluses and minuses, and industrialized at present process has only the steam reformation methane reaction.
Methane tri-reforming preparing synthetic gas is that reforming methane with carbon dioxide, steam reformation methane and three of methane portion oxidations are reflected at the reaction of carrying out simultaneously in the reactor.Except above-mentioned three reactions take place, also there is methane completing combustion reaction " formula (4) " in the tri-reforming process:
CH
4+O
2＝CO
2+2H
2O ΔH＝-880kJ/mol (4)
Like this, methyl hydride combustion and partial oxidation institute liberated heat can be supplied with steam reformation methane reaction and methane reforming reaction by using carbon dioxide, and entire reaction course is realized from heat supply, thereby can improve the efficiency of process greatly, reduce cost.In the reaction of methane tri-reforming, product is H
2/ CO is than being synthesis gas between 1.5～2.0, and this synthesis gas extremely is suitable for making downstream product such as methyl alcohol, dimethyl ether etc., and each components contents can be regulated in the raw material, thereby makes the H of the synthesis gas of generation
2/ CO is than adjustable, and therefore, this process operation is flexible.In addition, because H
2O and O
2" formula (5) and formula (6) " can react with the carbon deposit on the catalyst:
C+H
2O＝CO+H
2 ΔH＝131.4kJ/mol (5)
C+O
2＝CO
2 ΔH＝-393.7kJ/mol (6)
And help the alleviation and the elimination of carbon deposit on the catalyst, thereby prolong the service life of catalyst.Therefore, three of the methane tri-reforming big advantages: process efficiency height, synthesis gas H
2/ CO makes it be expected to substitute existing steam reformation methane process for preparing synthetic gas and produce the synthesis gas of downstream product such as being used for synthesizing methanol, dimethyl ether and clean fuel than suitable, alleviation catalyst carbon deposit.
Methane tri-reforming raw material has four components, and therefore, this process is specially adapted to the utilization of two components or three more coexistent gases of component, as the utilization of power-plant flue gas, coal bed gas and liquefied natural gas.With the coal steam-electric plant smoke is example, contain carbon dioxide, water vapour, these three kinds of primary raw materials of oxygen in the flue gas, if with flue gas and natural gas is raw material, by tri-reforming reaction preparing synthetic gas, then can save the energy that is used for separating carbon dioxide in a large number like this without separating the carbon dioxide that just directly utilizes in the power-plant flue gas.Like this, by the tri-reforming reaction, not only can reduce emission of carbon-dioxide in the flue gas, and this useless waste gas of flue gas can be changed into useful industrial chemicals.
Existing patent documentation report is used for methane reforming reaction by using carbon dioxide, steam reformation methane reaction, the catalyst of partial oxidation reaction of methane respectively separately.These catalyst mainly are divided into two classes, and a class is a noble metal catalyst, and another kind of is non-precious metal catalyst.The anti-carbon deposit performance of noble metal catalyst is strong, but expensive price makes it be difficult to realize industrialization.It is catalyst based that non-precious metal catalyst mostly is Ni, and it is easily because of the carbon deposit inactivation, but can suppress inactivation to wherein adding auxiliary agent, improves stability.CN 1309079 A have reported the catalyst based reforming methane with carbon dioxide that is used for of the Ni that is carried on the MCM-41, and under 700 ℃, normal pressure, the conversion ratio of methane and carbon dioxide can reach more than 90%.CN 1544311 A have reported that a kind of catalyst that is carried on the carborundum is used for partial oxidation reaction of methane, are 40000h at 700 ℃, air speed
-1Condition under, methane conversion is greater than 80%, carbon monoxide and hydrogen selective are all greater than 90%.But so far, do not see that patent report is used for methane tri-reforming catalysts.
Catalyst of the present invention can be used for the reaction of methane tri-reforming preparing synthetic gas, also can be used for flue gas (after desulfurization, the denitration) preparing synthetic gas by reforming methane, also can be used for coal bed gas and is aided with a small amount of water vapor and air preparing synthetic gas by reforming methane.Therefore, have broad application prospects.
Summary of the invention
The object of the present invention is to provide a kind of Preparation of catalysts method that is used for methane tri-reforming preparing synthetic gas.The catalyst of the present invention's preparation is used for the reaction of methane tri-reforming preparing synthetic gas, and the conversion ratio that makes carbon dioxide improves the stability of catalyst near equilibrium conversion.
Technical scheme of the present invention is as follows:
The Preparation of catalysts method that is used for methane tri-reforming preparing synthetic gas provided by the invention, its preparation process is as follows:
1) soluble nickel salt is dissolved in first solvent, forms first solution; The catalyst carrier for preparing be impregnated in first solution, flooded under the room temperature 24～48 hours, evaporate to dryness first solvent in rotary evaporator then, drying, roasting make the complex catalyst precursor thing again;
The consumption of the consumption of first solvent and soluble nickel salt is determined by the quality of catalyst carrier in described first solution:
Required first solvent of catalyst carrier of Y gram is 5Y～10Y milliliter; The nickel nitrate of the first dissolution with solvents 0.1402Y-0.5944Y gram of this 5Y～10Y milliliter or the nickelous sulfate of 0.0325Y-0.3900Y gram; Described Y is an any number;
Described soluble nickel salt is nickel nitrate or nickelous sulfate, and described first solvent is deionized water or ethanol;
2) the promoter soluble salt class is dissolved in the deionized water, forms second solution;
The consumption of the consumption of deionized water and promoter soluble salt class is determined by the quality of catalyst carrier in described second solution:
The required deionized water solvent of catalyst carrier of Y gram is 5Y～10Y milliliter; The promoter soluble salt class of the deionized water solvent dissolving 0.0014Y-0.3900Y gram of this 5Y～10Y milliliter; Described Y is a positive number;
Described promoter soluble salt class is chromic nitrate, cobalt nitrate, ammonium tungstate or ammonium molybdate; Described Y is a positive number;
3) the complex catalyst precursor thing that step 1) is prepared impregnated in second solution, flooded under the room temperature 24～48 hours, careful evaporate to dryness deionized water in rotary evaporator then, drying, roasting can get product of roasting again, will make the catalyst that is used for methane tri-reforming preparing synthetic gas after the product of roasting reduction;
Described catalyst carrier divided catalyst carrier A or catalyst carrier B;
Described catalyst carrier A the steps include: with the preparation of spatial induction coating method
(1) preparation mass concentration scope is 500～1000 milliliters of 1～15% dilute ammonia solutions, after wherein adding 1～5 gram surfactant, fully stirring 10～20 minutes, to wherein adding a certain amount of TiO
2, fully stirred again 30～40 minutes, make TiO
2Uniform particles is scattered in the weak aqua ammonia, and preparation has disperseed TiO
2Dilute ammonia solution; The described TiO that disperseed
2Dilute ammonia solution in TiO
2Content be 0.01～0.2 mole;
Described surfactant is Qu Latong, aliphatic polyoxy vinethene, lauryl sodium sulfate, sodium alkyl benzene sulfonate or aliphatic polyoxy vinethene ammonium sulfate;
(2) preparation mass concentration scope is 150～500 milliliters of 5%～20% hydrogen peroxide solutions;
(3) magnesium salt solution of preparation finite concentration scope is 300～500 milliliters; Wherein the content of magnesium ion is 0.01～0.23 mole;
(4) magnesium salt solution that makes of hydrogen peroxide solution that step (2) is made and step (3) drops to the TiO that is dispersed with that step (1) makes simultaneously with 2 milliliters～5 ml/min flow velocitys respectively
2Dilute ammonia solution in, the dropping process is equipped with stirring, continue to stir 2～6 hours after dropwising again, heavyization is 10～24 hours then, through washing, filtration, alcohol wash, filter, drying and roasting, promptly make catalyst carrier A;
Described catalyst carrier B uses the coprecipitation preparation, the steps include:
(1) preparation mass concentration scope is 500～1000 milliliters of 1～15% dilute ammonia solutions, to wherein adding 1～5 gram surfactant, fully stirs 10～20 minutes, and preparation contains the dilute ammonia solution of surfactant;
Described surfactant is Qu Latong, aliphatic polyoxy vinethene, lauryl sodium sulfate, sodium alkyl benzene sulfonate or aliphatic polyoxy vinethene ammonium sulfate;
(2) preparation mass concentration scope is 150～500 milliliters of 5%～20% hydrogen peroxide solutions;
(3) mixed solution that contains magnesium and titanium of preparation finite concentration scope is 300～500 milliliters; Magnesium salts content is 0.02～0.40 mole in this mixed solution, and the content of titanium salt is 0.01～0.2 mole;
(4) hydrogen peroxide solution of step (2) preparation and the mixed solution that contains magnesium and titanium of step (3) preparation are dropped in the dilute ammonia solution that contains surfactant of step (1) preparation simultaneously with 2 ml/min～5 ml/min flow velocitys respectively, the dropping process is equipped with stirring, continue again after dropwising to stir 2～6 hours, heavyization is 10～24 hours then, through alcohol wash, drying and roasting, can make catalyst carrier (B).
The ammonium molybdate of the chromic nitrate of the described 5Y that preparation second solution uses described step 2)～10Y ml deionized water dissolution with solvents 0.0325Y-0.3900Y gram, the cobalt nitrate of 0.0247Y-0.2964Y gram, 0.0018Y-0.0276Y gram or the ammonium tungstate of 0.0014Y-0.0216Y gram; Described Y is a positive number.
Used TiO in the described catalyst carrier A preparation
2Particle size range be 50 nanometers～1 micron.
The used magnesium salts of step (3) preparation magnesium salt solution in the described catalyst carrier A preparation is magnesium nitrate, magnesium chloride or magnesium acetate; Solvent for use is deionized water or ethanol; Used magnesium salts comprises magnesium nitrate, magnesium chloride or magnesium acetate when step (3) preparation magnesium salts in the described catalyst carrier B preparation and titanium salt mixed solution, and used titanium salt comprises butyl titanate and titanium tetraisopropylate, and solvent for use is an ethanol.
In the step (4) in described catalyst carrier A or the catalyst carrier B preparation, if the magnesium salts that is adopted is a magnesium chloride, water-washing step will carry out repeatedly, all will filter after each washing, detect less than chlorion with liquor argenti nitratis ophthalmicus in the filtrate after washing till.
It is that methyl alcohol, ethanol, normal propyl alcohol are or/and n-butanol that step (4) alcohol in described catalyst carrier A or the catalyst carrier B preparation is washed used alcohol; The consumption that described alcohol is washed used alcohol is 100～500 milliliters, and the alcohol time of washing is 0.5～2.5 hour, and washing times is 1～2 time.
Described drying is carried out under vacuum condition, and temperature is 80～150 ℃, and be 8～16 hours drying time.
Described roasting is carried out in the oxygen volume content is oxygen-nitrogen mixture of 8～10%, and mixed gas flow is 25～80 ml/min, and sintering temperature is 400～700 ℃, and roasting time is 4～6 hours.
With Mg
xTi
1-xThe made catalyst of O note is equipped with carrier, with Ni/Mg
xTi
1-xThe catalyst that O note is prepared, x/ (1-x) are represented the mol ratio of Mg and Ti in the catalyst carrier, and x value scope is 0.05～0.95.
The Preparation of catalysts method that is used for methane tri-reforming preparing synthetic gas provided by the invention has following advantage:
Institute's controlling catalyst has high activity and stability, and under the aerobic situation, the catalysis carbon dioxide conversion is near equilibrium conversion; 850 ℃, 1MPa, CH
4: CO
2: H
2O: O
2=1: 0.48: 0.54: 0.1, GHSV=10080h
-1Under the condition, methane conversion reaches 92.27%, and carbon dioxide conversion reaches 78.91%; Move 50h under this condition continuously and do not see active decline.
Description of drawings
Accompanying drawing 1 is the stability diagram that the catalyst methane tri-reforming of the x=0.75 of embodiment 9 preparations reacts.
The specific embodiment
Embodiment 1
Adopt spatial induction to coat legal system and be equipped with carrier A:
The preparation mass concentration is 1000 milliliters of 1% dilute ammonia solutions, to wherein adding 1 gram aliphatic polyoxy vinethene, fully stirs 10 minutes, to wherein adding 12.10 gram TiO
2(its amount of substance is 0.1515 mole, and its particle size range is 50 nanometers～1 micron) fully stirred 30 minutes again, made TiO
2Uniform particles is scattered in the weak aqua ammonia;
The preparation mass concentration is 500 milliliters of 5% hydrogen peroxide solutions;
Getting 2.07 (its amount of substance is 0.0080 mole) grams magnesium nitrate is dissolved in 300 ml deionized water and prepares magnesium salt solution;
Hydrogen peroxide solution and magnesium salt solution all be added dropwise to jointly with the flow velocity of 2 ml/min disperseed TiO
2Weak aqua ammonia in, the dropping process is equipped with stirring, dropwise back stirring, heavyization, filter, filter cake is scattered in 100 ml methanol stirs, get filter cake after the filtration and be scattered in stirring filtration after 0.5 hour in 100 ml methanol again, get filter cake in 80 ℃ of following vacuum drying 16 hours, again roasting in oxygen-nitrogen mixture (flow is 25～80 ml/min) of 8%, sintering temperature is 700 ℃, and roasting time is 4 hours.Can make about 10 grams of carrier A of x=0.05 like this.
Get Y gram carrier A (Y=5), under room temperature, impregnated in 50 milliliters contain 2.97 gram nickel nitrates, be in first solution of solvent with ethanol, flood after 24 hours and take out, in 110 ℃ of following vacuum drying 12 hours, again in the oxygen volume content be in 8% oxygen-nitrogen mixture body in 600 ℃ of following roastings 4 hours, can make the complex catalyst precursor thing;
With the complex catalyst precursor thing impregnated in 50 milliliters contain 1.95 gram chromic nitrates, be in second solution of solvent with ethanol, flood after 24 hours and take out, in 110 ℃ of following vacuum drying 12 hours, again in the oxygen volume content be in 8% oxygen-nitrogen mixture body in 600 ℃ of following roastings 4 hours, can make product of roasting;
Product of roasting is filled in the reactor, behind the temperature programmed reduction, can make catalyst, Preparation of Catalyst back direct-on-line evaluation well;
The described chromic nitrate of present embodiment can be optional in 0.1625 gram～1.95 gram scopes.
Embodiment 2
Adopt spatial induction to coat legal system and be equipped with carrier A:
The preparation mass concentration is 900 milliliters of 4% dilute ammonia solutions, to wherein adding 2 gram Qu Latong, fully stirs 15 minutes, to wherein adding 10.33 gram TiO
2(its amount of substance is 0.1294 mole, and its particle size range is 50 nanometers～1 micron) fully stirred 35 minutes again, made TiO
2Uniform particles is scattered in the weak aqua ammonia;
The preparation mass concentration is 400 milliliters of 10% hydrogen peroxide solutions;
Getting 8.94 gram magnesium chlorides (its amount of substance is 0.0431 mole) is dissolved in 350 ml deionized water and prepares magnesium salt solution;
Hydrogen peroxide solution and magnesium salt solution all be added dropwise to the flow velocity of 3 ml/min disperseed TiO
2Weak aqua ammonia in, the dropping process is equipped with stirring, dropwise back stirrings, heavyization, filter, with the abundant washing leaching cake of deionized water, extremely with the liquor argenti nitratis ophthalmicus detection less than till the chlorion existence arranged in the filtrate.Filter cake is scattered in 200 milliliters of ethanol stirred 1 hour, get filter cake after the filtration and be scattered in stirring filtration after 1 hour in 200 milliliters of ethanol again, get filter cake in 100 ℃ of following vacuum drying 14 hours, roasting in oxygen-nitrogen mixture (flow is 25～80 ml/min) of 9% again, sintering temperature is 600 ℃, and roasting time is 5 hours.Can make about 10 grams of carrier A of x=0.25 like this.
Get Y gram carrier A (Y=5), under room temperature, impregnated in 45 milliliters contain 2.40 gram nickel nitrates, be in first solution of solvent with water, flood after 32 hours and take out, in 110 ℃ of following vacuum drying 12 hours, again in the oxygen volume content be in 8% oxygen-nitrogen mixture body in 600 ℃ of following roastings 4 hours, can make the complex catalyst precursor thing;
With the complex catalyst precursor thing impregnated in 40 milliliters contain 0.80 gram cobalt nitrate, be in second solution of solvent with water, flood after 24 hours and take out, in 110 ℃ of following vacuum drying 12 hours, again in the oxygen volume content be in 8% oxygen-nitrogen mixture body in 600 ℃ of following roastings 4 hours, can make product of roasting;
Product of roasting is filled in the reactor, behind the temperature programmed reduction, can make catalyst, Preparation of Catalyst back direct-on-line evaluation well;
The described cobalt nitrate of present embodiment can be optional in 0.1235 gram～1.4822 gram scopes.
Embodiment 3
Adopt spatial induction to coat legal system and be equipped with carrier A:
The preparation mass concentration is 800 milliliters of 7% dilute ammonia solutions, to wherein adding 3 gram lauryl sodium sulfate, fully stirs 20 minutes, to wherein adding 7.67 gram TiO
2(its amount of substance is 0.0960 mole, and its particle size range is 50 nanometers～1 micron) fully stirred 40 minutes again, made TiO
2Uniform particles is scattered in the weak aqua ammonia;
The preparation mass concentration is 300 milliliters of 15% hydrogen peroxide solutions;
Getting 20.99 gram magnesium acetates (its amount of substance is 0.0960 mole) is dissolved in 400 ml deionized water and prepares magnesium salt solution;
Hydrogen peroxide solution and magnesium salt solution all be added dropwise to the flow velocity of 4 ml/min disperseed TiO
2Weak aqua ammonia in, the dropping process is equipped with stirring, dropwise back stirring, heavyization, filter, filter cake is scattered in 300 milliliters of normal propyl alcohols stirred 1.5 hours, get filter cake after the filtration in 120 ℃ of following vacuum drying 12 hours, roasting in oxygen-nitrogen mixture (flow is 25～80 ml/min) of 8% again, sintering temperature is 500 ℃, roasting time is 6 hours.Can make about 10 grams of carrier A of x=0.5 like this.
Get Y gram carrier A (Y=5), under room temperature, impregnated in 35 milliliters contain 1.84 gram nickel nitrates, be in first solution of solvent with water, flood after 40 hours and take out, in 110 ℃ of following vacuum drying 12 hours, again in the oxygen volume content be in 8% oxygen-nitrogen mixture body in 600 ℃ of following roastings 4 hours, can make the complex catalyst precursor thing;
With the complex catalyst precursor thing impregnated in 30 milliliters contain 0.04 gram ammonium molybdate, be in second solution of solvent with water, flood after 24 hours and take out, in 110 ℃ of following vacuum drying 12 hours, again in the oxygen volume content be in 8% oxygen-nitrogen mixture body in 600 ℃ of following roastings 4 hours, can make product of roasting;
Product of roasting is filled in the reactor, behind the temperature programmed reduction, can make catalyst, Preparation of Catalyst back direct-on-line evaluation well;
The described ammonium molybdate of present embodiment can be optional in 0.0092 gram～0.1381 gram scope.
Embodiment 4
Adopt spatial induction to coat legal system and be equipped with carrier A:
The preparation mass concentration is 700 milliliters of 11% dilute ammonia solutions, to wherein adding 4 gram sodium alkyl benzene sulfonates, fully stirs 10 minutes, to wherein adding 4.32 gram TiO
2(its amount of substance is 0.0541 mole, and its particle size range is 50 nanometers～1 micron) filled and stirred in 30 minutes minute, makes TiO
2Uniform particles is scattered in the weak aqua ammonia;
The preparation mass concentration is 200 milliliters of 20% hydrogen peroxide solutions;
Getting 42.05 gram magnesium nitrates (its amount of substance is 0.1623 mole) is dissolved in 450 ml deionized water and prepares magnesium salt solution;
Hydrogen peroxide solution and magnesium salt solution all be added dropwise to the flow velocity of 5 ml/min disperseed TiO
2Weak aqua ammonia in, the dropping process is equipped with stirring, dropwise back stirring, heavyization, filter, filter cake is scattered in 400 milliliters of n-butanols stirred 2 hours, get filter cake after the filtration in 140 ℃ of following vacuum drying 10 hours, roasting in oxygen-nitrogen mixture (flow is 25～80 ml/min) of 8% again, sintering temperature is 400 ℃, roasting time is 6 hours.Can make about 10 grams of carrier A of x=0.75 like this.
Get Y gram carrier A (Y=5), under room temperature, impregnated in 30 milliliters contain 1.27 gram nickel nitrates, be in first solution of solvent with water, flood after 48 hours and take out, in 110 ℃ of following vacuum drying 12 hours, again in the oxygen volume content be in 8% oxygen-nitrogen mixture body in 600 ℃ of following roastings 4 hours, can make the complex catalyst precursor thing;
With the complex catalyst precursor thing impregnated in 25 milliliters contain 0.06 gram ammonium tungstate, be in second solution of solvent with water, flood after 24 hours and take out, in 110 ℃ of following vacuum drying 12 hours, again in the oxygen volume content be in 8% oxygen-nitrogen mixture body in 600 ℃ of following roastings 4 hours, can make product of roasting;
Product of roasting is filled in the reactor, behind the temperature programmed reduction, can make catalyst, Preparation of Catalyst back direct-on-line evaluation well;
The described ammonium tungstate of present embodiment can be optional in 0.0072 gram～0.1079 gram scope.
Embodiment 5
Adopt spatial induction to coat legal system and be equipped with carrier A:
The preparation mass concentration is 500 milliliters of 15% dilute ammonia solutions, to wherein adding 5 gram aliphatic polyoxy vinethene ammonium sulfate, fully stirs 20 minutes, to wherein adding 0.96 gram TiO
2(its amount of substance is 0.0121 mole, and its particle size range is 50 nanometers～1 micron) fully stirred 40 minutes again, made TiO
2Uniform particles is scattered in the weak aqua ammonia;
The preparation mass concentration is 150 milliliters of 15% hydrogen peroxide solutions;
Get 47.50 gram magnesium chlorides (its amount of substance is 0.2290 mole) and be dissolved in preparation magnesium salt solution in 500 ml deionized water;
Hydrogen peroxide solution and magnesium salt solution all be added dropwise to the flow velocity of 3 ml/min disperseed TiO
2Weak aqua ammonia in, the dropping process is equipped with stirring, dropwise back stirrings, heavyization, filter, with the abundant washing leaching cake of deionized water, extremely with the liquor argenti nitratis ophthalmicus detection less than till the chlorion existence arranged in the filtrate.Filter cake is scattered in 500 milliliters of ethanol stirred 2.5 hours, get filter cake after the filtration in 150 ℃ of following vacuum drying 8 hours, roasting in oxygen-nitrogen mixture (flow is 25～80 ml/min) of 8% again, sintering temperature is 400 ℃, roasting time is 6 hours.Can make about 10 grams of carrier A of x=0.95 like this.
Get 5 gram carrier A, under room temperature, impregnated in 25 milliliters contain 0.70 gram nickel nitrate, be in first solution of solvent with water, flood after 24 hours and take out, in 110 ℃ of following vacuum drying 12 hours, again in the oxygen volume content be in 8% oxygen-nitrogen mixture body in 600 ℃ of following roastings 4 hours, can make the complex catalyst precursor thing;
With the complex catalyst precursor thing impregnated in 25 milliliters contain 0.11 gram ammonium tungstate, be in second solution of solvent with water, flood after 24 hours and take out, in 110 ℃ of following vacuum drying 12 hours, again in the oxygen volume content be in 8% oxygen-nitrogen mixture body in 600 ℃ of following roastings 4 hours, can make product of roasting;
Product of roasting is filled in the reactor, behind the temperature programmed reduction, can make catalyst, Preparation of Catalyst back direct-on-line evaluation well;
The described ammonium tungstate of present embodiment can be optional in 0.0072 gram～0.1079 gram scope.
The methane tri-reforming reaction of carrying out on the catalyst of the x=0.5 of present embodiment 5 preparations is at 850 ℃, 1atm, 10080h
-1, CH
4: CO
2: H
2O: O
2=1: under 0.48: 0.54: 0.1 the condition, carbon dioxide conversion reaches 85.08%, than document " Song C.-S.; Pan W.Catalysis Today 2004,98,463. " in carbon dioxide conversion (76%) under the similarity condition high by about 9%.
Embodiment 6
Adopt coprecipitation to prepare carrier B:
The preparation mass concentration is 1000 milliliters of 1% dilute ammonia solutions, to wherein adding 1 gram aliphatic polyoxy vinethene, fully stirs 10 minutes;
The preparation mass concentration is 500 milliliters of 5% hydrogen peroxide solutions, gets 2.07 gram magnesium nitrates (its amount of substance is 0.0080 mole) and 52.63 and restrains butyl titanates (its amount of substance is 0.1515 mole) and be dissolved in 300 milliliters of ethanol and form mixing salt solution;
All be added dropwise in the weak aqua ammonia jointly hydrogen peroxide solution and mixing salt solution with the flow velocity of 2 ml/min, the dropping process is equipped with stirring, dropwise back stirring, heavyization, filter, filter cake is scattered in 100 ml methanol stirs, get filter cake after the filtration and disperse to stir in 100 ml methanol filtration after 0.5 hour again, get filter cake in 80 ℃ of following vacuum drying 16 hours, roasting in oxygen-nitrogen mixture (flow is 25～80 ml/min) of 8% again, sintering temperature is 700 ℃, and roasting time is 4 hours.Can make about 10 grams of carrier A of x=0.05 like this.
Get Y gram carrier B (Y=5), under room temperature, impregnated in 50 milliliters contain 0.37 gram nickelous sulfate, be in first solution of solvent with ethanol, flood after 24 hours and take out, in 110 ℃ of following vacuum drying 12 hours, again in the oxygen volume content be in 8% oxygen-nitrogen mixture body in 600 ℃ of following roastings 4 hours, can make the complex catalyst precursor thing;
With the complex catalyst precursor thing impregnated in 25 milliliters contain 0.61 gram chromic nitrate, be in second solution of solvent with water, flood after 24 hours and take out, in 110 ℃ of following vacuum drying 12 hours, again in the oxygen volume content be in 8% oxygen-nitrogen mixture body in 600 ℃ of following roastings 4 hours, can make product of roasting;
Product of roasting is filled in the reactor, behind the temperature programmed reduction, can make catalyst, Preparation of Catalyst back direct-on-line evaluation well;
The described chromic nitrate of present embodiment can be optional in 0.1625 gram～1.95 gram scopes.
Embodiment 7
Adopt coprecipitation to prepare carrier B:
The preparation mass concentration is 900 milliliters of 4% dilute ammonia solutions, to wherein adding 2 gram Qu Latong, fully stirs 15 minutes;
The preparation mass concentration is 400 milliliters of 10% hydrogen peroxide solutions;
Getting 8.94 gram magnesium chlorides (its amount of substance is 0.0431 mole) and 37.52 restrains tetraisopropyl titanates (its amount of substance is 0.1294 mole) and is dissolved in 350 milliliters of ethanol and forms mixing salt solution;
Hydrogen peroxide solution and mixing salt solution all are added dropwise in the weak aqua ammonia with the flow velocity of 3 ml/min, the dropping process is equipped with stirring, dropwise back stirring, heavyization, filter, with the abundant washing leaching cake of deionized water, to detecting with liquor argenti nitratis ophthalmicus less than till having chlorion to exist in the filtrate.Filter cake is scattered in 200 milliliters of ethanol stirred 1 hour, get filter cake after the filtration and disperse to stir in 200 milliliters of ethanol filtration after 1 hour again, get filter cake in 100 ℃ of following vacuum drying 14 hours, roasting in oxygen-nitrogen mixture (flow is 25～80 ml/min) of 9% again, sintering temperature is 600 ℃, and roasting time is 5 hours.Can make about 10 grams of carrier A of x=0.25 like this.
Get Y gram carrier B (Y=5), under room temperature, impregnated in 45 milliliters contain 0.68 gram nickelous sulfate, be in first solution of solvent with water, flood after 32 hours and take out, in 110 ℃ of following vacuum drying 12 hours, again in the oxygen volume content be in 8% oxygen-nitrogen mixture body in 600 ℃ of following roastings 4 hours, can make the complex catalyst precursor thing;
With the complex catalyst precursor thing impregnated in 25 milliliters contain 0.14 gram ammonium molybdate, be in second solution of solvent with water, flood after 24 hours and take out, in 110 ℃ of following vacuum drying 12 hours, again in the oxygen volume content be in 8% oxygen-nitrogen mixture body in 600 ℃ of following roastings 4 hours, can make product of roasting;
Product of roasting is filled in the reactor, behind the temperature programmed reduction, can make catalyst, Preparation of Catalyst back direct-on-line evaluation well;
The described ammonium molybdate of present embodiment can be optional in 0.0092 gram～0.1381 gram scope.
Embodiment 8
Adopt coprecipitation to prepare carrier B:
The preparation mass concentration is 800 milliliters of 7% dilute ammonia solutions, to wherein adding 3 gram lauryl sodium sulfate, fully stirs 20 minutes;
The preparation mass concentration is 300 milliliters of 15% hydrogen peroxide solutions, gets 20.99 gram magnesium acetates (its amount of substance is 0.0960 mole) and 19.91 and restrains butyl titanates (its amount of substance is 0.0960 mole) and be dissolved in 400 milliliters of ethanol and form mixing salt solution;
Hydrogen peroxide solution and mixing salt solution all are added dropwise in the weak aqua ammonia with the flow velocity of 4 ml/min, the dropping process is equipped with stirring, dropwise back stirring, heavyization, filter, filter cake is scattered in 300 milliliters of normal propyl alcohols stirred 1.5 hours, get filter cake after the filtration in 120 ℃ of following vacuum drying 12 hours, roasting in oxygen-nitrogen mixture (flow is 25～80 ml/min) of 8% again, sintering temperature is 500 ℃, roasting time is 6 hours.Can make about 10 grams of carrier A of x=0.5 like this;
Get Y gram carrier B (Y=5), under room temperature, impregnated in 35 milliliters contain 0.98 gram nickelous sulfate, be in first solution of solvent with water, flood after 40 hours and take out, in 110 ℃ of following vacuum drying 12 hours, again in the oxygen volume content be in 8% oxygen-nitrogen mixture body in 600 ℃ of following roastings 4 hours, can make the complex catalyst precursor thing;
With the complex catalyst precursor thing impregnated in 25 milliliters contain 0.11 gram ammonium tungstate, be in second solution of solvent with water, flood after 24 hours and take out, in 110 ℃ of following vacuum drying 12 hours, again in the oxygen volume content be in 8% oxygen-nitrogen mixture body in 600 ℃ of following roastings 4 hours, can make product of roasting;
Product of roasting is filled in the reactor, behind the temperature programmed reduction, can make catalyst, Preparation of Catalyst back direct-on-line evaluation well.
Embodiment 9
Adopt coprecipitation to prepare carrier B:
The preparation mass concentration is 700 milliliters of 11% dilute ammonia solutions, to wherein adding 4 gram sodium alkyl benzene sulfonates, fully stirs 10 minutes;
The preparation mass concentration is 200 milliliters of 20% hydrogen peroxide solutions;
Getting 42.05 gram magnesium nitrates (its amount of substance is 0.1623 mole) and 15.70 restrains different two esters of metatitanic acid first (its amount of substance is 0.0541 mole) and is dissolved in 450 milliliters of ethanol and forms mixing salt solution;
Hydrogen peroxide solution and mixing salt solution all are added dropwise in the weak aqua ammonia with the flow velocity of 5 ml/min, the dropping process is equipped with stirring, dropwise back stirring, heavyization, filter, filter cake is scattered in 400 milliliters of n-butanols stirred 2 hours, get filter cake after the filtration in 140 ℃ of following vacuum drying 10 hours, roasting in oxygen-nitrogen mixture (flow is 25～80 ml/min) of 8% again, sintering temperature is 400 ℃, roasting time is 6 hours.Can make about 10 grams of carrier A of x=0.75 like this;
Get Y gram carrier B (Y=5), under room temperature, impregnated in 30 milliliters contain 1.28 gram nickelous sulfates, be in first solution of solvent with water, flood after 48 hours and take out, in 110 ℃ of following vacuum drying 12 hours, again in the oxygen volume content be in 8% oxygen-nitrogen mixture body in 600 ℃ of following roastings 4 hours, can make the complex catalyst precursor thing;
With the complex catalyst precursor thing impregnated in 25 milliliters contain 1.14 gram cobalt nitrates, be in second solution of solvent with water, flood after 24 hours and take out, in 110 ℃ of following vacuum drying 12 hours, again in the oxygen volume content be in 8% oxygen-nitrogen mixture body in 600 ℃ of following roastings 4 hours, can make product of roasting;
Product of roasting is filled in the reactor, behind the temperature programmed reduction, can make catalyst, Preparation of Catalyst back direct-on-line evaluation well;
The described ammonium tungstate of present embodiment can be optional in 0.0072 gram～0.1079 gram scope.
The methane tri-reforming reaction of carrying out on the catalyst of the x=0.75 of present embodiment 9 preparations is at 850 ℃, 1MPa, 10080h
-1, CH
4: CO
2: H
2O: O
2=1: under 0.48: 0.54: 0.1 the condition, carbon dioxide conversion reaches 79.01%, than document " Xu Dongyan, Li Wenzhao, Chen Yanxin, Xu Hengyong. coal journal 2004,29,469 " in carbon dioxide conversion (40%) under the similarity condition high by about 39%; At 850 ℃, 1MPa, 10080h
-1, CH
4: CO
2: H
2O: O
2=1: under 0.48: 0.54: 0.1 the condition, do not see active decline after moving 50 hours continuously.
Embodiment 10
Adopt coprecipitation to prepare carrier B:
The preparation mass concentration is 500 milliliters of 15% dilute ammonia solutions, to wherein adding 5 gram aliphatic polyoxy vinethene ammonium sulfate, fully stirs 20 minutes;
The preparation mass concentration is 150 milliliters of 15% hydrogen peroxide solutions, gets 47.50 gram magnesium chlorides (its amount of substance is 0.2290 mole) and 4.19 and restrains butyl titanates (its amount of substance is 0.0121 mole) and be dissolved in 500 milliliters of ethanol and be mixed with mixing salt solution;
Hydrogen peroxide solution and magnesium salt solution all are added dropwise in the weak aqua ammonia with the flow velocity of 3 ml/min, the dropping process is equipped with stirring, dropwise back stirring, heavyization, filter, with the abundant washing leaching cake of deionized water, to detecting with liquor argenti nitratis ophthalmicus less than till having chlorion to exist in the filtrate.Filter cake is scattered in 500 milliliters of ethanol stirred 2.5 hours, get filter cake after the filtration in 150 ℃ of following vacuum drying 8 hours, roasting in oxygen-nitrogen mixture (flow is 25～80 ml/min) of 8% again, sintering temperature is 400 ℃, roasting time is 6 hours.Can make about 10 grams of carrier A of x=0.95 like this;
Get Y gram carrier B (Y=5), under room temperature, impregnated in 25 milliliters contain 1.58 gram nickelous sulfates, be in first solution of solvent with ethanol, flood after 24 hours and take out, in 110 ℃ of following vacuum drying 12 hours, again in the oxygen volume content be in 8% oxygen-nitrogen mixture body in 600 ℃ of following roastings 4 hours, can make the complex catalyst precursor thing;
With the complex catalyst precursor thing impregnated in 25 milliliters contain 1.5 gram chromic nitrates, be in second solution of solvent with water, flood after 24 hours and take out, in 110 ℃ of following vacuum drying 12 hours, again in the oxygen volume content be in 8% oxygen-nitrogen mixture body in 600 ℃ of following roastings 4 hours, can make product of roasting;
Product of roasting is filled in the reactor, behind the temperature programmed reduction, can make catalyst, Preparation of Catalyst back direct-on-line evaluation well;
The described chromic nitrate of present embodiment can be optional in 0.1625 gram～1.95 gram scopes.
Catalyst of the present invention is used for catalytic methane tri-reforming when reaction, adopts fixed bed reactors, and reaction temperature is 750～950 ℃, with 800～900 ℃ for well, reaction pressure is 1atm～2MPa, with 1atm～1MPa for well.With 850 ℃, 1atm, CH
4: CO
2: H
2O: O
2=1: 0.48: 0.54: 0.1, GHSV=10080h
-1Condition and 850 ℃, 1MPa, CH
4: CO
2: H
2O: O
2=1: 0.48: 0.54: 0.1, GHSV=10080h
-1Condition be example, reaction result sees Table 1 and table 2.Table 1 is the evaluation result under the normal pressure, and table 2 is for adding the evaluation result of depressing.
Table 1: evaluating catalyst result under the normal pressure
Table 2: add and depress the evaluating catalyst result
Claims (8)
1, a kind of Preparation of catalysts method that is used for methane tri-reforming preparing synthetic gas, its preparation process is as follows:
1) soluble nickel salt is dissolved in first solvent, forms first solution; The catalyst carrier for preparing be impregnated in first solution, flooded under the room temperature 24～48 hours, evaporate to dryness first solvent in rotary evaporator then, drying, roasting make the complex catalyst precursor thing again;
The consumption of the consumption of first solvent and soluble nickel salt is determined by the quality of catalyst carrier in described first solution:
Required first solvent of catalyst carrier of Y gram is 5Y～10Y milliliter; The nickel nitrate of the first dissolution with solvents 0.1402Y-0.5944Y gram of this 5Y～10Y milliliter or the nickelous sulfate of 0.0325Y-0.3900Y gram; Described Y is a positive number;
Described soluble nickel salt is nickel nitrate or nickelous sulfate, and described first solvent is deionized water or ethanol;
2) the promoter soluble salt class is dissolved in the deionized water, forms second solution;
The consumption of the consumption of deionized water and promoter soluble salt class is determined by the quality of catalyst carrier in described second solution:
The required deionized water solvent of catalyst carrier of Y gram is 5Y～10Y milliliter; The promoter soluble salt class of the deionized water solvent dissolving 0.0014Y-0.3900Y gram of this 5Y～10Y milliliter; Described Y is a positive number;
Described promoter soluble salt class is chromic nitrate, cobalt nitrate, ammonium tungstate or ammonium molybdate;
3) the complex catalyst precursor thing that step 1) is prepared impregnated in second solution, flooded under the room temperature 24～48 hours, careful evaporate to dryness deionized water in rotary evaporator then, drying, roasting can make product of roasting again, will make the catalyst that is used for methane tri-reforming preparing synthetic gas after the product of roasting reduction;
Described catalyst carrier fractional bearer (A) or catalyst carrier (B);
Described catalyst carrier (A) the steps include: with the preparation of spatial induction coating method
(1) preparation mass concentration scope is 500～1000 milliliters of 1～15% dilute ammonia solutions, after wherein adding 1～5 gram surfactant, fully stirring 10～20 minutes, to wherein adding a certain amount of TiO
2, fully stirred again 30～40 minutes, make TiO
2Uniform particles is scattered in the weak aqua ammonia, and preparation has disperseed TiO
2Dilute ammonia solution; The described TiO that disperseed
2Dilute ammonia solution in TiO
2Content be 0.01～0.2 mole;
Described surfactant is Qu Latong, aliphatic polyoxy vinethene, lauryl sodium sulfate, sodium alkyl benzene sulfonate or aliphatic polyoxy vinethene ammonium sulfate;
(2) preparation mass concentration scope is 150～500 milliliters of 5%～20% hydrogen peroxide solutions;
(3) magnesium salt solution of preparation finite concentration scope is 300～500 milliliters; Wherein the content of magnesium ion is 0.01～0.23 mole;
(4) magnesium salt solution that makes of hydrogen peroxide solution that step (2) is made and step (3) drops to the TiO that is dispersed with that step (1) makes simultaneously with 2 milliliters～5 ml/min flow velocitys respectively
2Dilute ammonia solution in, the dropping process is equipped with stirring, continue to stir 2～6 hours after dropwising again, heavyization is 10～24 hours then, through washing, filtration, alcohol wash, filter, drying and roasting, promptly make catalyst carrier (A);
Described catalyst carrier (B) is used the coprecipitation preparation, the steps include:
(1) preparation mass concentration scope is 500～1000 milliliters of 1～15% dilute ammonia solutions, to wherein adding 1～5 gram surfactant, fully stirs 10～20 minutes, and preparation contains the dilute ammonia solution of surfactant;
Described surfactant is Qu Latong, aliphatic polyoxy vinethene, lauryl sodium sulfate, sodium alkyl benzene sulfonate or aliphatic polyoxy vinethene ammonium sulfate;
(2) preparation mass concentration scope is 150～500 milliliters of 5%～20% hydrogen peroxide solutions;
(3) mixed solution that contains magnesium and titanium of preparation finite concentration scope is 300～500 milliliters; Magnesium salts content is 0.02～0.40 mole in this mixed solution, and the content of titanium salt is 0.01～0.2 mole;
(4) hydrogen peroxide solution of step (2) preparation and the mixed solution that contains magnesium and titanium of step (3) preparation are dropped in the dilute ammonia solution that contains surfactant of step (1) preparation simultaneously with 2 ml/min～5 ml/min flow velocitys respectively, the dropping process is equipped with stirring, continue again after dropwising to stir 2～6 hours, heavyization is 10～24 hours then, through alcohol wash, drying and roasting, can make catalyst carrier (B).
2, by the described Preparation of catalysts method that is used for methane tri-reforming preparing synthetic gas of claim 1, it is characterized in that described step 2) in chromic nitrate, the cobalt nitrate of 0.0247Y-0.2964Y gram, the ammonium molybdate of 0.0018Y-0.0276Y gram or the ammonium tungstate of 0.0014Y-0.0216Y gram of described 5Y～10Y ml deionized water dissolution with solvents 0.0325Y-0.3900Y gram of using of preparation second solution; Described Y is a positive number.
3, by the described Preparation of catalysts method that is used for methane tri-reforming preparing synthetic gas of claim 1, it is characterized in that used TiO in described catalyst carrier (A) preparation
2Particle size range be 50 nanometers～1 micron.
By the described Preparation of catalysts method that is used for methane tri-reforming preparing synthetic gas of claim 1, it is characterized in that 4, the used magnesium salts of step (3) preparation magnesium salt solution in described catalyst carrier (A) preparation is magnesium nitrate, magnesium chloride or magnesium acetate; Solvent for use is deionized water or ethanol; Used magnesium salts comprises magnesium nitrate, magnesium chloride or magnesium acetate when step (3) preparation magnesium salts in described catalyst carrier (B) preparation and titanium salt mixed solution, and used titanium salt comprises butyl titanate and titanium tetraisopropylate, and solvent for use is an ethanol.
5, by the described Preparation of catalysts method that is used for methane tri-reforming preparing synthetic gas of claim 1, it is characterized in that, in the step (4) in described catalyst carrier (A) or catalyst carrier (B) preparation, if the magnesium salts that is adopted is a magnesium chloride, water-washing step will carry out repeatedly, all to filter after each washing, detect less than chlorion with liquor argenti nitratis ophthalmicus in the filtrate after washing till.
6, by the described Preparation of catalysts method that is used for methane tri-reforming preparing synthetic gas of claim 1, it is characterized in that it is that methyl alcohol, ethanol, normal propyl alcohol are or/and n-butanol that step (4) alcohol in described catalyst carrier (A) or catalyst carrier (B) preparation is washed used alcohol; The consumption that described alcohol is washed used alcohol is 100～500 milliliters, and the alcohol time of washing is 0.5～2.5 hour, and washing times is 1～2 time.
7, by the described Preparation of catalysts method that is used for methane tri-reforming preparing synthetic gas of claim 1, it is characterized in that described drying is carried out under vacuum condition, temperature is 80～150 ℃, and be 8～16 hours drying time.
8, by the described Preparation of catalysts method that is used for methane tri-reforming preparing synthetic gas of claim 1, it is characterized in that, described roasting is carried out in the oxygen volume content is oxygen-nitrogen mixture of 8～10%, mixed gas flow is 25～80 ml/min, sintering temperature is 400～700 ℃, and roasting time is 4～6 hours.
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| CN102189003B (en) * | 2010-03-19 | 2012-11-28 | 中国石油化工股份有限公司 | Preparation method of methanation catalyst carrier |
| CN104209127B (en) * | 2013-06-05 | 2017-10-17 | 中国石油天然气股份有限公司 | Ferronickel bimetallic methanation catalyst and preparation and application thereof |
| CN104193585A (en) * | 2014-08-06 | 2014-12-10 | 华南理工大学 | System and process for preparing methyl alcohol through coke-oven gas-assisted coal gasification |
| CN106564860B (en) * | 2016-11-02 | 2018-10-02 | 昆明理工大学 | A kind of method of metallurgical furnace kiln flue gas and methane reforming producing synthesis gas |
| CN107376919B (en) * | 2017-07-19 | 2020-03-10 | 太原理工大学 | Promoting CO2Catalyst for activation and dissociation and preparation method and application thereof |
| CN110508301B (en) * | 2019-08-29 | 2022-02-22 | 华南农业大学 | Biological methanol conversion catalyst SrNiO for full components of methane3/SiC-SiO2-Foam and preparation method thereof |
| CN110508304B (en) * | 2019-08-29 | 2021-09-14 | 华南农业大学 | Biological methanol catalyst NiCo for full-component conversion of biogas2O4/SiC-SiO2-Foam and preparation method |
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| US6953488B2 (en) * | 1999-10-01 | 2005-10-11 | Bp Corporation North America Inc. | Preparing synthesis gas using hydrotalcite-derived nickel catalysts |
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| Development of nickel catalyst supported on MgO-TiO2composite oxide for DIR-MCFC. Jae-Suk Choi,et al.Catalysis Today,Vol.93-95. 2004 * |
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