CN101734627B - Method for hydrogenating carbon disulfide by using magnesium-based hydrogen storage materials - Google Patents
Method for hydrogenating carbon disulfide by using magnesium-based hydrogen storage materials Download PDFInfo
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- CN101734627B CN101734627B CN2009102311470A CN200910231147A CN101734627B CN 101734627 B CN101734627 B CN 101734627B CN 2009102311470 A CN2009102311470 A CN 2009102311470A CN 200910231147 A CN200910231147 A CN 200910231147A CN 101734627 B CN101734627 B CN 101734627B
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Abstract
The invention discloses a method for hydrogenating carbon disulfide by using magnesium-based hydrogen storage materials, which is characterized by comprising the following steps: preparing hydrogen storage materials by using aluminum oxide, magnesium and carbon generated by thermal decomposition and deposition of methane as raw materials; and enabling the carbon disulfide to be in contact with the hydrogen storage materials obtained in the previous step for reacting under the temperature condition of 200-300 DEG C to generate hydrogen sulfide. In the invention, the magnesium-based hydrogen storage materials used as hydrogen sources and catalysts for hydrogenating the carbon disulfide, the technical mode of using rare metals and heavy metals as catalysts in the prior art is changed, the carbon disulfide is hydrogenated and converted into the hydrogen sulfide under ordinary pressure, the reaction temperature is not higher than 300 DEG C, and the requirement for the material quality of a hydrogenation reactor is low.
Description
Technical field
The present invention relates to a kind of method of dithiocarbonic anhydride being carried out hydrogenation with magnesium-base hydrogen storage material.
Background technology
When coke-oven gas was used for synthesizing methanol, conversion of methane in the technology and methyl alcohol building-up reactions were generally all used copper-based catalysts.Copper-based catalysts is easy to sulfur poisoning to sulfur sensitive, so need earlier coke-oven gas to be carried out deep purifying, removes sulfocompound wherein as much as possible.Coke-oven gas is earlier after wet desulphurization (hydramine method, AS method, ADA method, picric acid method, HPF method, 888 methods, tannin extract method) removes hydrogen sulfide, generally with hydroconversion process the dithiocarbonic anhydride in the coke-oven gas, thiophene, mercaptan etc. are converted into hydrogen sulfide through hydrogenation reaction again, use sweetening agent (ferrimanganic, zinc oxide) then hydrogen sulfide absorption.Dithiocarbonic anhydride hydrogenation reaction equation is CS
2+ 4H
2→ CH
4+ 2H
2S.Used sulfide hydrogenation catalyst is generally iron molybdenum, nickel molybdenum, cobalt molybdenum at present, 350～450 ℃ of temperature of reaction, reaction pressure 1.0～2.5MPa, the problem of its existence is, molybdenum, nickel, cobalt metal catalyst resource is few, cost is high, easy inactivation, hydrogenation reaction is carried out under high temperature and high pressure, causes equipment material requirement height.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method of dithiocarbonic anhydride being carried out hydrogenation with magnesium-base hydrogen storage material.
The technical scheme that the present invention is adopted for its purpose of realization is:
A kind ofly dithiocarbonic anhydride is carried out the method for hydrogenation, comprises step with magnesium-base hydrogen storage material:
A decomposes deposit carbon with aluminium sesquioxide, methane thermal and magnesium is that raw material is produced hydrogen storage material;
B makes dithiocarbonic anhydride contact with the hydrogen storage material that step a obtains, and reacts generation hydrogen sulfide under 200～300 ℃ of temperature condition.
Among the above-mentioned steps a, choose methane, aluminium sesquioxide powder and magnesium powder, methane gas is at high temperature contacted with the aluminium sesquioxide powder, methane carries out the methane thermal of thermolysis generation and decomposes the particle surface that deposit carbon is deposited on the aluminium sesquioxide powder, after the cooling, mix formation three mixture with the magnesium powder; With the above-mentioned three mixture ball grinder of packing into, reach certain pressure intensity after charging into the air in the hydrogen exchange ball grinder, place the ball mill ball milling can make above-mentioned hydrogen storage material again.
Among the above-mentioned steps a, the weight percent that aluminium sesquioxide powder, methane thermal are decomposed the amount of selecting for use of deposit carbon and magnesium powder is respectively 5%～15%, 5%～15% and 70%～90%.
Among the above-mentioned steps a, the mean particle size of aluminium sesquioxide powder is 10nm, and crystal is the γ phase, and the granularity of above-mentioned magnesium powder is less than 74 μ m; It is that 600～1000 ℃, reaction times are 15～30 minutes that methane carries out the pyrolysated temperature; The pressure that ball grinder charges into hydrogen is 1～3MPa, and the ball milling time is 2～5 hours.
Useful technique effect of the present invention is: with hydrogen source and the catalyzer of magnesium-base hydrogen storage material as the dithiocarbonic anhydride hydrogenation, change prior art and take rare metal and heavy metal technical approach as catalyzer, making the dithiocarbonic anhydride hydrocracking under normal pressure is hydrogen sulfide, temperature of reaction is no more than 300 ℃, requires low to the hydrogenator material.
Principle of the present invention is: methane produces deposit carbon on nano level γ aluminium sesquioxide surface in 600～1000 ℃ of pyrolysis, with this aluminium sesquioxide and deposit carbon grinding aid as magnesium sphere of powder mill, can prevent effectively that the magnesium powder ball is poly-, make the magnesium powder be easy to be milled to nano level, with suction hydrogen and the hydrogen desorption kinetics performance of improving magnesium; Change methane pyrolysis and produce the consumption of aluminium sesquioxide in the deposit carbon process and the pyrolysis temperature and the depositing time of methane, but the ratio of modulation deposit carbon and aluminium sesquioxide and crystalline structure thereof, and by changing the ratio with the magnesium powder, but behind the modulation ball milling hydrogen storage material put hydrogen and catalytic performance; The hydrogen discharging temperature of magnesium-base hydrogen storage material is 200～300 ℃, is released into high reactivity hydrogen and the dithiocarbonic anhydride that material shows and reacts, and makes dithiocarbonic anhydride can be converted into hydrogen sulfide under the condition of gentleness.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail:
Embodiment 1
With mean particle size is that 10nm, 15g and crystal are that the aluminium sesquioxide powder of the γ phase diameter of packing into is the reaction tubes of 20mm, electrically heated to 600 ℃, feed methane gas about 30 minutes, solids namely for methane thermal decomposed deposition carbon in managing and aluminium sesquioxide powder mixture are carried out weighing reach 30g and can take out, this solids and granularity are mixed formation three mixture less than the magnesium powder of 74 μ m, heavy 70g.Aluminium sesquioxide powder, methane thermal decomposition deposit carbon, magnesium powder three's weight proportion is 15: 15: 70 in above-mentioned three mixture.With the above-mentioned three mixture 250mL vacuum ball grinder of packing into, abrading-ball is 40: 1 with the quality of material ratio, logical hydrogen exchange is got rid of air in the ball grinder, charges into hydrogen again to 2MPa, and places ND7-2 type planetary ball mill ball milling 3 hours, the ball mill speed of mainshaft is 270r/ minute, make hydrogen storage material, the diameter of then hydrogen storage material being packed into is the reaction tubes of 20mm, is heated to 300 ℃, feeding is loaded with the nitrogen of dithiocarbonic anhydride, and air speed is 1000h
-1, record in the hydrogen storage material 25% hydrogen and dithiocarbonic anhydride reaction after the reaction and changed hydrogen sulfide over to.
Embodiment 2
Difference from Example 1 is that it is 1000 ℃ that methane carries out the pyrolysated temperature, and the time is 15 minutes.The weight proportion of aluminium sesquioxide powder, methane thermal decomposition deposit carbon, magnesium powder is 5: 5: 90 in three mixture.Obtained hydrogen storage material with dithiocarbonic anhydride reaction after, record in the hydrogen storage material 25% hydrogen and changed hydrogen sulfide over to.
Embodiment 3
Difference from Example 1 is that the weight proportion of aluminium sesquioxide powder, methane thermal decomposition deposit carbon, magnesium powder is 10: 10: 80 in three mixture.It is 1000 ℃ that methane carries out the pyrolysated temperature, and the time is 20 minutes.Obtained hydrogen storage material with dithiocarbonic anhydride reaction after, record in the hydrogen storage material 23% hydrogen and changed hydrogen sulfide over to.
Embodiment 4
Difference from Example 1 is that it is 1000 ℃ that methane carries out the pyrolysated temperature, and the time is 25 minutes.Obtained hydrogen storage material with dithiocarbonic anhydride reaction after, record in the hydrogen storage material 29% hydrogen and changed hydrogen sulfide over to.
Embodiment 5
Difference from Example 1 is that it is 800 ℃ that methane carries out the pyrolysated temperature, and the time is 20 minutes.Obtained hydrogen storage material with dithiocarbonic anhydride reaction after, record in the hydrogen storage material 26% hydrogen and changed hydrogen sulfide over to.
Embodiment 6
Difference from Example 1 is that the pressure that charges into hydrogen when ball milling prepares hydrogen storage material is 3MPa, and the ball milling time is 2 hours.Obtained hydrogen storage material with dithiocarbonic anhydride reaction after, record in the hydrogen storage material 17% hydrogen and changed hydrogen sulfide over to.
Embodiment 7
Difference from Example 1 is that the pressure that charges into hydrogen when ball milling prepares hydrogen storage material is 1MPa, and the ball milling time is 5 hours.Obtained hydrogen storage material with dithiocarbonic anhydride reaction after, record in the hydrogen storage material 19% hydrogen and changed hydrogen sulfide over to.
Embodiment 8
Difference from Example 1 is that the temperature of hydrogen storage material and dithiocarbonic anhydride reaction is 200 ℃.Obtained hydrogen storage material with dithiocarbonic anhydride reaction after, record in the hydrogen storage material 16% hydrogen and changed hydrogen sulfide over to.
Embodiment 9
Difference from Example 1 is that the weight proportion of aluminium sesquioxide powder, methane thermal decomposition deposit carbon, magnesium powder is 7: 7: 86 in three mixture.The pressure that charges into hydrogen is that 2MPa, ball milling time are 4 hours.The temperature of hydrogen storage material and dithiocarbonic anhydride reaction is 230 ℃.Obtained hydrogen storage material with dithiocarbonic anhydride reaction after, record in the hydrogen storage material 28% hydrogen and changed hydrogen sulfide over to.
Embodiment 10
Difference from Example 1 is that it is 700 ℃ that methane carries out the pyrolysated temperature.The weight proportion of aluminium sesquioxide powder, methane thermal decomposition deposit carbon, magnesium powder is 10: 15: 75 in three mixture.The pressure that charges into hydrogen is that 2MPa, ball milling time are 3 hours.The temperature of hydrogen storage material and dithiocarbonic anhydride reaction is 260 ℃.Obtained hydrogen storage material with dithiocarbonic anhydride reaction after, record in the hydrogen storage material 30% hydrogen and changed hydrogen sulfide over to.
Embodiment 11
Difference from Example 1 is that it is 840 ℃ that methane carries out the pyrolysated temperature.The weight proportion of aluminium sesquioxide powder, methane thermal decomposition deposit carbon, magnesium powder is 15: 10: 75 in three mixture.The pressure that charges into hydrogen is that 1MPa, ball milling time are 4 hours.The temperature of hydrogen storage material and dithiocarbonic anhydride reaction is 240 ℃.Obtained hydrogen storage material with dithiocarbonic anhydride reaction after, record in the hydrogen storage material 27% hydrogen and changed hydrogen sulfide over to.
Embodiment 12
Difference from Example 1 is that the temperature that it is heavy that methane carries out thermolysis is 650 ℃.The weight proportion of aluminium sesquioxide powder, methane thermal decomposition deposit carbon, magnesium powder is 12: 18: 70 in three mixture.The pressure that charges into hydrogen is that 2MPa, ball milling time are 2 hours.The temperature of hydrogen storage material and dithiocarbonic anhydride reaction is 220 ℃.Obtained hydrogen storage material with dithiocarbonic anhydride reaction after, record in the hydrogen storage material 31% hydrogen and changed hydrogen sulfide over to.
Claims (1)
1. one kind is carried out the method for hydrogenation with magnesium-base hydrogen storage material to dithiocarbonic anhydride, and feature is to comprise step:
A decomposes deposit carbon with aluminium sesquioxide, methane thermal and magnesium is that raw material is produced hydrogen storage material;
B makes dithiocarbonic anhydride contact with the hydrogen storage material that step a obtains, and reacts generation hydrogen sulfide under 200～300 ℃ of temperature condition;
Among the described step a, choose methane, aluminium sesquioxide powder and magnesium powder, methane gas is at high temperature contacted with the aluminium sesquioxide powder, methane carries out the methane thermal of thermolysis generation and decomposes the particle surface that deposit carbon is deposited on the aluminium sesquioxide powder, after the cooling, mix formation three mixture with the magnesium powder; With the above-mentioned three mixture ball grinder of packing into, reach certain pressure intensity after charging into the air in the hydrogen exchange ball grinder, place the ball mill ball milling can make above-mentioned hydrogen storage material again;
Among the described step a, the weight percent that aluminium sesquioxide powder, methane thermal are decomposed the amount of selecting for use of deposit carbon and magnesium powder is respectively 5%～15%, 5%～15% and 70%～90%;
Among the described step a, the mean particle size of aluminium sesquioxide powder is 10nm, and crystal is the γ phase, and the granularity of above-mentioned magnesium powder is less than 74 μ m; It is that 600～1000 ℃, reaction times are 15～30 minutes that methane carries out the pyrolysated temperature; The pressure that ball grinder charges into hydrogen is 1～3MPa, and the ball milling time is 2～5 hours.
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