CN102151568A - Catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation, and preparation and use thereof - Google Patents
Catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation, and preparation and use thereof Download PDFInfo
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- CN102151568A CN102151568A CN2011100326869A CN201110032686A CN102151568A CN 102151568 A CN102151568 A CN 102151568A CN 2011100326869 A CN2011100326869 A CN 2011100326869A CN 201110032686 A CN201110032686 A CN 201110032686A CN 102151568 A CN102151568 A CN 102151568A
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Abstract
The invention discloses a catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation, which is characterized by containing the following components by weight percent: 30 to 60% of active metal, 5 to 30% of metal additive and 20 to 60% of carrier, wherein the active metal is one or any combination of more than two of the group consisting of zinc, magnesium, aluminum, silver, ruthenium and iridium, and the carrier is silicon dioxide. The invention further discloses a preparation method of the catalyst, comprising the steps of: 1) mixing and dissolving soluble salts of the copper and soluble salts of the metal additive to prepare aqueous solution, adding a silicon source of the carrier to the aqueous solution to form a mixed liquid A; 2) dissolving precipitating agent in water, dropwise adding the mixed solution A to aqueous solution B under stir, and put the resultant solution on standing; 3) filtering; 4) drying; 5) calcining; 6) forming; and 7) reducing. The catalyst of the invention has the advantages of moderate reaction conditions, high activity, good stability, high selectivity, environmental friendliness and simple preparation process.
Description
Technical field
The present invention relates to a kind of coal system method and produce the catalyst of ethylene glycol, particularly about the Catalysts and its preparation method of hydrogenation of dimethyl oxalate to synthesizing ethylene glycol.
Background technology
Ethylene glycol, the popular name glycol, it is a kind of important Organic Chemicals, it can mix with water by arbitrary proportion, the boiling point height, freezing point is low, ethylene glycol and terephthaldehyde's acid reaction generate PETG, can be used as the raw material of polyester fiber and polyester plastics, be widely used in lubricant, plasticizer, paint, adhesive, surfactant, fields such as explosive, simultaneously also can be used to prepare anti-icing fluid or directly be used as organic solvent, the dinitrate of ethylene glycol can also be used as explosive in addition, the steam that the heating back produces can be used as the stage smoke screen, also is simultaneously to produce plasticizer, paint, adhesive, surfactant, the indispensable composition of agricultural chemicals and capacitor electrolyte.
The conventional method of producing ethylene glycol is the petrochemical industry route, and promptly epoxyethane water is legal.This method technological process is long, water is more relatively low than height, energy consumption selectivity big, ethylene glycol.In order to overcome above-mentioned shortcoming and to reduce production costs, since the seventies in 20th century, begun the research that green route is carbon one synthetic route gradually.This emerging route at first has CO gas-phase catalytic coupling synthesis of oxalate from synthesis gas, and oxalate catalytic hydrogenation again prepares ethylene glycol.This method technological process is simple, energy consumption is little, the selectivity of ethylene glycol is higher relatively, becomes the reaction that the industrial applications prospect is arranged most.Ripe relatively to CO gaseous oxidation preparing oxalate coupling reaction both at home and abroad at present, be to realize industrialized committed step and the oxalate catalytic hydrogenation is prepared this step of ethylene glycol, the life of catalyst problem is the emphasis problem of scientific research.
In the later stage seventies 20th century, dibutyl oxalate gas-phase catalytic hydrogenation process has at first been studied by U.S. Atlantic Richfield (ARCO) company on the basis of CO catalytic coupling synthesis of oxalate, and it is active component that catalyst adopts copper zinc chrome or copper chromium, with Al
2O
3, SiO
2Or glass marble etc. is carrier, is (4～30) in 200～230 ℃ of temperature, pressure 1.07～3.39MPa and hydrogen ester mol ratio: under the condition such as 1, obtain 11.7%～18.9% ethylene glycol yield.1986, U.S. ARCO company at first applied for the hydrogenation of oxalate for preparing ethylene glycol patent, adopted the Cu-Cr catalyst, and the yield of ethylene glycol reaches 97.2% under the pressure of 3.0MPa.Emerging product of space portion in the same year and UCC company unite and develop Cu/SiO
2Catalyst, EG yield 97.2%.Because the toxicity of chromium, even the chromium of trace also can cause great harm to human body, thereby the catalyst that exploitation does not contain chromium becomes emphasis of future research.
Since the eighties, the patent that a series of oxalates are ethylene glycol catalyst prepared has been applied in countries in the world, its shortcoming is that catalyst reaction condition harshness (temperature height, pressure height), energy and power consumption are big, and the conversion ratio of reaction and selectivity are not very desirable, and space-time yield is not high; Dependence to crome metal is big; Life of catalyst is short, is not suitable for suitability for industrialized production.
Summary of the invention
In order to solve the problems of the technologies described above, the present invention aims to provide a kind of catalyst and preparation and application that helps the oxalic ester hydrogenation synthesizing of ethylene glycol of suitability for industrialized production.This catalyst precursor is applied to have very high reactivity and selectivity in the hydrogenation of dimethyl oxalate to synthesizing ethylene glycol reaction after being treated to catalyst, and reaction controlled condition is gentle, can significantly reduce the energy and the power consumption of production, and catalyst stability is good, long service life.Not containing chromium in this catalyst composition, is a kind of eco-friendly catalyst.
The catalyst of a kind of preparation of ethanediol by dimethyl oxalate hydrogenation provided by the invention comprises following components in weight percentage:
Reactive metal 30-60%,
Promoter metal 5-30%,
Carrier 20-60%;
Wherein, described reactive metal is a copper, and described promoter metal is one or more any combinations in zinc, magnesium, aluminium, silver, ruthenium and the iridium, and described carrier is a silica.
Preferably, the catalyst of above-mentioned preparation of ethanediol by dimethyl oxalate hydrogenation comprises following components in weight percentage:
Reactive metal 54%
Promoter metal 6%
Carrier 40%
Wherein, described reactive metal is a copper, and described promoter metal is magnesium, zinc, aluminium, and described carrier is a silica.
The specific area of above-mentioned catalyst is 50-400m
2/ g, pore volume are 0.1-0.8cm
3/ g, average pore radius is 1-15nm.
The invention provides the method for the above-mentioned catalyst of preparation, comprise the steps:
1) gets the soluble-salt of described copper and the soluble-salt mixed dissolution of described promoter metal and be mixed with the aqueous solution, the total concentration of active metallic ion and promoter metal ion is 0.1-1.5M in the described aqueous solution, the silicon source that adds described carrier forms mixed liquor A, stirs;
2) precipitating reagent is soluble in water, the aqueous solution B that to be made into described precipitating reagent concentration be 0.1-1.5M, stir down, mixed liquor A is added dropwise among the aqueous solution B, the volume ratio of mixed liquor A and aqueous solution B is 1: 1～2, it is 50-90 ℃ that the dropping process keeps temperature, regulating the pH value is 6-9, after the dropping fully, continues to stir 2-4 hour, leave standstill, made precipitation aging 2-6 hour;
3) filter, solid washed with water, to the cleaning solution electrical conductivity at 10-500uS/cm;
4) solid drying, baking temperature 80-120 ℃, be 8-12 hour drying time;
5) roasting, temperature are 350-550 ℃, and roasting time is 3-8 hour;
6) moulding produces granularity, intensity, the satisfactory catalyst precursor of bulk density;
7) reduction is packed step 6) gained catalyst precursor in the reactor into, carries out reduction activation with reducibility gas, promptly.
In the step 1), the soluble-salt of described copper is one or more any combinations in copper nitrate, copper halide, Schweinfurt green and the copper sulphate; The soluble-salt of described promoter metal is one or more any combinations in nitrate, acetate or the sulfate of zinc, magnesium, aluminium, silver, ruthenium or iridium; The silicon source of described carrier is a Ludox, and preferred concentration is 10～30% Ludox.
Step 2) described precipitating reagent is sodium carbonate or sodium acid carbonate; The described reducibility gas of step 7) is the mist or the hydrogen of hydrogen and nitrogen.
The step 7) step of reducing is: described catalyst precursor is packed in the reactor, with hydrogen volume percentage is 20%～80% the hydrogen and the mist of nitrogen, and flow is 10～100ml/ming-Cat, and the control temperature is at 200～600 ℃, reductase 12～10 hour obtain catalyst.
The present invention also provides the application of described catalyst in the preparation of ethanediol by dimethyl oxalate hydrogenation reaction, comprises the steps:
1) 180～210 ℃ of temperature, the pressure 1～3MPa of the reactor of described catalyst is equipped with in adjusting, and dimethyl oxalate gasification back and hydrogen fully are mixed into reactor and carry out hydrogenation reaction;
2) product that obtains of step 1) separates through cooling off laggard promoting the circulation of qi liquid, collects liquid product.
Above-mentioned steps 1) in, dimethyl oxalate gasification back and hydrogen fully are mixed into reactor to carry out the concrete reaction condition of hydrogenation reaction and is: the liquid hourly space velocity (LHSV) 0.3～2g/g-cath of dimethyl oxalate, the air speed 2000～6000/h of hydrogen
-1
Catalyst of the present invention is compared with existing catalyst has following characteristics:
(1) reaction condition is relatively gentle.Reduce reaction condition, improving catalyst activity is the constant pursuit of Preparation of Catalyst, and the reaction temperature of this catalyst and pressure generally are lower than other patents, have reduced energy consumption, and greatly reduce the cost of investment of permanent plant, extremely beneficial to suitability for industrialized production.
(2) active height, good stability, selectivity height, the conversion ratio of oxalate can be greater than 99%, and the selectivity of ethylene glycol is greater than 95%., byproduct of reaction is few, and target product is easy to separate, and product purity reaches 99.9%.This catalyst turned round for a long time through 500 hours, stable reaction, and do not have obvious deactivation phenomenom.
(3) environmental friendliness.Exempt the use of Metal Cr in the oxalate gas-phase catalytic hydrogenation catalyst, and had very high selectivity.
(4) the Preparation of catalysts process is simple, easy operating.
The specific embodiment
The invention will be further described below in conjunction with specific embodiment, can be implemented so that those skilled in the art can better understand the present invention also, but illustrated embodiment is not as a limitation of the invention.
Preparation of catalysts method provided by the invention is as follows:
The soluble-salt (any combination of one or more in copper nitrate, copper halide, Schweinfurt green and the copper sulphate) of reactive metal and soluble-salt (one or more any combinations in the nitrate of zinc, magnesium, aluminium, silver, ruthenium or iridium, acetate or the sulfate) mixed dissolution of promoter metal are mixed with the aqueous solution, wherein the concentration of active metallic ion and promoter metal ion is 0.1-1.5M, the silicon source (Ludox) of carrier is joined in the mixed solution, form mixed liquor A, stir.Precipitating reagent is soluble in water, and being made into concentration is the aqueous solution B of 0.1-1.5M.Under stirring condition, mixed liquor A slowly is added dropwise among the precipitating reagent aqueous solution B, it is 50-90 ℃ that the dropping process keeps temperature, regulating the pH value is 6-9, after the dropping fully, continues to stir 2-4 hour, leaves standstill, and precipitation was worn out 2-6 hour.Filter, solid is washed until the cleaning solution electrical conductivity at 10-500uS/cm with water.The solid that drying obtains, baking temperature are at 80-120 ℃, and be 8-12 hour drying time.Sintering temperature is 350-550 ℃, and roasting time is 3-8 hour.Moulding.Produce the catalyst precursor that granularity, intensity, bulk density etc. meet production requirement.
Be reflected in the fixed bed stainless steel pressurized reactor and carry out, the long 1000mm of reactor, Ф 20mmX2.5mm.Reaction pressure is controlled by front and back pressure maintaining valve and counterbalance valve, pressure oscillation scope ± 0.05MPa, and temperature fluctuation range is at ± 0.5 ℃.The 20ml 40-60 purpose of packing in reactor catalyst precursor, bed respectively pack into up and down 10ml 20-40 order inert ceramic balls prevent to manage in the gas channel.Catalyst precursor is carried out online reduction activation, with hydrogen is 20%～80% the nitrogen and the mist of hydrogen, flow is 10～100ml/ming-Cat, the control temperature is at 200～600 ℃, reductase 12～10 hour, get catalyst, conditioned reaction temperature, reaction pressure and methyl oxalate inlet amount experimentize then.Pure dimethyl oxalate is squeezed into vaporizer by the high-pressure pump measuring pump and is gasified, from the hydrogen of steel cylinder after the pressure maintaining valve decompression, control and measure its flow by the high pressure mass flowmenter, entering vaporizer fully mixes the back and flows to into reactor with dimethyl oxalate from high-pressure metering pump and carry out hydrogenation reaction, product separates through cooling off laggard promoting the circulation of qi liquid, and the collection liquid phase is also analyzed.
Embodiment 1
It is soluble in water to take by weighing copper nitrate 25 gram, magnesium nitrate 5 grams, nitric acid iridium 3 grams, is made into the aqueous solution that the metal ion total concentration is 1.0M, and adding the 60mL mass percent concentration is 25% Ludox, makes mixed liquor.Weighing sodium carbonate 30 gram is dissolved in the 200ml water, and 60 ℃ of water-baths are stirred down, mixed liquor is slowly joined in the aqueous sodium carbonate, with nitric acid or sulphur acid for adjusting pH value about 7.5.Mix the back that finishes and continue to stir 2 hours, filter, wash to the cleaning solution electrical conductivity less than 500us/cm; dried 12 hours down for 100 ℃, be warming up to 400 ℃ with 10 ℃/h in Muffle furnace, constant temperature calcining is 4 hours under this temperature; granulation in the miniature comminutor gets catalyst precursor.The 20ml 40-60 purpose of packing in reactor catalyst precursor, bed respectively pack into up and down 10ml 20-40 order inert ceramic balls prevent to manage in the gas channel.Catalyst precursor is carried out online reduction activation, is 20%～40% the nitrogen and the mist of hydrogen with hydrogen, and flow is 10～100ml/ming-Cat, and the control temperature is at 200～600 ℃, reductase 12～10 hour, catalyst.
Reaction temperature, reaction pressure and methyl oxalate inlet amount that the reactor of catalyst is equipped with in adjusting experimentize.Pure dimethyl oxalate is squeezed into vaporizer by the high-pressure pump measuring pump and is gasified, from the hydrogen of steel cylinder after the pressure maintaining valve decompression, control and measure its flow by the high pressure mass flowmenter, entering vaporizer fully mixes the back and flows to into reactor with dimethyl oxalate from high-pressure metering pump and carry out hydrogenation reaction, product separates through cooling off laggard promoting the circulation of qi liquid, and the collection liquid phase is also analyzed.Reaction process condition and reaction result see the following form.
Each component percentage composition in the catalyst that present embodiment makes: copper 35%, magnesium 4%, iridium 6%, silica 55%.
After measured, the catalyst that makes of present embodiment: specific area is 50-400m
2/ g, pore volume are 0.1-0.8cm
3/ g, average pore radius is 1-15nm.
This catalyst turned round for a long time through 500 hours, stable reaction, and do not have obvious deactivation phenomenom.
Embodiment 2
It is soluble in water to take by weighing copper sulphate 20 gram, zinc sulfate 5 grams, nitric acid ruthenium 1 gram, is made into the aqueous solution that the metal ion total concentration is 0.5M, and adding the 50mL mass percent concentration is 30% Ludox, mixed liquor.Take by weighing sodium acid carbonate 30 grams and be dissolved in the 200ml water, 70 ℃ of water-baths are stirred down, mixed liquor is slowly joined in the sodium bicarbonate aqueous solution, and the control ph value of mixture are about 8.5.Mix the back that finishes and continue to stir 2 hours, filter, wash to the cleaning solution electrical conductivity less than 500us/cm; dried 12 hours down for 90 ℃, be warming up to 450 ℃ with 10 ℃/h in Muffle furnace, constant temperature calcining is 4 hours under this temperature; granulation in the miniature comminutor gets catalyst precursor.The 20ml 40-60 purpose of packing in reactor catalyst precursor, bed respectively pack into up and down 10ml 20-40 order inert ceramic balls prevent to manage in the gas channel.Catalyst precursor is carried out online reduction activation, is 20%～40% the nitrogen and the mist of hydrogen with hydrogen, and flow is 10～100ml/ming-Cat, and the control temperature is at 200～600 ℃, reductase 12～10 hour, catalyst.
Reaction temperature, reaction pressure and methyl oxalate inlet amount that the reactor of catalyst is equipped with in adjusting experimentize.Pure dimethyl oxalate is squeezed into vaporizer by the high-pressure pump measuring pump and is gasified, from the hydrogen of steel cylinder after the pressure maintaining valve decompression, control and measure its flow by the high pressure mass flowmenter, entering vaporizer fully mixes the back and flows to into reactor with dimethyl oxalate from high-pressure metering pump and carry out hydrogenation reaction, product separates through cooling off laggard promoting the circulation of qi liquid, and the collection liquid phase is also analyzed.Reaction process condition and reaction result see the following form.
Each component percentage composition in the catalyst that present embodiment makes: copper 31%, zinc 10%, ruthenium 1%, silica 58%.
After measured, the catalyst that makes of present embodiment: specific area is 50-400m
2/ g, pore volume are 0.1-0.8cm
3/ g, average pore radius is 1-15nm.
This catalyst turned round for a long time through 500 hours, stable reaction, and do not have obvious deactivation phenomenom.
Embodiment 3
It is soluble in water to take by weighing copper chloride 20 gram, copper sulphate 10 grams, silver nitrate 3 grams, is made into the aqueous solution that the metal ion total concentration is 1.5M, and adding the 70ml mass percent concentration is 25% Ludox, mixed liquor.Weighing sodium carbonate 30 grams are dissolved in the 100ml water, and 60 ℃ of water-baths are stirred down, mixed liquor is slowly joined in the aqueous sodium carbonate, and the control ph value of mixture are about 8.Mix the back that finishes and continue to stir 2 hours, filter, wash to the cleaning solution electrical conductivity less than 500us/cm; dried 12 hours down for 80 ℃, be warming up to 450 ℃ with 10 ℃/h in Muffle furnace, constant temperature calcining is 4 hours under this temperature; granulation in the miniature comminutor gets catalyst precursor.The 20ml 40-60 purpose of packing in reactor catalyst precursor, bed respectively pack into up and down 10ml 20-40 order inert ceramic balls prevent to manage in the gas channel.Catalyst precursor is carried out online reduction activation, is 20%～40% the nitrogen and the mist of hydrogen with hydrogen, and flow is 10～100ml/ming-Cat, and the control temperature is at 200～600 ℃, reductase 12～10 hour, catalyst.
Reaction temperature, reaction pressure and single sour methyl esters inlet amount that the reactor of catalyst is equipped with in adjusting experimentize.Pure dimethyl oxalate is squeezed into vaporizer by the high-pressure pump measuring pump and is gasified, from the hydrogen of steel cylinder after the pressure maintaining valve decompression, control and measure its flow by the high pressure mass flowmenter, entering vaporizer fully mixes the back and flows to into reactor with dimethyl oxalate from high-pressure metering pump and carry out hydrogenation reaction, product separates through cooling off laggard promoting the circulation of qi liquid, and the collection liquid phase is also analyzed.Reaction process condition and reaction result see the following form.
Each component percentage composition in the catalyst that present embodiment makes: copper 42%, silver 6%, silica 52%.
After measured, the catalyst that makes of present embodiment: specific area is 50-400m
2/ g, pore volume are 0.1-0.8cm
3/ g, average pore radius is 1-15nm.
This catalyst turned round for a long time through 500 hours, stable reaction, and do not have obvious deactivation phenomenom.
Embodiment 4
It is soluble in water to take by weighing Schweinfurt green 30 gram, magnesium acetate 1 gram, zinc nitrate 2 grams, aluminum nitrate 3 grams, and the total concentration that is made into metal ion is the aqueous solution of 0.8M, and 40ml mass percent concentration 20% Ludox is joined in the metallic solution.Take by weighing sodium acid carbonate 30 grams and be dissolved in the 200ml water, 65 ℃ of water-baths are stirred down, the metal ion aqueous solution is slowly joined in the aqueous sodium carbonate, and the control ph value of mixture are about 8.Mix the back that finishes and continue to stir 2 hours, filter, wash to the cleaning solution electrical conductivity less than 500us/cm; dried 12 hours down for 100 ℃, be warming up to 400 ℃ with 10 ℃/h in Muffle furnace, constant temperature calcining is 4 hours under this temperature; granulation in the miniature comminutor gets catalyst precursor.The 20ml 40-60 purpose of packing in reactor catalyst precursor, bed respectively pack into up and down 10ml 20-40 order inert ceramic balls prevent to manage in the gas channel.Catalyst precursor is carried out online reduction activation, is 20%～80% the nitrogen and the mist of hydrogen with hydrogen, and flow is 10～100ml/ming-Cat, and the control temperature is at 200～600 ℃, reductase 12～10 hour, catalyst.
Reaction temperature, reaction pressure and methyl oxalate inlet amount that the reactor of catalyst is equipped with in adjusting experimentize.Pure dimethyl oxalate is squeezed into vaporizer by the high-pressure pump measuring pump and is gasified, from the hydrogen of steel cylinder after the pressure maintaining valve decompression, control and measure its flow by the high pressure mass flowmenter, entering vaporizer fully mixes the back and flows to into reactor with dimethyl oxalate from high-pressure metering pump and carry out hydrogenation reaction, product separates through cooling off laggard promoting the circulation of qi liquid, and the collection liquid phase is also analyzed.Reaction process condition and reaction result see the following form.
Each component percentage composition in the catalyst that present embodiment makes: copper 54%, magnesium 1%, zinc 2%, aluminium 3%, silica 40%.
After measured, the catalyst that makes of present embodiment: specific area is 50-400m
2/ g, pore volume are 0.1-0.8cm
3/ g, average pore radius is 1-15nm.
This catalyst turned round for a long time through 500 hours, stable reaction, and do not have obvious deactivation phenomenom.
Embodiment 5
Take by weighing copper sulphate 30 gram, zinc sulfate 10 grams are soluble in water, are made into the aqueous solution that the metal ion total concentration is 1.5M, adding the 40ml mass percent concentration is 10% Ludox, mixed liquor.Weighing sodium carbonate 30 grams are dissolved in the 100ml water, and 60 ℃ of water-baths are stirred down, mixed liquor is slowly joined in the aqueous sodium carbonate, and the control ph value of mixture are about 8.Mix the back that finishes and continue to stir 2 hours, filter, wash to the cleaning solution electrical conductivity less than 500us/cm; dried 12 hours down for 80 ℃, be warming up to 450 ℃ with 10 ℃/h in Muffle furnace, constant temperature calcining is 4 hours under this temperature; granulation in the miniature comminutor gets catalyst precursor.The 20ml 40-60 purpose of packing in reactor catalyst precursor, bed respectively pack into up and down 10ml 20-40 order inert ceramic balls prevent to manage in the gas channel.Catalyst precursor is carried out online reduction activation, is 20%～40% the nitrogen and the mist of hydrogen with hydrogen, and flow is 10～100ml/ming-Cat, and the control temperature is at 200～600 ℃, reductase 12～10 hour, catalyst.
Reaction temperature, reaction pressure and methyl oxalate inlet amount that the reactor of catalyst is equipped with in adjusting experimentize.Pure dimethyl oxalate is squeezed into vaporizer by the high-pressure pump measuring pump and is gasified, from the hydrogen of steel cylinder after the pressure maintaining valve decompression, control and measure its flow by the high pressure mass flowmenter, entering vaporizer fully mixes the back and flows to into reactor with dimethyl oxalate from high-pressure metering pump and carry out hydrogenation reaction, product separates through cooling off laggard promoting the circulation of qi liquid, and the collection liquid phase is also analyzed.Reaction process condition and reaction result see the following form.
Each component percentage composition in the catalyst that present embodiment makes: copper 60%, zinc 20%, silica 20%.
After measured, the catalyst that makes of present embodiment: specific area is 50-400m
2/ g, pore volume are 0.1-0.8cm
3/ g, average pore radius is 1-15nm.
This catalyst turned round for a long time through 500 hours, stable reaction, and do not have obvious deactivation phenomenom.
Embodiment 6
Take by weighing copper chloride 15 gram, magnesium nitrate 20 grams are soluble in water, are made into the aqueous solution that the metal ion total concentration is 1.0M, adding the 50ml mass percent concentration is 25% Ludox, mixed liquor.Weighing sodium carbonate 30 grams are dissolved in the 100ml water, and 60 ℃ of water-baths are stirred down, mixed liquor is slowly joined in the aqueous sodium carbonate, and the control ph value of mixture are about 8.Mix the back that finishes and continue to stir 2 hours, filter, wash to the cleaning solution electrical conductivity less than 500us/cm; dried 12 hours down for 80 ℃, be warming up to 450 ℃ with 10 ℃/h in Muffle furnace, constant temperature calcining is 4 hours under this temperature; granulation in the miniature comminutor gets catalyst precursor.The 20ml 40-60 purpose of packing in reactor catalyst precursor, bed respectively pack into up and down 10ml 20-40 order inert ceramic balls prevent to manage in the gas channel.Catalyst precursor is carried out online reduction activation, is 20%～40% the nitrogen and the mist of hydrogen with hydrogen, and flow is 10～100ml/ming-Cat, and the control temperature is at 200～600 ℃, reductase 12～10 hour, catalyst.
Reaction temperature, reaction pressure and methyl oxalate inlet amount that the reactor of catalyst is equipped with in adjusting experimentize.Pure dimethyl oxalate is squeezed into vaporizer by the high-pressure pump measuring pump and is gasified, from the hydrogen of steel cylinder after the pressure maintaining valve decompression, control and measure its flow by the high pressure mass flowmenter, entering vaporizer fully mixes the back and flows to into reactor with dimethyl oxalate from high-pressure metering pump and carry out hydrogenation reaction, product separates through cooling off laggard promoting the circulation of qi liquid, and the collection liquid phase is also analyzed.Reaction process condition and reaction result see the following form.
Each component percentage composition in the catalyst that present embodiment makes: copper 30%, magnesium 15%, silica 55%.
After measured, the catalyst that makes of present embodiment: specific area is 50-400m
2/ g, pore volume are 0.1-0.8cm
3/ g, average pore radius is 1-15nm.
This catalyst turned round for a long time through 500 hours, stable reaction, and do not have obvious deactivation phenomenom.
Embodiment 7
Take by weighing copper nitrate 30 gram, aluminum nitrate 50 grams are soluble in water, are made into the aqueous solution that the metal ion total concentration is 1.0M, adding the 20ml mass percent concentration is 25% Ludox, mixed liquor.Weighing sodium carbonate 30 grams are dissolved in the 100ml water, and 60 ℃ of water-baths are stirred down, mixed liquor is slowly joined in the aqueous sodium carbonate, and the control ph value of mixture are about 8.Mix the back that finishes and continue to stir 2 hours, filter, wash to the cleaning solution electrical conductivity less than 500us/cm; dried 12 hours down for 80 ℃, be warming up to 450 ℃ with 10 ℃/h in Muffle furnace, constant temperature calcining is 4 hours under this temperature; granulation in the miniature comminutor gets catalyst precursor.The 20ml 40-60 purpose of packing in reactor catalyst precursor, bed respectively pack into up and down 10ml 20-40 order inert ceramic balls prevent to manage in the gas channel.Catalyst precursor is carried out online reduction activation, is 20%～40% the nitrogen and the mist of hydrogen with hydrogen, and flow is 10～100ml/ming-Cat, and the control temperature is at 200～600 ℃, reductase 12～10 hour, catalyst.
Reaction temperature, reaction pressure and methyl oxalate inlet amount that the reactor of catalyst is equipped with in adjusting experimentize.Pure dimethyl oxalate is squeezed into vaporizer by the high-pressure pump measuring pump and is gasified, from the hydrogen of steel cylinder after the pressure maintaining valve decompression, control and measure its flow by the high pressure mass flowmenter, entering vaporizer fully mixes the back and flows to into reactor with dimethyl oxalate from high-pressure metering pump and carry out hydrogenation reaction, product separates through cooling off laggard promoting the circulation of qi liquid, and the collection liquid phase is also analyzed.Reaction process condition and reaction result see the following form.
Each component percentage composition in the catalyst that present embodiment makes: copper 50%, aluminium 30%, silica 20%.
After measured, the catalyst that makes of present embodiment: specific area is 50-400m
2/ g, pore volume are 0.1-0.8cm
3/ g, average pore radius is 1-15nm.
This catalyst turned round for a long time through 500 hours, stable reaction, and do not have obvious deactivation phenomenom.
Embodiment 8
Take by weighing copper nitrate 30 gram, nitric acid ruthenium 2 grams are soluble in water, are made into the aqueous solution that the metal ion total concentration is 1.0M, adding the 60ml mass percent concentration is 25% Ludox, mixed liquor.Weighing sodium carbonate 30 grams are dissolved in the 100ml water, and 60 ℃ of water-baths are stirred down, mixed liquor is slowly joined in the aqueous sodium carbonate, and the control ph value of mixture are about 8.Mix the back that finishes and continue to stir 2 hours, filter, wash to the cleaning solution electrical conductivity less than 500us/cm; dried 12 hours down for 80 ℃, be warming up to 450 ℃ with 10 ℃/h in Muffle furnace, constant temperature calcining is 4 hours under this temperature; granulation in the miniature comminutor gets catalyst precursor.The 20ml 40-60 purpose of packing in reactor catalyst precursor, bed respectively pack into up and down 10ml 20-40 order inert ceramic balls prevent to manage in the gas channel.Catalyst precursor is carried out online reduction activation, is 20%～40% the nitrogen and the mist of hydrogen with hydrogen, and flow is 10～100ml/ming-Cat, and the control temperature is at 200～600 ℃, reductase 12～10 hour, catalyst.
Reaction temperature, reaction pressure and methyl oxalate inlet amount that the reactor of catalyst is equipped with in adjusting experimentize.Pure dimethyl oxalate is squeezed into vaporizer by the high-pressure pump measuring pump and is gasified, from the hydrogen of steel cylinder after the pressure maintaining valve decompression, control and measure its flow by the high pressure mass flowmenter, entering vaporizer fully mixes the back and flows to into reactor with dimethyl oxalate from high-pressure metering pump and carry out hydrogenation reaction, product separates through cooling off laggard promoting the circulation of qi liquid, and the collection liquid phase is also analyzed.Reaction process condition and reaction result see the following form.
Each component percentage composition in the catalyst that present embodiment makes: copper 40%, ruthenium 2%, silica 58%.
After measured, the catalyst that makes of present embodiment: specific area is 50-400m
2/ g, pore volume are 0.1-0.8cm
3/ g, average pore radius is 1-15nm.
This catalyst turned round for a long time through 500 hours, stable reaction, and do not have obvious deactivation phenomenom.
Embodiment 9
Take by weighing copper nitrate 25 gram, nitric acid iridium 1 gram is soluble in water, is made into the aqueous solution that the metal ion total concentration is 1.0M, adding the 60ml mass percent concentration is 25% Ludox, mixed liquor.Weighing sodium carbonate 30 grams are dissolved in the 100ml water, and 60 ℃ of water-baths are stirred down, mixed liquor is slowly joined in the aqueous sodium carbonate, and the control ph value of mixture are about 8.Mix the back that finishes and continue to stir 2 hours, filter, wash to the cleaning solution electrical conductivity less than 500us/cm; dried 12 hours down for 80 ℃, be warming up to 450 ℃ with 10 ℃/h in Muffle furnace, constant temperature calcining is 4 hours under this temperature; granulation in the miniature comminutor gets catalyst precursor.The 20ml 40-60 purpose of packing in reactor catalyst precursor, bed respectively pack into up and down 10ml 20-40 order inert ceramic balls prevent to manage in the gas channel.Catalyst precursor is carried out online reduction activation, is 20%～40% the nitrogen and the mist of hydrogen with hydrogen, and flow is 10～100ml/ming-Cat, and the control temperature is at 200～600 ℃, reductase 12～10 hour, catalyst.
Reaction temperature, reaction pressure and methyl oxalate inlet amount that the reactor of catalyst is equipped with in adjusting experimentize.Pure dimethyl oxalate is squeezed into vaporizer by the high-pressure pump measuring pump and is gasified, from the hydrogen of steel cylinder after the pressure maintaining valve decompression, control and measure its flow by the high pressure mass flowmenter, entering vaporizer fully mixes the back and flows to into reactor with dimethyl oxalate from high-pressure metering pump and carry out hydrogenation reaction, product separates through cooling off laggard promoting the circulation of qi liquid, and the collection liquid phase is also analyzed.Reaction process condition and reaction result see the following form.
Each component percentage composition in the catalyst that present embodiment makes: copper 35%, iridium 5%, silica 60%.
After measured, the catalyst that makes of present embodiment: specific area is 50-400m
2/ g, pore volume are 0.1-0.8cm
3/ g, average pore radius is 1-15nm.
This catalyst turned round for a long time through 500 hours, stable reaction, and do not have obvious deactivation phenomenom.
Catalyst test apparatus process conditions and evaluation result
The above embodiment is the preferred embodiment that proves absolutely that the present invention lifts, and protection scope of the present invention is not limited thereto.Being equal to that those skilled in the art are done on basis of the present invention substitutes or conversion, all within protection scope of the present invention.Protection scope of the present invention is as the criterion with claims.
Claims (10)
1. the catalyst of a preparation of ethanediol by dimethyl oxalate hydrogenation is characterized in that, comprises following components in weight percentage:
Reactive metal 30-60%,
Promoter metal 5-30%,
Carrier 20-60%;
Wherein, described reactive metal is a copper, and described promoter metal is one or more any combinations in zinc, magnesium, aluminium, silver, ruthenium and the iridium, and described carrier is a silica.
2. the catalyst of preparation of ethanediol by dimethyl oxalate hydrogenation according to claim 1 is characterized in that, comprises following components in weight percentage:
Reactive metal 54%
Promoter metal 6%
Carrier 40%
Wherein, described reactive metal is a copper, and described promoter metal is magnesium, zinc, aluminium, and described carrier is a silica.
3. catalyst according to claim 1 is characterized in that, the specific area of described catalyst is 50-400m
2/ g, pore volume are 0.1-0.8cm
3/ g, average pore radius is 1-15nm.
4. prepare the method for each described catalyst of claim 1～3, it is characterized in that, comprise the steps:
1) get the soluble-salt of copper and the soluble-salt mixed dissolution of described promoter metal and be mixed with the aqueous solution, the total concentration of active metallic ion and promoter metal ion is 0.1-1.5M in the described aqueous solution, adds the silicon source of described carrier, forms mixed liquor A, stirs;
2) precipitating reagent is soluble in water, the aqueous solution B that to be made into described precipitating reagent concentration be 0.1-1.5M, stir down, mixed liquor A is added dropwise among the aqueous solution B, the volume ratio of mixed liquor A and aqueous solution B is 1: 1～2, it is 50-90 ℃ that the dropping process keeps temperature, regulating the pH value is 6-9, after the dropping fully, continues to stir 2-4 hour, leave standstill, made precipitation aging 2-6 hour;
3) filter, solid washed with water, to the cleaning solution electrical conductivity at 10-500uS/cm;
4) solid drying, baking temperature 80-120 ℃, be 8-12 hour drying time;
5) roasting, temperature are 350-550 ℃, and roasting time is 3-8 hour;
6) moulding produces granularity, intensity, the satisfactory catalyst precursor of bulk density;
7) reduction is packed step 6) gained catalyst precursor in the reactor into, carries out reduction activation with reducibility gas, promptly.
5. method according to claim 4 is characterized in that, in the step 1), the soluble-salt of described copper is one or more any combinations in copper nitrate, copper halide, Schweinfurt green and the copper sulphate; The soluble-salt of described promoter metal is one or more any combinations in nitrate, acetate or the sulfate of zinc, magnesium, aluminium, silver, ruthenium or iridium; The silicon source of described carrier is a Ludox.
6. method according to claim 5 is characterized in that, described Ludox is that concentration is 10～30% Ludox.
7. method according to claim 4 is characterized in that step 2) described precipitating reagent is sodium carbonate or sodium acid carbonate; The described reducibility gas of step 7) is the mist or the hydrogen of hydrogen and nitrogen.
8. method according to claim 4, it is characterized in that, the step 7) step of reducing is: described catalyst precursor is packed in the reactor, with hydrogen volume percentage is 20%～80% the hydrogen and the mist of nitrogen, flow is 10～100ml/ming-Cat, the control temperature is at 200～600 ℃, and reductase 12～10 hour obtain catalyst.
9. the application of the described catalyst of claim 1 in the preparation of ethanediol by dimethyl oxalate hydrogenation reaction is characterized in that, comprises the steps:
1) 180～210 ℃ of temperature, the pressure 1～3MPa of the reactor of described catalyst is equipped with in adjusting, and dimethyl oxalate gasification back and hydrogen fully are mixed into reactor and carry out hydrogenation reaction;
2) product that obtains of step 1) separates through cooling off laggard promoting the circulation of qi liquid, collects liquid product.
10. the application of catalyst according to claim 9 in the preparation of ethanediol by dimethyl oxalate hydrogenation reaction, it is characterized in that, dimethyl oxalate gasification back and hydrogen fully are mixed into reactor and carry out hydrogenation reaction: the liquid hourly space velocity (LHSV) 0.3～2g/g-cath of dimethyl oxalate, the air speed 2000～6000/h of hydrogen
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