CN101993346A - Method for hydrogenating oxalic ester into glycol - Google Patents
Method for hydrogenating oxalic ester into glycol Download PDFInfo
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- CN101993346A CN101993346A CN2009100578519A CN200910057851A CN101993346A CN 101993346 A CN101993346 A CN 101993346A CN 2009100578519 A CN2009100578519 A CN 2009100578519A CN 200910057851 A CN200910057851 A CN 200910057851A CN 101993346 A CN101993346 A CN 101993346A
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention relates to a method for hydrogenating oxalic ester into glycol, mainly solving the technical problem of low raw material percent conversion and low target product selectivity in the process of hydrogenating oxalic ester into glycol in the prior art. In the method, oxalic ester is taken as a raw material; under the condition that the reaction temperature is 170-270 DEG C, the weight airspeed of the oxalic ester is 0.01-5h<-1>, the hydrogen/ ester molar ratio is 40-200:1 and the reaction pressure is 1.5-10 MPa, the raw material and high-selectivity catalyst contact with each other to generate effluent containing glycol; wherein the high-selectivity catalyst comprises active ingredients, accessory ingredients and carrier. The catalyst comprises the following components in parts by weight: a) 8-60 parts of the active ingredients selected from copper, copper oxide, or mixture thereof; b) more than 0-20 parts of the accessory ingredients selected from at least one of main group metallic elements, transition metallic elements or lanthanide compound; and c) 20-60 parts of the carrier. The invention better solves the problem and can be used in the industrial production of oxalic ester hydrogenation glycol.
Description
Technical field
The method that to the present invention relates to a kind of barkite hydrogenation be ethylene glycol is the method for ethylene glycol about dimethyl oxalate or oxalic acid diethyl ester hydrogenation particularly.
Background technology
Ethylene glycol (EG) is a kind of important Organic Chemicals, be mainly used in and produce poly-vinegar fiber, frostproofer, unsaturated polyester resin, lubricant, softening agent, nonionogenic tenside and explosive etc., can be used for industries such as coating, soup, brake fluid and printing ink in addition, solvent and medium as ammonium pertorate, be used to produce special solvent glycol ether etc., purposes is very extensive.
At present, China has surpassed the U.S. becomes the big ethylene glycol consumption of the first in the world big country, and the domestic apparent consumption average annual growth rate of 2001-2006 reaches 17.4%.Though China's ethylene glycol throughput and increase of production are very fast,, all need a large amount of imports every year, and import volume is growing trend year by year because the powerful development of industry such as polyester still can not be satisfied the growing market requirement.
Current, the suitability for industrialized production of domestic and international large-scale ethylene glycol all adopts the oxyethane direct hydration, i.e. the legal operational path of pressurized water, and production technology is monopolized by English lotus Shell, U.S. Halcon-SD and U.S. UCC three companies basically.In addition, the research-and-development activity of the new synthetic technology of ethylene glycol is also making progress always.Developed catalyzing epoxyethane hydration legal system ethylene glycol production technology in succession as Shell company, UCC company, Moscow Mendelyeev chemical engineering institute, Shanghai petrochemical industry institute etc.; Companies such as Halcon-SD, UCC, Dow chemistry, Japanese catalyst chemistry and Mitsubishi Chemical have developed NSC 11801 legal system ethylene glycol production technology in succession; Companies such as Dow chemistry have developed EG and methylcarbonate (DMC) coproduction preparing ethylene glycol production technology etc.
For reaction product water content height, follow-up equipment (vaporizer) long flow path of direct hydration method, equipment is big, energy consumption is high, the process total recovery has only about 70%, directly influences the production cost of EG.Direct hydration method is compared with catalytic hydration and has been reduced the water ratio significantly, has obtained higher EO transformation efficiency and EG selectivity simultaneously.If catalyst stability and correlation engineering technical problem solve well, EO catalytic hydration system EG replacement on-catalytic hydrating process is trend of the times so.No matter the technology that NSC 11801 (EC) legal system is equipped with EG aspect EO transformation efficiency, EG selectivity, still all has bigger advantage than EO direct hydration method aspect raw material, the energy expenditure, is a kind of method that maintains the leading position.EG and DMC co-production technology can make full use of the CO2 resource of oxidation of ethylene by-product, in existing EO production equipment, only need to increase the reactions steps of producing EC and just can produce two kinds of very value products, and be very attractive.
But the common drawback of aforesaid method is to need the consumption of ethylene resource, and mainly refine by traditional petroleum resources for present ethene, and under the situation of following one section global oil price in period high-order operation for a long time, replace oil production ethylene glycol (non-petroleum path with aboundresources, low-cost Sweet natural gas or coal, be the CO route again), can possess the advantage of competing mutually with traditional ethene route.Wherein, synthetic gas synthesizes the EG new technology, may produce great influence to the innovation of EG production technique.With the carbon monoxide is the feedstock production dimethyl oxalate, is a very attractive Coal Chemical Industry route then with preparation of ethanediol by dimethyl oxalate hydrogenation.Now both at home and abroad to being that the research of feedstock production dimethyl oxalate has obtained good effect with the carbon monoxide, industrial production is ripe.And, still have more need of work further investigation with preparation of ethanediol by dimethyl oxalate hydrogenation, and especially effectively improving feed stock conversion how, aspects such as the selectivity of ethylene glycol are still waiting to improve.
Document CN101138725A discloses a kind of Catalysts and its preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol, and it is active ingredient with the metallic copper, and zinc is auxiliary agent, adopt the coprecipitation method preparation, but this catalyzer barkite transformation efficiency is lower, and glycol selectivity is low.
Document CN200710061390.3 discloses a kind of Catalysts and its preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol, and catalyzer of the present invention is main active ingredient with metallic copper, is promotor with zinc, is prepared from by coprecipitation method.Its carrier is the silicon sol carrier of modification.Wherein metallic copper content is preferably 5%～45% of vehicle weight, and the best is 10%～40%; Metallic zinc content is 0.1%～15% of vehicle weight, and the best is 1%～8%.But this catalyzer is in barkite and the reaction of hydrogen synthesizing glycol, and the barkite transformation efficiency is low, is lower than 93% as the dimethyl oxalate transformation efficiency, and glycol selectivity is lower than 93%.
Document " petrochemical complex " was rolled up the 340th～343 page of the 4th phase in 2007 the 36th and has been introduced a kind of employing Cu/SiO
2Carry out the research of hydrogenation of dimethyl oxalate to synthesizing ethylene glycol reaction, but there is the problem of poor selectivity equally in this catalyzer.
Summary of the invention
Technical problem to be solved by this invention is to exist feed stock conversion low in the barkite hydrogenation process in the document in the past, the technical problem that the purpose selectivity of product is low, it is the method for ethylene glycol that a kind of new barkite hydrogenation is provided, this method has and have the feed stock conversion height in the barkite hydrogenation process, purpose glycol product selectivity advantages of higher.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of barkite hydrogenation is the method for ethylene glycol, is raw material with the barkite, is 170～270 ℃ in temperature of reaction, and the barkite weight space velocity is 0.01～5 hour
-1, hydrogen/ester mol ratio is 40～200: 1, and reaction pressure is under 1.5～10MPa condition, and raw material contacts with high-selectivity catalyst, generates the effluent that contains ethylene glycol; Wherein high-selectivity catalyst comprises active ingredient, auxiliary agent and carrier, and in the catalyst weight umber, catalyzer comprises following component:
A) oxide compound or its mixture that is selected from copper, copper is active ingredient, 8～60 parts of the content of active ingredient element;
B) be selected from least a for auxiliary agent in main group metal element, transition metal or the lanthanide compound, the content of auxiliary element is greater than 0～20 part;
C) 20～60 parts carrier;
Wherein, carrier is selected from ZSM-type molecular sieve without binding agent, and specific surface is 100～800 meters squared per gram, and the Si/Al mol ratio is 40～total silicon.
Support of the catalyst ZSM-type molecular sieve without binding agent preferred version is selected from least a among ZSM-5, ZSM-48, ZSM-22 or the ZSM-35 in the technique scheme, the specific surface preferable range is 150～600 meters squared per gram, and Si/Al mol ratio preferable range is 40～1000: 1; Carrier ZSM-type molecular sieve without binding agent more preferably scheme is selected from ZSM-5, and its specific surface more preferably scope is 150～500 meters squared per gram, and Si/Al mol ratio more preferably scope is 50～800: 1.
The auxiliary agent preferred version is selected from least a in K, Ba, V, Mn, Zn, La or the Ce compound in the technique scheme, auxiliary agent more preferably scheme is selected from least a in K, V, Mn, Zn, La or the Ce compound, in the catalyst weight umber, the preferable range of auxiliary element content is 0.01～15 part, the more preferably scope of auxiliary element content is 0.02～12 part, and most preferred range is 0.05～10 part.
The reaction conditions preferable range is in the technique scheme: temperature of reaction is 180～260 ℃, and the barkite weight space velocity is 0.05～3 hour
-1, hydrogen/ester mol ratio is 50～180: 1, the reaction pressure scope is 2.0～6.0MPa.The barkite preferred version is selected from dimethyl oxalate, oxalic acid diethyl ester or its mixture.Barkite and hydrogen feed can once be passed through reactor, and also segmentation is injected by different way.Reactor can be one or more.
The preparation process of high-selectivity catalyst is as follows in the inventive method:
At first prepare the ZSM-type molecular sieve without binding agent carrier, detailed process is: at first with silica alumina ratio SiO
2/ Al
2O
3Be that 40～1000 ZSM type molecular sieve powder mixes with the amorphous silica binding agent, wherein the weight concentration of silica binder is 10～40%, behind the shaping and drying, in the aqueous solution that contains halogenation organic amine and alkyl diamine or steam, be converted into the ZSM-type molecular sieve without binding agent carrier through hydrothermal treatment consists, wherein crystallization temperature is 80～250 ℃, and crystallization time is 8～260 hours.Wherein, ZSM type molecular screening is from ZSM-5, ZSM-48, ZSM-35 or ZSM-22, and silica binder can be selected from silicon sol, water glass or its mixture; Organic amine template halogenation organic amine can be selected from 4-propyl bromide, and alkyl diamine can be selected from 1,6-hexanediamine etc.
And then carry out the dipping of active ingredient and auxiliary agent, and roasting and activation, concrete steps are:
(1) it is stand-by to take by weighing the above-mentioned ZSM-type molecular sieve without binding agent carrier that makes;
(2) oxalate, acetate, vitriol or the nitrate dissolving with activity component metal copper is mixed with the aqueous solution, the concentration of solution is 0.003～2.0 mol, to in this solution, flood 6～48 hours through the ZSM-type molecular sieve without binding agent carrier that step (1) takes by weighing, then, vacuum-drying got solids in 4～12 hours;
(3) nitrate, acetate or oxalate and the water with metal promoter is mixed with the aqueous solution, the concentration of the aqueous solution is 0.001～0.2 mol, the solids that step (2) is made soaks in this aqueous solution after 3～24 hours and takes out, 80～130 ℃ of dryings 4～12 hours, again 200～500 ℃ of roastings after 2～8 hours solids;
(4) with flow be 30～80 milliliters/(minute. the gram. catalyzer), hydrogeneous be the mixed gas of 30% nitrogen and hydrogen or contain CO be the mixed gas of 25% CO and nitrogen 200 ℃～450 ℃ reductase 12～10 hour, just can be made into catalyzer of the present invention.
The present invention can prepare silica alumina ratio SiO by to hydrothermal treatment consists temperature, time and optimization of formulation
2/ Al
2O
3Scope is at 50～800 ZSM-5, ZSM-48, ZSM-35 and ZSM-22.Owing to adopted the mixed templates of halogenation organic amine and alkyl diamine, given full play to the high characteristics of organic amine template template index, improved molecular sieve catalyst degree of crystallinity, improved the specific surface of carrier.
As everyone knows, in the process of oxalic ester hydrogenation synthesizing of ethylene glycol, copper, oxide compound of copper and composition thereof is main active ingredient, and the quality of the dispersiveness of active ingredient all has remarkably influenced to feed stock conversion and product selectivity, the present invention adopts active ingredient, the synergy of the big surperficial Adhesive-free Molecular Sieve carrier of auxiliary agent and thermostability, both guaranteed the polymolecularity of active ingredient on the one hand, guaranteed simultaneously the good thermal stability of big surfactivity carrier again, improved activity of such catalysts greatly, can effectively improve feed stock conversion, the glycol monomethyl selectivity, in addition, but the significant prolongation life of catalyst.
Adopting the inventive method, is being raw material with the barkite, is 180～260 ℃ in temperature of reaction, and the barkite weight space velocity is 0.05～3 hour
-1, hydrogen/ester mol ratio is 50～180: 1, and the reaction pressure scope is under the condition of 2.0～6.0MPa, and the transformation efficiency of barkite is 100%, and the selectivity of ethylene glycol is the highest can to have obtained better technical effect near 98%.
The invention will be further elaborated below by embodiment and Comparative Examples, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
Preparation of Catalyst:
Take by weighing 120 gram silica alumina ratio SiO
2/ Al
2O
3Be 50 ZSM-5 molecular sieve, add after 75 gram 35% (weight) silicon sol mix that extrusion moulding through 110 ℃ of oven dry, obtains sample A-I.
The tetrapropyl amine bromide, 12 grams 1 that add 6 grams in reactor in advance, the mixture of 6-hexanediamine and 36 gram distilled water places sealing back, the online side of reactor Porous Stainless Steel to carry out gas-solid under 180 ℃ 12 gram sample A-I and handled mutually 160 hours.Product takes out the back and uses distilled water wash, dries the back and obtain adhesiveless ZSM-5 molecular sieve carrier A in 550 ℃ of roastings in air atmosphere, and its specific surface is 450 meters squared per gram, silica alumina ratio SiO
2/ Al
2O
3Be 50.
Take by weighing the above-mentioned adhesiveless ZSM-5 molecular sieve carrier A weight that makes 50 grams, press 28%Cu+10%Zn/ZSM-5 content preparation catalyzer, its step is as follows: choose cupric nitrate, be mixed with steeping fluid according to the Cu charge capacity, carrier A flooded 36 hours in this solution after, vacuum-drying 6 hours solids.Choose zinc nitrate, be mixed with steeping fluid according to the Zn charge capacity, for preventing that Hydrolysis Reactions of Metal-ions from generating oxyhydroxide or oxide precipitation, in steeping fluid, add a small amount of nitric acid, make PH=4～6 of steeping fluid, then above-mentioned solids was soaked 12 hours in stain liquid, after fully absorbing, in water-bath, be dried to solid, again with this solid 130 ℃ of dryings 15 hours, 500 ℃ of roastings 8 hours, be that 200 ml/min hydrogen are 20% the nitrogen and the mixed gas of hydrogen with flow then,, just make required Cu-Zn/ZSM-5 catalyzer 450 ℃ of reduction 6 hours.
Taking by weighing the catalyzer that the makes 20 grams diameter of packing into is that by beds, by bottom drawn, with oxalic acid diethyl ester be raw material from top to bottom by glycol product for unstripped gas in 18 millimeters the tubular reactor, and temperature of reaction is 220 ℃, and weight space velocity is 0.5 hour
-1, hydrogen/ester mol ratio is 100: 1, and reaction pressure is under the condition of 3.0MPa, and its reaction result is: oxalic acid diethyl ester transformation efficiency 100%, glycol selectivity 96.5%.
[embodiment 2]
Preparation of Catalyst:
Take by weighing 150 gram silica alumina ratio SiO
2/ Al
2O
3Be 150 ZSM-5 molecular sieve, add after 20 gram 30% (weight) silicon sol mix that extrusion moulding through 130 ℃ of oven dry, obtains sample B-I.
The tetrapropyl amine bromide, 15 grams 1 that add 3 grams in reactor in advance, the mixture of 6-hexanediamine and 40 gram distilled water places sealing back, the online side of reactor Porous Stainless Steel to carry out gas-solid under 140 ℃ 15 gram sample B-I and handled mutually 140 hours.Product takes out the back and uses distilled water wash, dries the back and obtain adhesiveless ZSM-5 molecular sieve carrier B in air atmosphere after 550 ℃ of roastings, and its specific surface is 500 meters squared per gram, silica alumina ratio SiO
2/ Al
2O
3Be 150.
Take by weighing the above-mentioned adhesiveless ZSM-5 molecular sieve carrier B weight that makes 50 grams, press 38%Cu+0.1%V+0.05%La+0.2%Zr/ZSM-5 content preparation catalyzer, its step is as follows: choose cupric nitrate, be mixed with steeping fluid according to the Cu charge capacity, carrier flooded 30 hours in this solution after, vacuum-drying 10 hours solids.Choose zinc nitrate, zirconium nitrate and lanthanum nitrate, according to Zn, Zr and La charge capacity are mixed with steeping fluid, for preventing that Hydrolysis Reactions of Metal-ions from generating oxyhydroxide or oxide precipitation, in steeping fluid, add a small amount of nitric acid, make PH=5～6 of steeping fluid, then above-mentioned solids was soaked 12 hours in stain liquid, after fully absorbing, in water-bath, be dried to solid, again with solid 130 ℃ of dryings 24 hours, 500 ℃ of roastings 6 hours, then with flow be 200 ml/min hydrogeneous be 20% the nitrogen and the mixed gas of hydrogen, 450 ℃ of reduction 6 hours, just make required Cu-V-La-Zr/ZSM-5 catalyzer.
Taking by weighing the catalyzer that the makes 20 grams diameter of packing into is that by beds, by bottom drawn, with dimethyl oxalate be raw material from top to bottom by glycol product for unstripped gas in 18 millimeters the tubular reactor, and temperature of reaction is 180 ℃, and weight space velocity is 0.02 hour
-1, hydrogen/ester mol ratio is 180: 1, and reaction pressure is under the condition of 8.0MPa, and its reaction result is: dimethyl oxalate transformation efficiency 99.60%, glycol selectivity 94.2%.
[embodiment 3]
Preparation of Catalyst:
Take by weighing 110 gram silica alumina ratio SiO
2/ Al
2O
3Be 300 ZSM-48 molecular sieve, after the water glass that adds 75 gram silica contents and be 30% (weight) mixed, extrusion moulding through 130 ℃ of oven dry, obtained sample C-I.
The tetrapropyl amine bromide, 5 grams 1 that add 12 grams in reactor in advance, the mixture of 6-hexanediamine and 35 gram distilled water places sealing back, the online side of reactor Porous Stainless Steel to carry out gas-solid under 2110 ℃ 12 gram sample C-I and handled mutually 180 hours.Product takes out the back and uses distilled water wash, dries the back and obtain binderless ZSM-5-48 molecular sieve carrier C in air atmosphere after 580 ℃ of roastings, and its specific surface is 560 meters squared per gram, silica alumina ratio SiO
2/ Al
2O
3Be 300.
Take by weighing the above-mentioned binderless ZSM-5 that makes-48 molecular sieve carrier C weight 100 grams, press 30%Cu+0.02%Sr+0.08%W/ZSM-48 content preparation catalyzer, its step is as follows: choose cupric nitrate, be mixed with steeping fluid according to the Cu charge capacity, carrier flooded 30 hours in this solution after, vacuum-drying 10 hours solids.Choose nitric acid tungsten and strontium nitrate, be mixed with steeping fluid according to W and Sr charge capacity, for preventing that Hydrolysis Reactions of Metal-ions from generating oxyhydroxide or oxide precipitation, in steeping fluid, add a small amount of nitric acid, make PH=5～6 of steeping fluid, then above-mentioned solids was soaked 16 hours in stain liquid, after fully absorbing, in water-bath, be dried to solid, again with solid 140 ℃ of dryings 8 hours, 550 ℃ of roastings 4 hours, then with flow be 450 ml/min hydrogeneous be 20% the nitrogen and the mixed gas of hydrogen, 450 ℃ of reduction 6 hours, just make required Cu-Sr-W/ZSM-48 catalyzer.
Taking by weighing the catalyzer that the makes 20 grams diameter of packing into is that by beds, by bottom drawn, with dimethyl oxalate be raw material from top to bottom by glycol product for unstripped gas in 18 millimeters the tubular reactor, and temperature of reaction is 200 ℃, and weight space velocity is 0.3 hour
-1, hydrogen/ester mol ratio is 150: 1, and reaction pressure is under the condition of 1.8MPa, and its reaction result is: dimethyl oxalate transformation efficiency 100%, glycol selectivity 96.4%.
[embodiment 4]
Preparation of Catalyst:
Take by weighing 90 gram silica alumina ratio SiO
2/ Al
2O
3Be 500 ZSM-22 molecular sieve, add after water glass, 50 gram 40% (weight) silicon sol that 70 gram silica contents are 30% (weight) mix that extrusion moulding through 130 ℃ of oven dry, obtains sample D-I.
The tetrapropyl amine bromide, 13 grams 1 that add 5 grams in reactor in advance, the mixture of 6-hexanediamine and 40 gram distilled water places sealing back, the online side of reactor Porous Stainless Steel to carry out gas-solid under 170 ℃ 12 gram sample D-I and handled mutually 200 hours.Product takes out the back and uses distilled water wash, dries the back and obtain binderless ZSM-5-22 molecular sieve carrier D in air atmosphere after 580 ℃ of roastings, and its specific surface is 460 meters squared per gram, silica alumina ratio SiO
2/ Al
2O
3Be 500.
Take by weighing the above-mentioned binderless ZSM-5 that makes-22 molecular sieve carrier D weight 100 grams, press 50%Cu+4%Mn+0.08%Bi/ZSM-22 content preparation catalyzer, its step is as follows: choose cupric nitrate, be mixed with steeping fluid according to the Cu charge capacity, carrier flooded 30 hours in this solution after, vacuum-drying 10 hours solids.Choose manganous nitrate and Bismuth trinitrate, be mixed with steeping fluid according to Mn and Bi charge capacity, for preventing that Hydrolysis Reactions of Metal-ions from generating oxyhydroxide or oxide precipitation, in steeping fluid, add a small amount of nitric acid, make PH=5～6 of steeping fluid, above-mentioned then solids soaked 12 hours in stain liquid, after fully absorbing, in water-bath, be dried to solid, again with solid 140 ℃ of dryings 8 hours, 550 ℃ of roastings 4 hours, then with flow be 450 ml/min hydrogeneous be 20% the nitrogen and the mixed gas of hydrogen, 450 ℃ of reduction 6 hours, just make required Cu-Mn-Bi/ZSM-22 catalyzer.
Taking by weighing the catalyzer that the makes 20 grams diameter of packing into is that by beds, by bottom drawn, with dimethyl oxalate be raw material from top to bottom by glycol product for unstripped gas in 18 millimeters the tubular reactor, and temperature of reaction is 230 ℃, and weight space velocity is 1.0 hours
-1, hydrogen/ester mol ratio is 80: 1, and reaction pressure is under the condition of 4.0MPa, and its reaction result is: dimethyl oxalate transformation efficiency 100%, glycol selectivity 96.7%.
[embodiment 5]
Preparation of Catalyst:
Take by weighing 150 gram silica alumina ratio SiO
2/ Al
2O
3Be 800 ZSM-5 molecular sieve, add after 50 grams, 40%/(weight) silicon sol mixes that extrusion moulding through 110 ℃ of oven dry, obtains sample E-I.
The tetrapropyl amine bromide, 15 grams 1 that in reactor, add 3 grams in advance, the mixture of 6-hexanediamine and 40 gram distilled water adds 15 gram sample E-I again, and handled under 130 ℃ 180 hours the sealing back.Product takes out the back and uses distilled water wash, dries the back and obtain adhesiveless ZSM-5 molecular sieve carrier E in air atmosphere after 550 ℃ of roastings, and its specific surface is 300 meters squared per gram, silica alumina ratio SiO
2/ Al
2O
3Be 800.
Take by weighing the above-mentioned adhesiveless ZSM-5 molecular sieve carrier E weight that makes 50 grams, press 60%Cu+0.5%Ni+1%Ba/ZSM-5 content preparation catalyzer, its step is as follows: choose cupric nitrate, be mixed with steeping fluid according to the Cu charge capacity, carrier flooded 36 hours in this solution after, vacuum-drying 10 hours solids.Choose nickelous nitrate and nitrate of baryta, be mixed with steeping fluid according to Ni and Ba charge capacity, for preventing that Hydrolysis Reactions of Metal-ions from generating oxyhydroxide or oxide precipitation, in steeping fluid, add a small amount of nitric acid, make PH=5～6 of steeping fluid, above-mentioned then solids soaked 18 hours in stain liquid, after fully absorbing, in water-bath, be dried to solid, again with solid 140 ℃ of dryings 12 hours, 550 ℃ of roastings 6 hours, then with flow be 200 ml/min hydrogeneous be 20% the nitrogen and the mixed gas of hydrogen, 450 ℃ of reduction 6 hours, just make required Cu-Ni-Ba/ZSM-5 catalyzer.
Taking by weighing the catalyzer that the makes 20 grams diameter of packing into is that by beds, by bottom drawn, with oxalic acid diethyl ester be raw material from top to bottom by glycol product for unstripped gas in 18 millimeters the tubular reactor, and temperature of reaction is 260 ℃, and weight space velocity is 4.0 hours
-1, hydrogen/ester mol ratio is 120: 1, and reaction pressure is under the condition of 3.0MPa, and its reaction result is: oxalic acid diethyl ester transformation efficiency 99.8%, glycol selectivity 95.8%.
[embodiment 6]
Preparation of Catalyst:
Take by weighing 100 gram silica alumina ratio SiO
2/ Al
2O
3Be 60 ZSM-35 molecular sieve, add after 50 gram 40% (weight) silicon sol mix that extrusion moulding through 130 ℃ of oven dry, obtains sample F-I.
The tetrapropyl amine bromide, 18 grams 1 that in reactor, add 3 grams in advance, the mixture of 6-hexanediamine and 40 gram distilled water adds 12 gram sample F-I again, and handled under 130 ℃ 200 hours the sealing back.Product takes out the back and uses distilled water wash, dries the back and obtain binderless ZSM-5-35 molecular sieve carrier F in air atmosphere after 550 ℃ of roastings, and its specific surface is 400 meters squared per gram, silica alumina ratio SiO
2/ Al
2O
3Be 60.
Take by weighing the above-mentioned adhesiveless ZSM-5 molecular sieve carrier F weight that makes 50 grams, press 30%Cu+3%Mn+1%Li/ZSM-35 content preparation catalyzer, its step is as follows: choose cupric nitrate, be mixed with steeping fluid according to the Cu charge capacity, carrier flooded 18 hours in this solution after, vacuum-drying 10 hours solids.Choose lithium nitrate and manganous nitrate, be mixed with steeping fluid according to Li and Mn charge capacity, for preventing that Hydrolysis Reactions of Metal-ions from generating oxyhydroxide or oxide precipitation, in steeping fluid, add a small amount of nitric acid, make PH=5～6 of steeping fluid, above-mentioned then solids soaked 12 hours in stain liquid, after fully absorbing, in water-bath, be dried to solid, again with solid 130 ℃ of dryings 8 hours, 550 ℃ of roastings 8 hours, then with flow be 200 ml/min hydrogeneous be 20% the nitrogen and the mixed gas of hydrogen, 450 ℃ of reduction 6 hours, just make required Cu-Mn-Li/ZSM-35 catalyzer.
Taking by weighing the catalyzer that the makes 20 grams diameter of packing into is that by beds, by bottom drawn, with oxalic acid diethyl ester be raw material from top to bottom by glycol product for unstripped gas in 18 millimeters the tubular reactor, and temperature of reaction is 250 ℃, and weight space velocity is 2.0 hours
-1, hydrogen/ester mol ratio is 100: 1, and reaction pressure is under the condition of 2.8MPa, and its reaction result is: oxalic acid diethyl ester transformation efficiency 100%, glycol selectivity 96.1%.
[embodiment 7]
Preparation of Catalyst:
Take by weighing 130 gram silica alumina ratio SiO
2/ Al
2O
3Be 200 ZSM-5 molecular sieve, add after 50 gram 30% (weight) silicon sol mix that extrusion moulding through 120 ℃ of oven dry, obtains sample G-I.
The tetrapropyl amine bromide, 15 grams 1 that in reactor, add 3 grams in advance, the mixture of 6-hexanediamine and 50 gram distilled water adds 15 gram sample G-I again, and handled under 130 ℃ 200 hours the sealing back.Product takes out the back and uses distilled water wash, dries the back and obtain adhesiveless ZSM-5 molecular sieve carrier G in air atmosphere after 550 ℃ of roastings, and its specific surface is 450 meters squared per gram, silica alumina ratio SiO
2/ Al
2O
3Be 200.
Take by weighing the above-mentioned adhesiveless ZSM-5 molecular sieve carrier G weight that makes 50 grams, press 40%Cu+3%Ga+1%Ti/ZSM-5 content preparation catalyzer, its step is as follows: choose cupric nitrate, be mixed with steeping fluid according to the Cu charge capacity, carrier flooded 18 hours in this solution after, vacuum-drying 10 hours solids.Choose acetic acid gallium and Titanium Nitrate, be mixed with steeping fluid according to Ga and Ti charge capacity, for preventing that Hydrolysis Reactions of Metal-ions from generating oxyhydroxide or oxide precipitation, in steeping fluid, add a small amount of nitric acid, make PH=5～6 of steeping fluid, above-mentioned then solids soaked 12 hours in stain liquid, after fully absorbing, in water-bath, be dried to solid, again with solid 130 ℃ of dryings 8 hours, 550 ℃ of roastings 8 hours, then with flow be 200 ml/min hydrogeneous be 20% the nitrogen and the mixed gas of hydrogen, 450 ℃ of reduction 6 hours, just make required Cu-Ga-Ti/ZSM-5 catalyzer.
Taking by weighing the catalyzer that the makes 20 grams diameter of packing into is that by beds, by bottom drawn, with oxalic acid diethyl ester be raw material from top to bottom by glycol product for unstripped gas in 18 millimeters the tubular reactor, and temperature of reaction is 240 ℃, and weight space velocity is 1.0 hours
-1, hydrogen/ester mol ratio is 80: 1, and reaction pressure is under the condition of 2.5MPa, and its reaction result is: oxalic acid diethyl ester transformation efficiency 100%, glycol selectivity 95.6%.
[embodiment 8]
Preparation of Catalyst:
Take by weighing 100 gram silica alumina ratio SiO
2/ Al
2O
3Be 100 ZSM-5 molecular sieve, add after 50 gram 38% (weight) silicon sol mix that extrusion moulding through 130 ℃ of oven dry, obtains sample H-I.
The tetrapropyl amine bromide, 18 grams 1 that in reactor, add 3 grams in advance, the mixture of 6-hexanediamine and 50 gram distilled water adds 12 gram sample H-I again, and handled under 130 ℃ 200 hours the sealing back.Product takes out the back and uses distilled water wash, dries the back and obtain adhesiveless ZSM-5 molecular sieve carrier H in air atmosphere after 550 ℃ of roastings, and its specific surface is 280 meters squared per gram, silica alumina ratio SiO
2/ Al
2O
3Be 100.
Take by weighing the above-mentioned adhesiveless ZSM-5 molecular sieve carrier H weight that makes 50 grams, press 30%Cu+3%Al+1%Ce/ZSM-35 content preparation catalyzer, its step is as follows: choose cupric nitrate, be mixed with steeping fluid according to the Cu charge capacity, carrier flooded 18 hours in this solution after, vacuum-drying 10 hours solids.Choose aluminum nitrate and cerous nitrate, be mixed with steeping fluid according to Al and Ce charge capacity, for preventing that Hydrolysis Reactions of Metal-ions from generating oxyhydroxide or oxide precipitation, in steeping fluid, add a small amount of nitric acid, make PH=5～6 of steeping fluid, above-mentioned then solids soaked 12 hours in stain liquid, after fully absorbing, in water-bath, be dried to solid, again with solid 130 ℃ of dryings 8 hours, 550 ℃ of roastings 8 hours, then with flow be 200 ml/min hydrogeneous be 20% the nitrogen and the mixed gas of hydrogen, 450 ℃ of reduction 6 hours, toilet need be made the Cu-Al-Ce/ZSM-5 catalyzer.
Taking by weighing the catalyzer that the makes 20 grams diameter of packing into is that by beds, by bottom drawn, with dimethyl oxalate be raw material from top to bottom by glycol product for unstripped gas in 18 millimeters the tubular reactor, and temperature of reaction is 220 ℃, and weight space velocity is 0.6 hour
-1, hydrogen/ester mol ratio is 60: 1, and reaction pressure is under the condition of 3.5MPa, and its reaction result is: dimethyl oxalate transformation efficiency 100%, glycol selectivity 95.8%.
[embodiment 9]
Preparation of Catalyst:
Catalysts Cu-Ga-Ti/ZSM-5 the catalyzer that adopts embodiment 7 to make is designated as catalyzer G, and the Catalysts Cu that embodiment 8 makes-Al-Ce/ZSM-5 catalyzer is designated as catalyzer H.
Adopt reactor I and two placed in-line reactors of reactor II, raw material is a dimethyl oxalate segmentation injecting scheme.Taking by weighing each 20 gram of the catalyzer G that makes and catalyzer H respectively is respectively charged in two tubular reactors that diameter is 18 millimeters, raw hydrogen is once passed through, the raw material dimethyl oxalate is divided into first strand and second strand, first strand and second strand of mass ratio are 1: 1, first strand of dimethyl oxalate and hydrogen are entered by first reactor, effluent and second strand of raw material that reaction generates are mixed into second reactor reaction, wherein each reactor feedstocks is and passes through beds from top to bottom, glycol product is drawn by the bottom, at reactor I reaction conditions be: temperature of reaction is 220 ℃, and weight space velocity is 0.4 hour
-1, hydrogen/ester mol ratio is 80: 1, and reaction pressure is 3.5MPa, and reactor II reaction conditions is: temperature of reaction is 230 ℃, and weight space velocity is 0.4 hour
-1, hydrogen/ester mol ratio is 80: 1, and reaction pressure is under the condition of 3.5MPa, and its reaction result is: dimethyl oxalate transformation efficiency 100%, glycol selectivity 97.6%.
[embodiment 10]
Preparation of Catalyst:
Take by weighing 100 gram silica alumina ratio SiO
2/ Al
2O
3Be 50 ZSM-5 molecular sieve, add after 50 gram 38% (weight) silicon sol mix that extrusion moulding through 130 ℃ of oven dry, obtains sample I-I.
The tetrapropyl amine bromide, 18 grams 1 that in reactor, add 3 grams in advance, the mixture of 6-hexanediamine and 50 gram distilled water adds 12 gram sample I-I again, and handled under 130 ℃ 200 hours the sealing back.Product takes out the back and uses distilled water wash, dries the back and obtain adhesiveless ZSM-5 molecular sieve carrier I in air atmosphere after 550 ℃ of roastings, and its specific surface is 280 meters squared per gram, silica alumina ratio SiO
2/ Al
2O
3Be 50.
Take by weighing the above-mentioned adhesiveless ZSM-5 molecular sieve carrier I weight that makes 50 grams, press 15%Cu+5%Al+1%Ce+0.08%Zn/ZSM-35 content preparation catalyzer, its step is as follows: choose cupric nitrate, be mixed with steeping fluid according to the Cu charge capacity, carrier flooded 18 hours in this solution after, vacuum-drying 10 hours solids.Choose aluminum nitrate, zinc nitrate and cerous nitrate, according to Al, Zn and Ce charge capacity are mixed with steeping fluid, for preventing that Hydrolysis Reactions of Metal-ions from generating oxyhydroxide or oxide precipitation, in steeping fluid, add a small amount of nitric acid, make PH=5～6 of steeping fluid, above-mentioned then solids soaked 12 hours in stain liquid, after fully absorbing, in water-bath, be dried to solid, again with solid 130 ℃ of dryings 8 hours, 550 ℃ of roastings 8 hours, then with flow be 200 ml/min hydrogeneous be 20% the nitrogen and the mixed gas of hydrogen, 450 ℃ of reduction 6 hours, toilet need be made the Cu-Al-Zn-Ce/ZSM-5 catalyzer.
Taking by weighing the catalyzer that the makes 20 grams diameter of packing into is that by beds, by bottom drawn, with dimethyl oxalate be raw material from top to bottom by glycol product for unstripped gas in 18 millimeters the tubular reactor, and temperature of reaction is 220 ℃, and weight space velocity is 0.5 hour
-1, hydrogen/ester mol ratio is 100: 1, and reaction pressure is under the condition of 2.5MPa, and its reaction result is: dimethyl oxalate transformation efficiency 100%, glycol selectivity 96.1%.
[embodiment 11]
Preparation of Catalyst:
Take by weighing 100 gram silica alumina ratio SiO
2/ Al
2O
3Be 60 ZSM-35 molecular sieve, add after 50 gram 40% (weight) silicon sol mix that extrusion moulding through 130 ℃ of oven dry, obtains sample J-I.
The tetrapropyl amine bromide, 18 grams 1 that in reactor, add 3 grams in advance, the mixture of 6-hexanediamine and 40 gram distilled water adds 12 gram sample J-I again, and handled under 130 ℃ 200 hours the sealing back.Product takes out the back and uses distilled water wash, dries the back and obtain binderless ZSM-5-35 molecular sieve carrier J in air atmosphere after 550 ℃ of roastings, and its specific surface is 400 meters squared per gram, silica alumina ratio SiO
2/ Al
2O
3Be 60.
Take by weighing the above-mentioned adhesiveless ZSM-5 molecular sieve carrier J weight that makes 50 grams, press 25%Cu+10%Zn content preparation catalyzer, its step is as follows: choose cupric nitrate, be mixed with steeping fluid according to the Cu charge capacity, carrier flooded 18 hours in this solution after, vacuum-drying 10 hours solids.Choose zinc nitrate, be mixed with steeping fluid according to the Zn charge capacity, for preventing that Hydrolysis Reactions of Metal-ions from generating oxyhydroxide or oxide precipitation, in steeping fluid, add a small amount of nitric acid, make PH=5～6 of steeping fluid, above-mentioned then solids soaked 12 hours in stain liquid, after fully absorbing, in water-bath, be dried to solid, again with solid 130 ℃ of dryings 8 hours, 550 ℃ of roastings 8 hours, then with flow be 200 ml/min hydrogeneous be 20% the nitrogen and the mixed gas of hydrogen, 450 ℃ of reduction 6 hours, just make required Cu-Zn/ZSM-35 catalyzer.
Taking by weighing the catalyzer that the makes 20 grams diameter of packing into is that by beds, by bottom drawn, with dimethyl oxalate be raw material from top to bottom by glycol product for unstripped gas in 18 millimeters the tubular reactor, and temperature of reaction is 220 ℃, and weight space velocity is 0.5 hour
-1, hydrogen/ester mol ratio is 100: 1, and reaction pressure is under the condition of 2.5MPa, and its reaction result is: dimethyl oxalate transformation efficiency 100%, glycol selectivity 97.2%.
[embodiment 12]
Preparation of Catalyst:
Take by weighing 100 gram silica alumina ratio SiO
2/ Al
2O
3Be 800 ZSM-5 molecular sieve, add after 50 gram 40% (weight) silicon sol mix that extrusion moulding through 130 ℃ of oven dry, obtains sample K-I.
The tetrapropyl amine bromide, 18 grams 1 that in reactor, add 3 grams in advance, the mixture of 6-hexanediamine and 40 gram distilled water adds 12 gram sample K-I again, and handled under 130 ℃ 200 hours the sealing back.Product takes out the back and uses distilled water wash, dries the back and obtain adhesiveless ZSM-5 molecular sieve carrier K in air atmosphere after 550 ℃ of roastings, and its specific surface is 400 meters squared per gram, silica alumina ratio SiO
2/ Al
2O
3Be 60.
Take by weighing the above-mentioned adhesiveless ZSM-5 molecular sieve carrier K weight that makes 50 grams, press 35%Cu+15%Zn content preparation catalyzer, its step is as follows: choose cupric nitrate, be mixed with steeping fluid according to the Cu charge capacity, carrier flooded 18 hours in this solution after, vacuum-drying 10 hours solids.Choose zinc nitrate, be mixed with steeping fluid according to the Zn charge capacity, for preventing that Hydrolysis Reactions of Metal-ions from generating oxyhydroxide or oxide precipitation, in steeping fluid, add a small amount of nitric acid, make PH=5～6 of steeping fluid, above-mentioned then solids soaked 12 hours in stain liquid, after fully absorbing, in water-bath, be dried to solid, again with solid 130 ℃ of dryings 8 hours, 550 ℃ of roastings 8 hours, then with flow be 200 ml/min hydrogeneous be 20% the nitrogen and the mixed gas of hydrogen, 450 ℃ of reduction 6 hours, just make required Cu-Zn/ZSM-5 catalyzer.
Taking by weighing the catalyzer that the makes 20 grams diameter of packing into is that by beds, by bottom drawn, with dimethyl oxalate be raw material from top to bottom by glycol product for unstripped gas in 18 millimeters the tubular reactor, and temperature of reaction is 220 ℃, and weight space velocity is 0.5 hour
-1, hydrogen/ester mol ratio is 100: 1, and reaction pressure is under the condition of 2.5MPa, and its reaction result is: dimethyl oxalate transformation efficiency 100%, glycol selectivity 96.8%.
[comparative example 1]
This Preparation of catalysts is shown in the embodiment in the patent CN200710061390.3 that mentions in the bibliography of front 1.Ultimate analysis shows that containing Cu according to the mass fraction meter with regard to whole catalyzer is 25%, and Zn is 10%, and carrier is silicon oxide (M).With reference to the identical reaction conditions of embodiment 11, its result is: dimethyl oxalate transformation efficiency 82%, glycol selectivity 86.0%.
[comparative example 2]
This Preparation of catalysts is shown in the embodiment in the patent CN200710061390.3 that mentions in the bibliography of front 2.Ultimate analysis shows that containing Cu according to the mass fraction meter with regard to whole catalyzer is 35%, and Zn is 15%, and carrier is silicon oxide (C).With reference to the identical reaction conditions of embodiment 12, its result is: dimethyl oxalate transformation efficiency 91%, glycol selectivity 92.0%.
Claims (9)
1. the method that barkite hydrogenation is ethylene glycol is a raw material with the barkite, is 170～270 ℃ in temperature of reaction, and the barkite weight space velocity is 0.01～5 hour
-1, hydrogen/ester mol ratio is 40～200: 1, and reaction pressure is under 1.5～10MPa condition, and raw material contacts with high-selectivity catalyst, generates the effluent that contains ethylene glycol; Wherein high-selectivity catalyst comprises active ingredient, auxiliary agent and carrier, and in the catalyst weight umber, catalyzer comprises following component:
A) oxide compound or its mixture that is selected from copper, copper is active ingredient, 8～60 parts of the content of active ingredient element;
B) be selected from least a for auxiliary agent in main group metal element, transition metal or the lanthanide compound, the content of auxiliary element is greater than 0～20 part;
C) 20～60 parts carrier;
Wherein, carrier is selected from ZSM-type molecular sieve without binding agent, and specific surface is 100～800 meters squared per gram, and the Si/Al mol ratio is 40～total silicon.
2. the method that described barkite hydrogenation is ethylene glycol according to claim 1, it is characterized in that ZSM-type molecular sieve without binding agent is selected from least a among ZSM-5, ZSM-48, ZSM-22 or the ZSM-35, specific surface is 150～600 meters squared per gram, and the Si/Al mol ratio is 40～1000: 1.
3. the method that described barkite hydrogenation is ethylene glycol according to claim 2 is characterized in that ZSM-type molecular sieve without binding agent is selected from ZSM-5, and its specific surface is 150～500 meters squared per gram, and the Si/Al mol ratio is 50～800: 1.
4. the method that described barkite hydrogenation is ethylene glycol according to claim 1 is characterized in that auxiliary agent is selected from least a in K, Ba, V, Mn, Zn, La or the Ce compound, and in the catalyst weight umber, the content of auxiliary element is 0.01～15 part.
5. the method that described barkite hydrogenation is ethylene glycol according to claim 4 is characterized in that auxiliary agent is selected from least a in K, V, Mn, Zn, La or the Ce compound, and in the catalyst weight umber, the content of auxiliary element is 0.02～12 part.
6. the method that described barkite hydrogenation is ethylene glycol according to claim 1 is characterized in that temperature of reaction is 180～260 ℃, and the barkite weight space velocity is 0.05～3 hour
-1, hydrogen/ester mol ratio is 50～180: 1, the reaction pressure scope is 2.0～6.0MPa.
7. the method that described barkite hydrogenation is ethylene glycol according to claim 1 is characterized in that barkite is selected from dimethyl oxalate, oxalic acid diethyl ester or its mixture.
8. the method that described barkite hydrogenation is ethylene glycol according to claim 1 is characterized in that barkite and hydrogen feed can once pass through reactor, and also segmentation is injected by different way.
9. the method that described barkite hydrogenation is ethylene glycol according to claim 1 is characterized in that reactor can be one or more.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111225742A (en) * | 2018-09-25 | 2020-06-02 | 高化学技术株式会社 | Copper-based catalyst, preparation method thereof and method for preparing ethylene glycol by using copper-based catalyst |
| CN111517916A (en) * | 2019-02-02 | 2020-08-11 | 航天长征化学工程股份有限公司 | Method for producing ethylene glycol from coal |
| CN116440946A (en) * | 2023-03-30 | 2023-07-18 | 华南理工大学 | A kind of Ni-Mo double transition metal catalyst and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1927714A (en) * | 2005-09-07 | 2007-03-14 | 中国石油化工股份有限公司 | Preparation method of ZSM-type molecular sieve without binding agent |
| CN101474561A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Catalyst for producing ethylene glycol from hydrogenation of oxalic ester |
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2009
- 2009-08-31 CN CN2009100578519A patent/CN101993346A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1927714A (en) * | 2005-09-07 | 2007-03-14 | 中国石油化工股份有限公司 | Preparation method of ZSM-type molecular sieve without binding agent |
| CN101474561A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Catalyst for producing ethylene glycol from hydrogenation of oxalic ester |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111225742A (en) * | 2018-09-25 | 2020-06-02 | 高化学技术株式会社 | Copper-based catalyst, preparation method thereof and method for preparing ethylene glycol by using copper-based catalyst |
| CN111517916A (en) * | 2019-02-02 | 2020-08-11 | 航天长征化学工程股份有限公司 | Method for producing ethylene glycol from coal |
| CN111517916B (en) * | 2019-02-02 | 2023-06-02 | 航天长征化学工程股份有限公司 | Method for producing glycol from coal |
| CN116440946A (en) * | 2023-03-30 | 2023-07-18 | 华南理工大学 | A kind of Ni-Mo double transition metal catalyst and its preparation method and application |
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