CN101342489A - Hydrogenation reaction catalyst, preparation and application thereof - Google Patents
Hydrogenation reaction catalyst, preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a hydrogenation reaction catalyst, the chemical formula is CuOx-ROy/SiO<2>, therein, R is selected from one or more than one alkaline earth metal elements, transition-metal elements or rare-metal elements, x is 1/2 of the valence number of Cu, y is 1/2 of the valence number of R; calculated with the total weight of the catalyst as 100 portions, the content of R element is greater than 0 or equal to 15 portions, the content of Cu element covers 10-70 portions. The catalyst can be applied to the reaction of polyprotic acid hydrogenation for preparing polyatomic alcohol, for example, the ethylene glycol prepared by oxalic acid ester or glycolic acid ester has sound activity, selectivity and stability, and the yield of target product is high, the liquid space velocity is big, the varieties of byproducts are less; particularly, the contents of multi-carbon alcohol, aldehyde, carboxylic acid ester, polycondensate, etc. which seriously influence the product quality are low. The catalyst is capable to largely reduce the energy consumption of production and effectively lower the production cost.
Description
Technical field
The invention belongs to the catalyst chemical field, particularly relate to a kind of catalyst for hydrogenation.
Background technology
Polyalcohol is a kind of important Organic Chemicals, wherein as ethylene glycol, be mainly used in and make polyester fiber, antifreezing agent, non-ionic surface active agent, monoethanolamine and explosive etc., also be used to prepare low-freezing cooling fluid (engine is used), also can directly be used as solvent.In addition, in tobacco industry, textile industry and cosmetic industry extensive use is arranged also.
The most of petroleum path that adopts of the existing production technology of ethylene glycol, promptly first direct oxidation method is produced oxirane, makes ethylene glycol through liquid-phase catalysis or on-catalytic hydration again.All this route is disclosed as Chinese patent 02112038.2, United States Patent (USP) 5874653, Japan Patent 82106631.This method is discharged a large amount of waste water in process of production, the product separation difficulty, the energy consumption height, pollute high, cost is high.
At the end of the seventies in last century, L R Jehner etc. at first proposes the technology path of oxalate gas phase hydrogenation preparing ethylene glycol in Japan Patent 5323011,5542971; Haruhiko Miyazaki in 1985 etc. disclose CuMo in United States Patent (USP) 4551565
kBa
pO
xCatalyst, than being diethy-aceto oxalate all can be transformed under 200 the condition, glycol selectivity is 97.7% to this catalyst at 0.1MPa, 177 ℃, hydrogen ester, and the shortcoming of this catalyst is that the reaction hydrogen ester is higher, liquid hourly space velocity (LHSV) lower (about 0.036g/g cat.h), catalyst life does not appear in the newspapers; United States Patent (USP) 4585890,4440873 discloses the copper base hydrogenation catalyst that uses the preparation of cuprammonium silica gel method in 1984, it is in diethy-aceto oxalate reduction preparation glycol reaction, at hydrogen ester than 300,0.05MPa, 188 ℃, during liquid hourly space velocity (LHSV) 0.024g/g cat.h, diethy-aceto oxalate 100% transforms, and glycol selectivity is 99.5%; Under the conditions of similarity, in the change condition: 215 ℃, hydrogen ester transform than 50 o'clock diethy-aceto oxalates 98%, and glycol selectivity reduces to 87%, and this catalyst shortcoming is that the liquid hourly space velocity (LHSV) that is suitable for is too low, in order to keep high conversion ratio and selectivity high hydrogen ester ratio must be arranged.
To produce the higher alcohols accessory substance in the preparing glycol by hydrogenating oxalate process, even such accessory substance content very low (0.1%wt) also can have a strong impact on product quality, and separation difficulty, energy consumption is big, reported a kind of catalyst in the European patent 0060787, it can control the mass fraction of this accessory substance in product under the situation of accurately controlling reaction condition be about 1%, but its shortcoming is Cr element and the controlled condition harshness that needs to add severe toxicity in its catalyst, is difficult to industrialization.KoichiHirai1985 has reported a kind of Cu/NH that does not add the Cr element in United States Patent (USP) 4614728
3-Si catalyst, they are under 220 ℃, the experiment condition of 2MPa, liquid hourly space velocity (LHSV) 0.92g/mL.h, the conversion ratio of dimethyl oxalate is 99.9%, glycol selectivity is 90.4%, the selectivity of such accessory substance is 0.1%, its shortcoming is the reaction temperature height, and copper crystal grain is easier grows up, and side reactions such as hydrogenation easily took place.
U.S. ARCO company in 1986 adopts the Cu-Cr catalyst, and under loaded catalyst 100mL, 3.0MPa pressure, the ethylene glycol yield is 95%, the long running 466h of catalyst.Chinese Academy of Sciences's Fujian thing structure finish the 200mL mould examination research work of diethy-aceto oxalate hydrogenation preparing ethylene glycol in the early 1990s.They use the Ec-13 Cu-Cr catalyst, under 0.6MPa～3.0MPa, 205 ℃～240 ℃, liquid hourly space velocity (LHSV) 0.327g/g cat.h condition, and running 1134h, space-time yield 142g/lh.Above catalyst is short service life, and the oxalate gas phase hydrogenation prepares ethylene glycol technology does not have the industrial applications precedent at present.
Summary of the invention
Technical problem to be solved
Technical problem to be solved by this invention provides a kind of catalyst of polybasic ester hydrogenation preparing polyalcohol, with the hydrogen ester that overcomes existing catalyst reaction than defective such as too high, that liquid hourly space velocity (LHSV) is little, impurity content height, reaction temperature height, active low, active temperature narrow range, heat and power consumption in product is big.
Technical scheme
First aspect of the present invention provides a kind of catalyst for hydrogenation, and its chemical formula is:
CuOx-ROy/SiO
2
Wherein, R is selected from one or more in alkali earth metal, transition metal or the thulium, and x is 1/2 of a Cu valence mumber, and y is 1/2 of a R valence mumber; In total catalyst weight is 100 parts, and the content of R element is less than or equal to 15 parts greater than 0, and the content of Cu element is 10～70 parts.
One of optimal way of above-mentioned catalyst for hydrogenation is, described R is selected from alkali earth metal Mg, Ca and Ba, the metallic element K of IA family, Na, the Ti of transition metal, V, Cr, Mn, Fe, Co, Ni and Zn, perhaps one or more among rare-earth metals La, Eu, Gd and the Tb.
Two of the optimal way of above-mentioned catalyst for hydrogenation is, is 100 parts in described total catalyst weight, and the content of R element is 0.01～10 part, and the content of Cu element is 20～60 parts.
Three of the optimal way of above-mentioned catalyst for hydrogenation is described SiO
2Carrier is that specific surface is at 5m
2/ g～1000m
2In/g the scope is the setting or the amorphous materials of agent structure with Si-O.Preferred described SiO
2Carrier be selected from silica gel, Ludox or diatomaceous one or more.
Four of the optimal way of above-mentioned catalyst for hydrogenation is that specific surface area of catalyst is 100～600m
2/ g, pore volume are 0.4～1.5cm
3/ g.
Second aspect of the present invention provides the preparation method of above-mentioned catalyst for hydrogenation, its steps in sequence is: with the salt solution mix of carrier and metal and regulate the pH value and be 1-6, this mixed liquor is mixed with the solution that is dissolved with precipitating reagent, the hybrid reaction endpoint pH is 7-14, compound through stirring, aging, washing, filter, dry, roasting, finally make the target catalyst.
One embodiment of the present invention are that CuOx and ROy co-precipitation are loaded on SiO
2On carry out Preparation of Catalyst and obtain CuOx-ROy/SiO
2The type catalyst, the concrete operations step is:
The first step is poured the silicon carrier of 1～85 (preferred 20～60) part weight in the round-bottomed flask into, with the deionized water dilution of 200 parts of weight;
Second step added the precipitating reagent of 1～100 (preferred 40～80) part weight, mixed;
The 3rd step, (in total catalyst weight was 100 parts with metal salts in proportion, the content of R element is less than or equal to 15 parts greater than 0, the content of Cu element is 10～70 parts, the content of preferred R element is 0.01～10 part, the content of Cu element is 20～60 parts) mix and then dilute with deionized water, regulate the pH value, wherein the content of metallic element is 10～70 (preferred 20～60) part weight.
The 4th step mixed this metallic solution mutually with aforementioned solution, and electronic stirring is placed on the water-bath back flow reaction 0.5～48 hour (preferred 10～30), and control reaction solution endpoint pH is 7～14 (preferred 8～12);
After the 5th step reaction finishes feed liquid filtered while hot through several deionized water or organic solvent washing;
The 6th step catalyst is through 80～120 ℃ of dryings 4～24 (preferred 10～16) hour;
The 7th step catalyst through 300～600 ℃ (preferred 350～500) down roasting more than 0.5 hour (preferred 2～6) make the catalyst of 90～120 parts of weight.
Preparation of catalysts method of the present invention can adopt direct precipitation method, sluggish precipitation or the precipitation method that other prior aries were suitable for.Precipitating reagent is alkaline precipitating agent or the preformed precipitate agent that can generate alkaline matter under certain condition, includes but not limited to carbonate, ammoniacal liquor, urea etc.Washing step adopts washing or alcohol to wash; Can adopt vacuum drying or aeration-drying when dry, baking temperature is 80～200 ℃, and preferred 90-120 ℃, sintering temperature is 300～600 ℃, and preferred 400-500 ℃, calcination atmosphere can carry out in air, nitrogen, carbon dioxide or ammonia atmosphere.
The 3rd aspect of the present invention provides a kind of hydrogenation reaction, adopts the described catalyst for hydrogenation of claim 1 in reaction, is reaction raw materials with the polybasic ester, the concrete operations step of application:
The first step selects suitable particle size to place reaction tube catalyst;
Second step reduced this catalyst 4～20 hours under 200～500 ℃, hydrogen atmosphere, and the density of hydrogen scope is 0.5%～100%;
The 3rd step was dissolved in the solvent by measuring pump with oxalate or ethyl glycolate raw material heat fused or with it and enters reaction system after hydrogen mixes with measuring.
Reaction process condition: the liquid hourly space velocity (LHSV) of oxalate or ethyl glycolate is 0.01～3g/g cat.h, and the hydrogen ester ratio is 20～500; Reaction temperature: 160～260 ℃; Reaction pressure: 1～10MPa.
One embodiment of the present invention are that with the vapor phase method hydrogenation reaction of this Application of Catalyst in preparation ethylene glycol, its raw material includes but not limited to oxalate or ethyl glycolate and hydrogen.Similarly, according to those of ordinary skills' general knowledge, this catalyst also can apply to prepare the hydrogenation preparing reaction of other polyalcohols such as glycerine analogically.This catalyst does not have the selectivity requirement to the raw material of preparation polyalcohol.
Beneficial effect
Catalyst of the present invention is compared with existing catalyst has following characteristics:
1. reaction temperature is low, and temperature range is wide.Catalyst of the present invention just has high activity at 160 ℃, and this temperature generally is lower than literature value 10-40 ℃; Optimal reaction temperature is 170 ℃-240 ℃, and whole active temperature scope reaches 100 ℃.The test easy operating, operating flexibility is big, and is very favourable for industrial applications.
2. reactivity height, target product selectivity height, space-time yield height.Catalyst of the present invention is under the process conditions of 0.7g/g cat.h in the liquid hourly space velocity (LHSV) of 180 ℃ of reaction temperatures, 3MPa reaction pressure, polybasic ester raw material, and feed stock conversion is more than 99%, and glycol selectivity reaches more than 95%, and the impurity selectivity is lower than 0.1%.
3. catalyst stability is good, and the life-span is long.Catalyst of the present invention was through long-time life-span examination in 3000 hours, and oxalate raw material average conversion 99%, polyalcohol average yield are 96.5%, and the impurity average selectivity is controlled at below 2%.
4. adopt catalyst of the present invention can significantly reduce heat and power consumption, reduce subsequent product separation equipment and operation, reduce production costs.
5. catalyst of the present invention does not have corrosion to equipment, environmentally safe.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, as the catalyst chemical operation manual, or the condition of advising according to manufacturer.
Embodiment 1
The first step is poured 40g diatomite in the round-bottomed flask into, adds 60g sodium carbonate solid with 200g deionized water dilution back, mix be placed in 90 ℃ of water-baths standby;
The preparation of second step contains 88g Cu (NO
3)
2With 3g Zn (NO
3)
2Copper nitrate/zinc nitrate solution.
The 3rd step slowly was added drop-wise to this metallic solution in the diatomite mixed solution, and electronic stirring and 75 ℃ of water-bath back flow reaction left standstill after 2 hours 8 hours, and control pH value is 10;
After filtering feed liquid while hot, the four-step reaction end, washs also suction filtration of back through ethanol again through the washing of several deionized water;
The 5th step catalyst filter cake through 95 ℃ of dryings after 12 hours 450 ℃ of following roastings 6 hours.
More than operate catalyst A.
The broken screening of catalyst A 40-60 order is placed reaction tube; Reaction tube is risen to 200 ℃ from room temperature with 2 ℃/min speed, and therebetween, hydrogen content increases to 100% gradually from 0.5%, and finally is adjusted to reaction process condition in reduction under the pure hydrogen after 6 hours and reacts.Reaction raw materials is selected diethy-aceto oxalate.
Catalyst reaction process conditions and the results are shown in Table 1.
Embodiment 2
The first step is poured the 140g30% Ludox in the round-bottomed flask into, and diluting and add acid for adjusting pH value with the 100g deionized water is 3.To contain 118g Cu (NO
3)
2Copper nitrate solution mix mutually with above-mentioned solution, mix be placed in 75 ℃ of water-baths standby;
5% the ammonia spirit that second step will prepare slowly is added drop-wise in the above-mentioned solution, keeps in the dropping process stirring, water-bath refluxes; Control terminal point pH value of solution value is 8.
Carry out the post-processing operation such as washing and drying of catalyst with reference to embodiment 1.The broken screening of catalyst B 20-40 order is placed reaction tube; Reaction tube is risen to 450 ℃ from room temperature with 4 ℃/min speed, and therebetween, hydrogen content increases to 100% gradually from 0.5%, and finally is adjusted to reaction process condition in reduction under the pure hydrogen after 4 hours and reacts.Reaction raw materials is selected methyl glycollate.
More than operate catalyst B.Catalyst reaction process conditions and the results are shown in Table 1.
Embodiment 3
Preparation of Catalyst is with embodiment 2, and reaction raw materials is a dimethyl oxalate.Reducing condition is for to rise to 300 ℃ from room temperature with 2 ℃/min speed with reaction tube, and therebetween, hydrogen content increases to 100% gradually from 10%, and finally is adjusted to reaction process condition in reduction under the pure hydrogen after 6 hours and reacts.Catalyst reaction process conditions and the results are shown in Table 1.
Embodiment 4
Preparation of Catalyst is with embodiment 2, and reaction raw materials is a dimethyl oxalate.Catalyst reaction process conditions and the results are shown in Table 1.
Embodiment 5
Preparation of Catalyst is with embodiment 2, and difference is to have added the 5g magnesium nitrate in virgin metal solution.More than operate catalyst C.Reaction raw materials is selected diethy-aceto oxalate.Catalyst reaction process conditions and the results are shown in Table 1.
Embodiment 6
The first step is poured 40g silica gel in the round-bottomed flask into, and diluting and add acid for adjusting pH value with the 200g deionized water is 3.
Second step, the 2g nickel nitrate mixed mutually with above-mentioned solution with 100g copper nitrate solid, and adding 80g urea also stirs.Stirring and dissolving is placed under 95 ℃ of water-baths and refluxed 20 hours, and control final solution pH value is 8.
Carry out the post-processing operation such as washing and drying of catalyst with reference to embodiment 1.Reaction raw materials is selected diethy-aceto oxalate.
More than operate catalyst D.Catalyst reaction process conditions and the results are shown in Table 1.
Embodiment 7
Preparation of Catalyst is with embodiment 6, and difference is to change the copper nitrate amount into 110g.More than operate catalyst E.Reaction raw materials is selected diethy-aceto oxalate.Catalyst reaction process conditions and the results are shown in Table 1.
Embodiment 8
Preparation of Catalyst is with embodiment 6, and difference is to change nickel nitrate into the 5g chromic nitrate.More than operate catalyst F.Reaction raw materials is selected dimethyl oxalate.Catalyst reaction process conditions and the results are shown in Table 1.
Embodiment 9
Preparation of Catalyst is with embodiment 7, and difference is to change nickel nitrate into 6g manganese nitrate and 2g zinc nitrate.More than operate catalyst G.Reaction raw materials is selected dimethyl oxalate.Catalyst reaction process conditions and the results are shown in Table 1.
Embodiment 10
Preparation of Catalyst is with embodiment 7, and reaction raw materials is a dimethyl oxalate.Catalyst reaction process conditions and the results are shown in Table 1.
Embodiment 11
Preparation of Catalyst is with embodiment 6, and reaction raw materials is selected dimethyl oxalate.This catalyst is carried out the examination of 3000 hour life-span.Catalyst reaction process conditions and the results are shown in Table 1.
The contrast of table 1 catalyst examination data
| Catalyst | Reaction temperature/℃ | Reaction pressure/MPa | The hydrogen ester ratio | Material liquid hourly space velocity/g/g cat.h | Feed stock conversion/% | Glycol selectivity/% | |
| 1 | A | 180 | 2 | 100 | 0.7 | 99 | 96 |
| 2 | B | 160 | 2 | 50 | 0.02 | 99 | 98 |
| 3 | B | 160 | 3 | 50 | 0.4 | 99 | 97 |
| 4 | B | 260 | 2 | 100 | 2.2 | 99 | 95 |
| 5 | C | 215 | 8 | 100 | 0.9 | 99 | 95 |
| 6 | D | 180 | 6 | 150 | 0.4 | 99 | 95 |
| 7 | E | 177 | 6 | 350 | 0.7 | 99 | 90 |
| 8 | F | 193 | 5 | 80 | 0.8 | 99 | 95 |
| 9 | G | 210 | 3 | 100 | 1.2 | 99 | 92 |
| 10 | E | 230 | 2 | 120 | 2.8 | 99 | 90 |
| 11 | D | 180- 200 | 3 | 100 | 0.7 | 99 | 96 |
| 12 | The emerging product of space portion | 205 | 3 | 90 | 0.38 | 99 | 95 |
| 13 | US4 4,408 73 catalyst | 215 | 0.05 | 50 | 0.024 | 99 | 87 |
Table 2 catalyst characterization parameter
| Catalyst | Specific surface (m 2/g) | Pore volume (cm 3/g) | Raw material SiO 2Specific surface (cm 3/g) |
| A | 482 | 0.77 | 10 |
| B | 544 | 1.44 | 280 |
| C | 525 | 1.08 | 280 |
| D | 218 | 0.45 | 380 |
| E | 320 | 0.8 | 380 |
| F | 180 | 0.55 | 380 |
| G | 340 | 0.9 | 380 |
Conclusion: above-mentioned catalyst is applied to the reaction that oxalate or ethyl glycolate gas phase hydrogenation prepare ethylene glycol, reaction-ure conversion-age, selectivity of product and yield all calculate by carbon number, feed stock conversion is more than 99%, glycol selectivity reaches more than 95%, and described catalyst is activity stabilized through experiment in 3000 hours.
Claims (10)
1. catalyst for hydrogenation, its chemical formula is:
CuOx-ROy/SiO
2
Wherein, R is selected from one or more in alkali earth metal, transition metal or the thulium, and x is 1/2 of a Cu valence mumber, and y is 1/2 of a R valence mumber; In total catalyst weight is 100 parts, and the content of R element is less than or equal to 15 parts greater than 0, and the content of Cu element is 10～70 parts.
2. catalyst for hydrogenation as claimed in claim 1, it is characterized in that, described R is selected from alkali earth metal Mg, Ca and Ba, the metallic element K of IA family, Na, the Ti of transition metal, V, Cr, Mn, Fe, Co, Ni and Zn, perhaps one or more among rare-earth metals La, Eu, Gd and the Tb.
3. catalyst for hydrogenation as claimed in claim 1 is characterized in that, is 100 parts in described total catalyst weight, and the content of R element is 0.01～10 part, and the content of Cu element is 20～60 parts.
4. catalyst for hydrogenation as claimed in claim 1 is characterized in that, described SiO
2Carrier is that specific surface is at 5m
2/ g～1000m
2In/g the scope is the setting or the amorphous materials of agent structure with Si-O.
5. catalyst for hydrogenation as claimed in claim 4 is characterized in that, described SiO
2Carrier be selected from silica gel, Ludox or diatomaceous one or more.
6. catalyst for hydrogenation as claimed in claim 1 is characterized in that, specific surface area of catalyst is 100～600m
2/ g, pore volume are 0.4～1.5cm
3/ g.
7. the preparation method of a catalyst for hydrogenation, its steps in sequence is: with the salt solution mix of carrier and metal and regulate the pH value and be 1-6, this mixed liquor is mixed with the solution that is dissolved with precipitating reagent, the hybrid reaction endpoint pH is 7-14, compound through stirring, aging, washing, filter, dry, roasting, finally make the target catalyst.
8. the preparation method of catalyst for hydrogenation as claimed in claim 7 is characterized in that, described Preparation of catalysts method is a kind of in direct precipitation method or the sluggish precipitation.
9. the preparation method of catalyst for hydrogenation as claimed in claim 8 is characterized in that, described precipitating reagent is alkaline precipitating agent or the preformed precipitate agent that can generate alkaline matter under certain condition.
10. hydrogenation reaction, it is characterized in that: adopt the described catalyst for hydrogenation of claim 1, with the polybasic ester is reaction raw materials, range of reaction temperature is 160～260 ℃, the reaction pressure scope is 1～10MPa, the liquid hourly space velocity (LHSV) of described polybasic ester is 0.01～3g/g cat.h, and hydrogen ester is than 50～400: 1.
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2007
- 2007-07-12 CN CNA200710043716XA patent/CN101342489A/en active Pending
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