CN107540548A - The method for preparing dibutyl carbonate - Google Patents
The method for preparing dibutyl carbonate Download PDFInfo
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- CN107540548A CN107540548A CN201610486360.6A CN201610486360A CN107540548A CN 107540548 A CN107540548 A CN 107540548A CN 201610486360 A CN201610486360 A CN 201610486360A CN 107540548 A CN107540548 A CN 107540548A
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Abstract
The invention belongs to chemosynthesis technical field, and in particular to a kind of method for preparing dibutyl carbonate.Cosolvent, n-butanol and urea are configured to reaction mass solution, load Cu Zn Al catalyst, reaction mass solution squeezes into reactor with measuring pump, reacts and is carried out in continuously flowing fixed bed, is produced.The addition of cosolvent of the present invention can be such that reaction mass is in homogeneous system, and reaction can be carried out with serialization, scale, and catalyst is not required to separate with product.
Description
Technical field
The invention belongs to chemosynthesis technical field, and in particular to a kind of method for preparing dibutyl carbonate.
Background technology
Dibutyl carbonate is a kind of colourless transparent liquid, and smell is gentle, not soluble in water, is a kind of important solvent and organic
Synthetic intermediate；The solvent of electrolyte in lithium ion battery is may be used as, there is the stabilization for improving battery relative to other solvents
The advantages of property and security；The host material of lubricating oil is also acted as, for industries such as metal degreasing, leather processing.With carbonic acid
Dibutyl ester and bisphenol-A are raw material, and organotin is catalyst, can be with polycarbonate synthesis, and this method is to substitute phosgenation synthesis to gather
The green syt route of carbonic ester.The synthetic method of industrial dibutyl carbonate mainly has phosgenation, oxidative carbonylation and ester to hand over
Change method.Phosgenation is just progressively eliminated there is the shortcomings of raw material severe toxicity, operation cycle length and accessory substance severe corrosion equipment.
Oxidative carbonylation is typically not easily recycled utilization using noble metal and its compound as catalyst, catalyst such as palladiums.Ester-interchange method by
In using dimethyl carbonate as raw material, cost of material is high, and reacts and react the side, it is necessary to using reactive distillation for parallel series
Method is to improve reaction yield.
Alcoholysis of urea is a kind of a kind of technology of carbonate synthesis Arrcostab of rising in recent years, due to the urine of one of raw material
Element belongs to large industrial chemicals, and wide material sources are cheap, in addition, carbon dioxide is consumed in urea preparation process, between the reaction
Connect and utilize greenhouse gases, reduce carbon emission, can solve resource, energy problem, and mitigate environmental pressure, therefore possess stronger
Competitiveness.The process route that urea prepares related alkyl carbonate to methanol, ethanol, butanol reaction all has been reported that.
CN102093221A discloses a kind of method of carbonate synthesis dibutyl ester, using butyl carbamate and n-butanol as original
Material, using MgO as catalyst, CO2For reaction promoter and ammonia absorbent, reacted in tank reactor, butyl carbamate
Conversion ratio reach 99%, but the problem of the price that raw material butyl carbamate be present is higher than product methyl-carbonate.
CN102557948A and CN102464588A is formed anti-using tank reactor and gas storage-condensation-carbamic acid amine capture device
Piece-rate system is answered, the controlling reaction temperature by the way of two sections of heatings, obtains higher dibutyl carbonate yield, but still suffer from
Complex process and the problem of need higher butanol, urea mol ratio.CN102093221A, CN102557948A and
Problem all be present simultaneously in CN102464588A：Reaction is all that interval is carried out, and limits production scale and continuity, exists simultaneously
Reaction terminate rear catalyst need from reaction system separate the problem of.Fixed bed reactors can preferably solve reaction scale
With serialization problem, while the problem of separated in the absence of catalyst with product, CN101121659B is reported with urea and methanol
For raw material, using fixed bed reactors Synthesis of dimethyl carbonate.
With the growth of carbochain, solubility of the urea in C1, C2, C3, C4 monohydric alcohol is gradually reduced, and urea is in n-butanol
In solubility it is very small, according to stoichiometric coefficient react generation 1mol dibutyl carbonates need 2mol n-butanols and 1mol urea,
Survey solubility test result to show, mol ratio 2:1 n-butanol and urea, under conditions of heating and ultrasonic oscillation, still
In the presence of a large amount of urea solids.Need urea to be dissolved in butanol using fixed bed reactors, squeezed into mixed solution using delivery pump
In reactor, solubility of the urea in butanol is confined to, has no fixed bed reactors in urea and n-butanol reaction system
The relevant report of application in standby dibutyl carbonate route.
The content of the invention
It is an object of the invention to provide a kind of method for preparing dibutyl carbonate, solves urea and is insoluble in asking for n-butanol
Topic, reaction can be carried out with serialization, scale, and catalyst is not required to separate with product.
The method of the present invention for preparing dibutyl carbonate is that cosolvent, n-butanol and urea are configured into reaction mass
Solution, Cu-Zn-Al catalyst is loaded, reaction mass solution squeezes into reactor with measuring pump, reacts in continuously flowing fixed bed
Carry out, produce.
Described cosolvent is one kind in dimethylformamide, sulfolane, 1-METHYLPYRROLIDONE or dimethyl sulfoxide (DMSO)
It is or several.
Described urea and the mol ratio of cosolvent are 1:0.5-10.
Described n-butanol and the mol ratio of urea are 2.5-6:1.
Described Cu-Zn-Al catalyst is counted using catalyst weight as 100%,
CuO 25-60%
ZnO 25-60%
Al2O310-30%.
Described Cu-Zn-Al catalyst is counted using catalyst weight as 100%, is preferably
CuO 30-50%
ZnO 30-50%
Al2O315-25%.
The preparation method of described Cu-Zn-Al catalyst is that Cu, Zn and Al nitrate are configured to 0.1- respectively
1mol/L solution, mother liquor is obtained after mixing；Na2CO30.1-1mol/L solution is configured to, is added drop-wise in mother liquor, filtering is heavy
Form sediment, 120 DEG C dry, pulverize to 200 mesh, are calcined 3-6 hours in 300-450 DEG C, then add graphite compression molding, obtain Cu-
Zn-Al catalyst.
The loadings of described Cu-Zn-Al catalyst are 40ml.
Described reaction mass solution air speed is 0.8-5h-1。
Described reaction temperature is 150-210 DEG C, reaction pressure 0.03-0.8MPa, reaction time 24-72h.
Described reaction pressure passes through the CO that continuously flows2Maintain, CO2Air speed is 500-2000h-1。
The mol ratio of urea and cosolvent is preferably：1:The mol ratio of 1-5, n-butanol and urea is preferably：3-5:1, instead
It is preferably 1-4h to answer material solution air speed-1, CO2Air speed is preferably 800-1800h-1, reaction temperature is preferably 180-205 DEG C, instead
It is preferably 0.1-0.3MPa to answer pressure, and the reaction time is preferably 30-70h.
The present invention compared with prior art, has the advantages that：
1. the addition of cosolvent can be such that reaction mass is in homogeneous system, reaction can be carried out with serialization, scale,
Catalyst is not required to separate with product.
2. method for preparing catalyst of the present invention is simple, raw materials used is commercially available prod, is adapted to industrialization large-scale production.
Embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
The preparation of catalyst：Cu (NO are weighed respectively3)2.3H2O、Zn(NO3)2.6H2O、Al(NO3)3.9H2O：211.4g、
293.8g, 367.7g, the 1mol/L aqueous solution is made into respectively, is mixed to get mother liquor；Weigh 301.1gNa2CO3It is made into 0.5mol/L
The aqueous solution, be added drop-wise to mother liquor, filtering precipitation, 120 DEG C dry, pulverize to 200 mesh, in 450 DEG C of roastings, then add graphite pressure
Sheetmolding, obtains Φ 3*3Cu-Zn-Al catalyst, and catalyst weight is than composition：CuO：ZnO：Al2O3=35%：40%：
25%.
It is 2 by the mol ratio of cosolvent dimethylformamide, urea and n-butanol:1:3, reaction mass solution is made into, is urged
Agent loadings are 40ml, react and are carried out in continuously flowing fixed bed, liquid air speed 1h-1, CO2Air speed is 900h-1, reaction temperature
180 DEG C, reaction pressure 0.1MPa, reaction time 24h of degree.Conversion rate of urea is 99%, and dibutyl carbonate yield is 75%.
Embodiment 2
The preparation of catalyst：Cu (NO are weighed respectively3)2.3H2O、Zn(NO3)2.6H2O、Al(NO3)3.9H2O：181.2g、
367.2g, 294.2g, the 1mol/L aqueous solution is made into respectively, is mixed to get mother liquor；Weigh 335.1gNa2CO3It is made into 1mol/L's
The aqueous solution, mother liquor is added drop-wise to, filtering precipitation, 120 DEG C dry, pulverize to 200 mesh, in 450 DEG C of roastings, then add graphite tabletting
Shaping, obtains Φ 3*3Cu-Zn-Al catalyst, catalyst weight is than composition：CuO：ZnO：Al2O3=30%：50%：20%.
It is 3 by the mol ratio of cosolvent dimethyl sulfoxide (DMSO), urea and n-butanol:1:4, reaction mass solution is made into, is catalyzed
Agent loadings are 40ml, react and are carried out in continuously flowing fixed bed, liquid air speed 1h-1, CO2Air speed is 1000h-1, reaction temperature
185 DEG C, reaction pressure 0.2MPa, reaction time 30h of degree.Conversion rate of urea is 99%, and dibutyl carbonate yield is 80%.
Embodiment 3
The preparation of catalyst：Cu (NO are weighed respectively3)2.3H2O、Zn(NO3)2.6H2O、Al(NO3)3.9H2O：199.3g、
323.2g, 485.5g, the 0.8mol/L aqueous solution is made into respectively, is mixed to get mother liquor；Weigh 408.3gNa2CO3It is made into 1mol/L
The aqueous solution, be added drop-wise to mother liquor, filtering precipitation, 120 DEG C dry, pulverize to 200 mesh, in 400 DEG C of roastings, then add graphite pressure
Sheetmolding, obtains Φ 3*3Cu-Zn-Al catalyst, and catalyst weight is than composition：CuO：ZnO：Al2O3=30%：40%：
30%.
It is 3 by the mol ratio of cosolvent sulfolane, urea and n-butanol:1:4, it is made into reaction mass solution, catalyst dress
The amount of filling out is 40ml, reacts and is carried out in continuously flowing fixed bed, liquid air speed 1h-1, CO2Air speed is 1200h-1, reaction temperature 190
DEG C, reaction pressure 0.2MPa, reaction time 40h.Conversion rate of urea is 97%, and dibutyl carbonate yield is 83%.
Embodiment 4
The preparation of catalyst：Cu (NO are weighed respectively3)2.3H2O、Zn(NO3)2.6H2O、Al(NO3)3.9H2O：241.6g、
293.8g, 294.2g, the 0.5mol/L aqueous solution is made into respectively, is mixed to get mother liquor；Weigh 335.4gNa2CO3It is made into
The 0.5mol/L aqueous solution, mother liquor is added drop-wise to, filtering precipitation, 120 DEG C dry, pulverize to 200 mesh, in 450 DEG C of roastings, Ran Houjia
Enter graphite compression molding, obtain Φ 3*3Cu-Zn-Al catalyst, catalyst weight is than composition：CuO：ZnO：Al2O3=30%：
40%：20%.
It is 1 by the mol ratio of cosolvent 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), urea and n-butanol:2:1:3.5, match somebody with somebody
Into reaction mass solution, loaded catalyst 40ml, react and carried out in continuously flowing fixed bed, liquid air speed 1.5h-1,
CO2Air speed is 1400h-1, 200 DEG C, reaction pressure 0.28MPa, reaction time 50h of reaction temperature.Conversion rate of urea is 96%, carbon
Dibutyl phthalate yield is 75%.
Embodiment 5
The preparation of catalyst：Cu (NO are weighed respectively3)2.3H2O、Zn(NO3)2.6H2O、Al(NO3)3.9H2O：407.7g、
385.6g, 441.3g, the 0.8mol/L aqueous solution is made into respectively, is mixed to get mother liquor；Weigh 503.3gNa2CO3It is made into
The 0.8mol/L aqueous solution, mother liquor is added drop-wise to, filtering precipitation, 120 DEG C dry, pulverize to 200 mesh, in 450 DEG C of roastings, Ran Houjia
Enter graphite compression molding, obtain Φ 3*3Cu-Zn-Al catalyst, catalyst weight is than composition：CuO：ZnO：Al2O3=45%：
35%：20%.
It is 1 by the mol ratio of cosolvent 1-METHYLPYRROLIDONE, sulfolane, urea and n-butanol:3:1:4, it is made into reaction
Material solution, loaded catalyst 40ml, react and carried out in continuously flowing fixed bed, liquid air speed 2h-1, CO2Air speed is
1000h-1, 200 DEG C, reaction pressure 0.3MPa, reaction time 60h of reaction temperature.Conversion rate of urea is 97%, and dibutyl carbonate is received
Rate is 81%.
Embodiment 6
The preparation of catalyst：Cu (NO are weighed respectively3)2.3H2O、Zn(NO3)2.6H2O、Al(NO3)3.9H2O：291.7g、
304.1g, 372.2g, the 0.5mol/L aqueous solution is made into respectively, is mixed to get mother liquor；Weigh 394.1gNa2CO3It is made into
The 0.5mol/L aqueous solution, mother liquor is added drop-wise to, filtering precipitation, 120 DEG C dry, pulverize to 200 mesh, in 450 DEG C of roastings, Ran Houjia
Enter graphite compression molding, obtain Φ 3*3Cu-Zn-Al catalyst, catalyst weight is than composition：CuO：ZnO：Al2O3=42%：
36%：22%.
It is 1 by the mol ratio of cosolvent dimethylformamide, dimethyl sulfoxide (DMSO), urea and n-butanol:3:1:4, it is made into anti-
Material solution is answered, loaded catalyst 40ml, reacts and is carried out in continuously flowing fixed bed, liquid air speed 1h-1, CO2Air speed
For 1200h-1, 200 DEG C, reaction pressure 0.3MPa, reaction time 60h of reaction temperature.Conversion rate of urea is 96.5%, the fourth of carbonic acid two
Ester yield is 79.5%.
Embodiment 7
The preparation of catalyst：Cu (NO are weighed respectively3)2.3H2O、Zn(NO3)2.6H2O、Al(NO3)3.9H2O：202.9g、
401.1g, 247.1g, the 0.4mol/L aqueous solution is made into respectively, is mixed to get mother liquor；Weigh 336.7gNa2CO3It is made into
The 0.4mol/L aqueous solution, mother liquor is added drop-wise to, filtering precipitation, 120 DEG C dry, pulverize to 200 mesh, in 400 DEG C of roastings, Ran Houjia
Enter graphite compression molding, obtain Φ 3*3Cu-Zn-Al catalyst, catalyst weight is than composition：CuO：ZnO：Al2O3=32%：
52%：16%.
It is 3 by the mol ratio of cosolvent 1-METHYLPYRROLIDONE, urea and n-butanol:1:4, reaction mass solution is made into,
Loaded catalyst is 40ml, reacts and is carried out in continuously flowing fixed bed, liquid air speed 1.3h-1, CO2Air speed is 1300h-1,
199 DEG C, reaction pressure 0.25MPa, reaction time 50h of reaction temperature.Conversion rate of urea is 98%, and dibutyl carbonate yield is
87.5%.
Embodiment 8
The preparation of catalyst：Cu (NO are weighed respectively3)2.3H2O、Zn(NO3)2.6H2O、Al(NO3)3.9H2O：347.3g、
330.5g, 165.5g, the 0.9mol/L aqueous solution is made into respectively, is mixed to get mother liquor；Weigh 340.3gNa2CO3It is made into
The 0.9mol/L aqueous solution, mother liquor is added drop-wise to, filtering precipitation, 120 DEG C dry, pulverize to 200 mesh, in 440 DEG C of roastings, Ran Houjia
Enter graphite compression molding, obtain Φ 3*3Cu-Zn-Al catalyst, catalyst weight is than composition：CuO：ZnO：Al2O3=46%：
36%：18%.
It is 4 by the mol ratio of cosolvent 1-METHYLPYRROLIDONE, urea and n-butanol:1:4, reaction mass solution is made into,
Loaded catalyst is 40ml, reacts and is carried out in continuously flowing fixed bed, liquid air speed 2h-1, CO2Air speed is 1500h-1, instead
Answer 190 DEG C, reaction pressure 0.25MPa, reaction time 60h of temperature.Conversion rate of urea is 95%, and dibutyl carbonate yield is
82.7%.
Embodiment 9
The preparation of catalyst：Cu (NO are weighed respectively3)2.3H2O、Zn(NO3)2.6H2O、Al(NO3)3.9H2O：190.3g、
330.5g, 198.6g, the 0.7mol/L aqueous solution is made into respectively, is mixed to get mother liquor；Weigh 285.4gNa2CO3It is made into
The 0.7mol/L aqueous solution, mother liquor is added drop-wise to, filtering precipitation, 120 DEG C dry, pulverize to 200 mesh, in 450 DEG C of roastings, Ran Houjia
Enter graphite compression molding, obtain Φ 3*3Cu-Zn-Al catalyst, catalyst weight is than composition：CuO：ZnO：Al2O3=35%：
50%：15%.
It is 1 by the mol ratio of cosolvent sulfolane, dimethylformamide, urea and n-butanol:3:1:5, it is made into reactant
Expect solution, loaded catalyst 40ml, react and carried out in continuously flowing fixed bed, liquid air speed 1.5h-1, CO2Air speed is
1400h-1, 190 DEG C, reaction pressure 0.15MPa, reaction time 70h of reaction temperature.Conversion rate of urea is 98.6%, the fourth of carbonic acid two
Ester yield is 89.4%.
Embodiment 10
The preparation of catalyst：Cu (NO are weighed respectively3)2.3H2O、Zn(NO3)2.6H2O、Al(NO3)3.9H2O：181.2g、
403.9g, 220.7g, the 0.5mol/L aqueous solution is made into respectively, is mixed to get mother liquor；Weigh 316.9gNa2CO3It is made into
The 0.5mol/L aqueous solution, mother liquor is added drop-wise to, filtering precipitation, 120 DEG C dry, pulverize to 200 mesh, in 450 DEG C of roastings, Ran Houjia
Enter graphite compression molding, obtain Φ 3*3Cu-Zn-Al catalyst, catalyst weight is than composition：CuO：ZnO：Al2O3=30%：
55%：15%.
It is 4 by the mol ratio of cosolvent sulfolane, dimethyl sulfoxide (DMSO), urea and n-butanol:1:1:4.5, it is made into reactant
Expect solution, loaded catalyst 40ml, react and carried out in continuously flowing fixed bed, liquid air speed 1.5h-1, CO2Air speed is
1300h-1, 195 DEG C, reaction pressure 0.3MPa, reaction time 65h of reaction temperature.Conversion rate of urea is 98.2%, dibutyl carbonate
Yield is 88.9%.
Comparative example 1
The preparation of catalyst：Cu (NO are weighed respectively3)2.3H2O、Zn(NO3)2.6H2O、Al(NO3)3.9H2O：407.7g、
385.6g, 441.3g, the 0.8mol/L aqueous solution is made into respectively, is mixed to get mother liquor；Weigh 503.3gNa2CO3It is made into
The 0.8mol/L aqueous solution, mother liquor is added drop-wise to, filtering precipitation, 120 DEG C dry, pulverize to 200 mesh, in 450 DEG C of roastings, Ran Houjia
Enter graphite compression molding, obtain Φ 3*3Cu-Zn-Al catalyst, catalyst weight is than composition：CuO：ZnO：Al2O3=45%：
35%：20%.
Any cosolvent is not added with, is 1 by the mol ratio of urea and n-butanol:4 two kinds of raw materials of mixing, under stirring condition,
60 DEG C of heating 4h, still there is a large amount of undissolved urea, therefore under conditions of cosolvent is not added with, delivery pump can not be used predetermined
Urea, the butanol mixed solution of ratio are squeezed into reactor and reacted.
Claims (10)
- A kind of 1. method for preparing dibutyl carbonate, it is characterised in that cosolvent, n-butanol and urea are configured to reaction mass Solution, Cu-Zn-Al catalyst is loaded, reaction mass solution squeezes into reactor with measuring pump, reacts in continuously flowing fixed bed Carry out, produce.
- 2. the method according to claim 1 for preparing dibutyl carbonate, it is characterised in that described cosolvent is dimethyl One or more in formamide, sulfolane, 1-METHYLPYRROLIDONE or dimethyl sulfoxide (DMSO).
- 3. the method according to claim 1 for preparing dibutyl carbonate, it is characterised in that described urea and cosolvent Mol ratio is 1:0.5-10.
- 4. the method according to claim 1 for preparing dibutyl carbonate, it is characterised in that described n-butanol and urea Mol ratio is 2.5-6:1.
- 5. the method according to claim 1 for preparing dibutyl carbonate, it is characterised in that described Cu-Zn-Al catalyst Counted using catalyst weight as 100%,CuO 25-60%ZnO 25-60%Al2O310-30%.
- 6. the method for dibutyl carbonate is prepared according to claim 1 or 5, it is characterised in that described Cu-Zn-Al catalysis The preparation method of agent is Cu, Zn and Al nitrate to be configured to respectively 0.1-1mol/L solution, and mother liquor is obtained after mixing； Na2CO30.1-1mol/L solution is configured to, is added drop-wise in mother liquor, filtering precipitation, 120 DEG C dry, pulverize to 200 mesh, in 300-450 DEG C of roasting 3-6 hour, graphite compression molding is then added, obtains Cu-Zn-Al catalyst.
- 7. the method according to claim 1 for preparing dibutyl carbonate, it is characterised in that described Cu-Zn-Al catalyst Loadings be 40ml.
- 8. the method according to claim 1 for preparing dibutyl carbonate, it is characterised in that described reaction mass solution is empty Speed is 0.8-5h-1。
- 9. the method according to claim 1 for preparing dibutyl carbonate, it is characterised in that described reaction temperature is 150- 210 DEG C, reaction pressure 0.03-0.8MPa, reaction time 24-72h.
- 10. the method according to claim 9 for preparing dibutyl carbonate, it is characterised in that described reaction pressure passes through company The dynamic CO of afterflow2Maintain, CO2Air speed is 500-2000h-1。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1121659A (en) * | 1995-07-13 | 1996-05-01 | 曾光橦 | Method for realizing exceeding-normal coding |
| JP2001354624A (en) * | 2000-06-12 | 2001-12-25 | Mitsubishi Gas Chem Co Inc | Method for feeding iodine |
| CN101659616A (en) * | 2009-09-17 | 2010-03-03 | 河北工业大学 | Technology of preparing diethyl carbonate by urea alcoholysis method |
-
2016
- 2016-06-28 CN CN201610486360.6A patent/CN107540548B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1121659A (en) * | 1995-07-13 | 1996-05-01 | 曾光橦 | Method for realizing exceeding-normal coding |
| JP2001354624A (en) * | 2000-06-12 | 2001-12-25 | Mitsubishi Gas Chem Co Inc | Method for feeding iodine |
| CN101659616A (en) * | 2009-09-17 | 2010-03-03 | 河北工业大学 | Technology of preparing diethyl carbonate by urea alcoholysis method |
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