CN105195122A - Preparation method for synthesizing propylene carbonate catalyst with urea and 1,2-propylene glycol - Google Patents
Preparation method for synthesizing propylene carbonate catalyst with urea and 1,2-propylene glycol Download PDFInfo
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- CN105195122A CN105195122A CN201410290191.XA CN201410290191A CN105195122A CN 105195122 A CN105195122 A CN 105195122A CN 201410290191 A CN201410290191 A CN 201410290191A CN 105195122 A CN105195122 A CN 105195122A
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Abstract
The invention relates to a preparation method for synthesizing propylene carbonate (PC) catalyst with urea and 1,2-propylene glycol (PG). The preparation method includes the steps that a definite proportion of soluble mixed metal salt solution (including divalent metal and trivalent metal), sodium hydroxide and a sodium carbonate solution are prepared into white slurry through a specific synthetic method, according to the divalent metal, magnesium salt, zinc salt, manganese salt and nickel salt are involved, and according to the trivalent metal, aluminum salt and iron (III) salt are involved; the white slurry is washed with deionized water to be neutral and dried at the temperature of 80 DEG C-120 DEG C; an obtained catalyst precursor is calcined at the temperature of 300 DEG C-600 DEG C to obtain the compound metal oxide catalyst. The synthesized catalyst is used for the reaction of synthesizing PC with urea and PG, the involved technological conditions include that reaction temperature is 130 DEG C-180 DEG C, the mole ratio of urea to PC is 0.75-5, the vacuum degree is 0.02-0.08 MPa, the amount of the catalyst accounts for 0.5-3% of the total mass of the reactants, and the time is 1-5 h. The catalyst shows high catalytic reaction activity and stability, is easy to separate and reuse and easy to prepare, has good catalysis service life and facilitates industrialization.
Description
Technical field
The invention belongs to catalyst preparation technical field, be specifically related to the preparation method that a kind of urea and PG synthesize PC catalyst, and study the reaction process condition that its catalyzing urea alcoholysis prepares PC.
Background technology
Propene carbonate (PC) is a kind of cyclic carbonate, and have a wide range of applications field, is mainly manifested in the following aspects: as a kind of organic solvent of higher boiling high polarity of function admirable, is applied on the indissoluble such as raw lacquer, plasticizer thing; As the intermediate of organic chemical industry, be applied in green chemical industry route and produce in Merlon technique; Due to CO
2, H
2s etc. have larger affinity, and to H
2, CO, N
2, CH
4, O
2lower etc. solubility, CO in natural gas and syngas for synthetic ammonia can be it can be used as
2and H
2the absorbent of S gas; Can be used as stable battery electrolyte, bear the light under mal-condition, heat and chemical change; As the raw material of dimethyl carbonate production by transesterification (DMC), thus the green economy of PG-PC-DMC and Chemical Manufacture chain capable of circulation can be realized in addition.
The method of producing propene carbonate (PC) mainly contains following several: phosgenation, ester-interchange method, trichloropropanol method, Ethylene Oxide and CO
2method, propylene and CO
2synthetic method, alcoholysis of urea, wherein alcoholysis of urea is the novel environment-friendly process of development in recent years, it is reaction condition gentleness compared with additive method above, cheaper starting materials is easy to get, separation of products is simple, the more important thing is that product P C can carry out ester exchange with methyl alcohol further and prepare DMC, thus coproduction accessory substance PG, thus realize recycling of PG in PG-PC-DMC building-up process, reduce production cost, and the ammonia obtained can be circulated to urea production unit, thus define a green economy, capable of circulation, the Chemical Manufacture chain of high benefit, to the product structure and Downstream Products of expanding chemical fertilizer factory, there is very strong attraction.
Current alcoholysis of urea prepares the research emphasis of PC and key technology thereof still in the exploitation of effective catalyst and the optimization of reaction process.Traditional organic tin compound catalyst, reactivity is higher, but organo-tin compound participation is homogeneous catalytic reaction, and catalyst and product are not easily separated.The exploitation of current heterogeneous catalyst is subject to the extensive attention of researcher, such as grandson gives rare grade and investigates the activity of different metal compound, shows that the catalytic performance of ZnO is better, reacts 20h at 105 DEG C, the yield of propene carbonate reaches 95%, but the reaction time is long; The people such as Jia Zhi light utilize zinc-iron oxides as the catalyst of reaction, the use amount of catalyst is 1.4% of reactant gross mass, PG: urea=4,170 DEG C, reaction time 2h, the highest yield of PC is 78.4%, but after catalytic reaction, this catalyst defines cenotype, causes activity and stability seriously to reduce; Doya etc. are under reduced pressure under condition, utilize the corresponding metal dust such as magnesium, zinc, calcium, lead or its corresponding compound to be studied urea alcoholysis synthesis PC for catalyst, and the yield of PC has had and significantly improves.In addition researcher and industry test amplify the higher PG of many employings and urea ratio (> 3) at present, and although higher alcoholuria ratio can suppress the decomposition of urea in course of reaction, but really ought be applied to PG a large amount of in industrial processes and be separated a large amount of energy consumption of needs, thus increase cost input.Therefore the industrialization promotion that catalytic activity is higher under low alcoholuria ratio catalyst prepares PC to urea alcoholysis is developed significant.
The MMO catalyst of the special ratios utilizing this patented method to prepare, preparation method is simply easy, under lower alcoholuria ratio, (PG: urea=2) has preferably catalytic activity and good catalysis service life, is easy to be separated and reuse, and is convenient to industrialization.
Summary of the invention
Object of the present invention aims to provide the preparation method of a kind of urea and 1,2-PD synthesizing acrylic fat catalyst and corresponding catalytic reaction process conditions.Obtain preferably catalytic reaction activity and good service life.
The present invention adopts and a certain proportion of hybrid metal soluble salt solutions and aqueous slkali is obtained catalyst precursor by specific synthetic method, afterwards prepared by its high-temperature calcination the MMO catalyst of certain metal ratio.
Method of the present invention comprises step:
By a certain proportion of soluble mixed meta salting liquid and NaOH and sodium carbonate liquor by specific synthetic method, obtained white slurries, the white slurries obtained are spent ionized water is centrifugal is washed till neutrality, dry at 80-120 DEG C, by the catalyst precursor obtained, calcining 3-5h, obtains composition metal (MMO) catalyst.
Involved by described soluble mixed meta salting liquid, active metal comprises divalent metal: magnesium salts, zinc salt, manganese salt, nickel salt, trivalent metal: aluminium salt, iron (III), wherein the mol ratio of divalent metal salt and trivalent metal salt is between 2:1-5:1.
Described NaOH and sodium carbonate liquor be, the concentration 0.8-5mol/L of NaOH, Na
2cO
3concentration at 0.1-1.5mol/L.
Described synthetic method is hydrothermal synthesis method, requires that hydrothermal temperature is at 100-150 DEG C, and the time is 5-20h; Or by the two method of dripping of salting liquid and aqueous slkali control pH8-10, two drip off into after at 20-80 DEG C crystallization 5-10h; Or by the method that alkali lye list drips, control to drip at 3-5 per second, final pH controls within the scope of 8-10.
The calcining heat of described catalyst precursor is 300-600 DEG C.
The MMO catalyst of above-mentioned preparation is used for the catalytic reaction that urea alcoholysis prepares PC, concrete reaction condition is: reaction temperature 150-180 DEG C, the vacuum of reaction is 0.02-0.08MPa, the molar ratio of urea and PG is 0.5-5, catalytic amount addition is the 0.5-3% of reactant gross mass, reaction time is 1-5h, has reacted rear catalyst through centrifuge washing 4 times, and at 80 DEG C, drying is carried out follow-uply repeating experiment.
The invention has the advantages that: provide the preparation method of a kind of urea and 1,2-PD synthesizing acrylic fat catalyst and corresponding catalytic reaction process conditions.Method for preparing catalyst of the present invention is simply easy, be easy to operation, under lower alcoholuria ratio (PG: urea=2), there is preferably catalytic activity, good stability, be easy to be separated and good service life, practical, be convenient to industrialization prepare on a large scale, the industrialization promotion being prepared by urea alcoholysis to PC is significant.
Accompanying drawing explanation
Fig. 1 is the catalyst precursor of embodiment 1 preparation and the XRD figure of catalyst.
Fig. 2 is catalyst A in embodiment
2be cycled to repeat the catalytic effect figure of use 6 times.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described:
The preparation of catalyst
Embodiment 1
By the Mg (NO of 51.28g
3)
2.6H
2al (the NO of O and correlated quality
3)
3.9H
2o (according to Mg:Al=2:1,3:1,4:1) adds in 250ml deionized water, stirs, and must mix MgAL salting liquid; By 48gNaOH and 15g anhydrous Na
2cO
3add in 500ml deionized water, obtain aqueous slkali; The pH of solution is controlled between 9-10 by two methods, obtained white slurries, room-temperature crystallization 5h, the white slurries obtained are spent ionized water is centrifugal is washed till Ph7.5-9, dry at 80 DEG C, by the catalyst precursor obtained, at 450 DEG C, calcine 3h, obtain MgAl composition metal (MgAl-MMO) catalyst.Wherein be labeled as A respectively according to the catalyst that Mg:Al=2:1,3:1,4:1 are obtained
1, A
2, A
3, the structure of gained presoma and composition metal (MgAl-MMO) catalyst is shown in that Fig. 1 XRD characterizes.
Embodiment 2
The catalyst precursor obtained embodiment 1 obtained, calcines 3h at 550 DEG C, obtains MgAl-MMO catalyst.Wherein be labeled as B respectively according to the catalyst that Mg:Al=2:1,3:1,4:1 are obtained
1, B
2, B
3.
Embodiment 3
The catalyst precursor obtained embodiment 1 obtained, calcines 3h at 650 DEG C, obtains MgAl-MMO catalyst.Wherein be labeled as C respectively according to the catalyst that Mg:Al=2:1,3:1,4:1 are obtained
1, C
2, C
3.。
Urea and 1,2-PD synthesizing acrylic fat
Embodiment 4
N (PG): n (urea)=2 is put in the single port flask of 100ml, wherein PG is 30g, vacuum 0.04MPa, reaction temperature 160 DEG C, catalyst input amount is 1% of reactant gross mass, and reaction time 3h, is cooled to room temperature after completion of the reaction, by the yield of gas chromatographic analysis product P C in table 1, A
2the situation of reusing of catalyst is shown in Fig. 2.
The productive rate of PC under table 1 different catalysts type
| Catalyst type | PC productive rate/% |
| A 1 | 76.1 |
| A 2 | 83.9 |
| A 3 | 73.4 |
| B 1 | 72.1 |
| B 2 | 78.5 |
| B 3 | 67.8 |
| C 1 | 68.4 |
| C 2 | 71.3 |
| C 3 | 62.6 |
Embodiment 5
N (PG): n (urea)=2 is put in the single port flask of 100ml, and wherein PG is 30g, vacuum 0.04MPa, and reaction temperature is respectively 150,160,170,180 DEG C, catalyst (A
2) input amount is 1% of reactant gross mass, reaction time 3h, is cooled to room temperature after completion of the reaction, by the yield of gas chromatographic analysis product P C, in table 2.
The productive rate of PC at table 2 differential responses temperature
| Reaction temperature/DEG C | PC productive rate/% |
| 140 | 59.6 |
| 150 | 67.2 |
| 160 | 83.9 |
| 170 | 81.3 |
Embodiment 6
N (PG): n (urea)=1.5,1.75,2,3 is put in the single port flask of 100ml, and wherein PG is 30g, vacuum 0.04MPa, and reaction temperature is respectively 160 DEG C, catalyst (A
2) input amount is 1% of reactant gross mass, reaction time 3h, is cooled to room temperature after completion of the reaction, by the yield of gas chromatographic analysis product P C, in table 3.
The productive rate of PC under the different rate of charge of table 3
| N (PG): n (urea) | PC productive rate/% |
| 1.5 | 62.3 |
| 1.75 | 74.6 |
| 2 | 83.9 |
| 3 | 79.8 |
Embodiment 7
N (PG): n (urea)=2 is put in the single port flask of 100ml, and wherein PG is 30g, vacuum is respectively 0.02,0.04,0.06,0.08MPa, reaction temperature is respectively 160 DEG C, catalyst (A
2) input amount is 1% of reactant gross mass, reaction time 3h, is cooled to room temperature after completion of the reaction, by the yield of gas chromatographic analysis product P C, in table 4.
The productive rate of PC under table 4 differential responses vacuum
| Vacuum/MPa | PC productive rate/% |
| 0.02 | 75.1 |
| 0.04 | 83.9 |
| 0.06 | 82.7 |
| 0.08 | 70.6 |
Embodiment 8
N (PG): n (urea)=2 is put in the single port flask of 100ml, and wherein PG is 30g, and vacuum is respectively 0.04MPa, and reaction temperature is respectively 160 DEG C, catalyst (A
2) input amount is 0.5,0.75,1,2% of reactant gross mass, reaction time 3h, is cooled to room temperature after completion of the reaction, by the yield of gas chromatographic analysis product P C, in table 5.
The productive rate of PC under table 5 different catalysts addition
Embodiment 9
N (PG): n (urea)=2 is put in the single port flask of 100ml, and wherein PG is 30g, and vacuum is respectively 0.04MPa, and reaction temperature is respectively 160 DEG C, catalyst (A
2) input amount is 1% of reactant gross mass, reaction time 1,2,3,4,5h, be cooled to room temperature after completion of the reaction, by the yield of gas chromatographic analysis product P C, in table 6.
The productive rate of PC under the table 6 differential responses time
| Reaction time/h | PC productive rate/% |
| 1 | 50.7 |
| 2 | 67.8 |
| 3 | 83.9 |
| 4 | 82.7 |
The more excellent catalyst of a class determined from table 1 is: when Mg, Al are 3:1, reaction solution pH between 9-10, the MgAl O composite metallic oxide catalyst that obtains after calcining at 450 DEG C.Can determine to react preferably Catalytic processes from table 2-6 is: reaction temperature 160-170 DEG C, vacuum 0.04-0.06MPa, catalyst amount is the 0.75-1% of reactant gross mass, 1, the mol ratio of 2-propane diols and urea is 2-3, and the reaction time is advisable at 3-4h.
As can be seen from Figure 1, catalyst precursor exists with the layer structure of hydrotalcite, and after calcining, the MgAl-MMO catalyst of preparation is then with MgO and unformed Al
2o
3version exist.
As can be seen from Figure 2, A is worked as
2catalyst is thrown away after reusing 6 times and is remain good catalytic effect, remains on the productive rate of more than 78%.
Claims (6)
1. a urea and 1, the preparation method of 2-propane diols synthesizing acrylic fat (PC) catalyst, the steps include: a certain proportion of soluble mixed meta salting liquid and NaOH and sodium carbonate liquor by specific synthetic method, obtained white slurries, the white slurries obtained are spent ionized water is centrifugal is washed till neutrality, dry at 80-120 DEG C, by the catalyst precursor obtained, calcining 3-5h, obtains composite metal oxide (MMO) catalyst.
2. the method for claim 1, it is characterized in that, involved by soluble mixed meta salting liquid, active metal comprises divalent metal: magnesium salts, zinc salt, manganese salt, nickel salt, trivalent metal: aluminium salt, iron (III), wherein the mol ratio of divalent metal salt and trivalent metal salt is between 2:1-5:1.
3. the method for claim 1, is characterized in that, synthetic method is hydrothermal synthesis method, requires that hydrothermal temperature is at 100-150 DEG C, and the time is 5-20h; Or by salting liquid and aqueous slkali control pH two method of dripping between 8-10, two drip off into after at 20-80 DEG C crystallization 5-10h; Or by the method that alkali lye list drips, control to drip at 3-5 per second, final pH controls within the scope of 8-10.
4. the method for claim 1, is characterized in that, NaOH and sodium carbonate liquor, and wherein the concentration of NaOH is 0.8-5mol/L, Na
2cO
3concentration be 0.1-1.5mol/L.
5. the method for claim 1, is characterized in that, the calcining heat of the catalyst precursor obtained is at 300-600 DEG C.
6. the MMO catalyst urea using the method for claim 1 to prepare and PG prepare the reaction of PC, it is characterized in that, reaction condition is: reaction temperature 130-180 DEG C, the vacuum of reaction is 0.02-0.08MPa, the molar ratio of urea and PG is 0.75-5, and the catalytic amount adding claim 1 preparation is the 0.5-3% of reactant gross mass, and the reaction time is 1-5h, reacted rear catalyst through centrifuge washing 4 times, at 80 DEG C, drying is carried out follow-uply repeating experiment.
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107815706A (en) * | 2017-11-07 | 2018-03-20 | 太原师范学院 | A kind of preparation method for photoelectrocatalysis water decomposition film |
| CN116328752A (en) * | 2022-12-13 | 2023-06-27 | 中国科学院大连化学物理研究所 | Catalyst, preparation method and application of catalyst in preparation of propylene carbonate |
-
2014
- 2014-06-25 CN CN201410290191.XA patent/CN105195122A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 舒婷等: "水滑石催化尿素与1,2-丙二醇合成碳酸丙烯酯研究", 《工业催化》 * |
| 舒婷等: "类水滑石催化尿素与1,2-丙二醇合成碳酸丙烯脂", 《石油化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107815706A (en) * | 2017-11-07 | 2018-03-20 | 太原师范学院 | A kind of preparation method for photoelectrocatalysis water decomposition film |
| CN107815706B (en) * | 2017-11-07 | 2019-07-23 | 太原师范学院 | A kind of preparation method for photoelectrocatalysis water decomposition film |
| CN116328752A (en) * | 2022-12-13 | 2023-06-27 | 中国科学院大连化学物理研究所 | Catalyst, preparation method and application of catalyst in preparation of propylene carbonate |
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Application publication date: 20151230 |