CN105713191A - Technology for producing polyether amine through continuous hydrogen ammonification - Google Patents
Technology for producing polyether amine through continuous hydrogen ammonification Download PDFInfo
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Abstract
The invention discloses a technology for producing polyether amine through continuous hudrogen ammonification. The technology comprises the steps that a reaction material containing polyether polyol, liquid ammonia and hydrogen flows through multiple reaction kettles connected in series, a reaction is conducted under the action of catalysts, and polyether amine is obtained, wherein the catalysts are fixed in the reaction kettles. According to the technology for producing polyether amine through continuous hydrogen ammonification, the catalysts are fixed in the reaction kettles, and the total amine value and primary amine rate of polyether amine obtained through the reaction can be greatly increased; the materials can flow in the reaction kettles more smoothly, and pipeline blocking is avoided; the materials can be mixed together to enter the reaction kettles, separate treatment of the materials is avoided, and operation is easy and convenient. According to the technology for producing polyether amine through continuous hudrogen ammonification, the multiple reaction kettles connected in series are adopted, the catalyst in the single reaction kettle can be replaced in time, the influence of generated water on the efficiency of the catalysts in the reaction is effectively reduced, and the production efficiency is greatly improved.
Description
Technical field
The present invention relates to and face hydrogen ammonification technical field, in particular it relates to the technique that hydrogen ammonification produces polyetheramine is faced in a kind of serialization.
Background technology
Polyetheramine is a class main chain is polyether structure, and end active functional group is the polymer of amido.By selecting different polyoxyalkyl structures, a series of performances such as the reactivity of scalable polyetheramine, toughness, viscosity and hydrophilic, and amido is supplied to the probability that polyetheramine reacts with multiple compounds.Its special molecular structure imparts the combination property that polyetheramine is excellent, and current business-like polyetheramine includes simple function, difunctionality, trifunctional, the molecular weight a series of products from 200 to 5000.Spray at polyureas, large-scale composite material makes and the various fields such as epoxy curing agent is widely applied.
The synthetic method of polyetheramine mainly has high-pressure catalytic ammoniation process, leaving group method, amino-butenate method and polyethers nitrile alkylation process etc..Catalytic ammoniation method synthesizing polyether amine has constant product quality and more meets the advantages such as environmental requirement, is the main method of current industrial production polyetheramine.
US3128311 discloses a kind of method preparing Armeen, and this reaction is with frame special nickel for catalyst, and the fat primary amine of preparation has higher selectivity, and this reaction is implemented in step reactor；The preparation method that CN102382294A discloses a kind of series products of polyether amine, polyether polyol, catalyst, promoter are dosed in autoclave by the method, and it is filled with a certain amount of aminating agent, hydrogen, heat autoclave to assigned temperature, pressure, insulation reaction number h, after reaction terminates, material is released, filters, reclaim filter cake, then filtrate is carried out processed, water white polyetheramine product can be obtained；CN102336903A discloses a kind of production process of aliphatic polyetheramine, this technique with number-average molecular weight be more than 100 polyether polyol for raw material, under hydrogen, aminating agent and skeletal nickel catalyst exist, prepare aliphatic poly ether amines by catalysis reduction amination.After reaction terminates, skeletal nickel catalyst needs through separating, and is circulated after treatment and applies mechanically.
Each technique belongs to batch technology above, and it is relatively simple that it produces equipment, and technology difficulty is little, but the auxiliary operations such as charging, discharging need to consume plenty of time and manpower, and the production cost that can make product is too high, is unfavorable for large-scale production.
Successive reaction can make constant product quality by contrast, reduces human cost.US3654370 and GB1185239 discloses the technology preparing fatty amine and polyetheramine, and reaction carries out in fixed-bed tube reactor, it is possible to continuous prodution.But, fixed bed reactors equipment requirements is high, investment is big, and for the polyetheramine product of small-molecular-weight, owing to generating substantial amounts of water in course of reaction, can make catalyst easy in inactivation, it is necessary to frequent more catalyst changeout, and the production time can be made to reduce in a large number.
CN103012769A discloses a kind of method that hydrogen ammonification is faced in serialization, it is to be in series by six reactors, and pump into first order reactor after polyether polyol being mixed according to a certain percentage with materials such as catalyst, then these materials by potential difference nature overflow to second and third, four, five and six order reaction stills, afterwards by material and catalyst separation.The method utilizes reactor to connect, it is achieved that more catalyst changeout in course of reaction, improves production efficiency, but total amine number of polyetheramine of obtaining of the method and primary amine rate still await further raising.
Summary of the invention
The invention aims to overcome total amine number of the polyetheramine obtained in prior art and the relatively low defect of primary amine rate, it is provided that the technique that hydrogen ammonification produces polyetheramine is faced in a kind of serialization that can improve total amine number and primary amine rate.
The present inventor finds under study for action, is fixed in reactor by catalyst, it is possible to increase total amine number of the polyetheramine being obtained by reacting and primary amine rate.
Therefore, to achieve these goals, the invention provides a kind of serialization and face the technique that hydrogen ammonification produces polyetheramine, described technique includes: make the reaction raw materials containing polyether polyol, liquefied ammonia and hydrogen flow through the reactor of multiple series connection, react under the effect of catalyst and obtain polyetheramine, wherein, described catalyst is fixed in reactor.
Preferably, described catalyst is Raney metal catalyst；It is highly preferred that at least one that described catalyst is in Raney's nickel, thunder Buddhist nun's cobalt, Lei Nitong, raney iron and Raney's nickel cobalt；It is further preferred that described catalyst is Raney's nickel, thunder Buddhist nun's cobalt and Raney's nickel cobalt, the weight ratio of Raney's nickel, thunder Buddhist nun's cobalt and Raney's nickel cobalt is 1:0.6-1:0.6-1.
Preferably, described reactor is 3-6.
Preferably, the number-average molecular weight of described polyether polyol is 200-5000.
Preferably, the weight ratio of described polyether polyol and described liquefied ammonia is 1:0.1-1, more preferably 1:0.2-0.5.
Preferably, relative to the described polyether polyol of 100g, the consumption of described hydrogen is 0.1-1L, more preferably 0.3-0.45L.
Preferably, it is 400-600g/h that polyether polyol enters the charging rate of reactor, and catalyst fixing in each reactor is 120-200g.
Preferably, the condition of described reaction includes: temperature is 170-250 DEG C, more preferably 200-215 DEG C；Pressure is 7-15MPa, more preferably 8-12MPa.
The serialization of the present invention is faced hydrogen ammonification and is produced the technique of polyetheramine, is fixed in reactor by catalyst, it is possible to be greatly enhanced total amine number and the primary amine rate of the polyetheramine being obtained by reacting；Material can be made to flow in reactor more unobstructed, it is to avoid pipeline blockage；Material can be mixed entrance reactor, it is to avoid separately the processing of material, easy and simple to handle.Present invention process adopts the reactor of multiple series connection, can change the catalyst in single reactor in time, effectively reduces and generates water in reaction for the impact of catalyst efficiency, drastically increases production efficiency.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
The invention provides a kind of serialization and face the technique that hydrogen ammonification produces polyetheramine, this technique includes: make the reaction raw materials containing polyether polyol, liquefied ammonia and hydrogen flow through the reactor of multiple series connection, reacting under the effect of catalyst and obtain polyetheramine, wherein, catalyst is fixed in reactor.
Although catalyst is fixed in reactor, the purpose of the present invention can be realized, namely total amine number and the primary amine rate of the polyetheramine being obtained by reacting are improved, but under preferable case, when catalyst is Raney metal catalyst, can improving total amine number and the primary amine rate of the polyetheramine being obtained by reacting further, therefore, catalyst is preferably Raney metal catalyst.
In the present invention, catalyst can be various Raney metal catalyst commonly used in the art, for instance, catalyst can be selected from least one in Raney's nickel, thunder Buddhist nun's cobalt, Lei Nitong, raney iron and Raney's nickel cobalt.But the present inventor finds under study for action, when catalyst is Raney's nickel, thunder Buddhist nun's cobalt and Raney's nickel cobalt, can further improve total amine number and the primary amine rate of the polyetheramine being obtained by reacting, therefore, preferably, catalyst is Raney's nickel, thunder Buddhist nun's cobalt and Raney's nickel cobalt, and the weight ratio of Raney's nickel, thunder Buddhist nun's cobalt and Raney's nickel cobalt is preferably 1:0.6-1:0.6-1.
In the present invention, Raney metal catalyst all can pass through commercially available.
In the present invention, the mode in reactor is fixed on without particular/special requirement for catalyst, it is possible to adopt the thinkable various modes of those skilled in the art, for instance, it is possible to catalyst hoop is installed in reactor, catalyst is fixed in catalyst hoop.
It will be understood by those skilled in the art that the reaction raw materials made containing polyether polyol, liquefied ammonia and hydrogen flows through the reactor of multiple series connection, it is preferred to reaction raw materials flows through the reactor of multiple series connection successively.
In the present invention, for reactor without particular/special requirement, it is possible to adopt reactor commonly used in the art, for instance, the volume of reactor can be 500mL, 1000mL, 2000mL equal-specification.Series system for reactor, also without particular/special requirement, the thinkable various modes of those skilled in the art can be adopted to connect, as long as reaction mass can be made to flow through the reactor of multiple series connection successively, such as, reactors at different levels can be sequentially connected in series in the way of forming potential difference, so that reaction mass nature overflow sequentially passes through reactor at different levels.
In the present invention, reactor is preferably 3-6.
In the present invention, the number-average molecular weight of polyether polyol is preferably 200-5000.What those skilled in the art should understand that is, polyether polyol for different number-average molecular weights, total amine number of the polyetheramine being obtained by reacting is different with the evaluation criterion of primary amine rate, such as, it is the polyether polyol of 230 for number-average molecular weight, total amine number of the polyetheramine being obtained by reacting is 8.1-8.7meq/g, primary amine rate >=97%, and it is qualified to be；Being the polyether polyol of 403 for number-average molecular weight, total amine number of the polyetheramine being obtained by reacting is 6.1-6.8meq/g, primary amine rate >=90%, and it is qualified to be；Being the polyether polyol of 2000 for number-average molecular weight, total amine number of the polyetheramine being obtained by reacting is 0.93-1.05meq/g, primary amine rate >=97%, and it is qualified to be；Being the polyether polyol of 5000 for number-average molecular weight, total amine number of the polyetheramine being obtained by reacting is 0.5-0.54meq/g, primary amine rate >=97%, and it is qualified to be.In respective scope, total amine number of the polyetheramine being obtained by reacting and primary amine rate are more high more good.
In the present invention, polyether polyol can be passed through commercially available.
In the present invention, the weight ratio of polyether polyol and liquefied ammonia is preferably 1:0.1-1, more preferably 1:0.2-0.5, under this preferable case, it is possible to improve total amine number and the primary amine rate of the polyetheramine being obtained by reacting further.
In the present invention, relative to the polyether polyol of 100g, the consumption of hydrogen is preferably 0.1-1L, more preferably 0.3-0.45L.
In the present invention, for the charging rate of polyether polyol without particular/special requirement, it is possible to adopt the charging rate that this area is conventional, for instance, it can be 400-600g/h that polyether polyol enters the charging rate of reactor.
In the present invention, catalyst fixing in each reactor is preferably 120-200g.
In the present invention, owing to catalyst is fixed in reactor, therefore, each material can be mixed entrance reactor, it is not necessary to separately processes, is greatly saved operating procedure.It will be understood by those skilled in the art that polyether polyol and liquefied ammonia enter back into reactor after being preferably preheated to reaction temperature.
In the present invention, the condition of reaction preferably includes: temperature is 170-250 DEG C, more preferably 200-215 DEG C；Pressure is 7-15MPa, more preferably 8-12MPa.
It will be understood by those skilled in the art that in the present invention, the discharging of reactor needs, through dehydration, except ammonia, except impurity such as other low-boiling by-products, just to obtain polyetheramine product.For dehydration, except ammonia, except the method for the impurity such as other low-boiling by-products is without particular/special requirement, method commonly used in the art can be adopted, such as, decompression distillation dehydration can be passed through, except ammonia, except impurity such as other low-boiling by-products, the condition of decompression distillation such as may include that temperature is 80-120 DEG C, vacuum is-0.08MPa to-0.1MPa, and the process time is 1-2h.
Embodiment
The present invention is further illustrated for below example, but and is not so limited the present invention.
In the following Examples and Comparative Examples:
Raney's nickel: purchased from the general Chemical Co., Ltd. in Dalian, RTH-2124.
Thunder Buddhist nun's cobalt: purchased from the general Chemical Co., Ltd. in Dalian, RTH-6110.
Raney's nickel cobalt: purchased from the general Chemical Co., Ltd. in Dalian, RTH-6120.
Total amine number, primary amine rate assay method: Unite States Standard ASTM2074.
Embodiment 1
The present embodiment is for illustrating that the technique that hydrogen ammonification produces polyetheramine is faced in the serialization of the present invention.
The reactor that 6 are fixed with catalyst hoop is in series, the volume of each reactor is 2000mL, it is fixed with 200g catalyst in catalyst hoop in each reactor, catalyst is Raney's nickel, thunder Buddhist nun's cobalt and Raney's nickel cobalt, and the weight ratio of Raney's nickel, thunder Buddhist nun's cobalt and Raney's nickel cobalt is 1:0.6:0.6.
By polyether polyol (purchased from Shandong Lanxing Dongda Chemical Co., Ltd, number-average molecular weight is 230) and liquefied ammonia be preheated to 210 DEG C after squeeze into first order reactor together with hydrogen, the material after first order reactor by potential difference nature overflow to the second level, the third level, the fourth stage, level V and the 6th order reaction still.The charging rate of polyether polyol is 400g/h, and liquefied ammonia is 200g/h, and hydrogen flowing quantity is 30mL/min, and the temperature of each reactor is 210 DEG C, pressure is 10MPa.Reactor discharging 80 DEG C, vacuum for obtaining product after processing 1.5h under-0.09MPa, be measured, the outward appearance of product, total amine number, primary amine rate are in Table 1.
Embodiment 2
The present embodiment is for illustrating that the technique that hydrogen ammonification produces polyetheramine is faced in the serialization of the present invention.
The reactor that 5 are fixed with catalyst hoop is in series, the volume of each reactor is 1000mL, being fixed with 180g catalyst in catalyst hoop in each reactor, catalyst is Raney's nickel, thunder Buddhist nun's cobalt and Raney's nickel cobalt, and the weight ratio that Raney's nickel, thunder Buddhist nun's cobalt and Raney's nickel are estimated is 1:1:1.
First order reactor is squeezed into together with hydrogen after polyether polyol (purchased from Shandong Lanxing Dongda Chemical Co., Ltd, number-average molecular weight is 403) and liquefied ammonia are preheated to 215 DEG C.Material after first order reactor by potential difference nature overflow to the second level, the third level, the fourth stage and level V reactor.The charging rate of polyether polyol is 400g/h, and liquefied ammonia is 170g/h, and hydrogen flowing quantity is 30mL/min, and the temperature of each reactor is 215 DEG C, pressure is 8MPa.Reactor discharging 100 DEG C, vacuum for obtaining product after processing 2h under-0.08MPa, be measured, the outward appearance of product, total amine number, primary amine rate are in Table 1.
Embodiment 3
The present embodiment is for illustrating that the technique that hydrogen ammonification produces polyetheramine is faced in the serialization of the present invention.
The reactor that 4 are fixed with catalyst hoop is in series, the volume of each reactor is 500mL, it is fixed with 150g catalyst in catalyst hoop in each reactor, catalyst is Raney's nickel, thunder Buddhist nun's cobalt and Raney's nickel cobalt, and the weight ratio of Raney's nickel, thunder Buddhist nun's cobalt and Raney's nickel cobalt is 1:0.8:0.7.
First order reactor is squeezed into together with hydrogen after polyether polyol (purchased from Shandong Lanxing Dongda Chemical Co., Ltd, number-average molecular weight is 2000) and liquefied ammonia are preheated to 205 DEG C.Material after first order reactor by potential difference nature overflow to the second level, the third level and fourth stage reactor.The charging rate of polyether polyol is 500g/h, and liquefied ammonia is 150g/h, and hydrogen flowing quantity is 30mL/min, and the temperature of each reactor is 205 DEG C, pressure is 9MPa.Reactor discharging 120 DEG C, vacuum for obtaining product after processing 1h under-0.1MPa, be measured, the outward appearance of product, total amine number, primary amine rate are in Table 1.
Embodiment 4
The present embodiment is for illustrating that the technique that hydrogen ammonification produces polyetheramine is faced in the serialization of the present invention.
The reactor that 3 are fixed with catalyst hoop is in series, the volume of each reactor is 500mL, it is fixed with 120g catalyst in catalyst hoop in each reactor, catalyst is Raney's nickel, thunder Buddhist nun's cobalt and Raney's nickel cobalt, and the weight ratio of Raney's nickel, thunder Buddhist nun's cobalt and Raney's nickel cobalt is 1:0.7:0.8.
First order reactor is squeezed into together with hydrogen after polyether polyol (purchased from Shandong Lanxing Dongda Chemical Co., Ltd, number-average molecular weight is 5000) and liquefied ammonia are preheated to 200 DEG C.Material after first order reactor is by potential difference nature overflow to the second level and third level reactor.The charging rate of polyether polyol is 600g/h, and liquefied ammonia is 120g/h, and hydrogen flowing quantity is 30mL/min, and the temperature of each reactor is 200 DEG C, pressure is 12MPa.Reactor discharging 110 DEG C, vacuum for obtaining product after processing 1.5h under-0.09MPa, be measured, the outward appearance of product, total amine number, primary amine rate are in Table 1.
Embodiment 5
The present embodiment is for illustrating that the technique that hydrogen ammonification produces polyetheramine is faced in the serialization of the present invention.
According to the explained hereafter polyetheramine of embodiment 1, the difference is that, catalyst is Raney's nickel.The outward appearance of product, total amine number, primary amine rate are in Table 1.
Embodiment 6
The present embodiment is for illustrating that the technique that hydrogen ammonification produces polyetheramine is faced in the serialization of the present invention.
According to the explained hereafter polyetheramine of embodiment 2, the difference is that, catalyst is thunder Buddhist nun's cobalt.The outward appearance of product, total amine number, primary amine rate are in Table 1.
Embodiment 7
The present embodiment is for illustrating that the technique that hydrogen ammonification produces polyetheramine is faced in the serialization of the present invention.
According to the explained hereafter polyetheramine of embodiment 3, the difference is that, catalyst is Raney's nickel cobalt.The outward appearance of product, total amine number, primary amine rate are in Table 1.
Embodiment 8
The present embodiment is for illustrating that the technique that hydrogen ammonification produces polyetheramine is faced in the serialization of the present invention.
According to the explained hereafter polyetheramine of embodiment 4, the difference is that, catalyst is Raney's nickel and Lei Ni cobalt, and the weight ratio of Raney's nickel and Lei Ni cobalt is 1:1.The outward appearance of product, total amine number, primary amine rate are in Table 1.
Embodiment 9
The present embodiment is for illustrating that the technique that hydrogen ammonification produces polyetheramine is faced in the serialization of the present invention.
According to the explained hereafter polyetheramine of embodiment 1, the difference is that, the charging rate of liquefied ammonia is 250g/h.The outward appearance of product, total amine number, primary amine rate are in Table 1.
Embodiment 10
The present embodiment is for illustrating that the technique that hydrogen ammonification produces polyetheramine is faced in the serialization of the present invention.
According to the explained hereafter polyetheramine of embodiment 4, the difference is that, the charging rate of liquefied ammonia is 100g/h.The outward appearance of product, total amine number, primary amine rate are in Table 1.
Comparative example 1
According to the explained hereafter polyetheramine of embodiment 1, the difference is that, catalyst is not fixed in reactor, and catalyst is preheated to 210 DEG C after mixing with polyether polyol and squeezes into reactor, and liquefied ammonia squeezes into reactor after being preheated to 210 DEG C together with hydrogen.The outward appearance of product, total amine number, primary amine rate are in Table 1.
Comparative example 2
According to the explained hereafter polyetheramine of embodiment 2, the difference is that, catalyst is not fixed in reactor, and catalyst is preheated to 215 DEG C after mixing with polyether polyol and squeezes into reactor, and liquefied ammonia squeezes into reactor after being preheated to 215 DEG C together with hydrogen.The outward appearance of product, total amine number, primary amine rate are in Table 1.
Comparative example 3
According to the explained hereafter polyetheramine of embodiment 3, the difference is that, catalyst is not fixed in reactor, and catalyst is preheated to 205 DEG C after mixing with polyether polyol and squeezes into reactor, and liquefied ammonia squeezes into reactor after being preheated to 205 DEG C together with hydrogen.The outward appearance of product, total amine number, primary amine rate are in Table 1.
Comparative example 4
According to the explained hereafter polyetheramine of embodiment 4, the difference is that, catalyst is not fixed in reactor, and catalyst is preheated to 200 DEG C after mixing with polyether polyol and squeezes into reactor, and liquefied ammonia squeezes into reactor after being preheated to 200 DEG C together with hydrogen.The outward appearance of product, total amine number, primary amine rate are in Table 1.
Table 1
| Outward appearance | Total amine number (meq/g) | Primary amine rate (%) | |
| Embodiment 1 | Water white transparency | 8.65 | 99.20 |
| Embodiment 2 | Water white transparency | 6.73 | 93.34 |
| Embodiment 3 | Water white transparency | 1.02 | 99.12 |
| Embodiment 4 | Water white transparency | 0.53 | 98.02 |
| Embodiment 5 | Water white transparency | 8.50 | 97.65 |
| Embodiment 6 | Water white transparency | 6.60 | 91.54 |
| Embodiment 7 | Water white transparency | 0.98 | 97.89 |
| Embodiment 8 | Water white transparency | 0.52 | 97.45 |
| Embodiment 9 | Water white transparency | 8.42 | 98.28 |
| Embodiment 10 | Water white transparency | 0.51 | 97.76 |
| Comparative example 1 | Pale yellow transparent | 8.15 | 97.21 |
| Comparative example 2 | Pale yellow transparent | 6.21 | 90.76 |
| Comparative example 3 | Pale yellow transparent | 0.94 | 97.19 |
| Comparative example 4 | Pale yellow transparent | 0.50 | 97.12 |
Embodiment 1 and comparative example 1 are compared, embodiment 2 and comparative example 2 are compared, embodiment 3 and comparative example 3 are compared, embodiment 4 and comparative example 4 are compared, can be seen that, the serialization of the present invention is faced hydrogen ammonification and is produced the technique of polyetheramine, is fixed in reactor by catalyst, it is possible to greatly improve total amine number and the primary amine rate of the polyetheramine being obtained by reacting.
Embodiment 1 and embodiment 5 are compared, embodiment 2 and embodiment 6 are compared, embodiment 3 and embodiment 7 are compared, embodiment 4 and embodiment 8 are compared, can be seen that, catalyst is Raney's nickel, thunder Buddhist nun's cobalt and Raney's nickel cobalt, and the weight ratio of Raney's nickel, thunder Buddhist nun's cobalt and Raney's nickel cobalt is 1:0.6-1:0.6-1, it is possible to improve total amine number and the primary amine rate of the polyetheramine being obtained by reacting further；Embodiment 1 and embodiment 9 are compared, embodiment 4 and embodiment 10 is compared, it can be seen that the weight ratio of polyether polyol and liquefied ammonia is 1:0.2-0.5, it is possible to improve total amine number and the primary amine rate of the polyetheramine being obtained by reacting further.
The serialization of the present invention is faced hydrogen ammonification and is produced the technique of polyetheramine, is fixed in reactor by catalyst, it is possible to be greatly enhanced total amine number and the primary amine rate of the polyetheramine being obtained by reacting；Material can be made to flow in reactor more unobstructed, it is to avoid pipeline blockage；Material can be mixed entrance reactor, it is to avoid separately the processing of material, easy and simple to handle.Present invention process adopts the reactor of multiple series connection, can change the catalyst in single reactor in time, effectively reduces and generates water in reaction for the impact of catalyst efficiency, drastically increases production efficiency.
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the technology concept of the present invention; technical scheme can being carried out multiple simple variant, these simple variant belong to protection scope of the present invention.
It is further to note that, each concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, it is possible to be combined by any suitable mode, in order to avoid unnecessary repetition, various possible compound modes are no longer illustrated by the present invention separately.
Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. the technique that hydrogen ammonification produces polyetheramine is faced in a serialization, it is characterized in that, described technique includes: make the reaction raw materials containing polyether polyol, liquefied ammonia and hydrogen flow through the reactor of multiple series connection, react under the effect of catalyst and obtain polyetheramine, wherein, described catalyst is fixed in reactor.
2. technique according to claim 1, wherein, described catalyst is Raney metal catalyst.
3. technique according to claim 2, wherein, described catalyst at least one in Raney's nickel, thunder Buddhist nun's cobalt, Lei Nitong, raney iron and Raney's nickel cobalt.
4. technique according to claim 3, wherein, described catalyst is Raney's nickel, thunder Buddhist nun's cobalt and Raney's nickel cobalt, and the weight ratio of Raney's nickel, thunder Buddhist nun's cobalt and Raney's nickel cobalt is 1:0.6-1:0.6-1.
5. the technique according to any one in claim 1-4, wherein, described reactor is 3-6.
6. the technique according to any one in claim 1-4, wherein, the number-average molecular weight of described polyether polyol is 200-5000.
7. the technique according to any one in claim 1-4, wherein, the weight ratio of described polyether polyol and described liquefied ammonia is 1:0.1-1, it is preferred to 1:0.2-0.5.
8. the technique according to any one in claim 1-4, wherein, relative to the described polyether polyol of 100g, the consumption of described hydrogen is 0.1-1L, it is preferred to 0.3-0.45L.
9. the technique according to any one in claim 1-4, wherein, it is 400-600g/h that described polyether polyol enters the charging rate of reactor, and catalyst fixing in each reactor is 120-200g.
10. the technique according to any one in claim 1-4, wherein, the condition of described reaction includes: temperature is 170-250 DEG C, it is preferred to 200-215 DEG C；Pressure is 7-15MPa, it is preferred to 8-12MPa.
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| CN106995378A (en) * | 2017-03-13 | 2017-08-01 | 浙江皇马表面活性剂研究有限公司 | A kind of continuous production method of polyetheramine |
| CN107141225A (en) * | 2017-06-22 | 2017-09-08 | 江苏飞翔化工股份有限公司 | A kind of polyetheramine synthetic method |
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| CN106995378A (en) * | 2017-03-13 | 2017-08-01 | 浙江皇马表面活性剂研究有限公司 | A kind of continuous production method of polyetheramine |
| CN106995378B (en) * | 2017-03-13 | 2019-05-24 | 浙江皇马表面活性剂研究有限公司 | A kind of continuous production method of polyetheramine |
| CN107141225A (en) * | 2017-06-22 | 2017-09-08 | 江苏飞翔化工股份有限公司 | A kind of polyetheramine synthetic method |
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