CN115449068B - Method for preparing amino-terminated polyether by continuous hydro-ammonification - Google Patents
Method for preparing amino-terminated polyether by continuous hydro-ammonification Download PDFInfo
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- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
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Abstract
The application discloses a method for preparing amino-terminated polyether by continuous hydro-ammoniation, which comprises the following steps: (1) Polyether, ammonia gas and hydrogen enter a reaction tower, a hydro-ammoniation reaction is carried out under the action of a supported metal catalyst, gas-phase materials are discharged from a top discharge port of the reaction tower, and amine-terminated polyether is discharged from a bottom discharge port of the reaction tower; (2) The gas phase material is separated after being cooled, and the separated crude hydrogen is returned to the reaction tower for recycling; (3) The separated separating liquid enters a membrane separator, concentrated solution returns to the reaction tower, permeate enters a water-ammonia separation tower, and crude ammonia discharged from the top of the water-ammonia separation tower returns to the reaction tower for recycling. The application establishes a separation section in the reaction tower, combines with the high-pressure separator and the nanofiltration membrane separator, effectively separates amine-terminated polyether from ammonia, hydrogen and water, improves the reaction efficiency and reduces the separation energy consumption while ensuring the reaction depth so as to save the operation cost.
Description
Technical Field
The application relates to a method for preparing amino-terminated polyether by continuous hydro-ammonification.
Background
Amine-terminated polyethers, also known as Polyetheramines (PEAs), are a class of polymers whose main chains are polyether structures and whose terminal reactive functional groups are amine groups, whose special chemical structure makes them exhibit unique properties in a wide variety of fields. The amino-terminated polyether is mainly applied to the fields of high-performance composite materials, high-speed railway bridge protection, offshore facility protection and the like. In addition, the amino-terminated polyether has lower viscosity, so that the amino-terminated polyether can realize complete zero emission when being applied to epoxy or polyurea coating, and is quite in accordance with the requirements of environmental protection, thereby having wide prospects in the fields of terraces, coating and the like.
The method for introducing amine groups into the polyether terminal is various, but the method really realizes large-scale industrial production at present, and mainly comprises the step of catalytic ammoniation of the hydroxyl groups at the polyether terminal under the action of a metal catalyst. The catalytic ammoniation of polyether hydroxyl can adopt two production processes of a continuous method and a batch method.
The intermittent process has the advantages of simpler production equipment and small process difficulty, but the auxiliary operations such as loading, unloading and the like consume a great deal of time and labor, so that the production cost of the product is too high, and the large-scale production is not facilitated. Meanwhile, in the process of recycling the catalyst, the activity of the catalyst is different, and the stability of the product is also affected.
The continuous method adopts a fixed bed reactor, and is characterized in that the fixed bed reactor is continuously fed and discharged, the ratio of liquid ammonia to polyether can be randomly adjusted, the higher ratio of liquid ammonia to polyether can be maintained, the reaction efficiency is improved, the residence time of reaction materials in the reactor is short, the side reaction is less, the product performance is stable, and the production cost is lower. But the production equipment is complex and the process conditions are high. The catalyst system for producing polyether amine mainly adopts nickel and cobalt as main catalytic metals, adds other metals as cocatalysts and takes alumina and silica as carrier. The catalyst can better realize the catalytic ammonification of the hydroxyl at the tail end of polyether. However, the catalyst is very sensitive to water generated in the reaction process, and if the water generated in the reaction is more, the activity of the catalyst is quickly reduced as the reaction proceeds. In order to solve the problem, a continuous production process with a plurality of reactors or reaction kettles connected in series is adopted by some manufacturers, so that the production efficiency is effectively improved, but the equipment investment cost is also increased.
Disclosure of Invention
In order to solve the problems, the application provides a method for preparing amino-terminated polyether by continuous hydro-ammonification, which comprises the following steps:
(1) Polyether, ammonia gas and hydrogen enter a reaction tower, a hydro-ammoniation reaction is carried out under the action of a supported metal catalyst, gas-phase materials are discharged from a top discharge port of the reaction tower, and amino-terminated polyether is discharged from a bottom discharge port of the reaction tower;
the reaction tower comprises a tower body extending along the vertical direction, wherein a reaction section and a separation section are arranged in the tower body, and the reaction section is positioned at the lower side of the separation section; at least two reaction beds are arranged in the reaction section, a supported metal catalyst is filled in each reaction bed, a feeding branch pipe is arranged above each reaction bed, and polyether enters the tower body through the feeding branch pipe and downwards enters the corresponding reaction bed; at least two layers of trays are arranged in the separation section;
an air inlet cavity is formed at the lower side of the reaction section; ammonia and hydrogen enter the air inlet cavity, flow upwards and contact polyether flowing downwards to carry out hydro-ammoniation reaction;
(2) The gas phase material enters a high-pressure separator for separation after being cooled, and crude hydrogen discharged from the top of the high-pressure separator returns to a reaction tower for recycling;
(3) Separating liquid discharged from the high-pressure separator enters the membrane separator, concentrated liquid discharged from the membrane separator returns to the reaction tower and flows downwards step by step along each layer of tower tray, penetrating liquid discharged from the membrane separator enters the water-ammonia separation tower, and crude ammonia discharged from the top of the water-ammonia separation tower returns to the reaction tower for recycling.
Further, in order to ensure that hydrogen and ammonia can uniformly contact polyether and react in the reaction tower, a polyether distributor is arranged above each reaction bed, the polyether distributor preferably adopts a tubular distributor, a feeding branch pipe is connected to the polyether distributor, polyether is uniformly sprayed downwards on the reaction bed through the distributor in a mist form, a gas distributor is arranged at the lower part of the reaction section, the gas distributor preferably adopts a tubular distributor, and liquid ammonia and hydrogen mixture upwards enter the reaction bed through the gas distributor.
The existing continuous method for producing amine-terminated polyether mostly adopts a fixed bed reactor or a tubular reactor, raw materials including polyether, ammonia and hydrogen enter from the top of the reactor, in the reaction process of downward flow, the concentration of ammonia and hydrogen is lower and lower, so that the reaction quantity at the lower part of the reactor is smaller, in addition, water generated in the reaction can flow downwards along with reaction materials, the deep hydro-ammoniation reaction is hindered, the whole reaction efficiency is lower, 4-6 reactors are usually connected in series at present, and a corresponding dehydration device is added after each 1-2 reactors to separate the water in the reaction materials, and fresh liquid ammonia and hydrogen are supplemented, so that the higher proportion of the liquid ammonia to the polyether is maintained, the depth of the hydro-reaction is ensured, and the reaction efficiency is improved.
In the prior art, a combined reactor of a fluidized bed reactor and a bubbling bed or a combined reactor of a fluidized bed reactor and a trickle bed is adopted, polyether enters from the upper part of the combined reactor, ammonia gas and hydrogen gas enter from the lower part of the combined reactor, counter-current flow upwards relative to the polyether is carried out, and water produced by carrying reaction is discharged from the reactor, so that the influence of water on the reaction is reduced. However, in this reaction scheme, the produced amine-terminated polyether is mixed with hydrogen, ammonia and water, and secondary separation is required, and the separation effect is poor.
The inventors of the present application have found in the study that the use of the above-described combination reactor for producing amine-terminated polyether has about 15 to 35wt% of the polyether entrained in the upward gas phase stream and exiting the top of the combination reactor and contains a significant amount of unreacted polyether feed therein, such that the conversion of polyether is not effectively increased. In addition, when the combined reactor is adopted to produce polyether, the liquid phase material discharged from the bottom of the combined reactor contains 5-8wt% of ammonia and 0.5-1wt% of water, which indicates that the water generated by the reaction is not thoroughly removed in the reaction process, and has a certain influence on the deep hydrogenation reaction of polyether, and meanwhile, a rectifying tower is required to be arranged to purify the amino-terminated polyether, so that the purity of the product reaches the corresponding requirement.
The traditional amine-terminated polyether separation technology adopts a rectifying tower separation method, but the method has the advantages of large equipment volume, high manufacturing cost and high energy consumption. The membrane separation technology is used as a novel separation technology, has the advantages of good separation effect, simple equipment, low energy consumption and the like, and is widely applied. However, the membrane separation technology has disadvantages such as limited lifetime of the membrane, limited flux of the membrane, limited concentration of the feed solution, and the like. At present, the membrane separation technology is mainly applied to water treatment and is mainly used for removing impurities in water or concentrating a solution.
In the application, besides the reaction section, a separation section mainly comprising a tray is also arranged in the reaction tower and is combined with the high-pressure separator and the nanofiltration membrane separator, so that amino-terminated polyether can be effectively separated from ammonia and hydrogen, especially from water, the reaction efficiency is improved while the reaction depth is ensured, the separation energy consumption is reduced, and the operation cost is saved.
In the application, the reaction section and the separation section are arranged in the reaction tower, and at least two reaction beds are arranged in the reaction section, so that the height of a single reaction bed is reduced, the pressure drop in the single reaction bed is reduced, a plurality of reaction beds can redistribute materials, the uniformity of the materials entering the next reaction bed is improved, the materials are fully contacted with the catalyst, and the reaction efficiency is improved. Polyether is fed in sections, so that the proportion of ammonia to polyether and the proportion of hydrogen to polyether in each section of reaction bed are improved.
In the application, the concentration of polyether is lower from top to bottom in the reaction tower, and the concentration of ammonia and hydrogen is higher, so that the proportion of ammonia to polyether is higher, the forward progress of the hydro-ammoniation reaction is promoted, and the reaction efficiency is improved. In the application, the effect of 4-6 fixed bed reactors or tubular reactors in the prior art can be achieved by adopting a single reaction tower, and the corresponding separation system is also omitted due to the reduction of the number of the reactors, so that the equipment acquisition cost is saved.
In the application, a high-pressure separator and a membrane separator are utilized to condense and separate gas phase materials discharged from the top of a reaction tower, the obtained concentrated solution is returned into the reaction tower, and the main components in the concentrated solution are a mixture of unreacted polyether and amino-terminated polyether.
By utilizing the application, the production of the amino-terminated polyether can be completed by adopting a single reaction tower, and the produced amino-terminated polyether does not need to be refined and can be directly used as commodity.
Specifically, 4-6 reaction beds are arranged in the reaction section, each reaction bed is filled with a supported metal catalyst with the same height, a polyether distributor is arranged at the upper part of each reaction bed, and a feeding branch pipe is communicated with the polyether distributor; 10-20 layers of trays are arranged in the separation section; in the application, the tray is preferably a float valve tray;
a gas distributor is arranged in the gas inlet cavity, and the mixed gas of ammonia and hydrogen enters the reaction tower through the gas distributor; the top of the reaction tower is not provided with a reflux tank, and the bottom of the reaction tower is not provided with a reboiler;
the inlet temperature of the gas phase material in the high pressure separator is 30-50 ℃, and the inlet pressure is 2-5MPa;
the membrane separator adopts nanofiltration membrane, the operation pressure difference of the membrane separator is 1.0-2.0MPa, and the molecular weight cut-off of the nanofiltration membrane is 100-500daltons.
The separation of the liquid component and the gaseous component can be effectively completed under the number of the trays, wherein the liquid component comprises polyether and amine-terminated polyether, the gaseous component comprises hydrogen, ammonia and water, the gaseous component in the upward gas flow is a mixture of hydrogen, ammonia and water vapor in the reaction tower, and a certain amount of polyether and amine-terminated polyether can be carried when the gas flow flows upwards, and the vaporization temperature of the polyether and the amine-terminated polyether is far higher than the reaction temperature in the reaction tower at the reaction temperature, so that the polyether and the amine-terminated polyether still remain in the liquid state.
In the application, when the concentrated solution returned from the membrane separator flows downwards step by step along the tray, a liquid film is formed, and polyether and amine-terminated polyether carried by the upward flowing air flow are at least partially absorbed by the liquid film in the process of passing through the liquid film, so that the content of polyether and amine-terminated polyether carried by the gas-phase material is reduced. The number of layers of tower tray is not enough, can't fully absorb polyether and amine-terminated polyether that carry in the upward air current for contain more polyether and amine-terminated polyether in the gaseous phase material that the reaction tower was discharged, need increase the separation pressure of membrane separator just can let liquid ammonia and water pass through the nanofiltration membrane, increase operating pressure can shorten the life of nanofiltration membrane, can harm the nanofiltration membrane even, causes the nanofiltration membrane to destroy. Meanwhile, if the concentration of the materials entering the membrane separator is too high or the pressure is too high, a small amount of polyether or amine-terminated polyether can inevitably pass through the nanofiltration membrane, so that the separation effect is affected, and the loss of products is caused.
Meanwhile, as the boiling point of the amine-terminated polyether is higher, the amine-terminated polyether is difficult to vaporize at the reaction temperature and the reaction pressure, a reboiler is eliminated, and only a certain amine-terminated polyether liquid level is maintained at the bottom of the tower, hydrogen and ammonia in the amine-terminated polyether can be released and separated by means of the heat of the amine-terminated polyether, so that the ammonia content in the amine-terminated polyether is reduced below the standard requirement, the amine-terminated polyether discharged from the bottom of the reaction tower can be directly sold as a commodity without setting a rectifying tower, and the amine-terminated polyether is purified again.
Specifically, polyether is a linear polymer prepared by ring-opening homo-polymerization or copolymerization of alkylene oxide under the action of a catalyst, the number average molecular weight of the polyether is 200-1000, 1000-2000 or 2000-5000, and each polyether molecule contains 2-3 terminal hydroxyl groups.
The amino-terminated polyether is mainly used as a synthetic raw material of polyurethane (polyurea) materials and a curing agent of epoxy resin because the amino-terminated polyether contains active hydrogen and can react with isocyanate groups, epoxy groups and the like. In addition, the amine-terminated polyethers can be used as anti-haze and anti-settling additives in motor fuel oils. However, due to the different number average molecular weights of the amine-terminated polyethers, the physicochemical properties of the amine-terminated polyethers are different, so that the application scenes are also biased. The amino-terminated polyether with the number average molecular weight of 200-1000 can be mixed with various organic solvents, and part of the amino-terminated polyether can be even mixed with water, and is mainly used as an epoxy resin curing agent or a thermoplastic polyamide adhesive; the amino-terminated polyether with the number average molecular weight of 1000-2000 is mostly used for spraying polyurea and polyurea elastomer, and the performance of the amino-terminated polyether as a gasoline detergent is better than that of other amino-terminated polyethers with the number average molecular weight; the amino-terminated polyether with the number average molecular weight of 2000-5000 has fewer rigid chain segments (urea bond groups) and lower strength and adhesive force in the polyurea material synthesized, so that the amino-terminated polyether is mostly used for spraying polyurea cross-linking agents, surfactants and corrosion inhibitors.
Preferably, the alkylene oxide is at least one of ethylene oxide, propylene oxide or butylene oxide.
Specifically, in step (1), the reaction temperature is 150-250 ℃ and the reaction pressure is 8.0-18.0MPa, and the mass space velocity of polyether is 0.1-1h during the hydro-ammoniation reaction -1 Hydrogen gasThe mass ratio of the polyether to the polyether is (0.2-1): 1, the feeding mass ratio of ammonia gas to polyether (3-5): 1.
the hydro-ammonification reaction needs to go through three steps, the first step is dehydrogenation of hydroxyl end groups into aldehyde or ketone, the second step is ammonification of aldehyde or ketone into dilute imine and water, the third step is hydrogenation of dilute imine into amine end polyether, but in the actual reaction process, because the reaction steps of different molecules are different, polyether, aldehyde or ketone, dilute imine, water and amine end polyether exist at the same time, so that hydrogenation reaction and dehydrogenation reaction exist at the same time, and because intermediate-state substances such as aldehyde, ketone, dilute imine exist, and the like, the following side reactions can also occur: the primary amine and aldehyde or ketone generated in the first step react to generate secondary amine and tertiary amine through addition amination, dehydration and hydrogenation, and the polymer breaks chain at high temperature to generate small molecular polymer, etc.
Therefore, proper reaction conditions are critical for the hydro-ammonification reaction, and under the reaction conditions, the terminal hydroxyl groups of the polyether can be smoothly subjected to the hydro-ammonification reaction to generate terminal amino groups, and meanwhile, fewer byproducts are generated.
The reaction temperature is too high, which is favorable for dehydrogenation of terminal hydroxyl groups into aldehyde or ketone, but when the reaction temperature is too high, the generation of secondary amine and tertiary amine serving as byproducts is also favorable, meanwhile, raw materials are cracked, small molecular polymers are generated, separation equipment is required to be added, the investment cost is increased, and the product quality is influenced. When the reaction temperature is too low, the dehydrogenation of hydroxyl ends into aldehyde or ketone is not facilitated, the conversion rate of hydro-ammoniation reaction is low, and the hydroxyl end polyether and amino end polyether are difficult to separate, so that the quality of the product is poor.
When the reaction pressure is too high, the hydrogenation of the dilute imine is facilitated, but the dehydrogenation of the terminal hydroxyl group is not facilitated, and the conversion rate is reduced; meanwhile, more hydrogen or ammonia is needed to reduce the partial pressure of water so as to effectively remove the generated water in the catalytic distillation stage, thus increasing the circulation quantity, increasing the investment cost and the operation cost of a circulation compressor, or increasing the reaction temperature to achieve the purpose of dehydration, but increasing byproducts; and after the pressure level of the equipment is increased, the investment cost of the equipment is increased. When the reaction pressure is too low, the dehydrogenation of hydroxyl ends is facilitated, but the hydrogenation of dilute imine is not facilitated, the conversion rate is reduced, and the product quality is poor.
When the mass space velocity is too high, the residence time of the raw materials on the surface of the catalyst is too short, the conversion rate is reduced, and the product quality is poor. When the mass space velocity is too low, the polyether throughput is reduced, and the utilization rate of the catalyst and the equipment is low; while secondary and tertiary amines are increased as byproducts.
When the feeding mass ratio of hydrogen to polyether is too high, the hydroxyl dehydrogenation reaction is inhibited due to the increase of the hydrogen proportion in the reaction system, so that the overall reaction efficiency is reduced, the content of hydrogen carried in gas phase materials is increased, the processing capacity of a corresponding hydrogen compressor is required to be increased, and the equipment investment and the operation cost are increased.
When the feed mass ratio of hydrogen to polyether is too low, the hydrogenation of the dilute imine is suppressed, and the reaction efficiency is also lowered. In the reaction process, as the aldehyde and the dilute imine are active in nature, if the aldehyde and the dilute imine are not hydrogenated in time, the aldehyde and the dilute imine are easy to polymerize into high molecules, remain in the catalyst pore channels, continue to react under the action of temperature and a catalyst, and finally cyclize and dehydrogenate to form polycyclic aromatic hydrocarbon until coke is formed, and adsorb on the catalyst to block the catalyst pore channels so as to deactivate the catalyst. Therefore, when the feeding mass ratio of hydrogen to polyether is too low, the carbon deposition speed of the catalyst is increased, and the service life of the catalyst is reduced.
When the feeding mass ratio of ammonia to polyether is too high, the content of ammonia carried in the gas phase material is increased, the processing capacity of a corresponding ammonia compressor is required to be increased, and the equipment investment and the operation cost are increased. When the feed mass ratio of ammonia to polyether is too low, the aldehyde or ketone ammoniation reaction is adversely affected, the conversion is lowered, and secondary and tertiary amines as byproducts are increased.
Further, the reaction efficiency is ensured, the feeding temperature of polyether is 150-250 ℃, hydrogen and liquid ammonia are mixed and then enter the reaction tower, and the feeding temperature of the mixed hydrogen and liquid ammonia is 150-250 ℃.
Specifically, the supported metal catalyst is a catalyst of an oxide carrier for supporting active metal, and the oxide carrier adopts at least one of alumina and silica; the active metals comprise main active metals and auxiliary active metals, wherein the main active metals are nickel, and the auxiliary active metals are tin and zinc. Specifically, the content of the main active metal is 10-40wt% based on the total weight of the supported metal catalyst, and the content of the auxiliary active metal tin and zinc is 5-10wt%.
In the application, because a plurality of reaction beds are adopted and polyether is fed in sections, the proportion of hydrogen to polyether in a single bed is higher than that in the prior art, so that the catalyst has higher requirements on the dehydrogenation performance of the catalyst. The inventor of the application finds that the transition metal tin can form an alloy with active main metal in the research process so as to prevent the main metal from gathering at high temperature and ensure the dispersity of the main metal; meanwhile, tin can form a structure similar to a tin-aluminum spinel with the carrier, so that the high-temperature stability of the carrier is improved, the acid content of the carrier is reduced, and the acid strength proportion of the carrier is regulated. Therefore, the dehydrogenation activity and stability of the catalyst are effectively improved by introducing the transition metal tin. The transition metal zinc also has similar effects, can form a zinc-aluminum spinel-like structure with the carrier, improves the pore channel structure of the carrier, adjusts the acid property proportion of the carrier, reduces the particle size of main active metal particles loaded on the carrier, disperses more uniformly, and effectively improves the dehydrogenation performance of the catalyst.
There are generally two ways of preparing the supported metal catalyst, one is an impregnation method and the other is a coprecipitation method. Compared with the coprecipitation method, the impregnation method has simpler process, but the particle size of the active metal is larger, and the distribution uniformity is inferior to that of the coprecipitation method. Meanwhile, the coprecipitation method is more conducive to the action of auxiliary active metal and a carrier, a spinel-like structure is generated, and the performance of the catalyst is improved. Therefore, the supported metal catalyst in the present application is preferably prepared by a coprecipitation method.
Specifically, the supported metal catalyst is prepared by the following steps:
(11) The nickel salt is folded into nickel, the tin salt is folded into tin, the zinc salt is folded into zinc, and the nickel salt, the tin salt and the zinc salt are dissolved into water according to the proportion of the nickel, the tin and the zinc in the supported metal catalyst to prepare an active metal water solution; the nickel salt and zinc salt are soluble salts such as nitrate or chloride, and the tin salt is tin tetrachloride;
(12) Adding the oxide carrier into the active metal aqueous solution according to the proportion of the oxide carrier in the supported metal catalyst, and uniformly stirring to prepare a reaction solution;
(13) Dripping sodium carbonate aqueous solution serving as a precipitant into the reaction liquid to perform precipitation reaction, and obtaining suspension when the pH value of the reaction liquid reaches 8-9 and precipitation is finished, wherein the concentration of the sodium carbonate aqueous solution is 10-30wt%;
(14) Filtering, washing, drying and roasting the suspension, and tabletting and forming to obtain the oxidation state supported metal catalyst;
(15) Carrying out high-temperature hydrogen pre-reduction on the oxidized supported metal catalyst, and then carrying out surface passivation to obtain the supported metal catalyst;
in the reaction tower, the supported metal catalyst is first reduced and then hydroammonified.
Specifically, in the step (13), when the precipitation reaction is carried out under normal pressure, the reaction temperature is 30-50 ℃; in the step (14), the drying temperature is 100-150 ℃, the drying time is 10-24h, the roasting temperature is 500-550 ℃, and the roasting time is 3-6h;
in the step (15), the reduction temperature in the high-temperature hydrogen pre-reduction is 350-450 ℃, and the volume ratio of the hydrogen flow per hour to the catalyst in the high-temperature hydrogen pre-reduction is 200-500:1, the reduction time is 10-30 hours;
before surface passivation is carried out, the hydrogen in the system is completely replaced by nitrogen, and in the process of replacing the hydrogen by the nitrogen, the volume ratio of the nitrogen flow per hour to the catalyst is 200-500:1, after the replacement of hydrogen by nitrogen is completed, carrying out surface passivation, gradually injecting air into the system when the surface passivation is carried out until the volume ratio of oxygen content in the gas in the system reaches 19-21%, starting the passivation temperature to be 20-30 ℃, keeping the temperature rise of the passivation bed layer within the range of 10-20 ℃ in the passivation process until the temperature of the passivation bed layer is not increased any more, and continuously carrying out surface passivation for 5-10 hours to complete the surface passivation.
The preparation of the supported metal catalyst can be successfully completed by using the method. In the preparation process of the supported metal catalyst, isomorphous substitution phenomenon is easy to occur among active metal precursors, and when the catalyst is roasted, interaction is promoted among the active metals and between the active metals and the carrier, so that the active metals are dispersed more uniformly, the aggregation condition of the active metals is reduced, the crystal grains of the active metals are finer, and the nano-scale can be achieved. At the same time, sodium carbonate is used to precipitate nickel, zinc and tin elements, and CO released during roasting 2 Is helpful to improve the pore canal and specific surface area of the catalyst. The active metal in the roasted catalyst is in an oxidation state and does not have hydrogenation activity, and the supported metal catalyst is subjected to hydrogen reduction before use, so that the active metal is reduced into a metal state. Since the reduction temperature of the active metal oxide exceeds the catalyst use temperature, if the reduction is performed in the use apparatus, it is necessary to raise the temperature level of the equipment such as the heating furnace and the reactor, and the investment cost increases. By adopting the manufacturing method, the catalyst is reduced at high temperature and then passivated at low temperature, so that the safety of the catalyst in transportation and filling can be ensured, and the investment cost of a manufacturer can be saved.
Drawings
FIG. 1 is a flow chart of an embodiment of the present application.
FIG. 2 is a schematic structural diagram of a polyether distributor.
Fig. 3 is a schematic view of the structure of the gas distributor.
FIG. 4 is a schematic representation of a prior art flow scheme for amino terminated polyethers.
Detailed Description
In the examples below, the hydroxyl number in the raw polyether was tested using GB/T12008.3-2009, plastic polyether polyol part 3 determination of hydroxyl number; sampling liquid-phase materials at a discharge hole at the bottom of a reaction tower, and measuring the water content in the liquid-phase materials by using a general method for measuring the moisture of chemical reagents, namely a Kalman method, a Fischer method; using the American Standard
Standard test method for determining total amine, primary amine, secondary amine and tertiary amine in fatty amine by using alternative indicator method, astm d2074-2007, total amine value and primary amine rate of amino terminated polyether product were tested, and conversion rate was calculated as follows:
the structure of the reaction column will be described first:
referring to fig. 1, the reaction tower 10 includes a tower body 19 extending in a vertical direction, and a reaction section 12 and a separation section 14 are disposed in the tower body, wherein the reaction section 12 is located at a lower side of the separation section 14; four reaction beds 121 are arranged in the reaction section, the same-height supported metal catalyst is filled in each reaction bed, and a polyether distributor 13 is arranged at the upper part of each reaction bed.
Referring to fig. 2, in this embodiment, the polyether distributor 13 is a tubular distributor, and the polyether distributor 13 includes a main feeding pipe 131 horizontally disposed and auxiliary feeding pipes 132 horizontally disposed at two sides of the main feeding pipe, wherein one end of the main feeding pipe extends out of the tower 19 to form a feeding hole 133, the main feeding pipe and the auxiliary feeding pipe are supported on the inner wall of the tower, and a feeding branch pipe 181 is connected to each feeding hole 133. To improve the dispersion uniformity of polyether, atomizing nozzles are installed at the lower sides of the main feeding pipe 131 and the auxiliary feeding pipe 132.
Within the separation section 14 are provided 18 trays 141, in particular in this embodiment, the trays 141 are all valve trays.
An air inlet cavity 11 is formed at the lower side of the reaction section, an air distributor 111 is installed in the air inlet cavity, referring to fig. 3, the air distributor 111 specifically includes a main air inlet pipe 112 horizontally arranged and auxiliary air inlet pipes 113 horizontally arranged at two sides of the main air inlet pipe, one end of the main air inlet pipe extends out of the tower body to form an air inlet 114, and the main air inlet pipe 112 and the auxiliary air inlet pipes 113 are both supported on the inner wall of the tower body. Air intake holes are opened at the lower sides of the main air intake pipe 112 and the auxiliary air intake pipe 113.
The top of the reaction tower is not provided with a reflux tank, and the bottom of the reaction tower is not provided with a reboiler;
the preparation of the supported metal catalyst is described below:
the supported metal catalysts used in the examples below were prepared using the following procedure:
(11) The nickel salt is converted into nickel, the tin salt is converted into tin, the zinc salt is converted into zinc, the nickel salt, the tin salt and the zinc salt are dissolved into water according to the proportion of the nickel, the tin and the zinc in the supported metal catalyst to prepare an active metal water solution, and the nickel salt, the tin salt and the zinc salt specifically adopt nickel nitrate, tin chloride and zinc nitrate.
(12) Adding the oxide carrier into the active metal aqueous solution according to the proportion of the oxide carrier in the supported metal catalyst, and uniformly stirring to prepare a reaction solution; in this example, the oxide support employed silica and alumina in a mass ratio of 3:7.
(13) Dropwise adding a sodium carbonate aqueous solution serving as a precipitant into the reaction solution at 35-40 ℃ for precipitation reaction, and obtaining a suspension after the precipitation is finished when the pH value of the reaction solution reaches 8-9; the concentration of the aqueous sodium carbonate solution was 15wt%.
(14) Filtering the suspension, washing filter residues with deionized water for three times, drying at 120-125 ℃ for 20h, roasting at 520 ℃ for 5h, tabletting and forming to obtain the oxidation state supported metal catalyst.
(15) The oxidation state supported metal catalyst is subjected to high-temperature hydrogen pre-reduction, the high-temperature pre-reduction temperature is 390 ℃, and when the high-temperature hydrogen pre-reduction is carried out, the hydrogen flow per hour and the catalyst volume ratio are 400:1, the reduction time was 12 hours. And (5) performing surface passivation after the high-temperature hydrogen pre-reduction is completed. Before surface passivation is carried out, the hydrogen of the system is replaced by nitrogen, and in the process of replacing the hydrogen by the nitrogen, the volume ratio of the nitrogen flow per hour to the catalyst is 500:1, after the replacement of hydrogen by nitrogen is completed, surface passivation is carried out, the initial passivation temperature is 40 ℃, air is slowly injected, the temperature rise of a passivation bed layer is controlled to be 10 ℃, the oxygen content in the system is controlled to be 20%, and when the temperature of the passivation bed layer is not increased any more, the passivation is continuously carried out for 8 hours, so that the supported metal catalyst is obtained.
In the reaction tower, the supported metal catalyst is first reduced and then hydroammonified. When the supported metal catalyst is subjected to hydrogen reduction, the pressure is 10-11MPa, and the temperature is 280-290 ℃.
The polyethers in the following examples and comparative examples are produced by the sea-An petrochemical plant in Jiangsu province.
Example 1
The preparation of the amino-terminated polyether comprises the following steps:
(1) Polyether 110 is heated to 200 ℃ after passing through the refrigerant channels of the first heat exchanger 15 and the second heat exchanger 16 and the first heating furnace 17 in sequence, enters each polyether distributor 13 through the feeding main pipe 18 and each feeding branch pipe 181 in sequence, is sprayed downwards onto the corresponding reaction bed 121 by each polyether distributor 13, and flows downwards along the reaction bed;
the liquid ammonia 120 and the hydrogen are mixed to form a mixture, and the mixture is heated to 200 ℃ by the third heat exchanger 21, the fourth heat exchanger 22 and the second heating furnace 23 in sequence to form a mixed gas of ammonia and hydrogen, and the mixed gas enters the gas distributor 111 through the gas inlet 114, then enters the gas inlet cavity and flows upwards.
The upward flowing mixed gas is contacted with downward flowing polyether, and the hydro-ammoniation reaction is carried out under the action of a supported metal catalyst. The gas phase materials discharged from the uppermost reaction bed layer pass through each layer of trays step by step and then are discharged from a top discharge hole 191 at the top of the reaction tower.
The liquid phase material in the reaction tower is discharged from a bottom discharge hole 192 at the bottom of the reaction tower, and then is cooled to normal temperature through a heating medium channel of the fourth heat exchanger 22, a heating medium channel of the third heat exchanger 21 and a finished product cooler 25 in sequence to be used as the amino-terminated polyether product 150.
(2) The gas phase material is cooled to 40 ℃ after passing through a heating medium channel of the second heat exchanger 16, a heating medium channel of the first heat exchanger 15 and a water cooler 151 in sequence, is decompressed to 4MPa through a pressure regulating valve 35, enters into the high-pressure separator 32 for separation, discharges crude hydrogen from a first exhaust port at the top of the high-pressure separator 32, and is mixed with fresh hydrogen 130, compressed by a first hydrogen compressor 33, mixed with liquid ammonia 120 and returned to the reaction tower, so that the crude hydrogen is recycled.
(3) Separating liquid discharged from the bottom of the high-pressure separator 32 enters the membrane separator 31 for separation, and the separating membrane adopts a BR20-35 nanofiltration membrane of Delamer, the throttle molecular weight of which is 200 daltons, and the operation pressure difference is 1.0MPa.
The concentrate discharged from the membrane separator 31 is returned to the reaction column from the upper side of the uppermost tray, and flows down stepwise along each tray, and during the downward flow, droplets contained in the upward flow gas, mainly polyether and amine-terminated polyether, are absorbed. The permeate discharged from the membrane separator 31 enters the first water-ammonia separation tower 40, the first water-ammonia separation tower is a tray tower, a liquid inlet 41 of the first water-ammonia separation tower is the middle part of the water-ammonia separation tower 40, 10 upper trays are arranged on the upper side of the liquid inlet 41, 10 lower trays are arranged on the lower side of the liquid inlet, and both the upper trays and the lower trays adopt floating valve trays.
The gas discharged from the top of the first water-ammonia separation tower 40 is cooled and enters the first reflux tank 43, the cooling liquid in the first reflux tank returns to the first water-ammonia separation tower 40, and the crude ammonia discharged from the top of the first reflux tank is compressed by the first ammonia compressor 34, is mixed with the liquid ammonia 120, and returns to the reaction tower for recycling. Crude ammonia discharged from the top of the water-ammonia separation tower is returned to the reaction tower for recycling.
The bottom liquid of the first water-ammonia separation tower 40 is partially discharged as wastewater 140, enters the wastewater treatment system, and partially returns to the bottom of the first water-ammonia separation tower 40 after being heated by the first reboiler 42.
In this example, the reaction column was provided with only one, and the supported metal catalyst contained 30wt% nickel, 8wt% tin and 5wt% zinc. Polyether of the model D-230 with a number average molecular weight of 230 and two terminal hydroxyl groups per polyether molecule is used, and the polyether is a linear polymer prepared by homopolymerizing propylene oxide under the action of a catalyst.
In the hydro-ammonification reaction, the reaction temperature is 200 ℃, the reaction pressure is 12.0MPa, and the mass airspeed of the polyether is 0.2h -1 The feed mass ratio of hydrogen, liquid ammonia and polyether is 0.5:5:1.
example 2
This embodiment is substantially the same as embodiment 1, except that:
the supported metal catalyst contained 35wt% nickel, 5wt% tin and 6wt% zinc. Polyether of the model D-1000, whose number average molecular weight is 1000, has two terminal hydroxyl groups per polyether molecule, is a linear polymer obtained by homopolymerizing butylene oxide under the action of a catalyst.
In the hydro-ammonification reaction, the reaction temperature is 180 ℃, the reaction pressure is 14.0MPa, and the mass airspeed of the polyether is 0.5h -1 The feed mass ratio of hydrogen, liquid ammonia and polyether is 0.8:4:1.
example 3
This embodiment is substantially the same as embodiment 1, except that:
the supported metal catalyst contained 28wt% nickel, 10wt% tin and 8wt% zinc. Polyether of the model D-2000 and number average molecular weight 2000 and with two terminal hydroxyl groups is used, and the polyether is linear polymer prepared through copolymerization of propylene oxide and butylene oxide in the presence of catalyst.
In the hydro-ammonification reaction, the reaction temperature is 190 ℃, the reaction pressure is 10.0MPa, and the mass airspeed of the polyether is 0.7h -1 The feed mass ratio of hydrogen, liquid ammonia and polyether is 0.3:3:1.
the separation membrane of the membrane separator 31 was a DED100 nanofiltration membrane of Delamell, U.S.A., having a molecular weight of 500daltons and an operating pressure differential of 1.5MPa.
Example 4
This embodiment is substantially the same as embodiment 1, except that:
the supported metal catalyst contained 32wt% nickel, 5wt% tin and 5wt% zinc. A polyether with the model number of T-4000 and the number average molecular weight of 4000 is adopted, each polyether molecule has three terminal hydroxyl groups, and the polyether is a polymer prepared by using trimethylolpropane to initiate epoxypropane under the action of a catalyst.
In the hydro-ammonification reaction, the reaction temperature is 220 ℃, the reaction pressure is 15.0MPa, and the mass airspeed of the polyether is 0.3h -1 Feeding hydrogen, liquid ammonia and polyetherMass ratio 0.6:5:1.
the separation membrane of the membrane separator 31 was a DED100 nanofiltration membrane of Delamell, U.S.A., having a molecular weight of 500daltons and an operating pressure differential of 1.05MPa.
Comparative example 1
Referring to fig. 4, the reactor of comparative example 1 employs a fixed bed reactor 53, and a supported metal catalyst in which 30wt% nickel, 8wt% tin and 5wt% zinc are contained is provided in the fixed bed reactor. Polyether of the model D-230 with a number average molecular weight of 230 and two terminal hydroxyl groups per polyether molecule is used, and the polyether is a linear polymer prepared by homopolymerizing propylene oxide under the action of a catalyst.
Polyether, liquid ammonia and hydrogen are mixed to form a raw material mixture, the raw material mixture is heated to 200 ℃ sequentially through a refrigerant channel of a fifth heat exchanger 51 and a material heating furnace 52, enters a fixed bed reactor from the top of the fixed bed reactor 53 to carry out hydro-ammonification reaction, the reaction temperature is 200 ℃ and the reaction pressure is 12.0MPa when the hydro-ammonification reaction is carried out, and the mass airspeed of the polyether is 0.2h -1 The feed mass ratio of hydrogen, liquid ammonia and polyether is 0.5:5:1.
after the reaction is completed, reaction products including ammonia, hydrogen, water, amine-terminated polyether and unreacted raw polyether are discharged from the bottom of the fixed bed reactor, enter a gas-liquid separation tank 62 after passing through a heating medium channel of a material heat exchanger 51 for gas-liquid separation, and crude hydrogen is discharged from the top of the gas-liquid separation tank 62 and then returned to the fixed bed reactor 53 for recycling through a second hydrogen compressor 63.
The liquid discharged from the bottom of the gas-liquid separation tank 62 enters the rectifying tower 70 for rectification and purification, the rectifying tower is a column plate rectifying tower with the number of column plates of 30, and the liquid discharged from the bottom of the gas-liquid separation tank 62 enters from the middle part of the rectifying tower. In the embodiment, the rectifying tower specifically adopts an overflow tray, the temperature of the top of the rectifying tower is 100 ℃, and the temperature of the bottom of the rectifying tower is 120 ℃.
The amino polyether is discharged from the bottom of the rectifying tower 70, a part of the amino polyether is heated by the reboiler 72 and then returned to the bottom of the rectifying tower to provide heat for rectification, and a part of the amino polyether is cooled by a heating medium channel of the sixth heat exchanger 74 and then used as a product discharging device. The gas phase discharged from the top of the rectifying column is cooled by a cooler and then enters a second reflux tank 73, the liquid discharged from the second reflux tank is divided into two parts, one part returns to the top of the rectifying column, and the reflux ratio is 1:2, the other part enters a steam-water separation tower 80 for separation after passing through a refrigerant channel of the sixth heat exchanger 74, wherein the steam-water separation tower is a rectifying tower, and the structure of the steam-water separation tower is the same as that of the rectifying tower.
The gas phase discharged from the top of the steam-water separation tower 80 is cooled and enters the third reflux tank 83, and the liquid in the third reflux tank returns to the steam-water separation tower. Crude ammonia discharged from the third reflux drum and the second reflux drum is returned to the fixed bed reactor for reaction by the second ammonia compressor 64.
Part of the bottom material of the steam-water separation tower 80 is heated by the third reboiler 82 and then returned to the bottom of the steam-water separation tower, and the other part of the bottom material is cooled and then used as sewage outlet device.
Comparative example 2
This comparative example 2 is substantially the same as example 1, except that:
the supported metal catalyst contained 8.5wt% nickel, 6.5wt% cobalt and 3wt% rhenium.
Table 1 data sheets for each example and comparative example
As can be seen from Table 1, the reaction tower type adopted by the application can effectively remove the generated water in the reaction stage, eliminates the influence of water on the reaction, promotes the forward direction of the hydro-ammoniation reaction, improves the reaction efficiency, saves part of reactors and corresponding separation systems, and saves investment and operation cost.
Claims (8)
1. A method for preparing amino-terminated polyether by continuous hydro-ammonification is characterized by comprising the following steps:
(1) Polyether, ammonia gas and hydrogen enter a reaction tower, a hydro-ammoniation reaction is carried out under the action of a supported metal catalyst, gas-phase materials are discharged from a top discharge port of the reaction tower, and amino-terminated polyether is discharged from a bottom discharge port of the reaction tower;
the reaction tower comprises a tower body extending along the vertical direction, wherein a reaction section and a separation section are arranged in the tower body, and the reaction section is positioned at the lower side of the separation section; at least two reaction beds are arranged in the reaction section, a supported metal catalyst is filled in each reaction bed, a feeding branch pipe is arranged above each reaction bed, and polyether enters the tower body through the feeding branch pipe and downwards enters the corresponding reaction bed; at least two layers of trays are arranged in the separation section;
an air inlet cavity is formed at the lower side of the reaction section; ammonia and hydrogen enter the air inlet cavity, flow upwards and contact polyether flowing downwards to carry out hydro-ammoniation reaction;
(2) The gas phase material enters a high-pressure separator for separation after being cooled, and crude hydrogen discharged from the top of the high-pressure separator returns to a reaction tower for recycling;
(3) Separating liquid discharged from the high-pressure separator enters the membrane separator, concentrated liquid discharged from the membrane separator returns to the reaction tower and flows downwards step by step along each layer of tower tray, penetrating liquid discharged from the membrane separator enters the water-ammonia separation tower, and crude ammonia discharged from the top of the water-ammonia separation tower returns to the reaction tower for recycling;
the supported metal catalyst is a catalyst of an oxide carrier for supporting active metal, and the oxide carrier adopts at least one of alumina and silica; the active metals comprise main active metals and auxiliary active metals, wherein the main active metals are nickel, and the auxiliary active metals are tin and zinc; based on the total weight of the supported metal catalyst, the content of the main active metal is 10-40wt%, and the content of the auxiliary active metal tin and zinc is 5-10wt%.
2. The method according to claim 1, wherein 4-6 reaction beds are arranged in the reaction section, each reaction bed is filled with a supported metal catalyst with the same height, a polyether distributor is arranged at the upper part of each reaction bed, and a feeding branch pipe is communicated with the polyether distributor; 10-20 layers of trays are arranged in the separation section;
a gas distributor is arranged in the gas inlet cavity, and the mixed gas of ammonia and hydrogen enters the reaction tower through the gas distributor; the top of the reaction tower is not provided with a reflux tank, and the bottom of the reaction tower is not provided with a reboiler;
the inlet temperature of the gas phase material in the high pressure separator is 30-50 ℃, and the inlet pressure is 2-5MPa;
the membrane separator adopts nanofiltration membrane, the operation pressure difference of the membrane separator is 1.0-2.0MPa, and the molecular weight cut-off of the nanofiltration membrane is 100-500daltons.
3. The process according to claim 1, wherein the polyether is a linear polymer obtained by ring-opening homo-or copolymerization of alkylene oxide with a catalyst, the polyether having a number average molecular weight of 200 to 1000, 1000 to 2000 or 2000 to 5000 and each polyether molecule containing 2 to 3 terminal hydroxyl groups.
4. A method according to claim 3, wherein the alkylene oxide is at least one of ethylene oxide, propylene oxide or butylene oxide.
5. The process according to claim 1, wherein in the step (1), the reaction temperature is 150 to 250℃and the reaction pressure is 8.0 to 18.0MPa, and the mass space velocity of the polyether is 0.1 to 1h -1 The feeding mass ratio of the hydrogen to the polyether is (0.2-1): 1, the feeding mass ratio of ammonia gas to polyether (3-5): 1.
6. the process of claim 1 wherein the polyether is fed at a temperature of 150 to 250 ℃ and the hydrogen is mixed with ammonia and fed to the reaction column at a temperature of 150 to 250 ℃.
7. The method according to claim 1, wherein the supported metal catalyst is prepared by:
(11) The nickel salt is folded into nickel, the tin salt is folded into tin, the zinc salt is folded into zinc, and the nickel salt, the tin salt and the zinc salt are dissolved into water according to the proportion of the nickel, the tin and the zinc in the supported metal catalyst to prepare an active metal water solution;
(12) Adding the oxide carrier into the active metal aqueous solution according to the proportion of the oxide carrier in the supported metal catalyst, and uniformly stirring to prepare a reaction solution;
(13) Dripping sodium carbonate aqueous solution serving as a precipitant into the reaction liquid to perform precipitation reaction, and obtaining suspension when the pH value of the reaction liquid reaches 8-9 and precipitation is finished, wherein the concentration of the sodium carbonate aqueous solution is 10-30wt%;
(14) Filtering, washing, drying and roasting the suspension, and tabletting and forming to obtain the oxidation state supported metal catalyst;
(15) Carrying out high-temperature hydrogen pre-reduction on the oxidized supported metal catalyst, and then carrying out surface passivation to obtain the supported metal catalyst;
in the reaction tower, the supported metal catalyst is first reduced and then hydroammonified.
8. The method according to claim 7, wherein in the step (13), the precipitation reaction is carried out at a temperature of 30 to 50 ℃ under normal pressure;
in the step (14), the drying temperature is 100-150 ℃, the drying time is 10-24h, the roasting temperature is 500-550 ℃, and the roasting time is 3-6h;
in the step (15), the reduction temperature in the high-temperature hydrogen pre-reduction is 350-450 ℃, and the volume ratio of the hydrogen flow per hour to the catalyst in the high-temperature hydrogen pre-reduction is 200-500:1, the reduction time is 10-30 hours;
before surface passivation is carried out, the hydrogen in the system is completely replaced by nitrogen, and in the process of replacing the hydrogen by the nitrogen, the volume ratio of the nitrogen flow per hour to the catalyst is 200-500:1, after the replacement of hydrogen by nitrogen, performing surface passivation; and when the surface passivation is carried out, gradually injecting air into the system until the volume ratio of the oxygen content in the gas in the system reaches 19-21%, wherein the initial passivation temperature is 20-30 ℃, and keeping the temperature rise of the passivation bed layer within the range of 10-20 ℃ in the passivation process until the temperature of the passivation bed layer is not increased any more, and continuously carrying out surface passivation for 5-10 hours to complete the surface passivation.
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| CN105295021A (en) * | 2015-12-01 | 2016-02-03 | 王伟跃 | Process of continuously producing amine-terminated polyether and reactor design of process |
| CN106633029A (en) * | 2017-01-04 | 2017-05-10 | 扬州晨化新材料股份有限公司 | Method of continuously preparing polyether amines |
| CN107880260A (en) * | 2017-12-21 | 2018-04-06 | 红宝丽集团股份有限公司 | A kind of continuous preparation device and preparation method of small-molecular-weight amine terminated polyether |
| CN114276533A (en) * | 2021-12-31 | 2022-04-05 | 岳阳昌德新材料有限公司 | Method and device for continuously preparing polyether amine |
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| CN105295021A (en) * | 2015-12-01 | 2016-02-03 | 王伟跃 | Process of continuously producing amine-terminated polyether and reactor design of process |
| CN106633029A (en) * | 2017-01-04 | 2017-05-10 | 扬州晨化新材料股份有限公司 | Method of continuously preparing polyether amines |
| CN107880260A (en) * | 2017-12-21 | 2018-04-06 | 红宝丽集团股份有限公司 | A kind of continuous preparation device and preparation method of small-molecular-weight amine terminated polyether |
| CN114276533A (en) * | 2021-12-31 | 2022-04-05 | 岳阳昌德新材料有限公司 | Method and device for continuously preparing polyether amine |
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