• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Methods for recovering melamine and oxyaminotriazine (OAT) from a melamine crystallization mother liquor include: a) adding an alkaline agent at elevated temperature to a pH of 11 or higher in an aqueous solution containing melamine and OAT; b) crystallizing most of the melamine by cooling the solution obtained in step a); c) separating and recovering the precipitated melamine; d) acidifying the resulting solution (mother liquor) so that the pH value is about 7 so as to precipitate almost all dissolved OAT after separating the precipitated melamine; e) filtering the suspension obtained in step d) according to the tangential filtration technique to obtain a dialyse retentate comprising a transparent permeate and an OAT dispersion containing all the undiluted melamine solution in step b) step; f) recycling the OAT-free mother liquor (said permeate) of step e) to the unpurified melamine solution preparation step, thereby recovering substantially the total amount of melamine not precipitated in step b); And g) recovering the OAT from the dialysis artifact of step e) using any conventional separation technique.
    公开号:KR20020075384A
    申请号:KR1020027007990
    申请日:2000-12-07
    公开日:2002-10-04
    发明作者:노에'세르지오；파메지아니마시모；모렐로지오바니
    申请人:유로테크니카 그룹 에스.에이.(스위스 브랜치)；
    IPC主号:
    专利说明:

    Technical Field [0001] The present invention relates to a high yield, high purity melamine manufacturing process,
    [2] More particularly, the present invention relates to a process for the preparation of melamine and its derivatives, which comprises a simple and inexpensive method of distinguishing and recovering melamine and some important by-products derived from melamine synthesis reactions or subsequent treatments, as well as containing solutions or dispersions of melamine and by- . In fact, in almost all of the catalytic or non-catalyzed melamine treatment starting from the element, the unpurified reaction product is dissolved in water and then subjected to one or more purification steps to finally produce the product with the required purity level ≪ / RTI > from the solution.
    [3] During the treatment of the melamine aqueous solution, the temperature is maintained at 130 캜 (preferably 160 캜 to 170 캜) or higher, in order to use the higher solubility of the melamine and eventually minimize the volume of the water to be handled.
    [4] Higher temperatures are undesirable because not only does the melamine loss due to hydrolysis become larger, but also more water vapor is formed in the waste gas, which is necessarily composed of emissions, so-called NH 3 and CO 2 , and corrosion of the equipment is intensified. The resulting product consisting of high purity melamine (≥99.8% grade) is eventually separated from the solution by cooling and subsequent crystallization at 40-50 ° C. Under these conditions, most of the melamine precipitates in a crystalline form, separated by filtration, centrifugation or any suitable conventional means. The aqueous solution contains oxyaminotriazine (OAT) which contains both melamine and amelin having the following structural formula, in addition to melamine after separating high purity melamine.
    [5]
    [6] OAT is not only a melamine synthesis reaction intermediate, but also formed in an aqueous solution due to melamine hydrolysis. Thus, there is always OAT in the aqueous solution from which the melamine is recovered.
    [7] OAT is a much lower water soluble product than melamine, but its solubility in water increases by tens of times as the pH increases, while melamine solubility remains unchanged especially within the pH range of 7-14.
    [8] This difference makes it possible to crystallize the melamine only when the melamine and OAT-containing solution is cooled at a pH of 7 or higher, preferably 11 or higher.
    [9] High pH values are obtained by adding an alkaline compound such as ammonia or sodium hydroxide to the solution.
    [10] Thus, the crystallized mother liquor recovered after the precipitation and separation process of melamine contains the total starting amount of OAT and the remainder of the melamine, which corresponds to the solubility of the melamine in the crystallization conditions.
    [11] For example, by causing the crystallization to occur at 40 占 폚 and a pH of 11 or higher, the resulting mother liquor contains the following amounts of melamine and OAT:
    [12] Melamine 0.7 to 1 wt%
    [13] OAT 0.3 to 0.5 wt%.
    [14] In order to obtain a high yield of melamine from this production process, it is necessary to recycle the total amount of this mother liquor or parts thereof. However, it is necessary to remove the OAT before the mother liquor is recycled, otherwise the OAT will accumulate in the recirculating solution to the saturation point and precipitate with the melamine contaminants.
    [15] To maintain cyclic equilibrium, it is necessary to remove the same amount of OAT formed in the reaction zone, which is formed in the reaction zone due to the melamine hydrolysis, from the mother liquor.
    [16] The above operation is carried out by removing the melamine crystals and acidifying the obtained mother liquor to pH 7 with a suitable acid. Acidifying agents typically use CO 2 to avoid introducing any foreign material during the fluid treatment process.
    [17] At pH 7, OAT is almost insoluble in water, so it is completely precipitated: conversely, melamine is not affected by pH because of its solubility in the range of pH 7-14 and does not precipitate. Thus, once the OAT is isolated, the mother liquor may be partially or fully recycled to recover the melamine partial or total content.
    [18] The precipitated OAT is difficult to separate due to the colloidal nature of the OAT precipitate.
    [19] In fact, even though the operation is performed using a high-speed centrifuge, the OAT suspended in the acidified mother liquor is hardly separated by precipitation. Also, the filtration tank is very small and can not actually be used because the filtration surface is quickly clogged by the colloidal filtration cake. The only system that allows separation is filtration aids, such as filtration aids such as red algae (dicalite or analogous products). However, in this case too, the filtration is not completely satisfactory and the life cycle of the filter (filtration aid load-filtration-cake removal-cleaning) typically does not operate for more than 4 hours. In addition, OAT is obtained as a mixture with external materials (filtration aids), making their separation difficult.
    [20] As a result, only industrially applicable operations for separating OAT (i.e. filtration in the presence of filtration aids) are very expensive in terms of:
    [21] - Requires high filtration surfaces and high investment costs due to operational complexity;
    [22] - requires a large workforce to perform a filtration cycle that repeats every four hours;
    [23] - consume large amounts of filtration aids (5 to 30% by weight per separated OAT);
    [24] - Due to incomplete filtration, it is only necessary to remove a substantial amount of filtrate to allow only a partial recovery of the melamine and avoid the accumulation of OAT in the water cycle;
    [25] - Recover an almost useless OAT / filtration aid mixture panel.
    [26] Due to these problems, methods have been studied and operated, suggesting total decomposition of the organic acids contained in the mother liquor into CO 2 and NH 3 . In addition to decomposing OAT, these methods also destroy melamine (which is advantageous to be recovered), consume a significant amount of energy, and require high investment costs.
    [27] The present invention is intended to eliminate all of the disadvantages mentioned above by a method capable of recovering both melamine and OAT that are remained dissolved from the melamine crystallization mother liquor.
    [1] The present invention relates to a high yield, high purity melamine preparation process starting from the element.
    [45] The present invention and its associated advantages will become more apparent from the following detailed description of various applications made with reference to the accompanying drawings. These descriptions and drawings are not intended to limit the invention in any way.
    [46] BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows an industrial application of the present invention using semi-continuously operating tangential filtration.
    [47] Fig. 2 is a schematic diagram showing continuously operating tangential filtration. Fig.
    [48] Figure 3 is a block diagram showing the tangential filtration of the OAT suspension during the melamine manufacturing process.
    [28] The process according to the invention comprises the following steps:
    [29] a) adding an alkaline agent to the aqueous solution containing melamine and OAT at a high temperature until the pH reaches 11 or higher;
    [30] b) crystallizing most of the melamine by cooling the solution obtained in step a);
    [31] c) separating and recovering the precipitated melamine;
    [32] d) acidifying the resulting solution (mother liquor) so that the pH value is about 7 so as to precipitate almost all dissolved OAT after separating the precipitated melamine;
    [33] e) filtering the suspension obtained in step d) according to the tangential filtration technique to obtain a dialyse retentate comprising a transparent permeate and an OAT dispersion containing all the undiluted melamine solution in step b) step;
    [34] f) recycling the OAT-free mother liquor (said permeate) of step e) to the unpurified melamine solution preparation step, thereby recovering substantially the total amount of melamine not precipitated in step b); And
    [35] g) recovering the OAT from the dialysis artifact of step e) using any conventional separation technique.
    [36] By operating in accordance with the above procedure and the so-called tangential filtration techniques, it is possible to recover up to about 96% to about 96% of the mother liquor (containing from 0.7 to 1% by weight of melamine) and to such mother liquor, less than 100 ppm OAT, Leaving a content corresponding to the solubility of the OAT at the operating temperature of 40 to < RTI ID = 0.0 > 50 C. < / RTI >
    [37] The temperature of the solution to which the alkali agent is added in step a) is 130 ° C or higher, preferably 160 to 180 ° C, and the crystallization temperature in step b) is about 40 to 50 ° C.
    [38] Tangential filtration is a filtration technique that causes the suspension to move at high speed along a direction parallel to the filtration surface to prevent the filter suspension from forming a filter cake as well as being frequently clogged by the formation of a suspension turbulence.
    [39] While the suspension flows at high speed in parallel to the filtration surface, the solute is continuously removed through the holes in the filtration surface due to the pressure difference.
    [40] The filtration surface is physically resistant to a pressure differential between the dialysis artifact compartment (i. E., The suspension concentrate compartment) and the permeate compartment (the clear filtrated solution from which the suspended particles have been removed), and further, the filtration surface is chemically It is resistant and has a porous structure to prevent the transport of suspended OAT colloid micelles and / or crystalline aggregates.
    [41] For certain applications of the present invention, the filtration surface can be made of commercially available high purity grade alumina.
    [42] However, other materials that do not satisfy the above requirements can also be advantageously used.
    [43] Of the materials useful for producing filtration surfaces, mention may be made of: silica alumina, zirconia, titania, boria, zeolites, tori and mixtures thereof.
    [44] The porosity of the filtration surface (i.e., the average diameter of the transport pores) is less than 5 micrometers, preferably less than 0.2 micrometers, and most preferably between 20 and 100 nanometers. Porosities less than 20 nanometers require large differential pressure. The same differential pressure permits a very low predetermined filtrate flow rate, resulting in low productivity. Porosity above 5 micrometers does not guarantee good separation.
    [49] 1, the OAT-containing feedstock is introduced into the vessel 1 through the pipe 11. The OAT suspension is maintained uniformly using any conventional stirring device not shown. The OAT suspension is sucked by the pump 2 through the pipe 12 and sent to the distal end of the filtration equipment 3 through the pipe 21.
    [50] The filtration equipment (3) is divided into two compartments: a dialysis artifact compartment (32) and a permeant compartment (33). The compartments are separated by a filtration surface 31.
    [51] The dialysis artifact or OAT suspension continuously enters the compartment 32 through the piping 21 and bumps the filtration surface 31 tangentially and is discharged from the opposite end of the filtration device 3 and then flows into the piping 4 ) To return to the suspension container (1).
    [52] Not only the associated control valve 35 but also the pump 2 maintains the desired pressure and tangential velocities in the compartments 32 of the equipment 3 during all operating hours. The permeate compartment 33 operates under a pressure lower than the pressure of the dialysis artifact compartment 32 so that the permeate passes through the filtration surface 31 in an amount dependent on the pressure difference between the compartments 32 and 33. The permeate is continuously discharged from the equipment 3 through the pipe 36 and recycled to the melamine treatment process.
    [53] If the dialysis artifact is increased to the desired concentration (typically 16 times, but may be about 24 times the starting concentration), the dialysis artifact is delivered to the tubing 23 via the valve 22 and sent to the solid (OAT) recovery section.
    [54] Referring to Fig. 2, the processing method of the present invention is described as a continuous operation mode.
    [55] For the sake of simplicity, a two-step process is considered. However, the number of steps may be two or more. The optimal number of steps depends on the economic estimate.
    [56] In fact, increasing the number of steps requires increased plant complexity, and eventually increases the number of required equipment, while a reduced filtration surface can be used to achieve the same result.
    [57] The pump 101 draws an OAT suspension from a storage vessel (not shown) through a piping 111 and the suspension passes through a piping 112 to a recirculation pump (104) and a recycling pump (105) with a filtration device (103).
    [58] The OAT suspension is circulated through a recirculation pump 104, a delivery line 142, an inlet line 121, a dialysis residue compartment 122, (located inside the filter 102), and a pump 104 Into the dialysis liquid circulation path of the filter 102 composed of the outlet piping 141 communicating with the outlet pipe 141. The OAT suspension flows continuously in the circulation path, characterized by having a predetermined solid concentrate which is an intermediate between the inlet and the outlet suspension. The pump 104 ensures the desired tangential velocity of the dialysis artifact relative to the filter surface 125 within the filter 102. The dialysate pressure in the compartment 122 is ensured by the pump 101 and the external pressure valve 114 located at the outlet of the two-stage filtration system. Due to the fact that the pressure in the permeate compartment 124 is maintained at a pressure lower than the pressure in the compartment 122, a continuous transport of the clear solution through the filtration surface 125 is established; This clear solution is withdrawn in compartment 124 and then exits through piping 126.
    [59] Since the flow rate of the pump 101 is designed to be higher than the amount of permeate passing through the filtration surface 125, surplus fluid passes through the piping 113 and then into the filtration process, (Which is located inside the filter 103), and a pipe 151 for returning the dialysis artifact returning to the pump 105. The piping 151 is connected to the circulation pump 151, the circulation pump 151, the recirculation pump 105, the delivery piping 152, the inlet piping 132, the dialysis product compartment 133, ) Into the relevant dialysis artifact circulation path. Also, the dialysis artifact circulates continuously using this circulation path, and its solid concentration is a predetermined final concentration. The dialysis artifact containing OAT is extracted via line 123; The dialyzed artifact concentration is 16 to 24 times or more the OAT concentration of the feedstock entering through the pipe 112.
    [60] In the second filtration process, the tangential velocity on the filtration surface 131 is maintained at a desired value using the circulation pump 105. The connection between the two filtration processes allows the dialysis residue 133 of the filtration device 103 to maintain substantially the same pressure as the dialysis residue 122 of the filtration device 102 while the filtration device 103 The permeate compartment 134 is maintained under the same pressure as the corresponding compartment 124 of the filtration device 102 because the piping 135 and 126 are connected.
    [61] The permeate emerging from compartments 124 and 134 are joined together by piping 126 and 135. Thereafter, it is discharged from the system through the piping 136 into a recovery storage container (not shown), and recycles the process.
    [62] The permeate flow rate from the piping 136 is at least 94%, at least 96%, of the suspension inlet flow into the piping 111. The permeate, which has been stripped of almost all OAT, can be completely recirculated through the melamine process.
    [63] In FIG. 3, a melamine synthesis process in which the water treatment process of the present invention is inserted is shown in a block diagram.
    [64] The element is converted to melamine with high conversion efficiency in the synthesis reactor (A). The effluent from all the reactors enters the aqueous circulation path (B) for the recovery and purification of melamine, where the by-products of the gas composed of ammonia and carbon dioxide are separated and discharged from the apparatus via piping (C) as a water saturated gas (waste gas).
    [65] The waste gas from the piping (C) is normally recovered by returning to the urea synthesis plant.
    [66] The flow of the melamine-containing liquid from the refinery circulation path is discharged through the pipe (D) at 130 ° C. The flow also contains OAT as an impurity to be removed. For this reason, in order to raise the pH to a value higher than 11, an alkali agent is added via a pipe (E) and the solution is sent to a crystallization vessel (F) whose temperature is lowered to 40/50 占 폚. Under these conditions, only melamine is precipitated and collected at high purity in separator (G). The high purity melamine is sent to the drying section through the pipe (H).
    [67] Because of the high pH value, OAT remains in solution. Liquid - OAT-rich mother liquor coming from the solids separator (G) is added to the acidifying agent (which is preferably CO 2) through a pipe (L) to lower the pH to 7. Under these conditions, OAT is almost insoluble and precipitates in the crystallization vessel (M) in the form of a very dilute suspension similar to milk.
    [68] The suspension is delivered to the tangential filtration system O via line N and is sent to the tangential filtration system O in the presence of a melamine solution in a quantity corresponding to saturation at 40/50 占 폚 and almost all of the solvent containing a negligible amount of OAT (less than 100 ppm) 94 to 96% or more).
    [69] The flow is entirely recycled to the melamine collection and purification cycle (B) via line (P) to allow complete recovery of the melamine content.
    [70] On the other hand, the OAT is collected in the form of a solid-rich suspension as a dialysis artifact, and is sent via piping Q to a conventional recovery section (not shown).
    [71] The OAT content in the flow Q is 16 to 24 times greater than the flow rate supplied to the tangential filtration device O through the pipe N. [
    [72] [Example 1]
    [73] 10 L of a mother liquor obtained as a result of melamine crystallization and separation and having a pH of 7 reduced by addition of CO 2 was fed to the system shown in Fig.
    [74] The CO 2 treated mother liquor looked like milk and contained approximately 40 g of OAT (4000 ppm) in suspension.
    [75] The filtration surface consists of an empty cylindrical candelab filter of 750 mm, with an outer diameter of 10 mm and an inner diameter of 7 mm. The candle filter is made of alumina with an average porosity of 50 nanometers. The suspension was circulated inside the cylindrical candle at an average flow rate of 4.5 m / s. The pressure in the dialysis artifact was maintained at a constant value of 2.5 bar during the entire time of the test. The permeate was directly recovered in a suitable container which was kept under atmospheric pressure.
    [76] The permeate flow rate was rapidly reduced during the first 10 minutes during circulation and then maintained at a flow rate of about 150-160 L / h · m 2 until the end of the test.
    [77] The permeate collected during the whole process of filtration was transparent.
    [78] After three consecutive hours of operation, the pump failed to start because of a small amount of circulating dialysis artifact and the test was stopped.
    [79] 9.42 L of clear permeate was collected and analyzed by chemical analysis, showing 0.91 ppm of melamine and 87 ppm of OAT. The solid concentration of OAT in dialysate artifacts was increased by 17.2 times compared with the original concentration.
    [80] [Example 2]
    [81] The system according to FIG. 1 was larger than that used in the previous example, but was loaded at 50 DEG C, pH 7 with 150 L of the same mother liquor as used in Example 1. The suspension contained almost all of the OAT in suspension, 570 grams of all melamine in solution.
    [82] Is an industrial filtration element made of the same material as the candle of Example 1, consisting of a 1020 mm length of hexagonal cross section and a parallel pipe of 28 mm thickness as the filtration surface. Inside the parallel pipe, there are provided 19 channels with an inner diameter of 4 mm, according to a hexagonal concentric configuration consisting of a central channel surrounded by six channels located at the vertices of a hexagon, and the hexagon is provided with a second hexagonal pattern It is surrounded by 12 equidistant channels.
    [83] The channels are parallel to the parallel pipe axis.
    [84] The inner surface of the entire channel is 0.24 m 2 .
    [85] The suspension circulated within the 19 channels at 4.3 m / s.
    [86] The pressure difference at the filter surface always maintained a value of 2.5 x 10 < 5 > Pa, as in Example 1.
    [87] Further, in the present embodiment, after the initial 2 hours, the dialyzing fluid flow rate was stabilized at 145 to 150 L / h · m 2 with a slight decrease.
    [88] A completely transparent permeate was collected for 4 hours. After 4 hours and 3 minutes, a very faint milky white color was observed and discontinued. The milky permeate obtained during the last 3 minutes of the test was not taken into account and only the clear permeate collected during the first 4 hours was evaluated. The total permeate collected was 144.8 L. The milky permeant corresponding to the last three minutes of the test was added to the dialyzed artifact with a solids content of 5.2 L, a solid content of 602 g (measured after moisture evaporation). The collected permeate reached 96.5% of the initial suspension and the OAT in the permeate was 92 ppm.
    [89] The total solid content in the dialysis artifact was 115.8 g / L, of which 110 g / L was a suspended solid. Since the initial solid dispersion amount of the suspension was 570/150 = 3.8 g / L, the suspended solids content of the dialysis fluid ultimately increased 29 times.
    权利要求:
    Claims (10)
    [1" claim-type="Currently amended] A method for recovering melamine and oxyaminotriazine (OAT) from a melamine crystallization mother liquor comprising the steps of:
    a) adding an alkaline agent to the aqueous solution containing melamine and OAT at a high temperature until the pH reaches 11 or higher;
    b) crystallizing most of the melamine by cooling the solution obtained in step a);
    c) separating and recovering the precipitated melamine;
    d) acidifying the resulting solution (mother liquor) so that the pH value is about 7 so as to precipitate almost all dissolved OAT after separating the precipitated melamine;
    e) filtering the suspension obtained in step d) according to the tangential filtration technique to obtain a dialyse retentate comprising a transparent permeate and an OAT dispersion containing all the undiluted melamine solution in step b) step;
    f) recycling the OAT-free mother liquor (said permeate) of step e) to the unpurified melamine solution preparation step, thereby recovering substantially the total amount of melamine not precipitated in step b); And
    g) recovering the OAT from the dialysis artifact of step e) using any conventional separation technique.
    [2" claim-type="Currently amended] The method according to claim 1, wherein the treatment of the alkaline solution in step a) is performed at a temperature of 130 ° C or higher, preferably 160-180 ° C.
    [3" claim-type="Currently amended] 2. Process according to claim 1, characterized in that in step b) the solution is cooled to 40 to 50 DEG C in order to crystallize the melamine.
    [4" claim-type="Currently amended] The process according to any one of claims 1 to 3, wherein the pH of step b) is 6.5 to 7.5.
    [5" claim-type="Currently amended] The method according to any one of claims 1 to 4, wherein the surface filtration material useful for tangential filtration is selected from pressure and chemical resistant materials.
    [6" claim-type="Currently amended] 6. A process according to any one of claims 1 to 5, characterized in that the surface filtration material useful for tangential filtration is alumina, silica alumina, zirconia, titania, boria, zeolite, toria and mixtures thereof.
    [7" claim-type="Currently amended] The method of claim 6, wherein the surface filtration material useful for tangential filtration in step e) is comprised of high purity alumina.
    [8" claim-type="Currently amended] 7. A method according to any one of claims 1 to 6, wherein the surface filtration material useful for tangential filtration exhibits a porosity of less than 5 micrometers (i.e., an average diameter through the conduits).
    [9" claim-type="Currently amended] The method of claim 8, wherein the surface filtration material useful for tangential filtration exhibits a porosity of less than 0.2 micrometers.
    [10" claim-type="Currently amended] 9. The method of claim 8, wherein the surface filtration material useful for tangential filtration exhibits a porosity of between 30 and 100 nanometers.
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    同族专利:
    公开号 | 公开日
    IT1315265B1|2003-02-03|
    CN1240689C|2006-02-08|
    DE60022387T2|2006-06-14|
    ITMI992684D0|1999-12-22|
    TWI224098B|2004-11-21|
    SA1298B1|2006-09-20|
    AT303368T|2005-09-15|
    EP1240151B1|2005-08-31|
    BR0016905A|2002-10-22|
    ITMI992684A1|2001-06-22|
    PL356324A1|2004-06-28|
    PL195651B1|2007-10-31|
    CA2394815A1|2001-06-28|
    US20030100758A1|2003-05-29|
    ES2248158T3|2006-03-16|
    WO2001046159A3|2001-09-27|
    US6891040B2|2005-05-10|
    AU2220001A|2001-07-03|
    CN1434809A|2003-08-06|
    AR027025A1|2003-03-12|
    KR100687097B1|2007-02-27|
    WO2001046159A2|2001-06-28|
    DE60022387D1|2005-10-06|
    EG22709A|2003-07-30|
    EP1240151A2|2002-09-18|
    EA003868B1|2003-10-30|
    EA200200701A1|2003-02-27|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1999-12-22|Priority to IT1999MI002684A
    1999-12-22|Priority to ITMI99A002684
    2000-12-07|Application filed by 유로테크니카 그룹 에스.에이.(스위스 브랜치)
    2002-10-04|Publication of KR20020075384A
    2007-02-27|Application granted
    2007-02-27|Publication of KR100687097B1
    优先权:
    申请号 | 申请日 | 专利标题
    IT1999MI002684A|IT1315265B1|1999-12-22|1999-12-22|Process for the production of melamine with other yields to elevatapurezza|
    ITMI99A002684|1999-12-22|
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