TW416940B - Processs for the preparation of a modified ammonium mordenite, its use for being catalyst and for preparation of methylamine - Google Patents

Abstract

Process for the preparation of a modified ammonium mordenite, characterized in that it comprises the steps of (1) drying an ammonium mordenite under conditions such that the mordenite is maintained in ammonium form and (2) treating the dried ammonium mordenite thus obtained with tetrachlorosilane in the gas phase at a temperature of between 300 and 600 DEG C. The modified ammonium mordenite obtained by this process is suitable for use as a catalyst in the production of methylamines by reaction of ammonia and methanol, allowing high selectivities in dimethylamine.

Description

416940 A7 B7 printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (/) Specifications The present invention relates to a method for manufacturing modified ammonium mordenite (Amaonium η 〇rde η 丨 te), especially for the method埴 A catalyst containing the modified ammonium mordenite, and a method for producing methylamine by using the catalyst to react M formase with ammonia in a gaseous state where the temperature is increased and pressure is increased if necessary. In the catalytic synthesis of methylamine from formic acid and ammonia M, a gasified mixture of methanol and ammonia is first prepared, and then passed through a catalyst bed in a reactor at a temperature of about 220 to about 5001 and at a pressure between atmospheric pressure to about Reaction under pressure between 50 Bar. The reaction products between ammonia and formazan include three amines, such as monomethylamine (MMA), dimethylamine (DMA), and trimethylamine (TMA). A mixture of water, ammonia, and unreacted methanol. In addition, dimethyl ether (DME) may become a by-product. Among these products, dimethylamine is the most sought-after amine in the industry; in fact, dimethylamine is a raw material for several industrial products, such as solvents, peony products, accelerators and surfactants for curing rubber. , Fungicides (such as tetramethylthiamine formamidine disulfide) and so on. The production of dimethylamine from ammonia and methanol requires a step of separating the products after the reaction. However, the separation of various methylamine mixtures by distillation becomes a result of the residual ammonia and the various methylamines forming an azeotrope. Quite complicated. Currently, amorphous silicon-aluminum catalysts are widely used in industrial mass production of methylamine from methanol and ammonia due to their excellent catalytic properties1. However, a large proportion of K in the methylamine mixture obtained using this catalyst contains trimethylamine, and as a result, the desired yield of dimethylamine is insufficient. -3- (Please read the notes on the back before filling this page) This paper size applies to China National Standard (CNS) A4 size (210X297 mm) 416940 Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 5. Description of the Invention u) This is why many investigations have been made to find a catalyst that can selectively obtain dimethylamine while suppressing the production of trimethylamine as much as possible. The star of various methylamines in the reaction product depends on the thermodynamic equilibrium of the reaction; among other factors, the amount depends on the reaction temperature and the mole ratio of the reactants. For example, when the reaction temperature is 300C, the ammonia and methanol feed is equivalent to an N / C atomic ratio of 2: 1, and the methanol feed rate is (K3 kg / h / kg catalyst, using an active non-selective catalyst and formazan When the total conversion is reached, the composition weight of each methylamine at equilibrium is 3; it is "} ^ 20! ^, 0〇22.5:!:," 57.5: 1 ;. The composition of this product is equivalent to the thermodynamic equilibrium composition. Here Under the circumstances, the formation of trimethylamine is dominant. On the other hand, if the production of trimethylamine is inhibited, under the same conditions and the full conversion of formazan is reached, K heavy star 3; indicates the composition, when MMA and DMA are balanced, HMA is 31.5¾ and DMA is 68.5¾. It can be seen that the development of selective catalysts makes it almost advantageous to almost completely prevent the formation of trimethylamine. A large number of catalysts have been proposed for this project. Many documents are specifically mentioned Such as synthetic or natural zeolites, such as zeolite X, ytterbium, KK-5, ZSH-5, ZSM-12, FU-1, SK, erionite, magnesite, faujasite, chabazite, clinoptilolite and more Special mordenites. These zeolites are either used as such or subjected to different treatments for K modification, Such as number of acid sites, pore size, or silicon / aluminum ratio. Suggested treatments include changing properties and cation ratios. • Treatment with acid * scorch in or without steam, or use various silylating agents to pre-k silylate. Various It is suggested that the treatment can improve the catalyst activity and / or selectively form methylamine or dimethylamine. 4-(Please read the precautions on the back before filling out this page} This paper size applies Chinese National Standard (CNS) Α4 Specifications (210X297 mm) 416940 A7 B7 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (3) 1 1 When this zeolite is used as a catalyst, its choice of dimethylamine production 1 1 The value of the embedded skin os is very low, which is often very close to the value obtained by mechanical equilibrium of three methylamines at thermal I 1 C CPlease 1 J For example &gt; In __. The paper discusses 各种 Various zeolites make methanol and ammonia selectivity first Read 1 I into dimethylamine (I »Mo chida et al., J. Cata 1, 8 2, (1983}, t face 1 Ϊ 1 3 1 3- 3 2 1) Those who reported that mordenite (Nor t 0 Ϊ1 company's attention 1 I Ze ο I on) can get the best conversion rate of methanase and dimethylamine selectivity, this matter 1 | another 1 mordenite is in proton form Or M cations are replaced with sodium, magnesium, or net-hydrogen manuscript ions. In this later- * form and at a temperature of 40 0 t, the methanol conversion rate is as high as 94.5% Moore, and The selectivity of methylamine (DMA) is 1 1 to obtain 51.51 '. However, the formation of trimethylamine is negligible 11 1 away, because the selectivity of trimethylamine (TMA) is also 11,9¾ mole. 1 Ordered in U.S. Patent Nos. 5,137,85 4 and 5,210,303. This shortcoming was overcome by the use of proton mordenite that had been treated elsewhere. The 1 1 treatment includes increasing the temperature of the nanomordenite in the cypress M Tetrachlorosilane by 1 1 (e.g., about 7 0 &gt; treatment, and thus the ion exchange in the conversion of the nano green zeolite. And it is processed into proton mordenite. In this exchange, the nano ions of f. Mordenite treated by 1 are replaced with ammonium ions, and the resulting zeolite 1 zeolite accepts 450 X for several hours. The treatment of the mordenite I 1 zeolite did not significantly change its S i / A 1 atomic ratio, in other words, the mordenite I I zeolite was not subjected to dealumination. .9 Mole a: and dimethylamine selectivity 6 1.2 Mole 5K. The methods described in these patents 1 1 thus provide a good methanol conversion and dimethylamine selectivity 10 while the production of methylamine remains -5 Jugao (see Example 4 below). I 1 1 1 This paper size applies the Chinese National Standard (CNS) A4 specification (2) OX 297 mm. Printed by the Consumer Bureau of Standards Bureau 416940 A7 B7 V. Description of Invention (/) In order to solve this problem, European Patent Application No. 593,086 proposes a method for manufacturing methylamines, which can selectively produce monomethylamine And dimethylamine to reduce the formation of trimethylamine to several%. To achieve this, the synthesis of methylamine is carried out under a specific catalyst. The catalyst is first silanized with a proton mordenite in the liquid phase. The agent is subjected to one or more silanization treatments, and then heat-treated in air oxygen at a temperature of W 300 to 6001 C. The silylation treatment is performed by dispersing the mordenite phosphine in a solution of the silanization agent in a solvent. However, in Before the silylation, the water content of the mordenite must be adjusted to a predetermined value. Therefore, when the solvent used is water-soluble (such as alcohol), the mordenite is calcined at a temperature of 350 to 6001C until the water content is 4% by weight: or Lower. When the solvent is water-insoluble (benzenes), the mordenite's moisture content must be between 3 and 40 heavy stars S before the K 5 alkylating agent treatment; this water content can be controlled by controlling the degree of mordenite drying or Simmer in a humid atmosphere This method can obtain a very good dimethylamine selectivity (about 6U, but the conversion of formazan is only about 90¾), which means that at the industrial level, the application of this method must be sufficient for unconverted methanol. Recycling. Furthermore, these effects are derived from ingenious technology. In fact, multiple high-temperature sintering in the air is required for the preparation of the catalyst; moreover, the moisture content of mordenite must be careful before the silane treatment Control, otherwise it is impossible to maintain the low production rate of trimethylamine (especially found in Examples 3, 6 and 8 of the patent application). Therefore, although several catalysts have been used to catalyze the synthesis of methylamines from ammonia and formazan, it is still necessary to find a catalyst that can have both: (a) a high degree of selection for the production of benzylamine and the desired dimethylamine Amines (such as dimethylamine with a selectivity of 70 moles; or higher), and in fact do not produce -6- (Please read the precautions on the back before filling this page) This paper size applies to Chinese national standards (CNS ) Α4 specification (210 X 297 mm) 416840 A7 B7 V. Description of the invention (Printed by the Consumer Cooperative of the Central Provincial Bureau of Economic Affairs, Ministry of Economic Affairs ο The gas medium super-two party, the degree of dryness is 10 stone. Touch for peace The material of the dry medium of the stone is close to the zeolite of the medium, and the amine stone is boiled so that the amine is in high contact with the light boiling point. The highest ammonium serazite ratio is not available in the above. The above mentioned ammonium serine is produced at the silk ammonium; the ammonium silicon is prepared by boiling the ammonium silicon and selected by the ammonium sulphate method. The dryness level contains the use of M to form a fh formula. The combination of stone and double-turned M is 'if ammonium methyl-οι V, especially when the azeotropic boiling is high; Jike, -ίτ' at two $ 10 to prepare the article 00, it is mixed with light to urge others.)) Basic ear-earning system: the 6th type of amylose K special alcohol is prone to contact with silicon species, and the contact state is 0 ± touch, and ammonium ammonia, A 2 is the step of this excellent e rate. 30, one alcohol, and one alcohol, and 81% melamine for sexual atmosphere, so the amine stone should be changed to four to make W-grade alcohol, up to a turn of the alkane-containing methyl alcohol can make the The anti-quantity is based on the medium-to-leavened silica. Looking forward to the future, it will make or cause the industry to produce very Jiaming Baoshi Jiashi a silk mingming into the amine ΜίΗ the human body, and issued in boiling chloride boiling ammonium alcohol stamping Mingming Nail 丨 In order to achieve the true percentage, the laser light of the four quality of this special method of the three living ears can be human nature of the human amine ear into a special silk phase to understand and change, which is originally high to make Minghuo special After the formation of ammonium, it caused the ammonium to be ammoniated according to)}. It was higher than 70% of the ether, and the combination was used by one method (bfc phase, 0 method). (Please read the notes on the back before filling this page) This paper size applies to Chinese National Standard (CNS) A4 size (210X297 mm) 416940 Μ Β7 Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. ) 1 1 Made from ammonium mordenite 〇 1 1 m zeolite is a crystalline aluminosilicate T which is hair-forming in the white world! I or M chemical synthesis 0 day m / · &gt; "mercerized The overall composition of the t7P stone can be generalized ^^ Please 1 | Table For Na S [(A 1 0 i) 8 is ΐ 0 2) 40] • 24H 2 0 ° Natural mercerizing first reading ijt I 1 zeolite therefore has-. Si / A 1 atomic ratio is 5: 1 0 m) It is also known that the synthetic fused mercerized backstone 1 1 has a si / A 1 ratio higher than 5; 1 (see E 1 sevier published picture 1 1 t 1987. A _ jac 〇bs and J .A By Ha Γ t en s: "High-silicon aluminosilicate matters 1 I and 1 Zeolite synthesis J Plant surface science and catalysis J Vol. 33» Vol. T 32 (32 1-332)) Replaced by hydrogen alkaline earth metal ions or ammonium ion 'W * · 1 I ions or other ones with other alkaline metal ions 0 I 1 According to the present invention, the mercerizing flux used as the original family for the preparation of catalysts is <7μ. Ammonium Mercerizing 1 | Zeolite whose Si / κ 1 atomic ratio is between 5: 1 to 20: 1, preferably 5: 1 to 1 and order 12: 1. Its sodium content must be very low, t is preferably low At 0 1% by weight relative to the weight of mordenite 0% ammonium silk m m sold in the mall * It can also be prepared from 1I mordenite M containing ammonium or alkaline earth metal ions and cations as ammonium pairs 1I these ion exchange. Ion exchange can be performed using conventional methods. Example 1 1 As * treatment with an aqueous solution of ammonium nitrate 0 1 The ammonium mordenite suitable for the catalyst of the present invention is mainly produced by a method comprising a drying step 1 1 followed by a M sarthanization step. 1 1 In the drying step &gt; must be carried out under conditions that enable the mordenite to maintain the ammonium state 0 In fact, I found that at a temperature of 4 0 0 M, the ammonium 1 I mordenite will not be converted into proton mordenite 〇This is why the drying step of the method of the present invention 1 1 is performed at a temperature of less than 40 in the dry inert gas (nitrogen) stream, and 1 is preferably 2301C to 350 1C. 0 Drying Degree and I 1 _ 8 1 I 1 This paper size applies to Chinese National Standard (CNS) A4 specification (210 × 297 mm) 418940 Μ Β7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (7) 1 1 It is sufficient to remove the water absorbed on the mercerized whisker, but its temperature is 1 1 It must not be too high and the drying time should not be too long anyway. Κ Avoid the volatilization of chemically bound ('chemical adsorption) bacteria. 0 The drying time is usually 180 To 540 ^ —V Please read 1 minute, preferably 360 to 480 minutes. Read 1 1 1 | Any dry m program according to the present invention can be used for m zeolite. Therefore, m 1 1 1 such as green zeolite can be used even at Dry at room temperature under vacuum 0, so drying can be performed at a pressure of 1 I lower or higher than atmospheric m-force 0, preferably below or equivalent 1 | A 1 at 3 For example, if you fill out this in mg, fill in 1 and the amount of water released during the drying step can be checked. For example, reverse the page 1 t. The device will be condensed or analyzed with a mass spectrometer. 0 Dry at the end of the water release. 1 1 stop. The released gas was bubbled into water for VX titration analysis. Measured 1 1 determined the amount of ammonia in the aqueous solution t. It has been shown that the ammonia released during the drying period 1 is less than 0.01 relative to the weight of mordenite. ; During the dry refining this--ammonia content 1 so the ammonia content in the original mercerized m stone should be ignored. 0 1 I At the end of the drying step * The dried material can be cooled in an inert gas stream (1 1) to make 1 I return to room temperature. 1 Dried ammonium mordenite M gas phase tetrachlorosilane for alkaneification * Heating from room temperature 1 Gradually increasing temperature at a rate of 1 to 5 υ per minute, preferably 1 l is 2.5 to 4 per minute VV up to 300 to 600 t! Temperature 9 is preferably 1 1 450 to 550 V 0 and then maintained at this temperature for 60 to 1 80 minutes, preferably 1 I is 120 to 1 60 minutes C. Better to use inert A gas mixture of gas and tetrachloromethane W 1 1 alkane, wherein the fraction of tetramethylene methyl silicon is &lt; 0.05 to 1. 0 1 1 bar »especially between 0.2 to 0.6 bar 0 in silicon During the firing step, a slight dealumination of the mordenite I zeolite occurred. The S i / A 1 atomic ratio was originally from 5: 1 to 20: 1. I 1 -9 1 1 1 This paper size applies to China National Standard (CNS) Α4 specifications (210X297 mm) 416940 A7 B7 Printed by the Consumer Cooperatives of the Central Government Bureau of the Ministry of Economic Affairs V. Invention Description (%) The value of 1 1 becomes between 10: 1 and 30: 1 Value 0 1 1 According to the present invention, tetrachlorosilane is mainly used as the silylating agent. Actually 1! Up * I have issued regulations to use other silicon chemical agents (dichlorodimethyl silicone or 1) (Simethicone complex) can not be obtained in the catalytic synthesis of ammonia and formazan M. 1 Selective catalyst for the formation of dimethylamine. 0 Threat 1 i 1 After cooling with M inert gas to room temperature. 1 | Wash with distilled water to remove the remaining aluminum chloride and aluminum salt. Wash the number of repetitions 1 I and 1 again until the pH value of the supernatant solution becomes neutral. 0 The resulting m mordenite is then filled in at 60 V and dried to The weight does not change. Page 1 | According to Zhao 1 «," The modified ammonium mordenite used in the catalyst of the present invention usually has an si / A 1 1 1 atomic ratio of 10: 1 to 30: 1. 15 ： 1 to 25 ： 1 0 1 | The method of manufacturing modified mordenite according to the present invention is more advanced than that of the prior art! The ordering method is simple and less expensive. 0 In fact, t is opposite to the US Nos. 5, 137, 854, and 5 , No. 21 0, 308 discloses a method for preparing modified mordenite, which includes 1 I contains four main steps &gt; two of them are sintering * and there are only two methods for preparing modified 1 | quality m-mordenite according to the present invention. Steps (drying and silylation) without involving 1 1 and calcining step 0 In addition, the method according to the present invention is easier to implement than the method of European Patent Application I No. 59 3, 086, because extreme care must be taken in this application 1 1 The water content M of the mordenite before the silylation is adjusted to a predetermined value and I 1 is subjected to several times of incineration. 1 I The method for producing a modified mordenite according to the present invention »Compared with the method of the prior art 1 1 Easier during delivery and The economy can use the method of synthesizing methylamine according to the present invention »Methanase and 1 ammonia, which are used as the starting materials, are pure products or industrial grade products can be used for economic reasons. 1 1 -1 0- 1 1 1 This paper size applies to China's National Standards (CNS) A4 specification (210X297 mm) 416940 at B7 Printed by the staff of the Central Bureau of Standards, Ministry of Economic Affairs, Consumer Consumption. 5. Description of the Invention (1) 1 1 The amount t of the raw materials used in the method 9 of the present invention should be such that the nitrogen / carbon (N / C) ratio of the original 1 1 is from 0.5: 1 to 5: 1 and preferably 0 · 8: 1 to 2: 1 0 1 1 when K / C atom ratio increases »The selectivity to dimethylamine decreases and when 1 IN / C atom ratio is decreased), the formation of trimethylamine increases 0 This is not recommended to read 1 f N / C atom ratio is not pm Swelling out 0.5 · 5: 1 to 5 :! Fan Yuan's reason 0 # 1 | I The feed rate of formazan is between 0.1 and 2 kg / h / kg catalyst Note that 1 1 is beneficial. 1 I i i The operating conditions used in the method of the present invention are usually gas-phase catalysis of ammonia and formazan. For the manufacture of methylamines 0 This method is usually in the range of 220 to 3 5 0 1 page temperature S__ «1 1 temperature» preferably 280 to 320 t pressure range from atmospheric pressure to about I 1 100 bar i preferably about Performed within the range of 1 to 50 bar. 0 1 1 The device used in the method of the present invention is limited. ♦ This method can be read continuously or 1 non-continuously. 0 The catalyst bed can be a fixed bed or a fluidized bed. 0 In the reactor The mixture of Pt gas and m is divided into 11 parts by conventional methods. For example, 9 is used in the fractional distillation method. 0 After the components in the reactor effluent gas are separated by 1 I, ammonia, monomethylamine and / or dimethylamine can be separated according to Partial or full 1 1 reflux cycles are needed. In the method of the present invention, it uses the above-mentioned modified ammonium m-zeolite as catalyst ϊ l Ϊ It is easy to produce dimethylamine with a high selectivity of 1 to 72 to 82. Moore 1 1 r and The methanol conversion rate is close to 100 mol%. 〇In addition, t is practically not available-methyl 1 1 amine is formed without by-products such as dimethyl ether. 0 1 1 further 1 when the gas mixture of methanol and ammonia contains monomethylamine and / 1 1 or dimethylamine trans / or methylamine. The same results are obtained. Therefore, the methylamine formed by i 1 can be fed into the reactor through a Ttm ring in a gas mixture with ammonia 1 1 -1 1- 1 1 1 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 416940 A7 _B7_ V. Description of invention (W) without affecting the selectivity of dimethylamine generate. This would lead to an industrial benefit. Finally, as shown in the examples below, the catalyst can maintain its activity and selectivity for a long time. The following examples of the present invention do not limit the present invention. The S / A1 atomic ratio shown in each example is based on 29A1 Magic Angle Spinning NMR (MAS NHR), and M is a fluorite containing aluminum atoms at the tetrahedron position as a standard. Measurement &gt; The aluminum content was determined using coupled induction plasma technology, which is described in DR Corbín et al., Anal. Chera. 59 (1937), 2? 22-2728. Cell Example 1 The catalyst prepared according to the present invention The mordenite used in this example is PQ zeolite CBV 20A (product of Valley Forge, PQ Company in the United States). It is a synthetic mordenite with low sodium content (relative to mercerized The zeolite weight was 0.01 weight! S). The mordenite has a Si / A1 atomic ratio of 10: 1 and a nitrogen content of 1.95 wt% in the form of ammonia. The determination of ammonia content is the ammonium ion of M mordenite, which is replaced with a concentrated aqueous solution of sodium hydroxide, followed by the ammonia produced by steam distillation, and then condensed to determine the ammonia in the obtained aqueous solution. The dry M is about 25 grams. The mordenite was granulated and sieved to obtain 10 grams of small particles with a particle size between 250 and 500 microns. The mordenite with this particle size was filled into a 25 mm diameter quartz tube with a temperature measuring sleeve. The tube was used in Externally heating M with an electric heating coil makes the catalyst bed have a uniform temperature. The mordenite is heated at a rate of atmospheric pressure M2.5 ° C / min in a nitrogen flow rate of 40 ml / min and kept at 300 t! At a temperature of 5 hours (please read the precautions on the back before filling in this Page] This paper size is applicable to the Chinese National Standard (CNS) M specifications (210X297 mm) when printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 416940 Μ B7 V. The invention description (&quot;). Then cooled in a dry nitrogen stream To room temperature. The analysis shows that the ammonium released during this drying step is negligible for the weight of the mordenite used. (2) Treating a nitrogen stream with tetrachlorosilane through a bubbler containing tetrachlorosilane, Maintain the temperature K to maintain the partial pressure of tetrachlorosilane at about 0.24 bar. The flow rate of a mixed gas of nitrogen and tetrachlorosilane M40 mm / min passes through the catalyst bed (dry green zeolite). The catalyst bed is 3.51 The mordenite is gradually heated to 550t: The mordenite is then maintained in the air stream for another 2 hours and then cooled to room temperature under nitrogen. The mordenite thus treated is suspended in 2 liters of distilled water and the water is poured out , And Several times until the pH value of the water in the surface layer is neutral. The mordenite thus obtained is dried at 60 ° C until the weight remains unchanged. The Si / A 丨 atomic ratio of the modified ammonium mordenite obtained is 25: 1. Nitrogen content Based on ammonia, it is 0.7 weight Ϊ1. Although the ammonia content is determined, the ammonium ion of mordenite is replaced with a concentrated hydrogenated aqueous solution of hydrogen, followed by the steam generated by M steam, and then condensed to determine the ammonia in the obtained aqueous solution. In this case, two types of mordenite were obtained, with an Si / ZU atomic ratio of 25: 1. This nitrogen content indicates that the mordenite is still ammonium after silanization. In fact, the theoretical formula of such mordenite should be (〇4) 1,85 &quot; Al〇2) 1,85 (Si〇2) 46.15] · 24H2 0, and its theoretical molecular weight is 3 5 50. The theoretical nitrogen content M relative to the total weight of mordenite The weight percentage expression is [(1 4 X 1. 8 5) / 35 50] X 1 00 = 0. 73 weight%. -13- (Please read the precautions on the back before filling this page) This paper size applies China National Standard (CNS) Α4 specification (210X297 mm)

41694Q B7 Printed by the Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs. 5. Description of the invention (M) 1 1 The nitrogen content obtained as a result of the experiment relative to the weight of mordenite is 0.7% by weight 1 1 * It is clear that the morden m stone is in accordance with the present invention. After the silylation treatment, it is in the form of 1 1 and then ammonium. 0 Poem 1 I Example 2 (Comparative Example) M Various zeolite preparation catalysts. Read 1 1 The method used in this example of Sfe is the same as Example 1 »But Commercially available or synthesized zeolite f 0 These catalysts are made with different zeolites 9 For the sake of comparison 1 J Its function for synthesizing methylamines from ammonia and methanol and matters in the method of the present invention 1 I Re1 Preparation of modified ammonium mordenite (see Example 4), the difference in the functions obtained 〇4 manuscripts ί 2. 1. The zeolite Be ta Η + sand sandification page 1 1 Fully implemented according to 眧 V » 1 Method for preparing catalyst r but starting mercerization 1 1 Zeolite for M Zeolite Be ta Η + CP81 1 -25 (Netherlands 9 Le id e η »1 1 PQ Zeolite Company), a synthetic proton zeolite, its S i / A 1 The original 1 order ratio is 13: 1 0 The Si / ft 1 1 ratio of the modified zeolite Be ta Η + thus obtained is 150: 1 &gt; 1 I 2. 2 · The zeolite Be ta Ν a 4 Silicidation 1 1 a) The zeolite Be ta Η + CP8 11 -25 used in Example 2.1 was converted to 1 1 and converted to the nano form of Be ta zeolite 1. The m-stone Be ta Η -h I was stirred at room temperature. In NH 3 aqueous solution and then at a stream temperature, search and stir in 1 L of sodium chloride aqueous solution for 4 hours. 0 Wash with distilled water until there are no chloride ions 1 1 and then dry at 60 1 1 b) From 2.2. a) The nano-Beta zeolite prepared was completely treated as described in Example 1 and treated with 0 μM * modified zeolite. Beta N a bucket has a Si / 1! A 1 atomic ratio of 40: 1 〇 2. 3. The silica chemical conversion of nanometer zeolite 1 I -1 4- I t 1 This paper size applies to Chinese national standards ( CNS) A4 specification (210X29? Mm) 416940 a? B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (/ 3) 1 1 a) Practical example 1 Ammonium mordenite PQ zeolite CB V 20 used A is converted 1 1 is nano-type &gt; is stirred in a sodium chloride aqueous solution at the temperature of wine flow for 1 I 4 hours conversion * and then washed with distilled water until no nano-ion is detected t please 1 first 1 then 60 V Drying The Si / A 1 atomic ratio of the obtained mordenite is 10: 1 Ί t 1 of the face 1 b) 2. 3. A) The obtained mordenite is dried according to the examples. 1 Note 1 | Modified Nano Mordenite »Its S ί / A 1 Atom Matter 1 | The ratio of 1 is 17: 1 〇 Example 1 (Comparative Example) According to the US Patent No. 5, 137, 8 5 4 to make a page 'ί— ^ 1 | 备 ΛΆ Catalyst 1 I is For comparison r was prepared according to the method described in the US Patent No. 5, 137, 854! I obtained a modified proton mordenite. Order 3.1. Example 1 The ammonium mordenite PQ zeolite CB V 20 A used in Example 1 was converted into nano-salt at m flow temperature in gas fb sodium aqueous solution 1 | for 4 hours »then washed with distilled water until no Nano ions were detected again) 1 I was dried at 60 0 1 1 The Si / A 1 atomic ratio of the nanomordenite was 1 0 · * 1 Λ 1 3.2. Secondly »using the above 3.1. The catalyst was made in accordance with the method described in the United States Patent No. 5, 137, 8 5 4 (paragraph 7 line 7 to line 7 to line 34). In this method, 4 nanomordenite II Heating in a nitrogen stream at 70 ου for 30 minutes, and then at this temperature for 1 hour, treated with tetragas silane and nitrogen gas stream for about 3 hours »I 1 fluorite treated in this way was washed with distilled m water until no chlorine Ions are detected t accept 煆 1 burned at 45〇υ, the nano ions of mordenite are dissolved in N Η 4 NO e 1 1 -1 5- 1 1 1 This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 416940 A7 _ B7 V. Description of invention (W) was processed The ammonium ion was exchanged, and the ammonium mordenite obtained finally received another 45 ° C for 2 hours. The obtained proton mordenite had an S i / A 1 atomic ratio of 10: 1. Example 4 Synthesis of methylamine In this example, the modified ammonium mordenite prepared according to the method of the present invention (the catalytic function of Example 1 丨 and various other zeolites treated or untreated with tetramethane silane) Comparison 4.1. The reactor used in the device and operating conditions is a Pyrex glass tube, 50 cm high, with an inner diameter of about 22 mm. A temperature-measuring sleeve with a sliding thermocouple runs in the center of the tube. The catalyst temperature is closely monitored. The tube is placed in a flowing sand bath and heated from the outside to maintain a uniform temperature distribution. Inside the tube, a layer of inert material (α-alumina) is added to the catalyst for testing. ) MH preheats gaseous reactants before passing through the catalyst bed. Μ7 grams of catalyst whose shape is ground into granules with a particle size between 300 and 400 microns for testing; the catalyst is additionally inert. Material dilution. The mixture of ammonia and methanol in the gas phase is fed to the human reactor from top to bottom. The reaction is carried out at a temperature of 300C and atmospheric pressure, and the feed rate of formazan is 0.3 kg / hour / kg of catalyst. The feed rate M enables the H / C atomic ratio of 2: 1 to prevail. Experiments show that some experiments At atmospheric pressure, M gas mixtures such as methanol, ammonia, and methylamine that may be recycled, constitute a good method for comparing various catalysts, and a reliable basis for using extrapolation methods at higher pressures. At the reactor outlet, Dilute the exhaust gas product with a known flow of nitrogen K -1 6 — n. II l · II-II Ln I- I -II! 1, I— In II I ——- i Iΐτ (Please read the note on the back first Please fill in this page again for this matter) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 416840 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (/ 5) Stop the condensation. The composition of the gas mixture was analyzed using an air chromatograph. 4.2. The results obtained by comparing the catalyst functions were obtained according to the conditions described in Example 4.1. The meaning of the words used in this table is as follows:-Zeolite Beta B +: Zeolite Beta H + CP811-25 is sold by PQ Zeolite Company, Le e de η, Netherlands;-Zeolite Beta H + * SiCl4: Silanized zeolite prepared according to Example 2.1;- Beta · SiCl4: Silanized zeolite prepared according to Example 2.2; -Hexazolite ZSM-12 NH4 +: Nanozeolite, published by Elsevier in 1987, by PA Jacobs and JA, Martens: "High Silicon Aluminum Silica Synthesis of acid salts "Study on Surface Science and Catalysts j Volume 33 book page 13 of the method described in Example 6a), which is exchanged with NH3 aqueous solution at room temperature and at 5001C with air Obtained by sintering for 4 hours;-sintered mordenite +: mordenite PQ zeolite CBV 2 0 Α (USA, Va 1 1 ey F ogge, PQ company), simmered in air for 5 hours . -Mordenite 100Η &quot;: Commercial high-aluminum deprotonated proton mordenite whose Si / iU ratio is 100: 1 (sold by Montoir de Bretagne, France, Zeocat 44550); -17- (Please read the notes on the back before filling (This page) The paper size applies to the Chinese national standard (CNS &gt; A4 size (210X297 mm) 416940 at B7. V. Description of the invention (/ ') Mordenite ^ + 3 丨 (: 14: manufactured according to Example 2.3, Silanized mordenite; mordenite SiCl4 _ H + ·· Spring Example 3 is a silylated mordenite prepared according to the method disclosed in US Patent No. 5, 1 37, 8 5 4. Mordenite N 丨 丨 4 * · S i C 1 4: Example 1 (according to the present invention) The modified mordenite was prepared; si / / U: the si / A 1 atomic ratio of the catalyst used; c Me (JH · · formazan obtained from the following formula Conversion rate (mol%); Number of unconverted methanol; C MeOH = 1 0 0 '-X 100; ----------- pack-- &lt; Please read the notes on the back before filling (This page)

Number of moles fed to DME: the selectivity of dimethyl ether (Mole! Π, Μ is calculated as follows: X DME (Mole) Order DME '2x DME (Mole) +1 X ΜΜΑ (Mole) + 2x DMA (Mole) + 3x ΤΜΑ (Mole &gt;

A Printed by the Central Laboratories of the Ministry of Economic Affairs, Consumer Cooperatives -SMMA: Monomethylamine (Mole!), The selection rate, calculated as T formula: 1XMMA f Moore X 100

S

MMA 2X DME (Mole) + lx HM / U Moore) + 2X DMA (Mole) + 3x TMA (Mole) SDMft: Dimethylamine (Mole 3;) Selection Rate • Calculate the following formula: -18 -This paper scale is applicable to the Chinese National Standard (CNS) A4 (210x297 mm) 41B940 Α7 Β7 V. Description of the invention (/ 7) 2x DME (Mole) X 100

S

The selection rate of DMA 'TMA · 2x DMEi Mole) + lx MMA (Mole W2x DMA (Mole) + 3x TMA (Mole) Trimethylamine (Mole 3;), the selection rate is calculated as follows: 3X ΤΜΑί 冥 耳) X 100 * ΤΗή X DME (莫尔) + lx ΜΜΑ (箅 耳 DMA (莫尔) + 3x ΤΜΑ (莫尔) Μ)

HeOH = methanol DME = dimethyl ether HHA = monomethylamine DMA = dimethylamine ΤΗ A = trimethylamine ------------ install-(please read the precautions on the back before filling this page) Ordered by the Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumer Cooperatives-19- This paper size applies to the Chinese National Standard (cns) A4 (210x297 mm) 416840 A7 _B7 V. Description of Invention (/ $) Table I Catalyst Si / Al C MeOH SDME SMMft S DMA STMA (Mole S) Zeolite Beta Η + 13: 1 &gt; 99 0.5 32 24 44 Zeolite Beta Η + * SiCl 4 150: 1 81 1 2 * 12 76 Zeolite Beta Ha + · SiCU 40 : 1 96 17 * 22 61 zeolite ZSM-12NIU + 45: 1 86 12 * 23 65 mordenite mordenite NIU + 8: 1 &gt; 98 0.5 15 25 60 mordenite 100H + 100: 1 93 2 Γ 21 58 Mordenite Na + · SiCU 17,2: 1 &gt; 98 2 38 38 22 Mordenite SiCU «H + 10: 1 97 2 20 51 27 Mordenite NH4 + * SiCU (Invention) 25: 1 97 0.4 27.2 72.1 0.3 S DME + S ΜΗή II-hi I-II— I -II 1- II I- Ding (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs I Chu indicates zeolite Beta and ZSM-12 increases the formation of trimethylamine and dimethylamine generated loss respectively. In fact, the methylamine composition obtained by these zeolites is close to the theoretical value when the mechanical equilibrium between the three methylamines is reached. This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) Printed by the Consumers ’Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 416S40 a? B7 V. Description of the invention (&quot;) Therefore, the production of dimethylamine by these zeolites Not very selective. Furthermore, Table I shows that mordenite generally exhibits good activity and has high methanol conversion. Non-silanized proton mordenites (mordenite mordenite HN4 + and mordenite 100H +) also increase the production of trimethylamine rather than dimethylamine. Silaneized nanomordenite (Mordenite N8 + 'SiClA) is relatively selective for the formation of dimethylamine (38 moles S;). However, its selectivity to trimethylamine is still high (22 mol; S). MS i C 丨 4 treated sodium mordenite that has been converted into a proton mordenite. It is made in accordance with the methods shown in US Patent Nos. 5,137,854 and 5,210,308, and has a higher choice for the production of dimethylamine (51 Mo Ear 3;). However, its selectivity to trimethylamine is still high at 27 萁. Table I clearly shows that the mordenite-based catalyst prepared according to the method of the present invention is superior to other zeolite-based catalysts whether or not they have been treated with SiCl4. In fact, according to the present invention, the ammonium mordenite is treated with tetrachlorosilane in the gas phase and the temperature is increased to become the most selective catalyst for the formation of dimethylamine, with a DMA selectivity of 72.1 mole%; For this catalyst, the formation of trimethylamine and dimethyl ether is low (0.7 mole%, the sum of the two products), and the conversion of formazan is almost complete (97 moles C Example 5 N / C atom In this example, the conditions for synthesizing methylamine were changed to determine the optimal conditions for using the catalyst of the present invention. According to the operating conditions of Example 4, the modified ammonium mordenite produced in Example 1 was used as the catalyst. Catalyst, at 30010, change N / C atomic ratio and methanol feed rate-2 1--1 ^ 1-two-I— t ^^ 1 — ^ 1 two-n (Please read the precautions on the back first (Fill in this page) This paper size is in accordance with Chinese National Standard (CNS) A4 specification (2 丨 0 X 297 mm) 416340 A7 B7 V. Description of invention u〇 (Kg of methanol per kg of catalyst per hour per hour). In Table n, the meanings of cMe0H, sDME, Sm, s_, and STMA are the same as in Example 4. Employees of the Central Bureau of Standards, Ministry of Economic Affairs, Consumer Cooperation Printed table E Atomic ratio N / C MeOH flow rate (kg / hour / kg catalyst) CMeOH S DME SMMfi S DMA S TMA (mole%) 1.3: 1 0.2 &gt; 99 0.8 16.2 77.0 6.0 1.3: 1 0.3 &gt; 99 0,6 17.7 81.6 0.1 1.6: 1 0.2 &gt; 99 0.7 21.1 76.2 2.0 1.6: 1 0.3 &gt; 99 0.5 21.3 77.7 0.4 2.0: 1 0.2 99 0.4 25.5 72.5 1.6 2.0: 1 0.3 97 0.4 27.2 72.1 0.3 At 300 ^ M methanol feed rate of 0.3 (kg / h / kg catalyst), the formation of trimethylamine is almost zero and the dimethylamine is also very low to close to 0.5%, and it is not related to the feed gas. N / C atomic ratio. The paper size of dimethylamine is applicable to China National Standard (CNS) A4 (210X297 mm) I — L --- „----- ^ ------ ir-- ---- Η (Please read the notes on the back before filling this page) 416940 A7 B7 V. Description of the invention (text /) The selection rate can reach 81.6 Moore 5K when the N / C atomic ratio is 1.3. It was proved that the choice of dimethyl group decreased with the increase of the H / C atomic ratio. Example 6 Effect of reaction temperature The reaction was performed under the same conditions as in Example 4 using modified ammonium mordenite prepared in Example 1 Catalyst but react The temperature decreases. The results obtained are shown in Table M. The meanings of CMeOH, SDHE, SMHft, SDMA and STMA are the same as those in Example 4. ------------ Equipment ----- ^-I Order ------ ^ (Please read the notes on the back before filling out this page) Staff Consumption of the Central Bureau of Standards, Ministry of Economic Affairs The cooperative printed table m proves that at low temperatures, in other words, incomplete methanol conversion, the catalyst function of the present invention is still very good; the formation of trimethylamine and dimethyl ether is still very low. Example 7 The synthesis of the stable methylamine of the catalyst was carried out as described in Example 4, using the temperature m prepared in Example 1 and the atomic ratio K / C MeOH flow rate (kg / hour / mm C MeOH S DHE SMHfl S DMA S TMA Catalyzer &gt; (Morch) 280 1.6: 1 0.1 &gt; 98 0.5 20 76 3.5 260 1.6: 1 0.1 64 2 46 52 &lt; 0.1 The paper wave standard is applicable to the Chinese National Standard (CNS) A4 specifications (210X297 mm &gt; 416940 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention! {7.Z) t 1 Modified ammonium mordenite as catalyst 〇 The catalyst is at 30 0 υ, atmospheric pressure Lower guarantee 1 1 for 70 days j Μ Feed gas N / C atomic ratio is 2: 1 and methanol feed rate 1 1 is 0.2 ί kg / hour / kg catalyst) &gt; During this period, the catalyst maintained It requires 1 j activity and the methanol conversion rate is higher than 99 mole%, and the selectivity of dimethylamine is still the same as before. 1 1 remains unchanged at 73 mole%. 〇Back 1 1 1 1 Example 8 Monomethylamine Attention! I'm here In »touch medium of the present invention functions to contain the ammonia and monomethyl amine A matters I 1 I and then mixed fermentation gas methylamine was synthesized to study the composition. The modified 4 manuscript 1 was prepared according to the same conditions as in Example 4, using the actual pickling example 1 page 1 I m mordenite as catalyst &gt; anti-nta- reaction temperature 30 0, but ammonia, formazan and mono 1 1 The gaseous compound of amine was fed into the reactor with a N / C atomic ratio of 2: 1, 1 with a methanol flow rate of 0, 1 kg / hour / kg catalyst, and a methylamine flow rate of 0.2 1 Order the kg / h / kg catalyst. Under these conditions, the methanol conversion rate is higher than 99 1 mol », and the selectivity of the dimethyl limb is 73 mol too. Therefore, it can be concluded that 1 I is the amount of monomethylamine produced. It is easily circulated in the gas mixture 1 1 1 fed to the reactor and can itself be converted into dimethylamine. 1 1 Example 9 1 In this example &gt; Μ dimethylamine-containing ammonia and formic acid mixed gas «rtrir body to synthesize methylamine 1 to study the function of the catalyst of the present invention 〇! M According to the same conditions as in Example 4 4 Proceed, using the modified 1 I m mordenite produced in Cell Example 1 as the catalyst. The reaction temperature was 3 0 0 t: but the gas mixture of ammonia, methanol and trimethylamine was fed into the reactor. The amount of N / C atomic ratio is 2: 1 i 1 methanol flow rate is 0.1 kg / hour / kg catalyst, and trimethylamine flow rate 1. * is 0.067 kg / hour / kg catalyst, Under these conditions, the conversion of methanol to 1 1 -24- i 1 1 1 This paper size is applicable to China National Standard (CNS) A4 (210'〆297 mm> 416940 A7 B7) V. Description of invention (M) 100 mol S; and the selectivity of dimethylamine is 70 mol $. In addition, the amount of trimethylamine found at the reactor outlet is the same as that entering the reactor. 0 ^ n- ^ —. ^ 1 n ^ if I ^^^ 1, I I --- (Please read the note on the back first Items and then Complete this page) book _

Du Yin I, Staff Consumption Cooperation of the Central Bureau of Standards, Ministry of Economic Affairs This paper size is applicable to China National Standard (CNS) A4 (210X297 mm)

Claims (1)

Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, Λ β416Π40 β8 D8 VI. Patent Application No. 85108042 "I method of modified ammonium mordenite, real media i · and the use of methylamine" patent case (&amp; year (Amended in December) Λ Application for patent scope 1. A method for manufacturing modified Araraonium Diordenite, which is characterized by including the following steps: (1) Si / A at a temperature lower than 400 = G 丨An ammonium mordenite having an atomic ratio of 5: 1 to 20: 1 is dried for 180 to 540 minutes, so that the mordenite maintains an ammonium form and the modified mordenite has an Si / Al atom of 10: 1 to 30: 1 The obtained dried ammonium mordenite is treated with tetramethylene silane in the gas phase and at a temperature between 300 and 6001 for 60-180 minutes. 2. The method according to item 1 of the patent application range, wherein the drying step is performed at a temperature in the range of 230 to 350C for 360 to 400 minutes. 3. The method according to item 1 of the patent application, wherein the drying step ⑴ is performed at a pressure of 3 bar or less. 4. The method according to any one of claims 1 to 3, wherein the silylation step &lt; 23 is performed at atmospheric pressure and a temperature of 450 to 5501C for 12Θ to 160 minutes. 5. The method according to item 1 of the patent scope, wherein the atom ratio of S i / A 1 is 15: 1 to 25: 1. 6. — A catalyst binding line containing modified ammonium mordenite prepared by the method of any of claims 1 to 5 of the scope of patent application-(Please read the precautions on the back before filling this one hundred) Applicable to China National Standards (CNS) A4 specifications (210X2mm) 416G40 A8 B8 C8 D8 Application scope of patents, please apply for a change in the scope of the amine project, including the amines that are covered by the t media Alcohols A and 5 and ammonia 0 are used by the first stone in the simmering process with Fan Guangse Lisi 1 and ammonium hypothermia and sulfonic phase. The gas and nitrogen are mixed with the special ammonia which is mixed with the alcohol method A Fang Zhiyi 1 thing 5 amine to a 1 make 5: make 0 kinds for a ratio of 8 to V under 5 bar to M 1 to Di Liwei. The fan who is a fan of gas is a junior college student who is full of energy. Lishen silk has a good quality and contains 22 medium items that change the method to 50%. Item 8 of the French method 8: Fan Li special request 8: Application 8 If 9 is the rate of feeding, the middle of the rule is 0, 8 hours of small law / Fan Fanli special 0 0 Shen Zaoru is in the middle of the term with his legal party 0 0 1 P 20th and 8 V 0th round 2 Fan Zaili is specifically requested to counterclaim his legal party 1 Ren Zhongxiang 50 10 to 1 As for 8 Jie Di Li Confined Fan Fanli should be counter-claimed (please read the precautions on the back before filling this page). Binding-Booking Ministry of Economic Affairs Member of the Central Bureau of Standards, M Consumer Cooperative, printed item 1 of the legal method and item 0, 1 of the amine in the amine. Alcohol amines are required to apply for the three or medium and amines two or the paper size applicable to China National Standard (CNS) A4 specifications (210 × 297 mm)