TW200409743A - Process for preparing succinonitrile and use of succinonitrile - Google Patents

Abstract

The invention relates to a process for preparing succinonitrile by contacting acrylonitrile (ACN) with hydrocyanic acid (HCN) in a reactor in the presence of a tertiary amine. The invention also relates to the use of succinonitrile prepared according to the process of the invention, for preparing diaminobutane. Succinonitrile is prepared by contacting ACN with HCN in the presence of a tertiary amine and a compound chosen from the group consisting of water, aliphatic alcohols, aromatic alcohols, carboxylic acids and mixtures thereof.

Description

200409743 A7 B7 V. Description of the invention (1) (Please read the notes on the back before filling this page) The present invention relates to a method for preparing succinonitrile (SN) by the presence of a tertiary amine in the reactor Next, acrylonitrile (ACN) as a reactant was contacted with hydrocyanic acid (HCN). The invention also relates to the use of succinonitrile (SN) prepared in accordance with the method of the invention to produce diaminobutane (DAB). A method known from DE-A-2,7 1 9,867 for the preparation of SN, based on the reaction of HCN and CAN in the reactor in the presence of a tertiary amine, for which a wide range of tertiary Grade amine. The disadvantage of this known method is the production of tricyanobutane (TCB) as a by-product. SN is known as a crude material for the production of 1,4-diaminobutane by hydrogenation. TCB interferes with hydrogenation processes because it poisons hydrogenation catalysts. Therefore, before hydrogenation, the SN must be purified by, for example, a distillation method. In this distillation method, because of the danger of exothermic polymerization of TCB, SN cannot be distilled off in large quantities and becomes a residue rich in TCB. Therefore, this purification method always results in a large loss of SN. The object of the present invention is to provide a method for preparing an SN, and the amount of TCB relative to SN is relatively low. To achieve the cost target, the method is performed in the presence of a compound selected from the group consisting of water, aliphatic alcohols, aromatic alcohols, carboxylic acids, and mixtures of them. 0 Consumption Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs In the presence of a compound selected from the group consisting of aliphatic alcohols, aromatic alcohols, carboxylic acids, and mixtures thereof, the utility is to reduce the amount of byproduct TCB relative to SN. A further advantage according to the invention is that the purified SN has a better yield. US-2,434,606 discloses a method for preparing SN from ACN and HCN, which method is performed in the presence of an alkaline catalyst. Alkaline catalyst can be alkaline paper size Applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) -5-200409743 A7 B7 V. Description of invention (2) (Please read the precautions on the back before filling this page ) t S hydroxides, alkaline earth metal hydroxides, alkali metal cyanides' metal carbonates or other weak acid salts of alkali metals and organics. Examples given are potassium cyanate, hydrogen Calcium oxide and benzylammonium hydroxide are used as catalysts, and the method is performed in the presence of water. However, a force method patented in US-2,434,606 involves reacting CAN with HCN in the presence of alkaline inorganic cyanide under anhydrous conditions and at a temperature of 30 ° C to 55 ° C. In other examples, the method is performed in the presence of aliphatic amines, and no mention is made of the presence of any water, aliphatic alcohol 'aromatic alcohol or carboxylic acid. No reference is made to the problem of TCB production in connection with processes carried out in the presence of tertiary amines, nor is it possible to carry out processes carried out according to the invention in the presence of water, aliphatic alcohols, aromatic alcohols, carboxylic acids, or mixtures thereof. There are any indications to reduce the generation of TCB. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs According to DE-B-1,007,3 1 3, the use of the catalysts mentioned in U.S.-2,434,606 cited above contains many disadvantages, such as, for example, the obtained product is not pure enough. Therefore, in DE-B-1,007,3 1 3, other catalysts such as the third-stage alkali metal phosphates and alkali metal pyrophosphates have been proposed for the reaction of ACN and HCN to prepare SN. The alkali metal phosphates can be used in the form of anhydrous or crystal water. According to DE-B-1,007,3 1 3, this method is preferably performed with anhydrous ACN and HCN, although a small amount of water such as 1 to 5% can be used without any particular disadvantages. However, larger amounts should be avoided as this can lead to lower yields. DE-B-1,007,3 1 3 does not indicate the problem pointed out by the present invention, nor does it suggest the solution as the present invention. The method of the present invention can be carried out in the following reactor. ACN, HCN, water, aliphatic alcohols, aromatic alcohols, carboxylic acids, and mixtures thereof are added to the paper. The Chinese paper standard (CNS) A4 is applicable for this paper. Specifications (210X297 mm) -6-200409743 A7 B7 V. Description of the invention (3) (Please read the notes on the back before filling this page) Selected compounds, tertiary amines and other optional compounds, such as non-reactive Alkaline diluents, thereby producing compounds selected from the group consisting of ACN, HCN and / or their reaction products, water, aliphatic alcohols, aromatic alcohols, carboxylic acids, and mixtures thereof, tertiary amines, and selective Other compounds appearing in the mixture. The process of the present invention can be carried out in any reactor suitable for the reaction of ACN and HCN. Examples of suitable reactors are, for example, stirred batch reactors, continuous stirred tank reactors, or loop reactors. Any method of assembly is suitable for the method of contacting ACN with HCN to prepare succinonitrile, and it can also be selected to perform the method of the present invention. Appropriate assembly methods such as batch method, continuous method, cascade method or loop method. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs for the purposes of this invention, ACN, HCN, compounds selected from the group consisting of water, aliphatic alcohols, aromatic alcohols, carboxylic acids, and mixtures thereof, and tertiary amines It can be added in a different order than other compounds that are selective. For example, in a batch method, the compound may be supplied before adding ACN or HCN or both, and the compound may be added in parallel or together with either of these two reactants. Compounds can be added or supplemented from different sources or via delivery of any tertiary amine, ACN and HCN, and the compounds can also be supplied from an internal circulating stream. If the compound is a carboxylic acid, the compound can also be supplied in the form of a salt of a carboxylic acid and a tertiary amine. The order of addition of ACN, HCN and tertiary amine is not important for obtaining the desired result of the method. For example, HCN is added to a reactor containing a compound selected from the group consisting of water, aliphatic alcohols, aromatic alcohols, carboxylic acids, and mixtures thereof, tertiary amines, and optionally other compounds such as non-reactive diluents. The contents were mixed, after which ACN was added and mixed with the reactor contents. Or, but not limited to this, after the addition of HCN and CAN, apply the third f paper size to the Chinese National Standard (CNS) A4 specification (210X29? Mm) 200409743 A7 __ B7 V. Description of the invention (4) Amine was added to the reactor. (Please read the notes on the back before filling out this page) In the method of the present invention, a reaction is performed between ACN and HCN. When the reaction is complete, the resulting reaction mixture can be separated, for example, fractionated into different parts under low pressure, containing SN as the main component, and if still present, water, aliphatic alcohols, aromatic alcohols, carboxylic acids, and mixtures thereof Selected compounds from the group, tertiary amines, and / or any excess ACN or HCN. The tertiary amine of the compound and / or if any excess ACN or HCN is still present and thus separated, can be reused in the method described. The concentration of ACN and HCN in the reaction mixture contained in the reactor may change with time and / or location. For example, if the method according to the present invention is performed in a batch method, the concentration will change with time due to the consumption of ACN and HCN, and the reactants are the same. For example, in a well-balanced continuous method, CAN, HCN, tertiary amines, and compounds are preferably added in a stable state. In the latter method, the concentration changes with location, but does not change substantially with time. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs when referring to the (maximum) concentration of any component of a reactant, compound, tertiary amine, or non-reactive diluent present in the reaction mixture (Discussion), this concentration in the batch process is related to the average concentration of the component in the reaction mixture at any given time in the process, while in the continuous process is related to the average concentration of this component in the reactor. In the method according to the present invention, the amount of a compound selected from the group consisting of water, an aliphatic alcohol, an aromatic alcohol, an acid, and a mixture thereof can vary widely. Preferably, the compound is present in an amount of at least 1% relative to the weight of the reactant. The weight of the reactants is equal to the size of the paper supplied to the reaction paper standard (CNS) A4 specification in the batch method (21〇 > < 297 public directors) ^ ------ 200409743 employees of the Bureau of Intellectual Property, Ministry of Economic Affairs Printed by the consumer cooperative A7 B7 V. Description of the invention p) The amount of ACN and HCN in the reactor, or the average amount present in the reactor in a continuous process. When the compound is present in an amount of at least 3% by weight relative to the reactant, an enhanced result of reducing TCB production can be obtained. Even more preferably, the compound is present in an amount of at least% by weight relative to the reactants. This embodiment of the present invention has the advantage that the amount of TCB produced relative to SN is further reduced. Even more preferably, the compound is present in an amount of at least 25% by weight relative to the reactants, and at such a high amount of the compound, the amount of TCB produced is extremely low if present. The amount of compound can be even higher, such as 50% by weight relative to the reactant. The amount is preferably less than 50%, so that the capacity of the reactor can be utilized better. The maximum amount of compounds in the reaction mixture in the reactor is, in principle, limited only by practical reasons, such as optimization of reactor volume utilization. For this reason, the amount of compounds is preferably at most relative to ACN, HCN, and / Or its reaction products, the total amount of compounds selected from the group of water, aliphatic alcohols, aromatic alcohols, carboxylic acids, and mixtures thereof, tertiary amines, and any non-reactive diluents present in the reactor 25% by weight. The amount of the compound is more preferably at most 15% by weight relative to the total amount. This particular example of the invention has the advantage that the relative amount of compounds isolated from the reaction mixture after the process has been performed is limited. In the method according to the present invention, since the compound is selected from the group consisting of water, aliphatic alcohols, aromatic alcohols, carboxylic acids, and mixtures thereof; it is preferred that the compound is selected from the group consisting of water, aliphatic alcohols, and mixtures thereof. Group; more preferably at least the presence of water. Water has a strong reduction effect on the relative amount of TCB produced relative to SN, and its effect has been observed when the amount of water present is extremely low. The paper size applies the Chinese National Standard (CNS) A4 specification (210X; 297 mm) -9-I ----- ^ --- yi ---- Ί .-- 1T ------ (Please read the notes on the back before filling out this page) 200409743 A7 B7 V. Description of the invention p) The best thing is that the compound is composed of water, because water can produce the best results and make the purification of SN easier. (Please read the notes on the back before filling this page) The compound may also contain at least one aliphatic alcohol, preferably a group of aliphatic purely selected from C1-C12 alcohols. Aliphatic alcohols can be straight or branched, and can be first, second, and third alcohols. Suitable aliphatic grades are, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol and 2-ethylhexyl alcohol. More preferred are low-boiling, short-chain aliphatic alcohols, which are more effective per unit weight and have the advantage of being easier to separate from SN by distillation. The compound may also contain at least one aromatic alcohol. Preferred aromatic alcohols are phenols or substituted phenols, most preferably phenols. The use of phenol as a compound results in lower TCB production relative to SN, and increases the conversion of ACN and HCN to SN. The compound may also contain at least one carboxylic acid, which has the advantage of a lower amount of TCB relative to SN and increases the conversion rate of ACN and HCN to SN. More preferably, the carboxylic acid is a carboxylic acid with a short alkyl chain, particularly selected from the group consisting of acetic acid, propionic acid, butyric acid, and isobutyric acid; the most preferred carboxylic acid is acetic acid. This has the advantage that the carboxylic acid compound has a higher efficiency per unit weight. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The method of the present invention is performed in the presence of a tertiary amine. Because there are various compounds of secondary amines, such as heterocyclic tertiary amines, bicyclic tertiary amines, and especially amines of formula (I): R2

R1, R2, and R3 may be an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group, respectively. Suitable tertiary amines are well known in the art ' such as those mentioned in DE-A-2,7 19,867. Preferably, the tertiary amine is a paper size applicable to the Chinese National Standard (CNS) A4 specification (21 × 297 mm) -10 _ 200409743 A7 ____B7 5. Description of the invention (7) trialkylamines. Particularly suitable trialkylamines are low-boiling trialkylamines, such as trialkylamines of formula (I), where R1, R2 and R3 are C1-C4 alkyl groups such as methyl, ethyl, Propyl, isopropyl, n-butyl, secondary butyl, isobutyl and tertiary butyl groups, and low-boiling bicyclic tertiary amines, such as triethylene glycol. More preferably, the low-boiling trialkylamine is trimethylamine, ethyldimethylamine, propyldimethylamine, butyldimethylamine, pentyldimethylamine, triethylamine, Diethylpropylamine, diethylbutylamine, diethylpentylamine, and tripropylamine. Preferably, the tertiary amine is used at a concentration of at least a compound selected from the group consisting of water, aliphatic alcohols, aromatic alcohols, carboxylic acids, and mixtures thereof relative to ACN, HCN and / or reaction products thereof, The total amount of tertiary amine and any non-reactive diluent present in the reactor is 2% by weight, which has the advantage of increasing the conversion rate of ACN and HCN. When the concentration of the tertiary amine exceeds the indicated 2% by weight, it can be changed within a certain limit range. When the concentration is increased to, or exceeds, for example, 20% by weight of the total amount, it can also be used if necessary. For actual needs, a concentration of 3 to 15% by weight relative to the total amount is appropriate. This has the advantage that the reaction rate can be further increased within a limited cost. Most preferably, the tertiary amine is triethylamine. The advantage of triethylamine is that it has a lower boiling point than SN, making it easy to fractionate the amount of ACN to HCN from SN by fractional distillation. It is better to use more ACN than HCN to ensure that all HCN will be converted. It has been found that maintaining ACn is beneficial for limited HCN excess. If the method is carried out in batch method, this paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297mm) -11-(Please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of the Property Bureau, 200409743 A7 ____ B7 V. Invention Description P) (Please read the notes on the back before filling this page) The mole ratio between ACN and HCN is preferably at least 1.00: 1 ACN: HCN, at most Up to 1.25: 1. This has a reduced TCB production relative to the SN production compared to a larger excess. More preferably, the molar ratio of ACN and HCN contact is preferably ACN: HCN at least ι · 〇〇: ι, up to ι.ι〇: ι, if there is TCB, this has the advantage of further reducing its production . In a continuous process, ACN is preferably present in a concentration exceeding HCN. For practical reasons, such as the use of reaction gas volume, the concentration of ACN exceeds HCN by at least 1%; more preferably, the concentration of ACN in the reaction mixture exceeds HCN by at least 3%. It has been found beneficial to maintain a maximum concentration of ACN in the reaction mixture in the reactor. Compared to the method performed at higher ACN concentrations, lower concentrations resulted in lower TCB production relative to SN production. Preferably, the ACN is present at a concentration of at most, relative to ACN, HCN and / or its reaction product, a compound selected from the group consisting of water, aliphatic alcohols, aromatic alcohols, carboxylic acids and mixtures thereof, the third 35% by weight of the total of the primary amine and any non-reactive diluents present in the reactor. Even better, the maximum ACN concentration is less than 20% by weight relative to the total, because this results in an even lower amount of TCB. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. One way to control ACN concentration is to perform this method in a non-reactive diluent. A non-reactive diluent is a liquid that is inert to ACN, HCN, tertiary amines, and compounds selected from the group consisting of water, aliphatic alcohols, aromatic alcohols, carboxylic acids, and mixtures thereof, and can be used as Solvents or diluents for these substances. The advantage of performing this method in this way is that the reaction mixture contains a non-reactive diluent, ACN can be kept at a low concentration, and the amount of TCB produced relative to the amount of SN produced is low. Appropriate reactive diluents such as hexane, toluene, and the size of this paper are applicable to Chinese National Standard (CNS) A4 specifications (210X 297 mm) -12-" '200409743 Printed by A7 ____B7 of the Intellectual Property Bureau of the Intellectual Property Bureau of the Ministry of Economic Affairs Description of the invention (9) SN; Preferably, the non-reactive diluent is SN. More preferably, the SN is present in an amount of at least a compound selected from the group consisting of water, aliphatic alcohols, aromatic alcohols, carboxylic acids, and mixtures thereof with respect to ACN, HCN, and / or their reaction products. 40% by weight based on the total amount of tertiary amine and succinonitrile present in the reactor. SN can even be present in extremely high amounts; for reasons of process efficiency, this amount, for example, does not exceed 95% by weight relative to the total amount. The method is advantageously carried out in a temperature range of about 50 ° C to about 110 ° C, preferably 60 ° C to 80 ° C, and usually at atmospheric pressure, although other pressures may be used. If necessary, the temperature can be controlled by external heating and cooling. Succinonitrile (SN) is a useful product, known as a crude raw material for the preparation of, for example, 1,4-diaminobutane, which can be used, for example, for the preparation of polymer Lamine_4,6. In the method for preparing diaminobutane from SN, SN is hydrogenated in the presence of a hydrogenation catalyst. The problem with this method is that TCB interferes with hydrogenation by poisoning the hydrogenation catalyst. This problem can be at least mitigated or completely solved using the SN prepared according to the method of the present invention. Therefore, the present invention also relates to a method for preparing diaminobutane using SN prepared according to the method of the present invention. The invention particularly relates to a method for preparing 1,4-diaminobutane (DAB), which comprises the step a) contacting acrylonitrile (ACN) with hydrocyanic acid (HCN) in the presence of a tertiary amine. , B) separating succinonitrile (SN) from the reaction mixture of step a), c) hydrogenating the SN of step b) with a suitable hydrogenation catalyst, d) separating DAB from the reaction mixture of step c). This method has the advantages that the yield of TCB relative to SN is lower in step a), the loss of SN can be reduced in step b), and the risk of poisoning the hydrogenation catalyst due to TCB in step c) can be measured on this paper. Shicai Guanjia County (CNS) A4 specifications (210X297 mm): 13-— '(Please read the precautions on the back before filling this page) • Installation.

1T — Λ 200409743 A7 B7 V. Description of the invention (10) Keep better under control. This method is particularly advantageous when the compound used is water. As for the tertiary amine, triethylamine is preferred. (Please read the notes on the back before filling out this page) The following non-limiting examples will further illustrate the present invention. Methods To determine the TCB content in the reaction mixture using a gas chromatograph, a Hewlett Packard gas chromatograph, HP 5890, Series II, equipped with a column HP-5, 25 m in length, 0.3 2 in diameter mm, the material is fused silica, the static phase is HP-5, and the film thickness is 1.05 μm. The temperature program is set to an initial temperature of 80 ° C, a heating rate of 10 ° C / min, and an end temperature of 250 ° C. The carrier gas is ammonia, with an average linear gas velocity of 25 cm / s. Prepare a sample of about 0.1-4% in water / pyridine (1: 1 by volume). A 10 μΐ sample was placed in the autosampler, and 1.0 μΐ was injected with a split ratio of 1: 100 at a injection temperature of 25 ° C. A flame-free detector was used in the analysis at a temperature of 300 ° C and a range of 3 The obtained chromatogram peaks are integrated by Packard LDS data system to determine the peak area. The concentration of the components is determined based on the peak area with the help of internal standards. The HCN titration printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs To determine the HCN content in the reaction mixture, 1 g of a sample of the reaction mixture was dissolved in about 10 ml of IN NaOH and stirred at room temperature for 1 hour. After adding about 75 ml of water, 0.01 mol / L silver nitrate (AgN03) ) Titrate this solution. The equilibrium point is based on the ion-selective Ag / Ag2S electrode with respect to the double junction. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -14-200409743 A7 B7 V. Description of the invention) Reference The electrode is measured. Example 1 (Please read the precautions on the back before filling this page) 150 ml double glass reactor with turbo stirrer and baffle and circulating cooler filled with 50 g of succinonitrile, 0.5 g of water and 10 g of triethyl Based amine. The temperature of the circulating cooler was maintained at 9 ° C, while the reactor contents were heated to 70 ° C. Then 20.0 grams of ACN and 9.3 grams of HCN were added simultaneously within 30 seconds. The reaction was then titrated to determine the HCN content until HCN was completely converted. The content of TCB in the reaction mixture was measured with a gas chromatograph and expressed as a percentage of the total reaction mixture. The resulting TCB content report is shown in Table I. Example 2 Example 2 was performed in the same manner as Example 1 except that 0.5 g of water was charged into the reactor instead of 0.5 g of water. The resulting TCB content report is shown in Table 1. Example 3 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Example 3 was performed in the same manner as Example 1 except that 0.5 g of water was filled into the reactor with 10 g of water. The resulting TCB content report is shown in Table 1.

Comparative experiment A Comparative experiment A was performed as in Example 1 except that the leeches were not charged to the reactor. The resulting TCB content report is shown in Table 1. This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -15-200409743 A7 B7 V. Description of the invention C12) Test and obtained TCB content and selectivity experiment / comparative ACN quantity HCN of water Quantity reactor quality TCB analysis TCB content TCB selection test (g) Quantity (g) (g) Weight% (mMol) Sex (%) Comparative experiment A 20 9.3 0 89.3 0.22 1.48 0.43 Experiment 1 20 9.3 0.5 89.8 0.175 1.18 0.34 Experiment 2 20 9.3 1.0 90.3 0.095 0.65 0.19 Experiment 3 20 9.3 10.0 99.3 0 0 0.0 (Please read the notes on the back before filling this page) The TCB content is calculated as follows: TCB content (m Μ ο 1) =

(Total mass of reactor contents) · (TCB weight%) · 10) / (Molar weight of TCB) and the selectivity of TCB is calculated as follows: D CB selectivity (%) = TCB content (ιπΜο1) · 100 / ( Added HCN (mMol)) · (HCN conversion) where the molar weight of TCB is 133, the added HCNin is 344 mMol, and the conversion of HCN is 1. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. It can be seen from Table I that when water is present in the reaction mixture, the amount of TCB produced in the method for producing succinonitrile from ACN and HCN in the presence of tertiary amine Will reduce. The results further show that when a large amount of water is present, TCB production is low. .

Comparative Example B A 150 ml double paper size with a turbo agitator and a baffle plate and a circulating cooler is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ~ " 200409743 Μ_Β7_ V. Description of the invention (13) ( Please read the notes on the back before filling this page) The glass reactor is filled with 50 g of succinonitrile and 11 ml (8.0 g) of triethylamine. The temperature of the circulating cooler was maintained at -9 ° C, while the reactor contents were heated to 70T :. Then 20.0 ml ACN (16.1 g, 300 mMol) and 10.6 ml (7.3 g, 270 mMol) HCN were added simultaneously within 30 seconds. After 30 minutes, a sample was taken from the reaction mixture, and the TCB content and HCN content in the reaction mixture were measured by a gas chromatograph, expressed as a percentage of the total reaction mixture. The obtained TCB content, HCN conversion and TCB selectivity report are shown in Table Π. Example 4 Experiment 4 was performed as comparative experiment B, except that succinonitrile and triethylamine were added and 5 ml (4.0 g) of methanol was pre-filled into the reactor. The resulting TCB content, HCN conversion and TCB selectivity report are shown in Table II. Example 5 Experiment 5 was performed as comparative experiment B, except that succinonitrile and triethylamine were added and 5 ml of g) ethanol was pre-filled into the reactor. The resulting TCB content, HCN conversion and TCB selectivity report are shown in Table II. Example 6 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, except that succinonitrile and triethylamine were added and 5 ml (4.0 g) of the third-level butanol was pre-filled into the reactor, Experiment 6 was similar to comparison Sexual experiment β was performed. The resulting TCB content, HCN conversion, and TCB selectivity report are as 袠 n. Example 7 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 200409743 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (14) ^-In addition to adding succinonitrile and three Ethylamine was pre-charged with 3.7 (3.9 g: phenol was removed from the reactor, and Experiment 7 was performed as a comparative experiment. The resulting TCB content, HCN conversion, and TCB selectivity were reported as 袠 π. Example 8 Except that succinonitrile and triethylamine were added and 4 ml (4.2 g) of acetic acid was prefilled into the reactor, experiment 8 was performed as comparative experiment B. The obtained TCB content, HCN conversion and TCB selectivity The report is shown in Table II. Table II. Experiments and TCB content obtained and selectivity / comparative experiment compound amount (g) TCB analysis (min%) TCB content (mMol) HCN conversion TCB selectivity (%) comparative experiment B 0.11 0.92 0.80 0.43 Example 4 Methanol 4.0 0.05 0.43 1.0 0.16 Example 5 Ethanol 3.9 0.07 0.61 0.97 0.23 Example 6 Tertiary butanol 4.0 0.10 0.86 0.99 0.32 Example 7 Phenol 3.9 0.04 0.35 1.0 0.13 Example 8 Acetic acid 4.2 0.11 0.92 1.0 0.34 TCB content Calculation As follows: TCB content (ιήΜο1) =

(Total mass of reactor contents) · (TCB weight%) · 10) / (Molar weight of TCB) and the selectivity of TCB is calculated as follows: TCB selectivity (%) = 1 ------- ^- --II ------ Λ. (Please read the notes on the back before filling in this page) The paper size applies to the Chinese National Standard (CNS) Α4 specifications ί 210 × 297 mm -18- 200409743 ΑΊ _ _ Β7_ 5 Description of the invention (15) TCB content (mMol). 100 / (added HCN (mMol)) · (HCN conversion) where the molar weight of TCB is 133, the added HCNin is 270 mMol 'and the content of the reactor contents The total mass is 111 g when not added, and about 115 g when added. As can be seen from Table II, when an alcohol or a carboxylic acid is present in the reaction mixture, the amount of TCB produced in the method for producing succinonitrile from ACN and HCN is reduced in the presence of a tertiary amine. The results further show that compared to comparative experiment B, in the absence of additional compounds selected from the group of water, aliphatic alcohols, aromatic alcohols, carboxylic acids, and mixtures thereof, when alcohol or HCN conversion is higher for carboxylic acids. .----- (Please read the notes on the back before filling this page)

、 1T -4 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -19-

Claims (1)

200409743 A8 B8 C8 D8 6. Application for patent scope 1 1. A method for preparing succinonitrile (SN), in the presence of a tertiary amine, ordering hydrocyanic acid (HCN) as a reactant in the reactor Contact with propionitrile (ACN), which is characterized in that the method is performed in the presence of a compound selected from the group consisting of water, aliphatic alcohols, aromatic alcohols, carboxylic acids and mixtures thereof. The method of item 1, wherein the compound is selected from the group consisting of water, an aliphatic alcohol, and a mixture thereof. 3. The method of claim 1 in the scope of patent application, characterized in that the compound is present in an amount of at least 1% by weight relative to the reactant. 4. The method of claim 1 in the scope of patent application, characterized in that the compound contains water. 5. The method of claim 1 in the scope of patent application, characterized in that the compound contains an aliphatic alcohol selected from the group of C1-C12 alcohols. 6. The method of claim 1 in the scope of patent application, characterized in that the compound contains phenol or substituted phenol. 7. The method according to item 1 of the scope of patent application, characterized in that the compound contains a carboxylic acid selected from the group of acetic acid, propionic acid, butyric acid and isobutyric acid. 8. The method of claim 1 in the scope of patent application, characterized in that the tertiary amine is a trialkylamine. 9. The method of claim 8 in the scope of patent application, characterized in that the trialkylamine is triethylamine. i. The method according to item 1 of the scope of patent application, characterized in that the tertiary amine is present at a concentration relative to ACN, HCN and / or its reaction product, from water, aliphatic alcohol, aromatic alcohol, carboxylic acid In the group consisting of acids and their mixtures ------.----- (Please read the notes on the back before filling out this page) Order printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs This paper applies Chinese national standards (CNS) A4 specification (210 X 297 mm) -20- 200409743 A8 B8 C8 D8 VI. Patent application scope 2 The total of the selected compound, the tertiary amine and any non-reactive diluent present in the reactor The amount is at least 2% by weight. 1 1. The method according to item 1 of the scope of patent application, characterized in that the molar ratio between ACN and HCN contact is at least 1.0: 1 from ACN: HCN, up to 1.25: 1. 0 2. A method characterized by the presence of ACN in a compound selected from the group consisting of water, aliphatic alcohols, aromatic alcohols, carboxylic acids, and mixtures thereof with respect to ACN, HCN and / or its reaction products, a third The total amount of primary amine and any non-reactive diluent present in the reactor is at most 35 weight percent. 1 3. The method according to item 1 of the scope of patent application, characterized in that the method is performed in the presence of a non-reactive diluent. 14. The method according to item 13 of the scope of patent application, characterized in that the non-reactive diluent is succinonitrile. 15. The method according to item 14 of the scope of patent application, characterized in that the succinonitrile is present at a concentration relative to ACN, HCN and / or its reaction product, from water, aliphatic alcohols, aromatic alcohols, carboxylic acids and The total amount of the compound selected from the group consisting of the mixture, the tertiary amine, and the succinonitrile present in the reactor was at least 40% by weight. 16. The method according to item 1 of the scope of patent application is characterized in that the method is performed at a temperature between 60 ° C and 8CTC. 17. The method according to any one of claims 1 to 16 in the scope of patent application, wherein the succinonitrile prepared is used to prepare diaminobutane. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) ---, I,-(Please read the precautions on the back before filling this page) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, 200409743 If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: formula (I): R1 -3-