Process for the synthesis of 1-chlorobutane by means of a fixed-bed gas-solid catalytic reaction

Abstract

The application belongs to the technical field of organic synthesis, and particularly relates to a method for synthesizing 1-chlorobutane through a fixed-bed gas-solid catalytic reaction. The method comprises the following steps: loading an activated carbon supported catalyst into a fixed-bed reactor; the active component of the activated carbon supported catalyst is composed of ZnCl2, FeCl3 and KCl; preheated hydrogen chloride and vaporized n-butanol are introduced into the fixed-bed reactor to contact the activated carbon supported catalyst to perform a catalytic reaction, and a mixed gas containing 1-chlorobutane is obtained; and after cooling, the mixed gas is subjected to gas-liquid separation to obtain 1-chlorobutane. The method uses n-butanol and hydrogen chloride as raw materials, loads the activated carbon supported catalyst into the fixed-bed reactor, and continuously produces 1-chlorobutane through a gas-solid catalytic reaction, thereby overcoming many deficiencies existing in the current production route of 1-chlorobutane through a liquid phase method and the use of an alumina and molecular sieve catalyst through a gas phase method.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of organic synthesis, and particularly relates to a method for synthesizing 1-chlorobutane through fixed-bed gas-solid catalytic reaction. BACKGROUND

[0002] Currently, the preparation methods of 1-chlorobutane include zinc chloride catalytic concentrated hydrochloric acid chlorination method, chlorosulfur dioxide chlorination method, phosphorus trichloride chlorination method and triphenylphosphine catalytic sodium chloride chlorination method, etc. The above preparation methods are all liquid phase reactions. The speed of substitution reaction of hydrogen chloride and n-butanol is slow, and in the traditional process, zinc chloride needs to be used as a catalyst in the liquid system, which will generate a large amount of salt-containing wastewater that is difficult to handle. The subsequent existing technology improvement uses chlorosulfur dioxide, phosphorus trichloride, ionic liquid, etc. as catalysts or reaction aids, which also cannot avoid the shortcomings of liquid phase method itself: back mixing of products and raw materials and intermittent reaction. Back mixing will lead to continuous decrease of reactant concentration, further slow down of reaction speed, long reaction time and low instantaneous yield, etc.; and the intermittent reaction process is not conducive to continuous production, and the production efficiency is low.

[0003] Patent CN104326863A discloses a preparation method of 1-chlorobutane, which uses hydrogen chloride and n-butanol as raw materials, and dimethyl sulfoxide as a catalyst to prepare 1-chlorobutane. The reaction residue is passed into hydrogen chloride gas, and the hydrogen chloride is reused by increasing the concentration of hydrogen chloride. The chlorination reaction process of the preparation method is slow, which needs 20-24 hours, and is not conducive to industrial application.

[0004] In order to solve the above technical problems existing in the liquid system, the fixed-bed catalytic technology has been used for the preparation of 1-chlorobutane. For example, patent CN118666633A discloses a method for continuously synthesizing 1-chlorobutane through fixed-bed catalytic oxidation, which uses alumina or molecular sieve carrier to impregnate nickel, lanthanum, aluminum, copper metal salt ions to prepare a catalyst. The catalyst is the core of the fixed-bed gas-solid catalytic reaction technology, but in the above technology, the treatment of waste alumina and molecular sieve catalyst becomes a problem, which generally needs to be landfilled. At the same time, the prices of carrier alumina, molecular sieve and active component raw materials lanthanum salt and nickel salt are relatively high, which greatly increases the production cost. SUMMARY

[0005] The present application aims to provide a method for synthesizing 1-chlorobutane through fixed-bed gas-solid catalytic reaction, which uses n-butanol and hydrogen chloride as raw materials, fills the active carbon supported catalyst in the fixed-bed reactor, and continuously produces 1-chlorobutane through gas-solid catalytic reaction, so as to overcome the many shortcomings of the existing liquid phase production route of 1-chlorobutane and the use of alumina and molecular sieve catalysts in gas phase method.

[0006] The specific technical solution is as follows:

[0007] A method for synthesizing 1-chlorobutane by fixed-bed gas-solid catalytic reaction, comprising the following steps:

[0008] (1) loading the activated carbon supported catalyst into a fixed-bed reactor;

[0009] The active component of the activated carbon supported catalyst is composed of ZnCl2, FeCl3 and KCl; wherein the mass ratio of ZnCl2: FeCl3: KCl is 1: (0.05-0.2): (0.05-0.15). FeCl3 can adjust the acidity of the catalyst, improve the selectivity of the reaction, and increase the yield; the potassium element in KCl can effectively reduce the carbon deposition generated by the catalytic reaction, prolonging the service life of the catalyst.

[0010] The active component is uniformly loaded on the surface and pores of the carrier activated carbon, and the loading amount of the active component is 15%-20% of the total mass of the activated carbon supported catalyst.

[0011] (2) passing preheated hydrogen chloride and vaporized n-butanol into the fixed-bed reactor to contact with the activated carbon supported catalyst, wherein the molar ratio of hydrogen chloride to n-butanol is (1-2): 1;

[0012] The catalytic reaction is carried out under the conditions of a reaction temperature of 150-250℃, a reaction pressure of 0.01-0.5MPa, and an n-butanol space velocity of (0.1-2)h -1 , to obtain a mixed gas containing 1-chlorobutane. After cooling the mixed gas, gas-liquid separation is carried out to obtain 1-chlorobutane.

[0013] In the present application, the activated carbon supported catalyst in step (1) of the method for synthesizing 1-chlorobutane by fixed-bed gas-solid catalytic reaction is a cylindrical particle with a diameter of Φ5mm and a length of (4-7)mm.

[0014] In the present application, the activated carbon supported catalyst in step (1) of the method for synthesizing 1-chlorobutane by fixed-bed gas-solid catalytic reaction is prepared by the following steps:

[0015] 1) adding activated carbon to a nitric acid solution, stirring, then suction filtering, washing with deionized water until neutral, and drying to obtain an activated carbon carrier; the activated carbon soaked in nitric acid can significantly increase the number of oxygen-containing groups on the surface of the activated carbon, enhance the surface polarity, and significantly improve the adsorption performance.

[0016] Activated carbon is prepared from wood, coal and petroleum coke and other carbon-containing raw materials by pyrolysis and activation, and has wide sources and low price, and has developed pore structure, large specific surface area and rich surface chemical groups, and has the function of anchoring metal active components; meanwhile, it is beneficial to improve the dispersion of metal components. In addition, carbon materials can be completely combusted, and when the catalyst is deactivated, a combustion aid can be added for direct combustion treatment.

[0017] 2) ZnCl2, FeCl3 and KCl are added to deionized water, stirred uniformly, and a mixed salt solution is prepared.

[0018] 3) The activated carbon carrier prepared in step 1) is immersed in the mixed salt solution prepared in step 2), stirred, and then placed, and after the solvent is evaporated in a water bath, drying is performed, and the activated carbon supported catalyst is obtained.

[0019] In the application, in the preparation step 1) of the activated carbon supported catalyst, 1.5-2.5 mL of nitric acid solution is added to each gram of activated carbon; wherein the concentration of the nitric acid solution is 1-12 mol / L.

[0020] Preferably, in the preparation step 1) of the activated carbon supported catalyst, 2 mL of nitric acid solution is added to each gram of activated carbon, and the concentration of the nitric acid solution is 4-10 mol / L.

[0021] Preferably, in the preparation step 1) of the activated carbon supported catalyst, the stirring speed is 50 rpm-100 rpm, and the stirring time is 4 h-6 h; and the drying time is 4 h-6 h.

[0022] Preferably, in the preparation step 3) of the activated carbon supported catalyst, the standing time is 1 h-4 h, and the drying time is 4 h-6 h.

[0023] In the application, in the step (2) of the method for synthesizing 1-chlorobutane by fixed bed gas-solid catalytic reaction, the preheating temperature of hydrogen chloride is 160-230℃, and the vaporization temperature of n-butanol is 160-230℃.

[0024] In the application, in the step (2) of the method for synthesizing 1-chlorobutane by fixed bed gas-solid catalytic reaction, the cooling and gas-liquid separation are specifically operated as follows:

[0025] First, the obtained mixed gas containing 1-chlorobutane is heat-exchanged and cooled in a condenser at a temperature of 10-25℃;

[0026] Then, the cooled mixed gas containing 1-chlorobutane is subjected to gas-liquid separation by using a gas-liquid separator to obtain a mixed liquid phase and a gas phase; the material of the gas-liquid separator can be fluorine-lined stainless steel 316L;

[0027] Wherein, the gas phase is treated by lye, and the unreacted hydrogen chloride contained in the gas phase is absorbed by the lye;

[0028] The obtained mixed liquid phase is allowed to stand and stratify, and the upper organic phase is the product 1-chlorobutane.

[0029] In the application, the fixed bed reactor is a tube fixed bed reactor with a specification of Φ38mm*4mm*2000mm. The material of the fixed bed reactor can be 316L.

[0030] The method for synthesizing 1-chlorobutane by fixed bed gas-solid catalytic reaction has the following advantages: the method uses n-butanol and hydrogen chloride as raw materials, fills the activated carbon supported catalyst in the fixed bed reactor, and continuously produces 1-chlorobutane by gas-solid catalytic reaction, which overcomes many deficiencies of the existing 1-chlorobutane liquid phase production route and the use of alumina and molecular sieve catalysts in the gas phase method.

[0031] In the provided method for synthesizing 1-chlorobutane, the activated carbon supported catalyst is prepared by impregnating the active components composed of zinc chloride, iron chloride and potassium chloride on the surface and pores of the activated carbon carrier. After impregnation, high temperature calcination is not required, which avoids the generation of toxic and harmful waste gas. Activated carbon is a widely available biomass material, and waste activated carbon catalyst can be recycled and treated by incineration, which is green and environmentally friendly. The catalyst is simple and easy to prepare, and belongs to an environmentally friendly and low-cost catalyst. The catalyst can adapt to long-term production and maintain stable performance, greatly reducing the production cost of industrial synthesis of 1-chlorobutane. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 The gas chromatogram of the product 1-chlorobutane prepared in Example 1.

[0033] Figure 2 The yield of 1-chlorobutane prepared in Example 1 as a function of time. DETAILED DESCRIPTION

[0034] The application will be further described below in combination with examples, comparative examples and drawings.

[0035] In the examples and comparative examples of the application, the raw materials and reagents used are commercially available raw materials and reagents, and their specific sources are not described here.

[0036] Example 1

[0037] The method for synthesizing 1-chlorobutane by fixed bed gas-solid catalytic reaction has the following advantages: the method uses n-butanol and hydrogen chloride as raw materials, fills the activated carbon supported catalyst in the fixed bed reactor, and continuously produces 1-chlorobutane by gas-solid catalytic reaction, which overcomes many deficiencies of the existing 1-chlorobutane liquid phase production route and the use of alumina and molecular sieve catalysts in the gas phase method.

[0038] (1) Preparation of activated carbon supported catalyst:

[0039] First, 10 kg of activated carbon was added to a 20 L solution of nitric acid with a concentration of 5 mol / L, stirred for 5 h, and then suction filtered, washed with deionized water until neutral, and then dried for 5 h to obtain an activated carbon carrier.

[0040] Then, 1.7 kg of zinc chloride, 0.2 kg of iron chloride, and 0.2 kg of potassium chloride were added to deionized water to prepare a 5 L mixed salt solution; the mass ratio of zinc chloride: iron chloride: potassium chloride was 1:0.12:0.12.

[0041] Finally, the activated carbon carrier was immersed in the mixed salt solution, stirred uniformly, and allowed to stand for 4 h, then the solvent was evaporated in a water bath, and dried to obtain an activated carbon supported catalyst.

[0042] The loading of the active component in the activated carbon supported catalyst was 17.4 wt%. Note: 2.1 / (2.1+10)=17.4% was calculated.

[0043] (2) 1 L of the activated carbon supported catalyst obtained in step (1) was loaded into a fixed bed reactor, the reactor specifications were Φ 38 mm x 4 mm x 2000 mm, the inner diameter was 38-2 x 4=30 mm, the catalyst loading was 1 L, and the calculated loading height of the catalyst was 1.41 m.

[0044] (3) Hydrogen chloride preheated to 180°C and vaporized n-butanol at 180°C were introduced into the fixed bed reactor, and the catalytic reaction was carried out under the conditions of a reaction temperature of 180°C, a reaction pressure of 0.1 MPa, a molar ratio of hydrogen chloride to n-butanol of 1.3:1, and a n-butanol volume space velocity of 0.3 h -1 to obtain a mixed gas containing 1-chlorobutane.

[0045] (4) The mixed gas containing 1-chlorobutane obtained was introduced into a condenser and cooled at 10°C to separate the gas and liquid phases, obtaining a mixed liquid phase of 1-chlorobutane and hydrochloric acid and a gas phase of unreacted hydrogen chloride; the gas phase hydrogen chloride was absorbed by alkali liquor; the mixed liquid phase was allowed to stand and separate into layers, and the upper organic phase was the product 1-chlorobutane.

[0046] After 1200 h of continuous reaction, the yield of the product 1-chlorobutane was 93.8%, and the GC purity of the product was 99.624%.

[0047] The gas chromatogram of the product 1-chlorobutane obtained in this example is shown in Figure 1. Figure 1The test conditions of the gas chromatogram shown are as follows: chromatographic column (7% cyanopropyl-7% phenyl-86% methyl polysiloxane capillary chromatographic column, 30 m x 0.32 mm x 1.0 μm); initial column temperature 50 °C, raised to 200 °C at a rate of 10 °C per minute, and maintained for 5 minutes; vaporization chamber temperature 200 °C; detection chamber temperature 200 °C; nitrogen carrier gas, flow rate 4 mL per minute; split ratio 30:1; sample size 0.2 μL; FID detector.

[0048] Figure 1 The peak table of the spectrum shown is shown in Table 1.

[0049] Table 1 Peak Table

[0050]

[0051] By Figure 1 In combination with the peak table of Table 1, it can be seen that the method provided in Example 1 successfully synthesized 1-chlorobutane.

[0052] Example 2

[0053] The difference between this example and Example 1 is that in step (3) of this example, the preheated hydrogen chloride to 200 °C and the vaporized n-butanol at 200 °C are passed into the fixed bed reactor, the reaction temperature is 200 °C, the reaction pressure is 0.25 MPa, the molar ratio of hydrogen chloride to n-butanol is 1.01:1, and the volume space velocity of n-butanol is 0.5 h -1 .

[0054] The others are the same as in Example 1.

[0055] After 1200 h of continuous reaction, the yield of the product 1-chlorobutane was 92.6%, and the GC purity of the product was 99.505%.

[0056] Example 3

[0057] The difference between this example and Example 1 is that in step (3) of this example, the preheated hydrogen chloride to 160 °C and the vaporized n-butanol at 160 °C are passed into the fixed bed reactor, the reaction temperature is 160 °C, the reaction pressure is 0.05 MPa, the molar ratio of hydrogen chloride to n-butanol is 1.15:1, and the volume space velocity of n-butanol is 0.1 h -1 .

[0058] The others are the same as in Example 1.

[0059] After 1200 h of continuous reaction, the yield of the product 1-chlorobutane was 93.5%, and the GC purity of the product was 99.637%.

[0060] Example 4

[0061] The difference between this embodiment and example 1 is that in step (3) of this embodiment, hydrogen chloride preheated to 190°C and vaporized n-butanol at 190°C are introduced into the fixed bed reactor, the reaction temperature is 190°C, the reaction pressure is 0.15 MPa, the molar ratio of hydrogen chloride to n-butanol is 1.3:1, and the volume space velocity of n-butanol is 0.6 h -1 .

[0062] The other steps are the same as example 1.

[0063] After 1200h of continuous reaction, the yield of product 1-chlorobutane is 92.2%, and the GC purity of the product is 99.440%.

[0064] Example 5

[0065] The difference between this embodiment and example 1 is that in step (1) of this embodiment, the metal salt used is 2.0 kg of zinc chloride, 0.1 kg of iron chloride, and 0.1 kg of potassium chloride. Among them, the mass ratio of zinc chloride: iron chloride: potassium chloride is 1:0.05:0.05.

[0066] In step (3), hydrogen chloride preheated to 190°C and vaporized n-butanol at 190°C are introduced into the fixed bed reactor, the reaction temperature is 190°C, the reaction pressure is 0.15 MPa, the molar ratio of hydrogen chloride to n-butanol is 1.2:1, and the volume space velocity of n-butanol is 0.8 h -1 .

[0067] The other steps are the same as example 1.

[0068] In this embodiment, the content of the active component in the activated carbon catalyst is 18.0wt%.

[0069] After 1200h of continuous reaction, the yield of product 1-chlorobutane is 91.9%, and the GC purity of the product is 99.511%.

[0070] Example 6

[0071] The difference between this embodiment and example 1 is that in step (1) of this embodiment, the metal salt used is 1.5 kg of zinc chloride, 0.3 kg of iron chloride, and 0.15 kg of potassium chloride. Among them, the mass ratio of zinc chloride: iron chloride: potassium chloride is 1:0.2:0.1.

[0072] In step (3), hydrogen chloride preheated to 210°C and vaporized n-butanol at 210°C are introduced into the fixed bed reactor, the reaction temperature is 210°C, the reaction pressure is 0.2 MPa, the molar ratio of hydrogen chloride to n-butanol is 1.5:1, and the volume space velocity of n-butanol is 1.3 h -1 .

[0073] The other steps are the same as example 1.

[0074] The content of the active component in the activated carbon catalyst in this embodiment is 16.3wt%.

[0075] After continuous reaction for 1200h, the yield of the product 1-chlorobutane is 92.0%, and the GC purity of the product is 99.530%.

[0076] Example 7

[0077] The difference between this embodiment and Example 1 is that the metal salt used in Step (1) in this embodiment is 1.4kg of zinc chloride, 0.25kg of iron chloride, and 0.20kg of potassium chloride. Among them, the mass ratio of zinc chloride: iron chloride: potassium chloride is 1:0.18:0.14.

[0078] In the step (3), hydrogen chloride preheated to 220℃ and vaporized n-butanol at 220℃ are introduced into the fixed bed reactor, the reaction temperature is 220℃, the reaction pressure is 0.3MPa, the molar ratio of hydrogen chloride to n-butanol is 1.1:1, and the volume space velocity of n-butanol is 2.0h -1 .

[0079] The others are the same as Example 1.

[0080] The content of the active component in the activated carbon catalyst in this embodiment is 15.6wt%.

[0081] After continuous reaction for 1200h, the yield of the product 1-chlorobutane is 91.4%, and the GC purity of the product is 99.614%.

[0082] Comparative Example 1

[0083] The difference between this embodiment and Example 1 is that the metal salt used in Step (1) in this embodiment is 1.7kg of zinc chloride, 0.20kg of iron chloride. That is, the active component of the catalyst in this comparative example is zinc chloride and iron chloride.

[0084] The others are the same as Example 1.

[0085] In this comparative example, the loading amount of the active component in the activated carbon supported catalyst is 16.0wt%.

[0086] After continuous reaction for 600h, the yield of the product 1-chlorobutane is 92.8%, and the GC purity of the product is 99.578%.

[0087] When the continuous reaction is carried out for 650h, the reactor bed is blocked due to serious carbon deposition.

[0088] Comparative Example 2

[0089] The difference between this embodiment and Example 1 is that the metal salt used in Step (1) in this embodiment is 1.7kg of zinc chloride, 0.20kg of potassium chloride. That is, the active component of the catalyst in this comparative example is zinc chloride and potassium chloride.

[0090] Other than Example 1.

[0091] In this comparative example, the loading of the active component in the activated carbon supported catalyst was 16.0 wt%.

[0092] After 1200 h of continuous reaction, the yield of the product 1-chlorobutane was 88.6% and the GC purity of the product was 99.052%.

[0093] Comparative Example 3

[0094] The difference between this comparative example and Example 1 is that the metal salt used in Step (1) of this comparative example was 1.7 kg of zinc chloride, 0.05 kg of iron chloride, and 0.05 kg of potassium chloride.

[0095] That is, the mass ratio of zinc chloride: iron chloride: potassium chloride was 1:0.03:0.03.

[0096] Other than Example 1.

[0097] In this comparative example, the loading of the active component in the activated carbon supported catalyst was 15.3 wt%.

[0098] After 1200 h of continuous reaction, the yield of the product 1-chlorobutane was 89.1% and the GC purity of the product was 99.102%.

[0099] Comparative Example 4

[0100] The difference between this comparative example and Example 1 is that the metal salt used in Step (1) of this comparative example was 0.85 kg of zinc chloride, 0.1 kg of iron chloride, and 0.1 kg of potassium chloride.

[0101] That is, the mass ratio of zinc chloride: iron chloride: potassium chloride was 1:0.12:0.12.

[0102] Other than Example 1.

[0103] In this comparative example, the loading of the active component in the activated carbon supported catalyst was 9.5 wt%.

[0104] After 1200 h of continuous reaction, the yield of the product 1-chlorobutane was 75.7% and the GC purity of the product was 99.033%.

[0105] Comparative Example 5

[0106] The difference between this comparative example and Example 1 is that the metal salt used in Step (1) of this comparative example was 1.7 kg of copper chloride and 0.2 kg of cobalt chloride. That is, the active component of the catalyst of this comparative example was copper chloride and cobalt chloride.

[0107] Other than Example 1.

[0108] In the present comparative example, the loading of the active component in the activated carbon supported catalyst was 16 wt%.

[0109] After 100 h of continuous reaction, the yield of the product 1-chlorobutane was 35.5% and the GC purity of the product was 69.849%.

[0110] The yield and purity of the product 1-chlorobutane obtained after the corresponding length of continuous reaction in each example and comparative example are shown in Table 2.

[0111] Table 2 Yield and purity of the product 1-chlorobutane

[0112]

[0113] As can be seen from the data in Table 2, the method for synthesizing 1-chlorobutane by fixed-bed gas-solid catalytic reaction according to the present application can continuously produce and maintain stable performance for a long time.

Claims

1. A process for the synthesis of 1-chlorobutane by a fixed-bed gas-solid catalytic reaction, characterized in that, The method comprises the following steps: (1) loading the activated carbon supported catalyst into a fixed bed reactor; The active component of the activated carbon supported catalyst is composed of ZnCl2, FeCl3 and KCl; wherein the mass ratio of ZnCl2: FeCl3: KCl is 1: (0.05-0.2): (0.05-0.15); The active component is uniformly loaded on the surface and pores of the carrier activated carbon, and the loading amount of the active component is 15%-20% of the total mass of the activated carbon supported catalyst; (2) passing preheated hydrogen chloride and vaporized n-butanol into the fixed bed reactor to contact with the activated carbon supported catalyst, wherein the molar ratio of hydrogen chloride to n-butanol is (1-2): 1; The catalytic reaction is carried out under the conditions that the reaction temperature is 150-250℃, the reaction pressure is 0.01-0.5MPa, the n-butanol space velocity is (0.1-2)h -1 The catalytic reaction is carried out under the conditions that the reaction temperature is 150-250℃, the reaction pressure is 0.01-0.5MPa, the n-butanol space velocity is (0.1-2)h -1 The catalytic reaction is carried out under the conditions that the reaction temperature is 150-250℃, the reaction pressure is 0.01-0.5MPa, the n-butanol space velocity is (0.1-2)h -1 The catalytic reaction is The activated carbon supported catalyst in step (1) is prepared by the following steps: 1) adding activated carbon into nitric acid solution, stirring, then suction filtering, washing with deionized water until neutral, and drying to obtain the activated carbon carrier; 2) taking ZnCl2, FeCl3 and KCl and adding into deionized water, stirring uniformly to prepare a mixed salt solution; 3) immersing the activated carbon carrier prepared in step 1) into the mixed salt solution prepared in step 2), stirring, then standing, water bath evaporating the solvent, and drying to obtain the activated carbon supported catalyst; In step 1) of the preparation of the activated carbon supported catalyst, 1.5-2.5 mL of nitric acid solution is added per gram of activated carbon; wherein the concentration of the nitric acid solution is 1-12 mol / L; In step 1) of the preparation of the activated carbon supported catalyst, the stirring speed is 50 rpm-100 rpm, and the stirring time is 4 h-6 h; the drying time is 4 h-6 h; In step 3) of the preparation of the activated carbon supported catalyst, the standing time is 1 h-4 h, and the drying time is 4 h-6 h.

2. The process for the synthesis of 1-chlorobutane by fixed bed gas-solid catalytic reaction according to claim 1, characterized in that, The activated carbon supported catalyst in step (1) is a cylindrical particle with a diameter of Φ5 mm and a length of (4-7) mm.

3. The process for the synthesis of 1-chlorobutane by fixed bed gas-solid catalytic reaction as claimed in claim 1 wherein, In step 1) of the preparation of the activated carbon supported catalyst, 2 mL of nitric acid solution is added per gram of activated carbon; wherein the concentration of the nitric acid solution is 4-10 mol / L.

4. The process for the synthesis of 1-chlorobutane by fixed bed gas-solid catalytic reaction as claimed in claim 1 wherein, In step (2), the preheating temperature of hydrogen chloride is 160-230℃, and the vaporization temperature of n-butanol is 160-230℃.

5. The process for the synthesis of 1-chlorobutane by fixed bed gas-solid catalytic reaction as claimed in claim 1 wherein, In step (2), the cooling and gas-liquid separation are specifically operated as follows: Firstly, the obtained mixed gas containing 1-chlorobutane is heat-exchanged and cooled in a condenser at a temperature of 10-25℃; Then, the cooled mixed gas containing 1-chlorobutane is subjected to gas-liquid separation by using a gas-liquid separator to obtain a mixed liquid phase and a gas phase; The gas phase is treated with lye, and the unreacted hydrogen chloride contained therein is absorbed by the lye; The obtained mixed liquid phase is allowed to stand and separate into layers, and the upper organic phase is the product 1-chlorobutane.

6. The process for the synthesis of 1-chlorobutane by fixed bed gas-solid catalytic reaction as claimed in claim 1 wherein, The fixed bed reactor is a tube type fixed bed reactor with a specification of Φ38 mm x 4 mm x 2000 mm.

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