Catalyst composition and application thereof

Abstract

The invention relates to the technical field of preparation of 1, 1, 1, 2, 3-pentachloropropane, in particular to a catalyst composition and application thereof.The catalyst composition comprises a combination of a main catalyst and a cocatalyst; the main catalyst comprises a fluoride modified metal oxide; the co-catalyst comprises a chlorate. The catalyst composition provided by the invention has the advantages of stable structure, good catalytic activity, gas-phase catalysis of olefin chlorination reaction, difficult deactivation, long catalyst life and the like; when the catalyst composition is used for preparing 1, 1, 1, 2, 3-pentachloropropane, the requirement for technological conditions is low, a high-yield and high-purity product can be obtained through a simple technological process, and industrial production is facilitated.

Description

Technical Field

[0001] This application relates to the technical field of preparing 1,1,1,2,3-pentachloropropane, and more specifically to a catalyst composition and its application. Background Technology

[0002] 1,1,1,2,3-Pentachloropropane (240dB) is an important intermediate in the synthesis of 1,1,2,3-tetrachloropropene. There are many existing methods for the preparation of 1,1,1,2,3-pentachloropropane.

[0003] WO2014134377A discloses a process for producing propane chloride, which uses chlorine (Cl2) to catalyze the chlorination of 1,1,1,3-tetrachloropropane (250fb) to synthesize 240db in the presence of antimony chloride, aluminum chloride, and aluminum chloride catalysts. Although the reaction process is simple, Cl2 is controlled and toxic, posing a risk of leakage in industrial production. The antimony chloride catalyst is highly toxic and easily corrodes equipment.

[0004] WO2014158785A discloses a method for improving the selectivity of 1,1,3-trichloropropane and / or 3,3,3-trichloropropane in the dehydrochlorination of 1,1,1,3-tetrachloropropane. It points out that when ferric chloride is used as a catalyst for the dehydrochlorination of 1,1,1,3-tetrachloropropane, the reaction products contain a large number of high-boiling-point compounds, such as pentachlorocyclohexene and / or hexachlorocyclohexane, which inhibit the synthesis of 3,3,3-trichloropropene when one or more UV stabilizers and / or antioxidant compounds or mixtures thereof are added to the dehydrochlorination reaction system.

[0005] CN104163750A discloses a method for preparing 1,1,1,2,3-pentachloropropane and 1,1,2,3-tetrachloropropene, which discloses the use of copper chloride as an oxychlorination catalyst to catalyze the production of 1,1,1,2,3-pentachloropropane and 1,1,2,3-tetrachloropropene from trichloropropene. However, the conversion rates of the raw materials and the products in the patent are not high, and multiple products are generated, indicating that the catalytic ability needs to be improved. Furthermore, the activity of the catalyst is not reported.

[0006] In summary, the selection of catalyst is crucial in the preparation of 1,1,1,2,3-pentachloropropane. However, existing catalysts need further improvement in terms of reaction conditions and catalytic activity. Therefore, it is essential to develop a catalyst that can overcome the above-mentioned shortcomings. Summary of the Invention

[0007] In view of the above problems, this application provides a catalyst composition and its application. The catalyst composition has a stable structure and high stability, and has the advantages of high catalytic activity and long catalyst lifetime. When the catalyst composition is used to prepare 1,1,1,2,3-pentachloropropane, the process conditions are less demanding, hydrogen chloride can be used to replace chlorine in the reaction raw materials, which is energy-saving and environmentally friendly. It can also obtain high-yield and high-purity products with a simple process, which is beneficial to industrial production.

[0008] In a first aspect, this application provides a catalyst composition comprising a combination of a main catalyst and a co-catalyst;

[0009] The main catalyst comprises fluoride-modified metal oxides;

[0010] The co-catalyst includes a chloride salt.

[0011] In the technical solution of this application, the oxychlorination reaction mechanism of the metal oxide is the Langmuir-Hinshelwood mechanism. Its surface has strong Lewis acidity, which can catalyze the generation of chlorine from hydrogen chloride, followed by chlorination of olefins. However, it will over-react and eliminate the terminal Cl group. Therefore, fluorides are introduced to reduce its surface acidity. The co-catalyst provides a chlorine source on the one hand, and assists the main catalyst on the other hand. The two work synergistically. The catalyst composition has a stable structure and high stability, and has the advantages of high catalytic activity and long catalyst lifetime. When the catalyst composition is used to prepare 1,1,1,2,3-pentachloropropane, the process conditions are less demanding. For example, hydrogen chloride can be used instead of chlorine in the reaction raw materials, which is energy-saving and environmentally friendly. It can also obtain high-yield and high-purity products with a simple process, which is beneficial to industrial production.

[0012] Preferably, the fluoride is selected from at least one of BaF2, CaF2, and SrF2.

[0013] Preferably, the metal element in the metal oxide includes at least one of vanadium series metals, lanthanide metals, transition metals from the fifth period, or transition metals from the sixth period.

[0014] Preferably, the metal element in the metal oxide includes at least one of vanadium (V), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), and gold (Au).

[0015] More preferably, the metal element in the metal oxide includes at least one of vanadium (V), lanthanum (La), cerium (Ce), erbium (Er), europium (Eu), ruthenium (Ru), yttrium (Y), iridium (Ir), zirconium (Zr), and rhodium (Rh).

[0016] Preferably, the chloride salt is selected from at least one of lithium chloride (LiCl), sodium chloride (NaCl), potassium chloride (KCl), magnesium chloride (MgCl2), cesium chloride (CsCl), rubidium chloride (RbCl), and calcium chloride (CaCl2).

[0017] Preferably, based on the molar amount of the metal oxide, the molar content of the fluoride is 1%-10%, for example, 1%, 2%, 4%, 6%, 8%, 10%, etc.

[0018] Preferably, based on the molar amount of the metal oxide, the molar content of the chloride salt is 0.1%-1%, for example 0.1%, 0.2%, 0.4%, 0.6%, 0.8%, 1%, etc.

[0019] As an example, the preparation method of the catalyst composition includes the following steps:

[0020] The first metal salt was precipitated with ammonia water, and the second metal salt was modified by ammonium fluoride precipitation. The two were then mixed and post-treated to obtain the main catalyst.

[0021] The main catalyst and the co-catalyst are mixed and calcined to obtain the catalyst composition.

[0022] Preferably, the first metallic element in the first metal salt includes any one or a combination of at least two of the following: vanadium (V), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), and gold (Au).

[0023] More preferably, the first metallic element includes any one or a combination of at least two of vanadium (V), lanthanum (La), cerium (Ce), erbium (Er), europium (Eu), ruthenium (Ru), yttrium (Y), iridium (Ir), zirconium (Zr), and rhodium (Rh).

[0024] Preferably, the second metal element in the second metal salt includes any one or a combination of at least two of barium (Ba), magnesium (Mg), calcium (Ca) or strontium (Sr).

[0025] As an example, the post-processing includes filtration (such as vacuum filtration) and washing (the washing endpoint is confirmed by detecting the Cl in the eluent). - Concentration below 100 mg / L) and drying (e.g., drying temperature of 100-150℃, such as 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, etc.).

[0026] As an example, the mixing of the main catalyst and the co-catalyst may be carried out by immersing the main catalyst in a solution containing the co-catalyst.

[0027] As an example, the calcination temperature is 400-800℃ (e.g., 400℃, 450℃, 500℃, 550℃, 600℃, 650℃, 700℃, 750℃, 800℃, etc.); and / or;

[0028] The roasting time is 1-10 hours, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, etc.

[0029] As an example, the roasting process requires programmed temperature increase. First, the temperature is increased to 250-350℃ (e.g., 250℃, 300℃, 350℃) at a rate of 1-4℃ / min (e.g., 1℃ / min, 2℃ / min, 3℃ / min, 4℃ / min), and held at that temperature for 1-2 hours. Then, the temperature is increased to 400-800℃ (e.g., 400℃, 500℃, 600℃, 700℃, 800℃) at a rate of 0.5-1.5℃ / min (e.g., 0.5℃ / min, 1℃ / min, 1.5℃ / min), and held at that temperature for 1-2 hours.

[0030] As a preferred technical solution, the catalyst composition is obtained by the following preparation method:

[0031] The first metal salt was precipitated with ammonia water. The precipitate was then mixed with fluoride, washed, and dried at 100-150℃ to obtain the main catalyst.

[0032] The main catalyst is impregnated in a solution containing a co-catalyst and calcined at 400-800°C for 1-10 hours to obtain the catalyst composition.

[0033] The roasting process requires a programmed temperature increase. First, the temperature is increased to 250-350℃ at a rate of 1-4℃ / min and held for 1-2 hours. Then, the temperature is increased to 400-800℃ at a rate of 0.5-1.5℃ / min and held for 1-2 hours.

[0034] The first metallic element in the first metallic salt includes any one or a combination of at least two of the following: vanadium (V), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), and gold (Au).

[0035] More preferably, the first metal element in the first metal salt includes any one or a combination of at least two of vanadium (V), lanthanum (La), cerium (Ce), erbium (Er), europium (Eu), ruthenium (Ru), yttrium (Y), iridium (Ir), zirconium (Zr), and rhodium (Rh).

[0036] As an example, a method for preparing fluorides includes: modifying a second metal salt by precipitation with ammonium fluoride, wherein the second metal element of the second metal salt includes any one or a combination of at least two of barium (Ba), magnesium (Mg), calcium (Ca) or strontium (Sr).

[0037] In a second aspect, this application provides the use of the catalyst composition described in the first aspect in the preparation of 1,1,1,2,3-pentachloropropane.

[0038] Thirdly, this application provides a method for preparing 1,1,1,2,3-pentachloropropane, the method comprising the following steps:

[0039] The 1,1,1,2,3-pentachloropropane is obtained by reacting trichloropropylene and a mixed gas with the catalyst composition described in the first aspect.

[0040] In the technical solution of this application, the catalyst composition has excellent activity. Under the action of the catalyst composition, hydrogen chloride can replace chlorine in the traditional technology, and no light conditions are required. The preparation process is simple and has industrialization prospects.

[0041] Preferably, the reaction temperature is 300-500℃, such as 300℃, 350℃, 400℃, 450℃, 500℃, etc.

[0042] Preferably, the space velocity of the reaction is 400-800 h⁻¹. -1 For example, 400h -1 500h -1 600h -1 700h -1 800h -1 wait.

[0043] Preferably, the reaction is carried out in the gas phase.

[0044] Preferably, the mixed gas includes oxygen and hydrogen chloride.

[0045] Preferably, the molar ratio of oxygen, hydrogen chloride and trichloropropylene is (0.1-10):(1-10):(1-10), wherein 0.1-10 can be 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.; and 1-10 can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.

[0046] Preferably, the catalyst composition is activated and / or the trichloropropylene and mixed gas are preheated before the reaction.

[0047] Preferably, the activation treatment is carried out under an inert atmosphere.

[0048] Preferably, the flow rate of the inert atmosphere is 50-250 L / min.

[0049] Preferably, the activation treatment temperature is 200-400℃, such as 200℃, 220℃, 240℃, 260℃, 280℃, 300℃, 320℃, 340℃, 360℃, 380℃, 400℃, etc.

[0050] Preferably, the activation treatment time is 1-10 hours, such as 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, etc.

[0051] Preferably, the preheating temperature is 100-300℃, such as 100℃, 120℃, 140℃, 160℃, 180℃, 200℃, 220℃, 240℃, 260℃, 280℃, 300℃, etc.

[0052] As a preferred technical solution, the preparation method of 1,1,1,2,3-pentachloropropane includes the following steps:

[0053] In the presence of an inert gas, the catalyst composition is activated at 200-400°C for 1-10 h. Trichloropropylene and the mixed gas are preheated at 100-300°C, and then reacted at 300-500°C under the action of the catalyst composition. The mixed gas includes oxygen and hydrogen chloride, and the molar ratio of oxygen, hydrogen chloride and trichloropropylene is (0.1-10):(1-10):(1-10), with a space velocity of 400-800 h⁻¹. -1 The 1,1,1,2,3-pentachloropropane was obtained.

[0054] In this application, the trichloropropylene can be commercially available or manufactured in-house.

[0055] Preferably, the method for preparing trichloropropylene includes the following steps:

[0056] 1,1,1,3-Tetrachloropropane was reacted in the presence of a first catalyst to obtain the trichloropropene;

[0057] The first catalyst comprises a metal phosphate.

[0058] In the technical solution of this application, metal phosphate is used to catalyze the preparation of trichloropropane from 1,1,1,3-tetrachloropropane. Compared with iron-based catalysts, this method is less expensive and less prone to deactivation due to water absorption. Furthermore, hydrogen chloride is produced as a byproduct during the formation of trichloropropane from 1,1,1,3-tetrachloropropane, and the metal phosphate hardly reacts with hydrogen chloride, thus preventing the catalyst from adsorbing Cl. - This leads to catalyst poisoning and deactivation. However, the catalyst exhibits high activity and long catalytic lifetime during the reaction. Therefore, the preparation of trichloropropylene from 1,1,1,3-tetrachloropropane using metal phosphate catalysis has excellent comprehensive performance and promising industrial application prospects.

[0059] In the technical solution of this application, the byproduct hydrogen chloride can participate in the next reaction, saving energy and reducing costs.

[0060] Preferably, the metal element in the metal phosphate includes any one or a combination of at least two of the following: transition metal elements, group IIA metal elements, or group IIIA metal elements.

[0061] Preferably, the metal element in the metal phosphate includes any one or a combination of at least two of manganese, iron, zinc, nickel, copper, cobalt, aluminum, magnesium, gallium, indium, yttrium, zirconium, titanium, niobium, chromium, molybdenum, rubidium, palladium, silver, lanthanum, cerium, praseodymium, dysprosium, thulium, gadolinium, samarium, or erbium, and more preferably any one or a combination of at least two of magnesium, nickel, zinc, cerium, or aluminum.

[0062] Preferably, the reaction is carried out in the gas phase.

[0063] In the technical solution of this application, the reaction is carried out in the gas phase. Compared with the liquid phase method, it hardly generates byproducts such as pentachlorocyclohexene and / or hexachlorocyclohexane. The product is almost 3,3,3-trichloropropene (1240zf), with few other isomers. The purity, yield and selectivity of the product are all at a high level.

[0064] Preferably, the first catalyst further includes graphite.

[0065] In this application, the graphite serves as a crosslinking agent for the core component metal phosphate, facilitating catalyst granulation and increasing the specific surface area of ​​the catalyst.

[0066] Preferably, the graphite content is 0.1%-5% based on the total mass of metal phosphates (100%), for example, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, etc.

[0067] In this application, the preparation method of the first catalyst includes the following steps:

[0068] The metal chloride salt solution and the phosphoric acid solution are mixed, filtered, washed, dried, and then calcined to form a metal phosphate, thus obtaining the first catalyst.

[0069] Preferably, the mass concentration of the metal chloride salt is 10%-20%, such as 10%, 12%, 14%, 16%, 18%, 20%, etc.

[0070] Preferably, the mass concentration of the phosphoric acid solution is 80%-90%, such as 80%, 82%, 84%, 86%, 88%, 90%, etc.

[0071] Preferably, the calcination is carried out in an inert atmosphere.

[0072] Preferably, the roasting temperature is 200-400℃, such as 200℃, 250℃, 300℃, 350℃, 400℃, etc.

[0073] Preferably, the roasting time is 1-10 hours, such as 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, etc.

[0074] Optionally, the calcination process also includes granulation of the metal phosphate and graphite mixture.

[0075] Preferably, the reaction temperature is 200-400℃, such as 200℃, 250℃, 300℃, 350℃, 400℃, etc.

[0076] Preferably, the space velocity of the reaction is 500-1000 h⁻¹. -1 For example, 500h -1 600h -1 700h -1 800h -1 900h -1 wait.

[0077] Preferably, the reaction further includes activating the first catalyst and / or vaporizing the 1,1,1,3-tetrachloropropane.

[0078] Preferably, the activation treatment is carried out under an inert atmosphere.

[0079] Preferably, the activation treatment temperature is 300-700℃, such as 300℃, 400℃, 500℃, 600℃, 700℃, etc.

[0080] Preferably, the activation treatment pressure is ≤1MPa, for example 1.0MPa, 0.8MPa, 0.6MPa, 0.4MPa, etc.

[0081] Preferably, the activation treatment time is 1-24h, such as 1h, 3h, 5h, 7h, 9h, 12h, 14h, 16h, 18h, 20h, 24h, etc.

[0082] Preferably, the vaporization temperature is 200-300℃, such as 200℃, 220℃, 240℃, 260℃, 280℃, 300℃, etc.

[0083] As a preferred technical solution, the preparation method of trichloropropylene includes the following steps:

[0084] In an inert atmosphere, the first catalyst is activated at a temperature of 300-700℃ and a pressure ≤1MPa for 1-24 hours. 1,1,1,3-Tetrachloropropane is vaporized at 200-300℃, and then, under the action of the first catalyst, the 1,1,1,3-tetrachloropropane is vaporized at a space velocity of 500-1000 h⁻¹. -1 The reaction is carried out at 200-400℃ to obtain the trichloropropylene;

[0085] The first catalyst comprises a metal phosphate.

[0086] In this application, the preparation method contains hydrogen chloride as a byproduct, which can participate in the next reaction, saving energy and reducing costs.

[0087] Preferably, the method for preparing 1,1,1,3-tetrachloropropane includes the following steps:

[0088] Carbon tetrachloride and ethylene were reacted in the presence of a second catalyst to obtain the 1,1,1,3-tetrachloropropane.

[0089] The second catalyst comprises a combination of a metal catalyst and a phosphate ester catalyst.

[0090] Preferably, the mass ratio of the metal catalyst to the phosphate ester catalyst is (1-20):1, for example, 1:1, 2:1, 4:1, 6:1, 8:1, 10:1, 12:1, 14:1, 16:1, 18:1, 20:1, and more preferably (1-10):1.

[0091] As an example, the particle size of the metal catalyst is 10-500 mesh, such as 10 mesh, 50 mesh, 100 mesh, 150 mesh, 200 mesh, 250 mesh, 300 mesh, 350 mesh, 400 mesh, 450 mesh, 500 mesh, etc.; preferably a combination of 100-500 mesh and 10-60 mesh, with a mass ratio of (1-10):1, such as 1:1, 2:1, 4:1, 6:1, 8:1, etc.

[0092] As an example, the molar ratio of carbon tetrachloride to ethylene is (1-5):1, for example, it can be 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, etc., and is more preferably (1-2):1.

[0093] Preferably, the reaction temperature is 50-500℃, such as 50℃, 100℃, 150℃, 200℃, 250℃, 300℃, 350℃, 400℃, 450℃, 500℃, etc.

[0094] Preferably, the reaction time is 1-10 hours, such as 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, etc.

[0095] Preferably, the reaction pressure is 0.5-2 MPa, for example 0.5 MPa, 0.6 MPa, 0.8 MPa, 1 MPa, 1.2 MPa, 1.4 MPa, 1.6 MPa, 1.8 MPa, 2 MPa, etc.

[0096] As a preferred technical solution, the preparation method of 1,1,1,3-tetrachloropropane includes the following steps:

[0097] Carbon tetrachloride and ethylene in a molar ratio of (1-5):1 were reacted with a second catalyst at a temperature of 50-500℃ and a pressure of 0.5-2MPa for 1-10h to obtain the 1,1,1,3-tetrachloropropane.

[0098] The second catalyst comprises a combination of a metal catalyst and a phosphate ester catalyst.

[0099] As a preferred technical solution, the preparation method of 1,1,1,2,3-pentachloropropane includes the following steps:

[0100] (1) In an inert atmosphere, the first catalyst is activated, and 1,1,1,3-tetrachloropropane is vaporized at 200-300℃. Then, 1,1,1,3-tetrachloropropane is vaporized at a space velocity of 500-1000 h⁻¹ under the action of the first catalyst. -1 The reaction is carried out at 200-400℃ to obtain the trichloropropylene;

[0101] The first catalyst comprises a metal phosphate;

[0102] Optionally, purification is performed after the reaction;

[0103] (2) In the presence of an inert gas, the catalyst composition described in the first aspect is activated by preheating trichloropropylene and the mixed gas at 100-300°C, and then reacting at 300-500°C under the action of the catalyst composition, wherein the mixed gas includes oxygen and hydrogen chloride, the molar ratio of oxygen, hydrogen chloride and trichloropropylene is (0.1-10):(1-10):(1-10), and the space velocity is 400-800 h⁻¹. -1 The 1,1,1,2,3-pentachloropropane was obtained.

[0104] As a further preferred technical solution, the preparation method of 1,1,1,2,3-pentachloropropane includes the following steps:

[0105] (1) Carbon tetrachloride and ethylene are reacted with a second catalyst at a temperature of 50-500℃ and a pressure of 0.5-2MPa for 1-10h to obtain the 1,1,1,3-tetrachloropropane.

[0106] The second catalyst comprises a combination of a metal catalyst and a phosphate ester catalyst;

[0107] Optionally, purification is performed after the reaction;

[0108] The reaction process is shown in the following reaction equation:

[0109]

[0110] (2) In an inert atmosphere, the first catalyst is activated at a temperature of 300-700℃ and a pressure ≤1MPa for 1-24h. 1,1,1,3-Tetrachloropropane is vaporized at 200-300℃, and then 1,1,1,3-tetrachloropropane is vaporized at a space velocity of 500-1000h under the action of the first catalyst. -1 The reaction is carried out at 200-400℃ to obtain the trichloropropylene;

[0111] The first catalyst comprises a metal phosphate;

[0112] Optionally, purification is performed after the reaction;

[0113] The reaction process is shown in the following reaction equation:

[0114]

[0115] (3) In the presence of an inert gas, the catalyst composition is activated at 200-400℃ for 1-10 h, and the trichloropropylene and mixture are preheated at 100-300℃. Then, under the action of the catalyst composition, the reaction is carried out at a temperature of 300-500℃. The mixed gas includes oxygen and hydrogen chloride, and the molar ratio of oxygen, hydrogen chloride and trichloropropylene is (0.1-10):(1-10):(1-10), with a space velocity of 400-800 h⁻¹. -1 The 1,1,1,2,3-pentachloropropane was obtained.

[0116] The reaction process and principle change as shown in the following reaction equation:

[0117]

[0118] In this context, "*" refers to an electron.

[0119] Compared with the prior art, the technical solution of this application has at least the following beneficial effects:

[0120] (1) The catalyst composition described in this application has a stable structure, good catalytic activity, gas-phase catalytic chlorination of olefins, is not easily deactivated, and has a long catalyst life.

[0121] (2) When the catalyst composition described in this application is used to prepare 1,1,1,2,3-pentachloropropane, the process conditions are less demanding. Hydrogen chloride can be used to replace chlorine in the reaction raw materials, which is energy-saving and environmentally friendly. It can also obtain high-yield and high-purity products with a simple process and can be produced continuously, which is conducive to industrial production.

[0122] (3) This application uses metal phosphate to catalyze the preparation of trichloropropane from 1,1,1,3-tetrachloropropane. Compared with iron-based catalysts, it has a lower cost and is less prone to water absorption and deactivation, which improves the selectivity of trichloropropane and eliminates the formation of high-boiling-point byproducts. In addition, 1,1,1,3-tetrachloropropane produces hydrogen chloride as a byproduct during the formation of trichloropropane. Metal phosphate hardly reacts with hydrogen chloride, exhibiting high activity and long catalytic lifetime during the reaction, and has industrialization prospects.

[0123] The above description is only an overview of the technical solution of this application. In order to better understand the technical means of this application and to implement it in accordance with the contents of the specification, and to make the above and other objects, features and advantages of this application more obvious and understandable, the following are specific embodiments of this application. Detailed Implementation

[0124] The embodiments of the technical solution of this application will be described in detail below. The following embodiments are only used to illustrate the technical solution of this application more clearly, and are therefore only examples, and should not be used to limit the scope of protection of this application.

[0125] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the application; the terms “comprising” and “having”, and any variations thereof, in the specification and claims of this application are intended to cover non-exclusive inclusion.

[0126] In the description of the embodiments of this application, technical terms such as "first" and "second" are used only to distinguish different objects and should not be construed as indicating or implying relative importance or implicitly specifying the number, specific order, or primary and secondary relationship of the indicated technical features. In the description of the embodiments of this application, "multiple" means two or more, unless otherwise explicitly defined.

[0127] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments.

[0128] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60–120 and 80–110 are listed for a specific parameter, it is also expected that ranges of 60–110 and 80–120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1–3, 1–4, 1–5, 2–3, 2–4, and 2–5. In this application, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "2-10" indicates that all real numbers between "2-10" have been listed in this article; "2-10" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0129] In the description of the embodiments in this application, the term "and / or" is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent three cases: A exists, A and B exist simultaneously, and B exists. In addition, the character " / " in this document generally indicates that the related objects before and after it have an "or" relationship.

[0130] [Preparation of 1,1,1,3-Tetrachloropropane]

[0131] Preparation Example 1

[0132] This preparation example provides a method for preparing 1,1,1,3-tetrachloropropane (250fb), the preparation method comprising the following steps.

[0133]

[0134] Carbon tetrachloride and ethylene were added to a high-pressure reactor at a molar ratio of 1.5:1. Under the action of a second catalyst (iron powder and triethyl phosphite in a mass ratio of 1.5:1, the iron powder being a mixture of 400-mesh and 50-mesh iron powder in a mass ratio of 3:1), the system pressure was adjusted to 1 MPa and the temperature to 100 °C. The reaction time was 10 h, followed by distillation to obtain the product, 1,1,1,3-tetrachloropropane. The results showed that the initial conversion of ethylene was 100%, and the initial selectivity at 250 fb was 98%.

[0135] In this application, the testing methods for conversion rate and selectivity are as follows:

[0136] (1) Conversion rate: The reactants were analyzed by gas chromatography (GC), and the conversion rate was calculated using the results.

[0137] (2) Selectivity: The reactants are analyzed by gas chromatography (GC), and the conversion rate is calculated using the results.

[0138] (3) Lifetime evaluation: The catalyst was evaluated after 1000h of reaction. Samples were taken every 8h and the products were detected by GC. The conversion rate and selectivity were calculated to determine the changes in conversion rate and selectivity during the 1000h reaction.

[0139] The following sections describe the conversion rate and selectivity tests, as well as lifetime evaluations.

[0140] [Preparation of trichloropropylene]

[0141] Preparation Examples 2-6 and Preparation Comparative Examples 1-5

[0142] The key preparation parameters are shown in Table 1. Taking Preparation Example 3 as an example, a method for preparing trichloropropylene is provided, which specifically includes the following steps. The other preparation examples are similar:

[0143]

[0144] Nickel chloride solution was added dropwise to 85% phosphoric acid solution with stirring. The molar ratio of nickel chloride to phosphoric acid was 1:1. Then, 1M ammonia water was added to adjust the pH of the system to 7. The mixture was filtered, washed, and dried overnight at 120°C. Under N2 conditions, the mixture was first kept at 250°C for 2 hours and then at 350°C for 3 hours. The resulting solid was pulverized, mixed with 2wt% graphite, and then compressed into tablets and granulated to obtain the first catalyst.

[0145] 100 mL of the first catalyst was packed into a tubular reactor, and nitrogen gas (N2) was introduced at a flow rate of 2.5 L / min. The first catalyst was activated for 15 h at a pressure of 0.1 MPa and a temperature of 400 °C. Then the N2 was stopped.

[0146] 1,1,1,3-Tetrachloropropane is introduced into a preheater and vaporized at 250°C.

[0147] Subsequently, 1,1,1,3-tetrachloropropane underwent a deHCl removal reaction under the action of a first catalyst, with the reactor temperature adjusted to 260℃ and the space velocity of 1,1,1,3-tetrachloropropene adjusted to 800 h⁻¹. -1 The reaction product, trichloropropylene, is obtained.

[0148] The product was passed through an alkaline solution, dried, and subjected to GC detection. The conversion rate and selectivity were calculated and summarized in Table 1.

[0149] Table 1

[0150]

[0151] As can be seen from the results of Comparative Examples 1-5 and Preparation Examples 2-6 in Table 1, when the first catalyst prepared in this application is used to catalyze the preparation of trichloropropylene, the initial conversion rate of the reactants is above 94.37% and the initial selectivity of the products is above 96.49%; both reach above 94%, and the optimal value can reach above 99%. Moreover, the first catalyst still maintains high activity after running for 1000 hours, specifically reflected in the conversion rate of reactants above 93.61% and the selectivity of products above 94.28%.

[0152] In summary, the use of metal phosphate catalysis to prepare trichloropropylene from 1,1,1,3-tetrachloropropane is less costly and less prone to deactivation due to water absorption compared to iron-based or other catalysts, thus improving the selectivity of trichloropropylene and eliminating the formation of high-boiling-point byproducts. Furthermore, while 1,1,1,3-tetrachloropropane produces hydrogen chloride as a byproduct during trichloropropylene formation, metal phosphates show almost no reaction with hydrogen chloride, exhibiting high activity and long catalytic lifetime during the reaction. Therefore, the use of metal phosphate catalysis for the preparation of trichloropropylene from 1,1,1,3-tetrachloropropane demonstrates excellent overall performance and promising industrial application prospects.

[0153] [Preparation of 1,1,1,2,3-pentachloropropane]

[0154] Example 1

[0155] This embodiment provides a method for preparing 1,1,1,2,3-pentachloropropane, specifically including the following steps:

[0156]

[0157] 24.64 g of CeCl2 was dissolved in 100 mL of water and precipitated with an equal volume of 3 mol / L ammonia. 1.04 g of BaCl2 was dissolved in 10 mL of water and precipitated with an equal volume of 1 mol / L NH4F. The two solutions were then mixed and stirred for 10 min, vacuum filtered, washed, and dried overnight at 120 °C to obtain the main catalyst. The main catalyst was then impregnated in potassium chloride solution for 24 h, dried by rotary evaporation, and calcined at 540 °C for 4 h. The final KCl loading was 0.5%, yielding the catalyst composition, BaCeOF2-KCl.

[0158] A quartz reaction tube with a length of 30 mL and an inner diameter of 1 cm is filled with 1 g of catalyst composition, and a steel column is filled to 10 cm.

[0159] Activate in an N2 atmosphere with a flow rate of 100 mL / min at 250 °C for 2 h;

[0160] Trichloropropene, HCl, and oxygen were preheated in a vaporization chamber at 200°C; then introduced into the reactor at a reaction temperature of 400°C and a space velocity of 600 h⁻¹. -1 The reaction mixture was prepared with an O2:HCl:trichloropropene molar ratio of 1:3.7:2.5. The reaction product was washed with alkali and dried, and then analyzed by GC. The conversion and selectivity were calculated. The final product was 1,1,1,2,3-pentachloropropane.

[0161] Examples 2-4 and Comparative Examples 1-6

[0162] Same as Example 1, see Table 2 for specific parameters.

[0163] Table 2

[0164]

[0165]

[0166] As can be seen from the results in Table 2, Comparative Examples 1-6 and Examples 1-4, the catalyst composition prepared in this application can achieve an initial conversion rate of over 96.62% for the raw materials and a product selectivity of over 96.32%. Furthermore, the catalyst maintains high activity even after 1000 hours of operation, specifically with a raw material conversion rate of over 95.33% and a product selectivity of over 96.01%.

[0167] As can be seen from the results of Example 1 and Comparative Example 6, the synergistic effect of the co-catalyst and the main catalyst can improve the selectivity of the product. Therefore, the catalyst composition prepared in this application is more suitable for the preparation of 1,1,1,2,3-pentachloropropane.

[0168] Example 5

[0169] This embodiment provides a method for the continuous production of 1,1,1,2,3-pentachloropropane, specifically including the following steps:

[0170] (1) Preparation of 1,1,1,3-tetrachloropropane (250fb):

[0171] Carbon tetrachloride and ethylene were added to a high-pressure reactor at a molar ratio of 5:1. Under the action of a second catalyst (iron powder and triethyl phosphite in a mass ratio of 20:1, wherein the iron powder was a mixture of 400 mesh and 50 mesh iron powder in a mass ratio of 10:1), the system pressure was adjusted to 0.5 MPa and the temperature to 400 °C. The reaction time was 5 h, and the product, 1,1,1,3-tetrachloropropane, was obtained by distillation.

[0172] (2) Preparation of trichloropropylene:

[0173] 100 mL of the catalyst Zn3(PO4)2 from Preparation Example 5 was packed into a tubular reactor and reacted using the activation and reaction conditions of Preparation Example 5. The product was sampled and tested, then dried, distilled, and introduced into the next reactor for oxychlorination.

[0174] (3) Preparation of 1,1,1,2,3-pentachloropropane:

[0175] 10 mL of the BaCeOF2-KCl catalyst composition of Example 1 was packed into a tubular reactor, and the reaction was carried out using the activation and reaction conditions of Example 1. The reactant HCl was derived from the product of step (2).

[0176] The product was analyzed by GC, and the conversion and selectivity were calculated. A continuous gas-phase reaction of 1,1,1,2,3-pentachloropropane was achieved. The results are summarized in Table 3.

[0177] Table 3

[0178]

[0179] As can be seen from Table 3, the 1,1,1,2,3-pentachloropropane described in this application can be produced using a continuous production process, which is beneficial for industrial production.

[0180] A comprehensive analysis of the data in Tables 2 and 3 shows that the catalyst composition described in this application exhibits excellent catalytic activity in the gas-phase catalytic chlorination reaction of olefins, is not easily deactivated, and has a long catalyst life. When used in the preparation of 1,1,1,2,3-pentachloropropane, it has lower requirements for process conditions, can use hydrogen chloride instead of chlorine in the reaction feedstock, is energy-saving and environmentally friendly, and can obtain high-yield and high-purity products with a simple process. Furthermore, it allows for continuous production, which is beneficial for industrial production.

[0181] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and not to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. These modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application, and they should all be covered within the scope of the claims and specification of this application. In particular, as long as there is no structural conflict, the various technical features mentioned in the embodiments can be combined in any way. This application is not limited to the specific embodiments disclosed herein, but includes all technical solutions falling within the scope of the claims.

Claims

1. A catalyst composition, characterized in that, The catalyst composition comprises a combination of a main catalyst and a co-catalyst; The main catalyst comprises fluoride-modified metal oxides; The co-catalyst includes a chloride salt.

2. The catalyst composition according to claim 1, characterized in that, The fluoride is selected from at least one of BaF2, CaF2, and SrF2; Preferably, the metal element in the metal oxide includes at least one of vanadium series metals, lanthanide metals, transition metals from the fifth period, or transition metals from the sixth period. Preferably, the metal element in the metal oxide includes at least one of vanadium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, and gold; more preferably, the metal element in the metal oxide includes at least one of vanadium, lanthanum, cerium, erbium, europium, ruthenium, yttrium, iridium, zirconium, and rhodium.

3. The catalyst composition according to claim 1, characterized in that, The chloride salt is selected from at least one of lithium chloride, sodium chloride, potassium chloride, magnesium chloride, cesium chloride, rubidium chloride, and calcium chloride.

4. The catalyst composition according to claim 1, characterized in that, Based on the molar amount of the metal oxide, the molar content of the fluoride is 1%-10%; Preferably, the molar content of the chloride salt is 0.1%-1% based on the molar amount of the metal oxide.

5. The use of a catalyst composition according to any one of claims 1-4 in the preparation of 1,1,1,2,3-pentachloropropane.

6. A method for preparing 1,1,1,2,3-pentachloropropane, characterized in that, The preparation method includes the following steps: Trichloropropylene and a mixed gas are reacted under the action of the catalyst composition according to any one of claims 1-4 to obtain the 1,1,1,2,3-pentachloropropane.

7. The preparation method according to claim 6, characterized in that, The reaction temperature is 300-500℃; Preferably, the space velocity of the reaction is 400-800 h⁻¹. -1 ; Preferably, the mixed gas includes oxygen and hydrogen chloride; Preferably, the molar ratio of oxygen, hydrogen chloride, and trichloropropylene is (0.1-10):(1-10):(1-10); Preferably, the catalyst composition is activated and / or the trichloropropylene and mixed gas are preheated before the reaction; Preferably, the preheating temperature is 100-300℃.

8. The preparation method according to claim 6 or 7, characterized in that, The preparation method of the trichloropropylene includes the following steps: 1,1,1,3-Tetrachloropropane was reacted in the presence of a first catalyst to obtain the trichloropropene; The first catalyst comprises a metal phosphate, wherein the metal element in the metal phosphate includes any one or a combination of at least two of transition metal elements, Group IIA metal elements, or Group IIIA metal elements; Preferably, the metal element in the metal phosphate includes any one or a combination of at least two of manganese, iron, zinc, nickel, copper, cobalt, aluminum, magnesium, gallium, indium, yttrium, zirconium, titanium, niobium, chromium, molybdenum, rubidium, palladium, silver, lanthanum, cerium, praseodymium, dysprosium, thulium, gadolinium, samarium, or erbium; more preferably, any one or a combination of at least two of magnesium, nickel, zinc, cerium, or aluminum. Preferably, the first catalyst further includes graphite; Preferably, the graphite comprises 0.1%-5% of the total mass of metal phosphates (100%).

9. The preparation method according to claim 8, characterized in that, The reaction temperature is 200-400℃; Preferably, the space velocity of the reaction is 500-1000 h⁻¹. -1 ; Preferably, the reaction further includes activating the first catalyst and / or vaporizing the 1,1,1,3-tetrachloropropane; Preferably, the vaporization temperature is 200-300℃.

10. The preparation method according to any one of claims 6-9, characterized in that, The preparation method of the 1,1,1,2,3-pentachloropropane includes the following steps: (1) In an inert atmosphere, the first catalyst is activated, and 1,1,1,3-tetrachloropropane is vaporized at 200-300℃. Then, 1,1,1,3-tetrachloropropane is reacted at 200-400℃ under the action of the first catalyst, with a space velocity of 500-1000 h⁻¹. -1 The trichloropropylene is obtained; The first catalyst comprises a metal phosphate; (2) In the presence of an inert gas, the catalyst composition according to any one of claims 1-4 is activated by preheating trichloropropylene and the mixed gas at 100-300°C, and then reacting at 300-500°C under the action of the catalyst composition, wherein the mixed gas comprises oxygen and hydrogen chloride, the molar ratio of oxygen, hydrogen chloride and trichloropropylene is (0.1-10):(1-10):(1-10), and the space velocity is 400-800 h⁻¹. -1 The 1,1,1,2,3-pentachloropropane was obtained.

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